TEST BANK for Organic Chemistry A Learner Centered Approach 1st Edition by Richard Mullins by ACADEMIAMILL

Chapter 1

There are no test bank questions in chapter 1.

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 2 General Chemistry Translated: Finding the Electrons 1) Atoms with the same number of protons but different numbers of neutrons are called ________. Answer: isotopes Diff: 1 Section: 2.1 LO: G1 | 2.0.1

2) The atomic number of boron is 5. The correct electronic configuration of boron is: A) 1s22s3 B) 1s22p3 C) 1s22s22p1 D) 2s22p3 E) 1s22s23s1 Answer: C Diff: 1 Section: 2.2 LO: G1 | 2.0.1

LO: G1 | 2.0.1

4) The ________ tells us that each orbital can hold a maximum of 2 electrons. A) aufbau principle B) Pauli exclusion principle C) Hund's rule principle D) LeChatelier principle E) uncertainty principle Answer: B Diff: 1 Section: 2.2 LO: G1 | 2.0.4

5) A node is a region of high electron density between the two atoms in a covalent bond. Answer: FALSE Diff: 1 Section: 2.2 LO: G1 | 2.0.3

6) When filling two or more orbitals of the same energy with electrons, the electrons will go into different orbitals rather than pair up in the same orbital. Answer: TRUE Diff: 1 Section: 2.2 LO: G1 | 2.0.3

Section: 2.2 G1 | 2.0.1 | 2.0.3 8) An oxygen atom has ________ valence electrons. Answer: 6 Diff: 1 Section: 2.2 LO: G1 | 2.0.4

9) In a carbon atom, the 2s and 2p orbitals are the same energy. Answer: FALSE Diff: 2 Section: 2.2 LO: G1 | 2.0.3

10) The element with the electronic configuration 1s22s22p63s1 is ________. Answer: sodium Diff: 2 Section: 2.2 LO: G1 | 2.0.1

11) Provide the electron configuration of phosphorus. Answer: 1s22s22p63s23p3 Diff: 2 Section: 2.2 LO: G1 | 2.0.1

12) A carbon-hydrogen bond in ethane (CH3CH3) is best described a ________. A) highly polar B) essentially nonpolar C) ionic D) a multiple bond E) resonance stabilized Answer: B Diff: 1 Section: 2.3 LO: G2 | 2.1.5 MCAT LO: MCAT1.3

13) The electronegativity of elements on the periodic table increases going ________ a column and to the ________ in each row. A) up; right B) up; left C) down; right D) down; left Answer: A Diff: 1 Section: 2.3 LO: G1 | 2.1.4 MCAT LO: MCAT1.5

14) Which of the following molecules contains a polar covalent bond? A) H2 B) F2 C) CH3Cl D) NaCl E) He Answer: C Diff: 1 Section: 2.3 LO: G2 | 2.1.5 MCAT LO: MCAT1.3

15) Covalent bonds may be polar or nonpolar. What property of the atoms forming a given bond determines this? Answer: Electronegativity Diff: 2 Section: 2.3 LO: G2 | 2.1.3

16) The compound methylamine, CH3NH2, contains a C-N bond. In this bond, which of the following best describes the charge on the carbon atom? A) +1 B) slightly positive C) neutral D) slightly negative E) -1 Answer: B Diff: 3 Section: 2.3 LO: G2 | 2.1.2 MCAT LO: MCAT1.5

17) Provide a Lewis structure for a molecule with molecular formula CH2O2. Answer:

Diff: 2 Section: 2.4 LO: G2 | 2.2.2 GO: G2 MCAT LO: MCAT11.2

18) Write a Lewis structure for a compound with the molecular formula H2N2. Answer:

Diff: 2 Section: 2.4 LO: G2 | 2.2.2 MCAT LO: MCAT1.2

19) The formal charge on oxygen in dimethyl ether, CH3OCH3, is ________. A) +2 B) +1 C) 0 D) -1 E) -2 Answer: C Diff: 1 Section: 2.4 LO: G4 | 2.2.3 MCAT LO: MCAT1.2

20) For most compounds in which a nitrogen atom bears no formal charge, the valence of this nitrogen atom is ________. Answer: 3 Diff: 1 Section: 2.4 LO: G1 | 2.2.1

21) Assign the correct formal charge to each nitrogen atom in the following Lewis structure. (All nonbonding electrons are included.)

Answer:

Diff: 2 Section: 2.4 LO: G4 | 2.2.3 MCAT LO: MCAT1.2

22) Add the appropriate formal charge to each atom in the molecule below. It is not necessary to indicate formal charges when zero. (All non-bonding electrons are included.)

Answer:

23) Add the appropriate formal charge to each atom in the molecule below. It is not necessary to indicate formal charges when zero. (All non-bonding electrons are included.)

Answer:

Diff: 2 Section: 2.4 LO: G4 | 2.2.3 MCAT LO: MCAT1.2 24) One or more of the atoms in the structure shown should have nonzero formal charges. Redraw the structure and the atoms with non-zero formal charges.

Answer:

25) Which of the following are acceptable Lewis structures, including formal charges, for nitric acid, HNO3?

A) A only B) B only C) C only D) both B and C E) A, B, and C Answer: B Diff: 3 Section: 2.4 LO: G2 | 2.2.2 | 2.2.3 MCAT LO: MCAT1.3

26) A molecule of acetylene (C2H2) has a ________ geometry and a molecular dipole moment that is ________. A) tetrahedral; nonzero B) bent; nonzero C) bent; zero D) linear; nonzero E) linear; zero Answer: E Diff: 1 11 Copyright © 2021 Pearson Education, Inc.

Section: 2.5 LO: G2 | 2.3.1 | 2.3.2 MCAT LO: MCAT2.6

27) Which one of the molecules shown below has no net molecular dipole moment? A) CH3Cl B) H2C CH2 C) CH2O D) CH2Cl2 E) CH3OH Answer: B Diff: 2 Section: 2.5 LO: G2 | 2.3.1 | 2.3.2 MCAT LO: MCAT2.6

28) Which one of the molecules shown below has a net molecular dipole moment? A) CCl4 B) CO2 C) CH3CCl3 D) BeCl2 Answer: C Diff: 2 Section: 2.5 LO: G2 | 2.3.2 MCAT LO: MCAT2.6

29) Does 1,1-dichloroethene (Cl2C CH2) have a net molecular dipole moment? If it does, draw the molecule and indicate the direction of this molecular dipole moment. Answer: Net molecular dipole moment present.

Diff: 2 Section: 2.1 LO: G2 | 2.3.2 MCAT LO: MCAT2.6

30) Draw the three-dimensional structure of chloroform (CHCl3) and show the direction of the molecular dipole moment. Answer:

Diff: 2 Section: 2.5 LO: G2 | 2.3.2 MCAT LO: MCAT2.6

31) When a negatively charged species is most appropriately depicted as a hybrid of several resonance forms, the negative charge present is considered to be rapidly moving between the resonance forms bearing the formal negative charge. Answer: FALSE Diff: 1 Section: 2.8 LO: G1 | 2.6.4 MCAT LO: MCAT1.3

32) When a molecule can best be represented as a series of resonance forms, each of these forms always contributes to the same degree in the hybrid. Answer: FALSE Diff: 1 Section: 2.8 LO: G1 | 2.6.3 MCAT LO: MCAT1.3

33) Which of the following structures (a-d) is another resonance structure of the following organic molecule?

Diff: 2 Section: 2.8 LO: G2 | 2.6.2 MCAT LO: MCAT1.3

34) One resonance structure of a cation is shown. Provide the other reasonable resonance structures.

Answer:

Diff: 2 Section: 2.8 LO: G2 | 2.6.2 MCAT LO: MCAT2.3

35) Draw additional resonance contributors for:

Answer:

Section: 2.8 LO: G2 | 2.6.2 MCAT LO: MCAT2.3

36) Which of the following choices represent(s) a pair of resonance forms? A)

D) both A and C E) both B and C Answer: E Diff: 3 Section: 2.8 LO: G2 | 2.6.2 MCAT LO: MCAT1.3

37) Structures ________, shown below, are resonance structures, and structure ________ is the major contributor to the overall resonance hybrid.

A) 2 & 4; 2 B) 1, 3 & 5; 3 C) 4 & 6; 6 D) 1, 3 & 5; 1 E) 1, 3, 4 & 5; 3 Answer: B Diff: 3 Section: 2.8 LO: G2 | 2.6.3 MCAT LO: MCAT1.3

38) Nitroamines are common functional groups found in energetic materials, such as RDX and HMX. For the structure below, draw two other significant resonance structures, include any formal charges, and indicate the hybridization on each nitrogen and oxygen.

Answer: All nitrogen and oxygen atoms are sp2 hybridized.

Diff: 3 Section: 2.8 LO: G2 | 2.6.2 GO: G5 MCAT LO: MCAT2.3

39) Draw the other important resonance form of:

Answer:

Diff: 3 Section: 2.8 LO: G2 | 2.6.2 MCAT LO: MCAT2.3

40) Draw the important resonance forms for the structure shown below.

Answer:

Diff: 3 Section: 2.8 LO: G2 | 2.6.3 MCAT LO: MCAT2.3

41) Draw the important resonance forms for the structure shown below.

Answer:

Diff: 3 Section: 2.8 LO: G2 | 2.6.2

MCAT LO: MCAT2.3

42) Draw 3 significant resonance structures for the compound shown below. Place a box around the major contributor. Fill in any missing formal charges.

Answer:

Diff: 3 Section: 2.8 LO: G2 | 2.6.2 MCAT LO: MCAT2.3

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 3 Alkanes and Cycloalkanes: Properties and Conformational Analysis 1) Draw the structure of any hydrocarbon alkane which contains 5 carbon atoms. Answer: CH3CH2CH2CH2CH3

(CH3)2CHCH2CH3

(CH3)4C

Diff: 2 Section: 3.1 LO: 3.0.1 GO: G2

2) Which of the statements below accurately describe(s) alkanes? A) Alkanes are hydrocarbons which contain only single bonds. B) Alkanes belong to the class of unsaturated hydrocarbons. C) Alkanes are the simplest and least reactive class of organic compounds. D) both A and B E) both A and C Answer: E Diff: 1 Section: 3.1 LO: 3.0.1 GO: G1

3) Which of the following types of hydrocarbons is(are) saturated? A) alkanes B) alkenes C) alkynes D) aromatics E) All of the above are saturated. Answer: A Diff: 1 Section: 3.1 LO: 3.0.1 GO: G1

4) If a hydrocarbon has no double or triple bonds, it is said to be ________. Answer: saturated Diff: 1 Section: 3.1 LO: 3.0.1 GO: G1

5) If an acyclic alkane hydrocarbon contains n carbon atoms, how many hydrogen atoms must it also contain? A) n B) 2n C) n + 2 D) 2n + 2 E) n - 2 Answer: D Diff: 2 Section: 3.2 LO: 3.0.1 GO: G1

6) Triacontane is an unbranched alkane that contains 30 carbon atoms in each molecule. How many hydrogen atoms are present in each molecule of triacontane? A) 30 B) 32 C) 58 D) 60 E) 62 Answer: E Diff: 3 Section: 3.1 LO: 3.0.1 GO: G2

7) When one compares the densities of n-hexane and water, one finds ________. A) that n-hexane is less dense than water B) that n-hexane is more dense than water C) that these two compounds have the same density D) that the relative densities of two immiscible compounds cannot be measured Answer: A Diff: 1 Section: 3.1 LO: 3.0.2 GO: G2 MCAT LO: MCAT3.

8) A branched alkane has ________ boiling point relative to the isomeric linear alkane. There are ________ London force interactions in the branched alkane. A) a higher; stronger B) a higher; weaker C) a lower, stronger D) a lower; weaker E) the same; similar Answer: D Diff: 1 Section: 3.1 LO: 3.0.2 GO: G1 MCAT LO: MCAT3.3

9) ________ is the n-alkane of greatest molecular weight which is a gas at room temperature and pressure. Answer: Butane Diff: 2 Section: 3.1 LO: 3.0.2 GO: G1 MCAT LO: MCAT3.3

10) Place the following alkanes in order of increasing boiling point: CH3(CH2)6CH3, CH3(CH2)5CH3, (CH3)3CCH2CH2CH3 Answer: (CH3)3CCH2CH2CH3 < CH3(CH2)5CH3 < CH3(CH2)6CH3 Diff: 2 Section: 3.1 LO: 3.0.2 GO: G2 MCAT LO: MCAT3.3

11) Which intermolecular force is primarily responsible for the interactions among alkane molecules? Answer: van der Waals or London forces Diff: 2 Section: 3.1 LO: 3.0.4 GO: G1 MCAT LO: MCAT3.3

12) Draw a line-angle formula for (CH3)2CHCH2CH2NH2. Answer:

Diff: 1 Section: 3.2 LO: 3.1.1 GO: G2 MCAT LO: MCAT1.2

13) The Lewis structure of trimethylamine is shown below. Draw the condensed structural formula which corresponds to this Lewis structure.

Answer: (CH3)3N Diff: 1 Section: 3.2 LO: 3.1.1 GO: G2

14) The Lewis structure of pentane is shown below. Draw the condensed structural formula which corresponds to this Lewis structure.

Answer: CH3(CH2)3CH3 Diff: 1 Section: 3.2 LO: 3.1.1 GO: G2 MCAT LO: MCAT1.2

15) Which of the following condensed formulas represents the same compound as the line-angle structure shown?

A) CH3CH2CH2OCH2CH2CH2N(CH2CH2CH3)2 B) CH3CH2CH2OCH2N(CH2CH3)2 C) CH3CH2OCH2N(CH2CH3)2 D) CH3CH2OCH2N(CH2CH2CH3)2 E) CH3ON(CH3)2 Answer: C Diff: 2 Section: 3.2 LO: 3.1.2 GO: G2 MCAT LO: MCAT1.2 7 Copyright © 2021 Pearson Education, Inc.

16) Indicate the line-angle structure that corresponds to the condensed structure, HOCH2C(O)CH(CH3)2.

Answer: A Diff: 2 Section: 3.2 LO: 3.1.2 GO: G2 MCAT LO: MCAT1.2

17) A condensed structure for acetone is CH3COCH3. Provide the structural formula for acetone. Answer:

Diff: 2 Section: 3.2 LO: 3.1.1 GO: G2 MCAT LO: MCAT1.2

18) Provide the line-angle formula for the alcohol CH3CH2CH(OH)CH2CH2CH(CH3)2. Answer:

Diff: 2 Section: 3.2 LO: 3.1.1 GO: G2 MCAT LO: MCAT1.2

19) Provide the line-angle formula (skeletal structure) for (CH3CH2)2C=O. Answer:

Diff: 2 Section: 3.2 LO: 3.1.1 GO: G2 MCAT LO: MCAT1.2

20 Provide the line-angle formula (skeletal structure) for (CH3)2CHCH2CHO. Answer:

Diff: 2 Section: 3.2 LO: 3.1.1 GO: G2 MCAT LO: MCAT1.2

21) Draw an acceptable line-angle formula for cyclobutanol (shown below).

Answer:

Diff: 2 Section: 3.2 LO: 3.1.1 GO: G2 MCAT LO: MCAT1.2

22) Draw an acceptable line-angle formula for the compound shown below.

Answer:

Diff: 2 Section: 3.2 LO: 3.1.1 GO: G2 MCAT LO: MCAT1.2

23) Draw a correct Lewis structure for acetaldehyde, CH3CHO. Answer:

Diff: 2 Section: 3.2 LO: 3.1.1 GO: G2 MCAT LO: MCAT1.2

24) Draw a correct Lewis structure for CH3CHCHCOOH. Answer:

Diff: 2 Section: 3.2 LO: 3.1.1 GO: G2 MCAT LO: MCAT1.2

25) Which of the following condensed formulas correctly represents the line-angle structure shown below?

A) CH(CH3)2CH(CH3)CO2H B) C2(CH3)3CO2H C) (CH3)2CC(CH3)CO2H D) C(CH3)2C(CH3)CH2CO2H Answer: C Diff: 2 Section: 3.2 LO: 3.1.1 GO: G2 MCAT LO: MCAT1.2

26) Draw the line-angle formula for three compounds with molecular formula C3H8O. Answer:

Diff: 2 Section: 3.2 LO: 3.1.1 | 3.2.1 GO: G2 MCAT LO: MCAT1.1

27) Provide the line-angle formula for CH3CH2C(CH3)2CH2CHO Answer:

Diff: 2 Section: 3.2 LO: 3.1.1 GO: G2 MCAT LO: MCAT1.2

28) Draw condensed structures for the four compounds with formula C3H9N. Answer: CH3CH2CH2NH2

CH3CH2NHCH3

(CH3)2CHNH2

(CH3)3N Diff: 3 Section: 3.2 LO: 3.1.1 | 3.2.1 GO: G2 MCAT LO: MCAT1.1

29) The structure below is a potent analgesic agent (pain reliever) (J. Med. Chem., 2009, 5685). How many secondary carbons are in this structure?

A) 2 B) 4 C) 6 D) 12 Answer: A

Diff: 2 Section: 3.3 LO: 3.2.3 GO: G2

30) How many secondary (2°) carbons are found in 5-ethyl-3,3,4-trimethylheptane? A) 1 B) 4 C) 2 D) 3 E) 6 Answer: D Diff: 1 Section: 3.3 LO: 3.2.3 GO: G2

31) Provide an acceptable name for (CH3CH2CH2)3CH. Answer: 4-propylheptane Diff: 1 Section: 3.3 LO: 3.2.2 GO: G2 MCAT LO: MCAT3.1

32) Provide the name of the compound below.

Answer: 2,3,6,7-tetramethylnonane Diff: 1 Section: 3.3 LO: 3.2 MCAT LO: MCAT3.1

33) Provide an acceptable name for the alkane shown below.

CH3CH2CH2CH2CH2CH3 Answer:

hexane or n-hexane

Diff: 1 Section: 3.3 LO: 3.2.2 GO: G2

MCAT LO: MCAT3.1

34) Provide an acceptable name for the alkane shown below.

Answer: 2,5-dimethylheptane Diff: 1 Section: 3.3 LO: 3.2.2 GO: G2 MCAT LO: MCAT3.1

35) Draw an acceptable structure for 3-ethyl-3-methylhexane. Answer:

Diff: 1 Section: 3.3 LO: 3.1.1 GO: G2 MCAT LO: MCAT3.1

36) Draw an acceptable structure for 6-ethyl-2,6,7-trimethyl-5-propylnonane. Answer:

Diff: 2 Section: 3.3 LO: 3.1.1 GO: G2 MCAT LO: MCAT3.1 37) Provide an acceptable name for the alkane shown below.

Answer: 2,2,3,6-tetramethylheptane Diff: 2 Section: 3.3 LO: 3.2.2 GO: G2 MCAT LO: MCAT3.1

38) Provide an acceptable name for the alkane shown below.

Answer: 6-ethyl-2-methyl-5-propyldecane Diff: 2 Section: 3.3 LO: 3.2.4 GO: G2 MCAT LO: MCAT3.1

39) Name the alkane shown.

[(CH3)2CH]2CHCH3 Answer: 2,3,4-trimethylpentane Diff: 2 Section: 3.3 LO: 3.2.2 GO: G2 MCAT LO: MCAT3.1

40) Name the alkane shown.

Answer: 5-ethyl-2,2-dimethyloctane Diff: 2 Section: 3.3 LO: 3.2.4 GO: G2 MCAT LO: MCAT3.1

41) Give structures for the three isomers with molecular formula C5H12 and provide the common name of each. Answer:

Diff: 3 Section: 3.3 LO: 3.2.1 GO: G2 MCAT LO: MCAT3.2

42) Provide an acceptable name for the alkane shown below.

Answer: 3-ethyl-7-methyl-5-propylnonane Diff: 3 Section: 3.3 LO: 3.2.4 GO: G2 MCAT LO: MCAT3.1

43) Draw an acceptable structure for 4-ethyl-6-(1,2-dimethylpropyl)decane. Answer:

Diff: 3 Section: 3.3 LO: 3.2.1 GO: G2 MCAT LO: MCAT3.1

44) Consider the three isomeric alkanes n-hexane, 2,3-dimethylbutane, and 2-methylpentane. Which of the following correctly lists these compounds in order of increasing boiling point? A) 2,3-dimethylbutane < 2-methylpentane < n-hexane B) 2-methylpentane < n-hexane < 2,3-dimethylbutane C) 2-methylpentane < 2,3-dimethylbutane < n-hexane D) n-hexane < 2-methylpentane < 2,3-dimethylbutane E) n-hexane < 2,3-dimethylbutane < 2-methylpentane Answer: A Diff: 2 Section: 3.3 LO: 3.3.4 GO: G2 MCAT LO: MCAT3.3

45) The energy barrier for carbon-carbon bond rotation in propane is mainly due to ________. A) angle strain B) bond strain C) muscle strain D) steric strain E) torsion strain Answer: E Diff: 1 Section: 3.4 LO: 3.3.3 GO: G1

46) The structures below are ________.

A) not isomers B) conformational isomers C) cis-trans isomers D) structural isomers E) both B and D Answer: D Diff: 2 Section: 3.4 LO: 3.3.5 GO: G2 MCAT LO: MCAT2.4

47) Define the term conformation. Answer: Conformations are different arrangements of the same molecule formed by rotations about single bonds. Diff: 2 Section: 3.4 LO: 3.3.5 GO: G1

48) Which of the following statements concerning the conformers of butane is true? A) Unlike ethane, all butane conformers are classified as eclipsed. B) The lowest energy conformer of butane is the gauche conformer. C) There is more torsional strain in the anti conformer than in the totally eclipsed conformer. D) The eclipsed and totally eclipsed conformers have the same amount of nonbonded strain. E) The gauche and anti conformers differ primarily in the amount of nonbonded strain present. Answer: E Diff: 2 Section: 3.4 LO: 3.3.5 GO: G2 MCAT LO: MCAT3.4

49) Arrange the following conformers of butane in order of energy, lowest to highest: eclipsed, totally eclipsed, gauche, and anti. Answer: anti < gauche < eclipsed < totally eclipsed Diff: 2 Section: 3.4 LO: 3.3.5 GO: G2 MCAT LO: MCAT3.4

50) Among the butane conformers, which occur at energy minima on a graph of potential energy versus dihedral angle? A) gauche only B) eclipsed and totally eclipsed C) gauche and anti D) eclipsed only E) anti only Answer: C Diff: 3 Section: 3.4 LO: 3.3.5 GO: G2 MCAT LO: MCAT3.4

51) A bicyclic alkane contains 12 carbon atoms. How many hydrogen atoms does it contain? A) 20 B) 22 C) 24 D) 26 E) 28 Answer: B Diff: 2 Section: 3.5 LO: 3.4.1 GO: G2

52) Identify the correct IUPAC name for the following structure.

A) 6-bromo-1-cyclopentyl-3,6-dimethylhexane B) 1-bromo-5-cyclopentyl-1,4-dimethylpentane C) 2-bromo-6-cyclopentyl-5-methylhexane D) 5-bromo-1-cyclopentyl-2-methylhexane E) none of the above Answer: D Diff: 3 Section: 3.5 LO: 3.4.1 GO: G2 MCAT LO: MCAT6.1

53) Draw an acceptable structure for 1-ethyl-2-(2,2-dimethylpentyl)cyclopentane. Answer:

Diff: 3 Section: 3.5 LO: 3.4.1 GO: G2 MCAT LO: MCAT3.1

54) If a monocyclic alkane hydrocarbon contains n carbon atoms, how many hydrogen atoms must it also contain? A) n B) 2n C) n + 2 D) 2n + 2 E) n - 2 Answer: B Diff: 1 Section: 3.5 LO: 3.4.1 GO: G2

55) Give the IUPAC name for the cycloalkane shown below.

Answer: trans-1-ethyl-2-methylcyclopentane Diff: 1 Section: 3.5 LO: 3.2.4 | 3.4.2 GO: G2 MCAT LO: MCAT3.1

56) Give the IUPAC name for the cycloalkane shown below.

Answer: cis-1-isopropyl-3-methylcycloheptane Diff: 1 Section: 3.5 LO: 3.2.4 | 3.4.2 GO: G2 MCAT LO: MCAT3.1

57) Provide an acceptable name for the following compound.

Answer: isobutylcyclopentane or (2-methylpropyl)cyclopentane Diff: 2 Section: 3.5 LO: 3.2.4 | 3.4.1 GO: G2 MCAT LO: MCAT3.1

58) Provide the name of the compound below.

Answer: sec-butylcycloheptane Diff: 2 Section: 3.5 LO: 3.2.4 | 3.4.1 GO: G2 MCAT LO: MCAT3.1

59) Given the following heats of combustion per CH2 group within the structure, which cyclic alkane has essentially no angle strain? (Ref: long-chain Alkane = 659 kJ/mol) A) cyclobutane = 686 kJ/mol B) cyclopentane = 664 kJ/mol C) cyclohexane = 659 kJ/mol D) cycloheptane = 662 kJ/mol E) cyclooctane = 663 kJ/mol Answer: C Diff: 1 Section: 3.6 LO: 3.5.2 GO: G2

60) Which of the following correctly ranks the cycloalkanes in order of increasing ring strain per methylene? A) cyclopropane < cyclobutane < cyclohexane < cyclopentane B) cyclohexane < cyclopentane < cyclobutane < cyclopropane C) cyclohexane < cyclobutane < cyclopentane < cyclopropane D) cyclopentane < cyclopropane < cyclobutane < cyclohexane E) cyclopropane < cyclopentane < cyclobutane < cyclohexane Answer: B Diff: 2 Section: 3.6 LO: 3.5.1 GO: G2

61) Which of the following cycloalkanes has the smallest heat of combustion per CH2 group? A) cyclopropane B) cyclobutane C) cyclopentane D) cyclohexane E) cycloheptane Answer: D Diff: 2 Section: 3.6 LO: 3.5.2 GO: G2

62) Which of the following statements regarding cyclobutane is correct? A) The lowest energy conformation of cyclobutane is a planar one in which all of the bond angles is 90°. B) The lowest energy conformation of cyclobutane is known as the chair conformation. C) The lowest energy conformation is one in which the bond angles are slightly less than 90° even though this increases angle strain. D) The lowest energy conformation is one in which the bond angles are greater than 90° so that angle strain is significantly reduced. E) None of the above statements is correct. Answer: C Diff: 3 Section: 3.6 LO: 3.5.1 GO: G2

63) Describe the sources of angle strain and torsional strain present in cyclopropane. Answer: The angle strain arises from the compression of the ideal tetrahedral bond angle of 109.5° to 60°. The large torsional strain occurs since all C—H bonds on adjacent carbons are eclipsed. Diff: 3 Section: 3.6 LO: | 3.3.3 | 3.3.4 | 3.5.1 GO: G2

64) The twisted boat conformation of cyclohexane is actually a slightly lower energy conformation than the boat conformation. Which of the following accurately describes one factor involved in this structural behavior? A) lower angle strain in the boat B) higher torsional strain in the twisted boat C) fewer unfavorable steric factors in the twisted boat D) increased rotational freedom in the boat E) lower bond strain in the boat Answer: C Diff: 1 Section: 3.7 LO: 3.3.4 | 3.5.1 GO: G2

65) In the boat conformation of cyclohexane, the "flagpole" hydrogens are located ________. A) on the same carbon B) on adjacent carbons C) on C-1 and C-3 D) on C-1 and C-4 E) none of the above Answer: D Diff: 2 Section: 3.7 LO: 3.6.2 GO: G2

66) Which of the following correctly lists the conformations of cyclohexane in order of increasing energy? A) chair < boat < twist < half-chair B) half-chair < boat < twist < chair C) chair < twist < half-chair < boat D) chair < twist < boat < half-chair E) half-chair < twist < boat < chair Answer: D Diff: 3 Section: 3.7 LO: 3.6.3 GO: G2

67) In the lowest energy chair conformation of cis-1,3-dimethylcyclohexane, how many axial positions are occupied by hydrogen atoms? A) 2 B) 3 C) 4 D) 5 E) 6 Answer: E Diff: 3 Section: 3.7 LO: 3.6.2 | 3.6.4 GO: G2

68) Which of the statements below correctly describes the chair conformations of A) The two chair conformations are of equal energy. B) The higher energy chair conformation contains one axial methyl group and one equatorial methyl group. C) The lower energy chair conformation contains one axial methyl group and one equatorial methyl group. D) The higher energy chair conformation contains two axial methyl groups. E) The lower energy chair conformation contains two axial methyl groups. Answer: D Diff: 2 Section: 3.7 LO: 3.6.4 GO: G2

69) Which of the statements below correctly describes the chair conformations of A) The two chair conformations are equal in energy. B) The higher energy chair conformation contains two axial ethyl groups. C) The higher energy chair conformation contains two equatorial ethyl groups. D) The lower energy chair conformation contains two axial ethyl groups. E) The lower energy chair conformation contains two equatorial ethyl groups. Answer: A Diff: 2 Section: 3.7 LO: 3.6.4 GO: G2

70) In the lowest energy conformation of the compound below, how many alkyl substituents are equatorial?

A) 0 B) 1 C) 2 D) 3 E) 6 Answer: C Diff: 2 Section: 3.7 LO: 3.6.2 | 3.6.4 GO: G2

71) In the lowest energy conformation of the compound below, how many alkyl substituents are axial?

A) 0 B) 1 C) 2 D) 3 E) 6 Answer: A Diff: 2 Section: 3.7 LO: 3.6.2 | 3.6.4 GO: G2

72) Assuming a chair conformation, which of the following configurations will always have both methyl groups in relative axial/equatorial positions? A) trans-1,3-dimethylcyclohexane B) cis-1,3-dimethylcyclohexane C) cis-1,2-dimethylcyclohexane D) trans-1,2-dimethylcyclohexane E) Both B and D are correct. F) Both A and C are correct. Answer: F Diff: 2 Section: 3.7 LO: 3.6.2 GO: G2

73) Which of the following correctly lists the conformations of cis-1,4-di-t-butylcylcohexane in order of increasing energy? A) chair < boat < twist boat < half-chair B) twist boat < boat < chair < half-chair C) chair < twist boat < half-chair < boat D) boat < chair < twisted boat < half-chair E) half-chair < chair < boat < twisted boat Answer: B Diff: 3 Section: 3.7 LO: 3.6.4 GO: G2 MCAT LO: MCAT3.4

74) Dopamine is shown below. What functional group, or structural element is not present in this compound?

A) hydroxyl B) amino C) methylene D) aromatic ring E) carboxyl Answer: E Diff: 1 Section: 3.8 LO: 3.7.1 GO: G2

Saquinavir Structure

75) Which of the following functional groups is not present in the HIV protease inhibitor drug called Saquinavir? A) alcohol B) amide C) aromatic D) amine E) ketone Answer: E Diff: 2 Section: 3.8 LO: 3.7.1 GO: G2

76) Vildagliptin is a recently released antidiabetic drug (J. Med. Chem. 2010, 7902). Circle and name each functional group in vildagliptin.

Answer:

Diff: 2 Section: 3.8 LO: 3.7.1 GO: G2

77) The structure of Tamiflu, an antiinfluenza drug, is shown below (Organic Lett. 2007, 259). Circle and identify each functional group in Tamiflu.

Answer:

Diff: 3 Section: 3.8 LO: 3.7.1 GO: G2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 4 Acids and Bases/ Electron Flow 1) Which of the following is not a conjugate acid-base pair? A) H2O, HOB) H2O, H3O+ C) HSO4-, H2SO4 D) -OH, O2E) NO3-, NO2Answer: E Section: 4.2 LO: 4.1 MCAT: 1.4 2) What is the product of the following acid-base reaction?

A) CH3O- + +NH4 B) CH2OH + +NH3 C) CH3OH2+ + -NH2 D) CH3NH2 + H2O E) CH4 + NH2OH Answer: A Section: 4.2.2 LO: 4.1 MCAT: 1.4 3) The conjugate acid of H2O is A) H3O-. B) H3O. C) H3O+. D) HO-. E) H2O+. Answer: C Section: 4.2 LO: 4.1 MCAT: 1.4

4) Which of the following is the strongest acid? A) HB) HOC) HSO4D) H2O E) H3O+ Answer: E Section: 4.4.1 LO: 4.4 MCAT: 1.4 5) Which two species act as bases in the acid-base reaction shown below?

A) 1 and 2 B) 3 and 4 C) 2 and 4 D) 1 and 3 E) 2 and 3 Answer: C Section: 4.2.2 LO: 4.1 MCAT: 1.4 6) What is the conjugate acid of NH3? A) +NH3 B) -NH C) +NH4 D) -NH2 E) +NH2 Answer: C Section: 4.2 LO: 4.1 MCAT: 1.4

7) What is the conjugate acid of CH3NH2? A) CH3NH3+ B) CH3NHC) +NH4 D) -NH2 Answer: A Section: 4.2 LO: 4.1 MCAT: 1.4 8) What is the conjugate base of CH3NH2? A) CH3NH3+ B) CH3NHC) +NH4 D) -NH2 Answer: B Section: 4.2 LO: 4.1

9) What is the conjugate acid of HSO4-? What is the conjugate base of HSO4-? Answer: conjugate acid: H2SO4 conjugate base: SO42Section: 4.2 LO: 4.1 MCAT: 1.4 10) Write the products of the following acid-base reaction. HCO2H + -NH2 → Answer: HCO2H + -NH2 → HCO2- + NH3 Section: 4.2.2 LO: 4.1 MCAT: 1.4

11) What is the pH of a 0.1 M solution of HCl? A) 6 B) -6 C) 1 D) -8 E) -1 Answer: C Section: 4.3.3 LO: 4.3 MCAT: 1.4 12) If H2O has a pKa value of 15.7 and HF has a pKa value of 3.2, which is a stronger base, HOor F-? Explain. Answer: HO- is a stronger base than F- because HF is a stronger acid than H2O, and the stronger the acid the weaker its conjugate base. Section: 4.3.1 LO: 4.3 MCAT: 1.4 13) What base is formed in the following acid-base reaction? A) CH2O B) CH3OH C) CH3SH2+ D) CH3SE) H2O Answer: D Section: 4.2.2 LO: 4.1 MCAT: 1.4 14) What acid is formed in the following acid-base reaction? A) CH2O B) CH3OH C) CH3SH2+ D) CH3SE) H2O Answer: B Section: 4.2.2 LO: 4.1 MCAT: 1.4 4 Copyright © 2021 Pearson Education, Inc.

15) Which of the following is the strongest acid? A) CH3OH B) CH3OH2+ C) -NH2 D) CH3NH2 E) CH3NH3+ Answer: B Section: 4.4.1 LO: 4.4 16) The pKa of CH3COOH is 4.8 and the pKa of HCOOH is 3.8. Given this information, one knows that A) CH3COOH completely ionizes in water. B) HCOOH is a weaker acid than CH3COOH. C) HCOO- is a weaker base than CH3COO-. D) CH3COOH reacts with HO- while HCOOH does not. E) HCOOH reacts with HO- while CH3COOH does not. Answer: C Section: 4.3.2 LO: 4.3 MCAT: 20.2 17) Which of the following is the strongest acid? A) HF B) H2O C) NH3 D) CH4 E) CH3OH Answer: A Section: 4.4.1 LO: 4.4 MCAT: 1.4

18) Which of the following is the strongest acid? A) CH3CH2OH B) CH3OCH3 C) CH3NHCH3 D) CH3C CH E) CH3CH CH2 Answer: A Section: 4.4 LO: 4.4 MCAT: 1.4

19) Rank NH3, HF, and H2O in order of increasing acidity and explain your rationale. Answer: NH3 < H2O < HF Because N, F, and O are about the same size, we know that the strongest acid has its H attached to the most electronegative atom. Of the three atoms, F is the most electronegative and N is the least electronegative. Therefore, NH3 is the weakest acid and HF is the strongest acid. Section: 4.4.1 LO: 4.4 MCAT: 1.4 20) Which of the following has the highest pKa? A) CH3NH2 B) CH3OH C) CH3COOH D) H2O E) CH3NH3+ Answer: A Section: 4.3.1 LO: 4.3 MCAT: 1.4

21) Which of the following has the highest pKa? A) CH3CH3 B) HC CH C) CH2 CH2 D) CH3OH E) CH3NH2 Answer: A Section: 4.3.1 LO: 4.3 MCAT: 1.4 22) Which of the following carboxylic acids is the strongest acid? A) ICH2COOH B) BrCH2COOH C) CH3COOH D) FCH2COOH E) ClCH2COOH Answer: D Section: 4.4.1 LO: 4.4 MCAT: 1.4, 20.2 23) Which of the following is the strongest acid?

Section: 4.4.1 LO: 4.4 MCAT: 1.4, 20.2

24) Explain why NF3 is a weaker base than NH3. Answer: The electron withdrawing fluorine atoms reduce the availability of the lone-pair electrons on nitrogen. Therefore, NF3 is a weaker base than NH3. Section: 4.4.1 LO: 4.4 MCAT: 1.4,20.2

25) Which is a stronger acid, CF3SO3H or CH3SO3H? Explain your reasoning. Answer: CF3SO3H is a stronger acid. The F atoms withdraw electrons inductively, causing its conjugate base to be more stable than the conjugate base of CH3SO3H. The more stable the base, the stronger its conjugate acid. Section: 4.4.1 LO: 4.4 MCAT: 1.4 26) Is CH3CHBrCO2- or CH3CHFCO2- the stronger base? Explain your choice. Answer: CH3CHBrCO2- is the stronger base. F is better at withdrawing electrons inductively than Br because F is more electronegative. This greater inductive electron withdrawal stabilizes CH3CHFCO2- relative to CH3CHBrCO2-, which makes the latter a stronger base. Section: 4.4.1 LO: 4.4 MCAT: 1.4, 20.2

27) Draw a resonance contributor and the resonance hybrid for HOCO2-. Answer: resonance contributor: resonance hybrid:

Section: 2.8 LO: 2.6 MCAT: 20.8

28) The structure of Lorazepam, a drug used for short-term anxiety, is shown below. Is the indicated lone pair localized or delocalized?

Answer: Delocalized Section: 2.8 LO: 2.6 MCAT: 2.3 29) The pKa of CH3COOH is 4.8. If the pH of an aqueous solution of CH3COOH and CH3COO- is 4.8, then one knows A) CH3COOH is completely ionized. B) [CH3COOH] > [CH3COO-]. C) [CH3COOH] = [CH3COO-]. D) [CH3COOH] < [CH3COO-]. E) CH3COOH is completely unionized. Answer: C Section: 4.3.1,4.3.2 LO: 4.3 30) When a small amount of CH3(CH2)4CO2H, (pKa ~4.8) is added to a separatory funnel that contains ether and water with a pH = 2.0, it is found mainly in the ________ layer as ________. A) ether; CH3(CH2)4CO2B) water; CH3(CH2)4CO2C) ether; CH3(CH2)4CO2H D) water; CH3(CH2)4CO2H E) none of the above Answer: C Section: 4.3.2 LO: 4.3

31) When a small amount of CH3(CH2)4CO2H (pKa ~4.8) is added to a separatory funnel that contains ether and water with a pH = 12.0, it is found mainly in the ________ layer as ________. A) ether; CH3(CH2)4CO2B) water; CH3(CH2)4CO2C) ether; CH3(CH2)4CO2H D) water; CH3(CH2)4CO2H E) none of the above Answer: B Section: 4.3.2 LO: 4.3

32) At what pH will 25% of a compound with a pKa of 5.3 be in its basic form? Answer: 4.8 Section: 4.3.2 LO: 4.3

33) The amino acid glycine (H3N+CH2CO2H) has two acidic hydrogens, one with pKa = 2.34 and the other with pKa = 9.60. Draw the structure of the amino acid that predominates at pH = 12. Answer:

Section: 4.3.1,4.3.2 LO: 4.3 MCAT: 24.3

34) H-A is an acid with a pKa = 4.5. Which of the following statements about an aqueous solution of H-A is true? A) At pH = 4.5, the solution contains much more H-A than A-. B) At pH = 4.5, the solution contains much more A- than H-A. C) At pH- 3.5, the solution contains about 90% A- and 10% H-A. D) At pH = 6.5, the solution contains about 80% A- and 20% H-A. E) At pH = 5.5, the solution contains about 90% A- and 10% H-A. Answer: E Section: 4.3.1 LO: 4.3 35) At what pH will the concentration of a compound with a pKa = 5.7 be 100 times greater in its acidic form than in its basic form? Answer: 3.7 Section: 4.3.3 LO: 4.3 GLO: G2, G4 36) HCN has a pKa = 9.1. What form of the compound, HCN or CN-, predominates in a solution with pH = 7.0 Answer: HCN Section: 4.3.1 LO: 4.3

37) CH3CH2COOH, has a pKa = 4.9. Draw the structure of its conjugate base and give the pH at which the concentration of the basic form will be 10 times greater than the concentration of the acidic form. Answer: CH3CH2COO-; 5.9 Section: 4.3.1,4.3.2 LO: 4.3

38) A buffer is used to maintain the pH of human blood at ~ 7.4. Which acid/base pair buffers the blood? A) H2O / HOB) H3O+ / H2O C) H2CO3 / HCO3D) NH4+ / NH3 E) HCl / ClAnswer: C Section: 4.3.1,4.3.2 LO: 4.3 11 Copyright © 2021 Pearson Education, Inc.

39) Which of the following is not a Lewis acid? A) H+ B) BH3 C) AlCl3 D) NH4+ E) -NH2 Answer: E Section: 4.5 LO: 4.5 MCAT: 1.4

40) Draw curved arrows to show how CH3CH=CHCH3 reacts with HBr to form a carbocation. Answer:

Section: 4.2.1 LO: 4.1 MCAT: 1.4

41) Using curved arrows, show the movement of electrons in the following reaction step:

Answer:

Section: 4.2.1 LO: 4.1 MCAT: 1.4

42 Draw curved arrows to show how CH3CH=CHCH3 reacts with HBr to form a carbocation. Answer:

Section: 4.2.1 LO: 4.1 MCAT: 1.4

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 5 Chemical Reaction Analysis: Thermodynamics and Kinetics 1) Consider the reaction of A being converted into B at 25°C. If the ΔG° of this reaction is the Keq is ________ and the % conversion is ________. A) 0.18; 15% B) 0.43; 30% C) 1.0; 50% D) 2.3; 70% E) 5.4; 84% Answer: A Diff: 2 Section: 5.1 LO: 5.0.2 GO: G4

2) Consider the reaction of A being converted into B at 25°C. If the ΔG° of this reaction is the Keq is ________ and the % conversion is ________. A) 0.18; 15% B) 0.43; 30% C) 1.0; 50% D) 2.3; 70% E) 5.4; 84% Answer: B Diff: 2 Section: 5.1 LO: 5.0.2 GO: G4

3) Consider the reaction of A being converted into B at 25°C. If the ΔG° of this reaction is the Keq is ________ and the % conversion is ________. A) 0.18; 15% B) 0.43; 30% C) 1.0; 50% D) 2.3; 70% E) 5.4; 84% Answer: D Diff: 2 Section: 5.1 LO: 5.0.2 GO: G4

4) Given a reaction in which reactant A is converted only to product B at 25°C, what Keq results if at equilibrium 80% of A has become B? Answer: 4 Diff: 2 Section: 5.1 LO: 5.0.2 GO: G4

5) Given a K of 2.2 at 25°C, calculate the corresponding ΔG° in kJ/mol. [R = 8.314 J/K∙ mol] Answer: -2.0 kJ/mol Diff: 2 Section: 5.1 LO: 5.0.2 GO: G4

6) Given a K of 0.45 at 25°C, calculate the corresponding ΔG° in kJ/mol. [R = 8.314 J/K∙ mol] Answer: 2.0 kJ/mol Diff: 2 Section: 5.1 LO: 5.0.2 GO: G4

7) Given a ΔG° of -8.0 kJ/mol at 25°C, calculate the corresponding K. [R = 8.314 J/K∙ mol] Answer: 25 Diff: 2 Section: 5.1 LO: 5.0.2 GO: G4

8) Consider the transformation of A to B (i.e., A → B). If at equilibrium at 25°C the concentration of A is 20% of the initial concentration of A, determine the value of 1.987 cal/mol∙K.

(in kcal/mol) for this reaction. R =

Answer: -0.82 kcal/mol Diff: 2 Section: 5.1 LO: 5.0.2 GO: G4

9) If the equilibrium constant (Keq) of a reaction is 0.5 then which of the following that must be true? A) The reaction will have an early transition state. B) Reaction equilibrium will favor the products. C) Gibbs free energy (G) is positive. D) Gibbs free energy (G) is negative. Answer: C Diff: 2 Section: 5.1 LO: 5.0.1 GO: G2

10) Assume the reaction A + B → C + D proceeds to equilibrium. Calculate the equilibrium concentration of D at

given that the starting concentrations of A and B are 2M and that △G° for the reaction is

A) 0.40M B) 0.60M C) 1.00M D) 1.40M E) 1.60M Answer: B Diff: 3 Section: 5.1 LO: 5.0.2 GO: G4

11) Consider the following substitution reaction with a ΔG° value of -91.1 kJ/mole.

HO- + CH3Cl ↔ CH3OH + Cl-

Given this information which of the following statements must be true? (R = 8.315 J/mole K) A) The Keq at 25°C for this reaction is very large, in other words this reaction proceeds to near completion as written, left to right under standard conditions. B) The Keq at 25°C for this reaction is very small (<1), in other words this reaction does not proceed from left to right but rather is favored from right to left under standard conditions . C) At 250°C the equilibrium concentration is shifted right in favor of the products (CH3OH and Cl-). In other words there is more product than at 25°C. D) At 250°C the equilibrium concentration of products and reactants is nearly the same. E) Both A and C are correct. Answer: A Diff: 3 Section: 5.1 LO: 5.0.1 GO: G2

12) For the reaction A + B → C + D, ΔG° = -5.00 kcal/mol. What is the corresponding equilibrium constant at

R = 1.987 cal/mol∙K.

Answer: 4648 Diff: 3 Section: 5.1 LO: 5.0.2 GO: G4

13) Which is a measure of the randomness of a system? A) entropy B) enthalpy C) free energy D) halogenation E) stoichiometry Answer: A Diff: 1 Section: 5.1 LO: 5.0.4 GO: G1

14) In an exothermic reaction, are stronger bonds broken and weaker bonds formed or are weaker bonds broken and stronger bonds formed? Answer: In an exothermic reaction, weaker bonds are broken and stronger bonds are formed. Diff: 1 Section: 5.1 LO: 5.0.4 GO: G2

15) Which of the following statements correctly describes the contribution of

A) The entropy term makes a greater contribution to ΔG° at low temperatures. B) The entropy term makes a greater contribution to ΔG° at high temperatures. C) The entropy term makes a greater contribution to ΔG° in exothermic reactions. D) The entropy term makes a greater contribution to ΔG° in endothermic reactions. E) The entropy term always makes a more significant contribution to ΔG° than does the enthalpy term. Answer: B Diff: 2 Section: 5.1 LO: 5.0.4 GO: G2

16) If a reaction is exothermic, then ________. A) ΔS° < 0 B) ΔS° > 0 C) ΔH° < 0 D) ΔH° > 0 E) both B and D Answer: C Diff: 2 Section: 5.1 LO: 5.0.4 GO: G1

17) Which of the following correctly expresses the standard Gibbs free energy change of a reaction in terms of the changes in enthalpy and entropy? A) ΔG° = ΔH° - TΔS° B) ΔG° = ΔH° + TΔS° C) ΔG° = ΔS° - TΔH° D) ΔG° = ΔS° + TΔH° E) none of the above Answer: A Diff: 2 Section: 5.1 LO: 5.0.3 GO: G2

18) If stronger bonds are formed and weaker bonds are broken, then the reaction is ________. Answer: exothermic Diff: 2 Section: 5.1 LO: 5.0.4 | 5.0.5 GO: G2

19) Does one expect ΔS° in a propagation step of the free-radical chlorination of methane to be greater than zero, less than zero, or approximately equal to zero? Briefly explain your choice. Answer: The propagation steps of the free-radical chlorination of methane are shown below.

CH4 + Cl∙ → CH3∙ + H—Cl

CH3∙ + Cl—Cl → CH3Cl + Cl∙

In each of the steps, two reactant molecules generate two product molecules. This similarity in the number of molecular species means that the disorder in the reaction is neither greatly increased nor diminished. Therefore, one expects ΔS° in either propagation step to be approximately equal to zero. Diff: 2 Section: 5.1 LO: 5.0.6 GO: G2

20) The hydrogenation of acetylene to produce ethane is shown below. Is ΔS° for this reaction positive, negative, or impossible to predict? Explain your reasoning.

C2H2 (g) + 2H2 (g) → C2H6 (g) Answer: ΔS° < 0. The three reactant molecules have significantly more freedom of motion, and randomness, than does the single molecule of product into which they are converted. Diff: 2 Section: 5.1 LO: 5.0.6 GO: G2

21) Which of the following correctly expresses the standard Gibbs free energy change of a reaction in terms of the reaction temperature (T) and equilibrium constant (K)? A) ΔG° = e-K/RT B) ΔG° = eK/RT C) ΔG° = RTlnK D) ΔG° = -RTlnK E) none of the above Answer: D Diff: 2 Section: 5.1 LO: 5.0.2 GO: G2

22) Consider the reaction (CH3)3CBr + CH3CH2OH → Experimentally one finds that if the concentration of (CH3)3CBr is tripled, the rate of the reaction triples. One also finds that if the concentration of CH3CH2OH is doubled, the rate of the reaction is unchanged. Which of the following correctly describes the kinetics of this reaction? A) The reaction is third order in (CH3)3CBr. B) The reaction is first order in CH3CH2OH. C) The reaction is second order overall. D) The reaction is first order overall. E) none of the above Answer: D Diff: 2 Section: 5.2 LO: 5.3.6 GO: G2 MCAT LO: MCAT4.1

23) Given that the theoretical reaction below was found to be second order and bimolecular, provide a rate equation for the reaction.

A-B

C-D

→

A-C

B-D

Answer: Rate = kr[AB][CD] Diff: 2 Section: 5.2 LO: 5.3.6 GO: G2 MCAT LO: MCAT4.1

24) The following reaction occurs readily: Experimentally one finds that if the concentration of I- is doubled, the rate doubles. Also if the concentration of CH3Br is halved, the rate is halved. What is the rate equation for this reaction? Answer: rate = k[CH3Br][I-] Diff: 2 Section: 5.2 LO: 5.3.6 GO: G2 MCAT LO: MCAT4.1

25) The Arrhenius equation mathematically models which of the following statements? A) The rate of a chemical reaction increases exponentially with increasing concentration of reactants. B) The rate of a chemical reaction is directly related to the Ea and that increasing the temperature will alter the Ea for that reaction. C) Increasing the temperature of a chemical reaction increases the number of particles in the reaction that have the minimum energy required to meet the Ea. D) The rate of a chemical reaction is exponentially related to the Ea and relatively small differences in the Ea can dramatically affect the reaction rates of similar reactions at the same temperature. E) both C and D Answer: E Diff: 2 Section: 5.2 LO: 5.1.1 GO: G2

26) What term describes the highest-energy structure in a molecular collision which leads to reaction? Answer: transition state Diff: 1 Section: 5.2 LO: 5.2.1 GO: G1

27) Consider the conversion of X to Z through the sole intermediate Y. Given the reaction-energy diagram shown below, which step is the rate-limiting step? Explain your reasoning.

Answer: The conversion of Y to Z has a higher Ea than does the conversion of X to Y. The conversion of Y to Z is therefore rate-limiting. Diff: 2 Section: 5.2 LO: 5.2.2 GO: G3

28) Consider the three-step mechanism for the reaction of A through intermediates B and C to produce D shown below.

A → B Ea = 15 kcal/mol, ΔH° = 13 kcal/mol B → C Ea = 10 kcal/mol, ΔH° = -6 kcal/mol C → D Ea = 2 kcal/mol, ΔH° = -20 kcal/mol

Which of the three steps is rate-limiting? A) The reaction of A to B. B) The reaction of B to C. C) The reaction of C to D. D) All three steps occur at the same rate; there is no rate-limiting step. E) The most exothermic step is rate-limiting. Answer: A Diff: 2 Section: 5.2 LO: 5.1.1 GO: G2 29) Consider the three-step mechanism for the reaction of A through intermediates B and C to produce D shown below.

A → B Ea = 15 kcal/mol, ΔH° = 13 kcal/mol B → C Ea = 10 kcal/mol, ΔH° = -6 kcal/mol C → D Ea = 2 kcal/mol, ΔH° = -20 kcal/mol

What's the enthalpy difference between reactant A and intermediate C? Answer: +7 kcal/mol Diff: 2 Section: 5.2

LO: 5.1.1 GO: G2

30) The difference in energy between reactants and the transition state is known as ________. Answer: the activation energy or Ea Diff: 1 Section: 5.2 LO: 5.1.1 GO: G1

31) The rate of a reaction typically increases as the temperature increases because ________. A) the A term in the Arrhenius equation increases B) the fraction of molecules with kinetic energy greater than Ea increases C) the activation energy decreases D) the activation energy increases E) the molecules make more collisions with the wall of the reaction vessel Answer: B Diff: 2 Section: 5.2 LO: 5.1.2 GO: G2

32) Explain the significance of the frequency factor A in the Arrhenius equation. Answer: The frequency factor accounts for the number of collisions between reacting molecules and the fraction of these collisions with the proper orientation for the reaction to happen. There is a linear relationship between the number of these collisions and the rate constant of the reaction. For a given reaction A is a constant. Diff: 2 Section: 5.2 LO: 5.1.1 GO: G2

33) Given an activation energy of 15 kcal/mol, use the Arrhenius equation to estimate how much faster the reaction will occur if the temperature is increased from Answer: The reaction will occur about 2.8 times faster. Diff: 3 Section: 5.2 LO: G4 | 5.1.1 | 5.1.2

GO: G4

34) Which of the following statements is the best statement of the Hammond Postulate? A) In an endothermic reaction, the transition state is closer to the reactants in structure. B) In an exothermic reaction, the transition state is closer in energy to the products. C) Related species that are similar in energy are also similar in structure. D) The structure of the transition state in an organic reaction is always modeled on the structure of the reactants leading to that transition state. E) Transition states are molecular species of finite lifetime whose properties can be probed through free radical reactions. Answer: C Diff: 2 Section: 5.2 LO: 5.3.4 GO: G2

35) Which of the following depictions most closely resembles the structure of the transition state for the following acid-base reaction?

Answer: C Diff: 3 Section: 5.2 LO: 5.3.4 GO: G2

36) Which of the following species is not formed through a termination reaction in the chlorination of methane? A) CH3Cl B) HCl C) H2 D) CH3CH3 Answer: C Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2

37) Species with unpaired electrons are called ________. Answer:

radicals or free radicals

Diff: 1 Section: 5.3 LO: 5.4.2 GO: G1

38) Which of the following is not a possible termination step in the free radical chlorination of methane? A) ∙CH3 + Cl2 → CH3Cl + Cl∙ B) ∙CH3 + Cl∙ → CH3Cl C) ∙CH3 + ∙CH3 → CH3CH3 D) ∙CH3 + wall → CH3-wall E) Cl∙ + wall → Cl-wall Answer: A Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2

39) In the first propagation step of the free radical chlorination of methane, which of the following occurs? A) Cl2 dissociates. B) A chlorine radical abstracts a hydrogen. C) A carbon radical reacts with Cl2. D) A carbon radical reacts with a chlorine radical. E) Two chlorine radicals combine. Answer: B Diff: 2 Section: 5.3 LO: 5.4.2 GO: G2

40) In the reaction of Cl2 with ethane and UV light, which of the following reactions would be a chain termination event(s)?

Cl∙ + CH3-CH3 → CH3-CH2-Cl + H∙

II)

Cl∙ + CH3-CH3 → CH3-H2C∙ + HCl

III)

Cl∙ + CH3-H2C∙ → CH3-CH2-Cl

IV)

Cl2 + CH3-H2C∙ → CH3-CH2-Cl + Cl∙

Cl2 + UV light → Cl∙ + Cl∙

A) reaction V B) reactions I and IV C) reactions III and IV D) reactions I and II E) reaction III Answer: E Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2 41) In the reaction of Cl2 with ethane and UV light, which of the following reactions would be a propagation event(s)?

Cl∙ + CH3-CH3 → CH3-CH2-Cl + H∙

II)

Cl∙ + CH3-CH3 → CH3-H2C∙ + HCl

III)

Cl∙ + CH3-H2C∙ → CH3-CH2-Cl

IV)

Cl2 + CH3-H2C∙ → CH3-CH2-Cl + Cl∙

Cl2 + UV light → C l∙ + Cl∙

A) reactions I and V

B) reactions II, III and IV C) reactions I and IV D) reactions II and IV E) reactions I, II and IV Answer: D Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2

42) Which of the following is a propagation step in the free radical chlorination of dichloromethane? A) ∙ CHCl2 + Cl2 → CHCl3 + Cl∙ B) ∙ CHCl2 + Cl∙ → CHCl3 C) CH2Cl2 + Cl∙ → CHCl3 + H∙ D) Cl2 + UV light → 2 Cl∙ E) ∙ CHCl2 + ∙ CHCl2 → CHCl2CHCl2 Answer: A Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2

43) Write an equation to describe the initiation step in the chlorination of methane. Answer: Cl-Cl + photon (hν) → 2 Cl∙ Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2

44) When the reaction between methane and chlorine is photochemically initiated, which of the following compounds cannot be formed through a termination reaction? A) CH3Cl B) HCl C) CH3CH3 D) Cl2 Answer: B Diff: 3 Section: 5.3 LO: 5.5.2 GO: G2

45) Which of the following is true for the initiation step of a free radical chlorination reaction? A) ΔH° > 0 and ΔS° > 0 B) ΔH° > 0 and ΔS° < 0 C) ΔH° < 0 and ΔS° > 0 D) ΔH° < 0 and ΔS° < 0 E) ΔH° = 0 and ΔS° = 0 Answer: A Diff: 2 Section: 5.3 LO: 5.0.5 GO: G2

46) Which of the following is true for the termination step of a free radical chlorination reaction? A) ΔH° > 0 and ΔS° > 0 B) ΔH° > 0 and ΔS° < 0 C) ΔH° < 0 and ΔS° > 0 D) ΔH° < 0 and ΔS° < 0 E) ΔH° = 0 and ΔS° = 0 Answer: D Diff: 2 Section: 5.3 LO: 5.0.5 GO: G2

47) The bond dissociation energy is the amount of energy required to break a bond ________. A) homolytically B) heterolytically C) so as to produce the more stable pair of ions D) via hydrogenation E) none of the above Answer: A Diff: 1 Section: 5.3 LO: 5.4.2 GO: G1

48) What reactive species is produced in the initiation step of the free radical chlorination of 2,2dimethylpropane? A) a chlorine atom B) a chlorine radical anion C) a carbon radical D) a carbocation Answer: A Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2

49) Predict the enthalpy (ΔH) value for the theoretical reaction below, and indicate whether it is endothermic or exothermic. The bond dissociation energy for each bond in Kcal/mol is shown below each reactant and product. A-B 63

C-D 88

→

A-C 47

B-D 96

A) +8 Kcal/mol, endothermic B) -8 Kcal/mol, exothermic C) +16 Kcal/mol, endothermic D) +8 Kcal/mol, exothermic Answer: A Diff: 2 Section: 5.3 LO: 5.0.5 GO: G4

50) Energy is ________ when bonds are formed and is ________ when bonds are broken; therefore, bond dissociation energies are always ________. A) released; consumed; exothermic B) released; consumed; endothermic C) consumed; released; exothermic D) consumed; released; endothermic E) consumed; released; isothermic Answer: B Diff: 2 Section: 5.3 LO: 5.0.5 GO: G2

51) Which compound has the smaller bond dissociation energy for its carbon-chlorine bond, CH3Cl or (CH3)3CCl? Explain your reasoning. Answer: The carbon-chlorine bond of (CH3)3CCl has the smaller bond dissociation energy. The carbon radical that results upon bond cleavage is a tertiary radical. Tertiary alkyl radicals are more stable than primary due to hyerconjugative or inductive stabilization. Diff: 2 Section: 5.3 LO: 5.4.2 GO: G2

52) Which of the presented mechanisms would be the most energetically favorable and thus the most likely mechanism to actually occur for the following free radical chain reaction? (bond dissociation energies — H-H = 104 kcal/mol; Cl-Cl = 58 kcal/mol; H-Cl = 103 kcal/mol)

H2 + Cl2

A) H2

2 HCl

H∙ + H∙

H∙ + Cl2 → Cl∙ + HCl

H∙ + Cl∙ → HCl B) Cl2

Cl∙ + Cl∙

Cl∙ + H2 → H∙ + HCl

H∙ + Cl2 → HCl + Cl∙ C) H2

H∙ + H∙

H∙ + Cl2 → Cl∙ + HCl

Cl∙ + H2 → HCl + H∙ D) Cl2

Cl∙ + Cl∙

Cl∙ + H2 → H∙ + HCl

Diff: 3 Section: 5.3 LO: 5.4.2 GO: G2

53) Consider the bond dissociation energies listed below in kcal/mol.

CH3-Br 70 CH3CH2-Br

(CH3)2CH-Br

(CH3)3C-Br

These data show that the carbon-bromine bond is weakest when bromine is bound to a ________. A) methyl carbon B) primary carbon C) secondary carbon D) tertiary carbon E) quaternary carbon Answer: D Diff: 1 Section: 5.3 LO: 5.4.2 GO: G2

54) Given the bond dissociation energies below (in kcal/mol), estimate the ΔH° for the propagation step

CH3CH2CH2—H (CH3)2CH—H

98 95

Cl—Cl 58 H—Cl 103 CH3CH2CH2—Cl 81 (CH3)2CH—Cl

A) -22 kcal/mol B) +22 kcal/mol C) -40 kcal/mol D) +45 kcal/mol Answer: A Diff: 2 Section: 5.3 LO: 5.4.2 GO: G2

55) Given the chlorination of acetone shown below, choose the correct rate law.

CH3COCH3 + Cl2 → CH3COCH2Cl + HCl

A) rate = [CH3COCH3] B) rate = [Cl2] C) rate = [CH3COCH3][Cl2] D) rate = [CH3COCH3][Cl2]1/2 E) cannot be determined from stoichiometry; must be determined experimentally Answer: E Diff: 2 Section: 5.3 LO: 5.3.6 GO: G2 MCAT LO: MCAT4.2

56) Given the bond dissociation energies below (in kcal/mol), calculate the overall ΔH° for the following reaction:

(CH3)3CH + Br2 → (CH3)3CBr + HBr

(CH3)3C—H

(CH3)3C—Br

Br—Br

H—Br

CH3—Br

LO: 5.4.1 | 5.4.2 GO: G4

57) Of the two C-H bonds shown, which has the smaller bond dissociation energy? Explain your choice.

(CH3)2CH-H

vs.

CH3CH2-H

Answer: (CH3)2CH-H has the smaller bond dissociation energy. This homolytic bond cleavage yields a more stable secondary radical. Diff: 2 Section: 5.3 LO: 5.4.2 GO: G2

58) Consider the elementary step in the solvolysis of isopropyl chloride shown below and write the rate equation for this step.

(CH3)2CHCl

→

(CH3)2CH+

Cl-

Answer: rate = k[(CH3)2CHCl] Diff: 2 Section: 5.3 LO: 5.3.6 GO: G2 MCAT LO: MCAT4.1

59) How many distinct monochlorinated products can result when cyclopentane is subjected to free radical chlorination? A) 1 B) 2 C) 3 D) 4 E) 5 Answer: A Diff: 1 Section: 5.3 LO: 5.5.2 GO: G2

60) What C5H12 isomer will give only a single monochlorination product? Answer: (CH3)4C or neopentane or 2,2-dimethylpropane Diff: 1 Section: 5.3 LO: 5.5.2

GO: G2 61) The major monobrominated product which results when ethylcyclohexane is subjected to free radical bromination is ________. A) a primary bromide B) a secondary bromide C) a tertiary bromide D) a quaternary bromide E) bromomethane Answer: C Diff: 1 Section: 5.3 LO: 5.5.2 GO: G2

62) Which of the halogens below undergoes free radical halogenation with ethane most rapidly? A) fluorine B) chlorine C) iodine D) bromine E) pyridine Answer: A Diff: 1 Section: 5.3 33 Copyright © 2021 Pearson Education, Inc.

LO: 5.4.2 GO: G2

63) Write the structures of all of the monobromination products of 1,1,3,3-tetramethylcyclobutane. Answer:

Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2

64) Provide the major organic product that results when 2,2,4-trimethylpentane is subjected to free radical bromination. Answer:

Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2

65) Predict the major monobromination product in the following reaction. (CH3)3CCH2CH3 + Br2 Answer: (CH3)3CCHBrCH3 Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2

66) Predict the major monobromination product in the following reaction.

Answer:

Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2

67) What is the name of the major monobrominated product which results when 3-methylpentane is subjected to Br2/hν conditions? Answer: 3-bromo-3-methylpentane Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2

68) What is the name of the major monobrominated product which results when methylcyclohexane is subjected to Br2/hν conditions? Answer: 1-bromo-1-methylcyclohexane Diff: 2 Section: 5.3 LO: 5.5.2 GO: G2

69) Rank the free radicals (I-III) shown below in order of decreasing stability (i.e., from most stable to least stable).

Diff: 2 Section: 5.3 LO: 5.4.2 GO: G2

MCAT LO: MCAT4.2

70) Which H atom in the molecule shown will be most readily abstracted by a bromine radical?

A) Ha B) Hb C) Hc D) Hd E) He Answer: C Diff: 2 Section: 5.3 LO: 5.4.2 GO: G2

71) List the following radicals in order of increasing stability (i.e., from least stable to most stable).

Section: 5.3 LO: 5.4.2 GO: G2 MCAT LO: MCAT4.2

72) Free radical bromination of pentane results in poor yields of 1-bromopentane, while cyclopentane can be readily brominated under similar conditions to yield bromocyclopentane. Offer an explanation. Answer: In the bromination of pentane, the lowest energy reaction pathways go through secondary free radical intermediates to produce secondary alkyl bromides (2-bromopentane and 3bromopentane). Thus 1-bromopentane is a very minor product. All of the hydrogen atom abstractions of cyclopentane lead to the same secondary radical which eventually leads to bromocyclopentane. Diff: 2 Section: 5.3 LO: 5.4.4 GO: G2

73) When compound I, C7H16, was treated with chlorine and light it yielded 3 monochlorination products that could be separated by chromatography. Two of the products were primary alkyl halides and the other was a secondary alkyl halide. Provide a possible structure for compound I. Answer:

Diff: 3 Section: 5.3 LO: 5.5.2 GO: G2

74) Given that tertiary H atoms react with a chlorine radical about 5.5 times faster than primary ones, estimate the ratio of the two monochlorinated products that result when 2,3-dimethylbutane undergoes free radical chlorination. Answer: 1-chloro-2,3-dimethylbutane, 52%; 2-chloro-2,3-dimethylbutane, 48% Diff: 3 Section: 5.3 LO: 5.4.5 GO: G4

75) When 1,1,3,3-tetramethylcyclobutane is brominated at 125°C, the relative reactivity of the 1°: 2°: 3° hydrogens is approximately 1:82:1600. Estimate the amount of each monobromination product. Answer: primary bromide, 3.5%; secondary bromide, 96.5% Diff: 3 Section: 5.3 LO: G4 | 5.4.5 GO: G4

76) The relative reactivity of the 1°: 2°: 3° hydrogens of (CH3)3CCH2CH3 in free radical chlorination is 1: 3.8: 5.0. Provide the structure of each monochlorination product, and estimate the relative amount of each in the mixture of monochlorinated products. Answer: ClCH2C(CH3)2CH2CH3, 45.9%; (CH3)3CCHClCH3, 38.8%; (CH3)3CCH2CH2Cl, 15.3% Diff: 3 Section: 5.3 LO: 5.4.5 | 5.5.2 GO: G2 | G4

77) What is the relative reactivity of 2° vs 1° hydrogens in the free radical bromination of n-butane if the ratio of 1-bromobutane to 2-bromobutane formed is 7:93? Answer: The 2° hydrogens are 20 times more reactive than the 1° ones. Diff: 3 Section: 5.3 LO: 5.4.5 GO: G4

78) Draw all monochlorination products expected from reaction of chlorine with 3,4-dimethylhexane. Circle the major product.

Answer:

Diff: 3 Section: 5.3 LO: 5.5.2 GO: G2

79) Use the Hammond Postulate to explain why free radical brominations are more selective than free radical chlorinations. Answer: The first propagation step in free radical bromination is endothermic while the analogous step in free radical chlorination is exothermic. From the Hammond Postulate, this means that the transition state for the bromination is product-like (ie, radical-like) while the transition state for the chlorination is reactant-like. The product-like transition state for bromination has the C-H bond nearly broken and a great deal of radical character on the carbon atom. The energy of this transition state reflects most of the energy difference of the radical products. This is not true in the chlorination case where the transition state possesses little radical character. Diff: 2 Section: 5.3 LO: 5.4.3 | 5.4.4 GO: G2

80) The hydrogen atom abstraction step in the free radical bromination of methane is endothermic. Use the Hammond Postulate to speculate on the extent of bond formation and bond cleavage in the transition state. Answer: The endothermic nature of this step means that the energy of the transition state is closer to that of the step's products than to its reactants. Using the Hammond Postulate this means the transition state more closely resembles a carbon radical than a bromine radical. The carbon-hydrogen bond is almost completely broken and the hydrogen-bromine bond completely formed in the transition state. Diff: 3 Section: 5.3 LO: 5.4.3 GO: G2

81) The hydrogen atom abstraction step in the free radical chlorine of methane is exothermic. Use the Hammond Postulate to speculate on the extent of bond formation and bond cleavage in the transition state. Answer: The exothermic nature of this step means that the energy of the transition state is closer to that of the step's reactants than to its products. Using the Hammond Postulate this means the transition state more closely resembles a chlorine radical than a carbon radical. The carbon-hydrogen bond has broken very little and the hydrogen-chlorine bond has formed very little in the transition state. Diff: 3 Section: 5.3 LO: 5.4.3 GO: G2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 6 Stereoisomerism: Arrangement of Atoms in Space 1) ________ are isomers which have the same bonding sequence but differ in the orientation of their atoms in space. Answer: Stereoisomers Diff: 1 Section: 6.2 LO: 6.0.4 GO: G1

2) What is the structural relationship between the two molecules shown below?

A) constitutional isomers B) enantiomers C) diastereomers D) conformational isomers E) not isomers Answer: A Diff: 2 Section: 6.2 LO: 6.0.4 GO: G2 MCAT LO: MCAT2.4 3) Is the molecule shown below chiral or achiral? (CH3)3CCH(CH3)2 Answer: achiral Diff: 1 Section: 6.2 LO: 6.0.3 GO: G2 MCAT LO: MCAT5.2 1 Copyright © 2021 Pearson Education, Inc.

4) How many asymmetric carbon atoms are present in the following compound?

A) 0 B) 1 C) 2 D) 3 E) 4 Answer: B Diff: 1 Section: 6.2 LO: 6.4.1 GO: G2 MCAT LO: MCAT5.3 5) How many asymmetric carbon atoms are present in the following compound?

A) 0 B) 1 C) 2 D) 3 E) 4 Answer: A Diff: 1 Section: 6.2 LO: 6.4.1 GO: G2 MCAT LO: MCAT5.3

6) How many asymmetric carbons are present in the compound below?

Answer: 1 Diff: 1 Section: 6.2 LO: 6.4.1 GO: G2 MCAT LO: MCAT5.3 7) How many asymmetric carbons are present in the compound below?

Answer: none Diff: 1 Section: 6.2 LO: 6.4.1 GO: G2 MCAT LO: MCAT5.3 8) How many asymmetric carbons are present in the compound below?

Answer: 5 Diff: 1 Section: 6.2 LO: 6.4.1 GO: G2 MCAT LO: MCAT5.3

9) How many asymmetric carbon atoms are present in the molecule shown?

A) 0 B) 1 C) 2 D) 3 E) 4 Answer: B Diff: 1 Section: 6.2 LO: 6.4.1 GO: G2 MCAT LO: MCAT5.3 10) How many asymmetric carbon atoms are present in the molecule shown?

A) 0 B) 1 C) 2 D) 3 E) 4 Answer: C Diff: 1 Section: 6.2 LO: 6.4.1 GO: G2 MCAT LO: MCAT5.3

11) If possible, draw the structure of the enantiomer of the molecule shown below.

Answer:

Diff: 2 Section: 6.2 LO: 6.1.1 | 6.1.4 | 6.4.5 GO: G2 MCAT LO: MCAT5.2 12) Is the mirror image of the following molecule an enantiomer or is it superimposable with it?

Answer: Superimposable. The molecule is achiral. Diff: 2 Section: 6.2 LO: 6.0.2 GO: G2 MCAT LO: MCAT5.2 13) Is the molecule shown below chiral or achiral? CH3CH2CH(CH3)CH2CH3 Answer: achiral Diff: 2 Section: 6.2 LO: 6.0.3 GO: G2 5 Copyright © 2021 Pearson Education, Inc.

MCAT LO: MCAT5.2 14) Is the molecule shown below chiral or achiral?

Answer: achiral Diff: 2 Section: 6.2 LO: 6.0.3 GO: G2 MCAT LO: MCAT5.2 15) Is the molecule shown below chiral or achiral?

Answer: achiral Diff: 2 Section: 6.2 LO: 6.0.3 GO: G2 MCAT LO: MCAT5.2 16) Is the molecule shown below chiral or achiral?

Answer: chiral Diff: 2 Section: 6.2 LO: 6.0.3 GO: G2 MCAT LO: MCAT5.2

17) How many asymmetric carbons are present in the compound below? 3-ethyl-2,2,4-trimethylpentane Answer: 1 Diff: 2 Section: 5.2 LO: 6.4.1 GO: G2 MCAT LO: MCAT5.3 18) Label each asymmetric carbon in the compound below as R or S.

Answer:

Diff: 1 Section: 6.3 LO: 6.1.2 | 6.1.3 GO: G2 MCAT LO: MCAT5.3

19) Draw the structure of (S)-1-bromo-1-chloropropane. Take particular care to indicate threedimensional stereochemical detail properly. Answer:

Diff: 1 Section: 6.3 LO: 6.1.1 | 6.1.4 GO: G2 MCAT LO: MCAT5.3

20) Draw the structure of (2R,3R)-2,3-dibromo-3-chloropentane. Answer:

Diff: 2 Section: 6.3 LO: LO: 6.1.1 | 6.1.4 GO: G2 MCAT LO: MCAT5.1

21) Label each asymmetric carbon in the molecule below as having the R or S configuration.

Answer:

Diff: 2 Section: 6.3 LO: 6.2.4 | 6.2.5 GO: G2 MCAT LO: MCAT5.3

22) Label each asymmetric carbon in the compound below as R or S.

Answer:

Diff: 2 Section: 6.3 LO: 6.2.4 | 6.2.5 GO: G2 MCAT LO: MCAT5.3

23) Draw the structure of (2R,3S)-2,3-dichloropentane. Take particular care to indicate threedimensional stereochemical detail properly. Answer:

Diff: 2 Section: 6.3 LO: 6.1.1 | 6.2.4 GO: G2 MCAT LO: MCAT5.3 24) Draw the structure of the enantiomer of (2S, 3R)-2,3-dichloropentane. Take particular care to indicate three-dimensional stereochemical detail properly. Answer:

Diff: 2 Section: 6.3 LO: 6.1.1 | 6.2.4 GO: G2 MCAT LO: MCAT5.3

25) Draw the structure of any diastereomer of (2S, 3R)-2,3-dichloropentane. Take particular care to indicate three-dimensional stereochemical detail properly. Answer:

Diff: 2 Section: 6.3 LO: 6.1.1 | 6.2.4 GO: G2 MCAT LO: MCAT5.3 26) Draw the structure of (1R, 2R)-1-bromo-2-chlorocyclobutane. Take particular care to indicate stereochemistry properly. Answer:

Diff: 2 Section: 6.3 LO: 6.1.1 | 6.2.4 GO: G2 MCAT LO: MCAT5.3 27) Draw the structure of (S)-3-chloro-3-methylhexane. Take particular care to indicate stereochemistry properly. Answer: Diff: 2 Section: 6.3 LO: 6.1.1 | 6.2.4 GO: G2 MCAT LO: MCAT5.3

28) Draw the structure of (1R, 2S, 3S)-1,2-dibromo-3-ethylcyclohexane. Take particular care to indicate stereochemistry properly. Answer:

Diff: 2 Section: 6.3 LO: 6.1.1 | 6.2.4 GO: G2 MCAT LO: MCAT5.3 29) Label each asymmetric carbon in the compound below as R or S.

Answer:

Diff: 2 Section: 6.3 LO: 6.2.4 GO: G2 MCAT LO: MCAT5.3

30) Label each asymmetric carbon in the compound below as R or S.

Answer:

Diff: 2 Section: 6.3 LO: 6.2.4 GO: G2 MCAT LO: MCAT5.3 31) Which of the following configurations corresponds to the structure below?

A) (4R, 5R) B) (4R, 5S) C) (4S, 5R) D) (4S, 5S) Answer: A Diff: 3 Section: 6.3 LO: 6.2.4 | 6.2.5 GO: G2 MCAT LO: MCAT5.3

32) For the structure shown below, draw the stereoisomer having a configuration of (1R,3S,4S) in a perspective structure.

Answer:

Diff: 3 Section: 6.3 LO: 6.2.4 GO: G2 MCAT LO: MCAT5.3 33) Label each asymmetric carbon in the compound below as R or S.

Answer:

Diff: 3 Section: 6.3 LO: 6.1.2 | 6.1.3 GO: G2

34) Label each asymmetric carbon in the compound below as R or S.

Answer:

Diff: 3 Section: 6.3 LO: 6.2.4 GO: G2 MCAT LO: MCAT5.3

35) Phantasmidine, shown below, is found in poisonous frog skin and has analgesic properties (J. Nat. Prod. 2010, 331). Assign each chiral center as having either R or S configuration.

Answer:

Diff: 3 Section: 6.3 LO: 6.2.4 GO: G2 MCAT LO: MCAT5.3

36) Compounds that rotate the plane of polarized light clockwise are called ________. Answer: dextrorotatory Diff: 1 Section: 6.4 LO: 6.3.1 GO: G1 37) Which of the following statements is (are) true for the compound (R)-2-butanol? A) This compound is chiral. B) This compound is optically active. C) This compound has an enantiomer. D) all of the above E) none of the above Answer: D Diff: 2 Section: 6.4 LO: 6.3.3 | 6.3.4 | 6.3.6 GO: G2 38) Which of the following statements correctly pertains to a pair of enantiomers? A) They rotate the plane of polarized light by exactly the same amount and in opposite directions. B) They rotate the plane of polarized light by differing amounts and in opposite directions. C) They rotate the plane of polarized light by differing amounts and in the same direction. D) The have different melting points. E) They have the same melting point, but they have different boiling points. Answer: A Diff: 2 Section: 6.4 LO: 6.3.4 GO: G1 MCAT LO: MCAT5.6

39) If (S)-glyceraldehyde has a specific rotation of -8.7°, what is the specific rotation of (R)glyceraldehyde? A) 0.0° B) -8.7° C) +8.7° D) cannot be determined from the information given Answer: C Diff: 2 Section: 6.4 LO: 6.3.3 GO: G2 MCAT LO: MCAT5.4 16 Copyright © 2021 Pearson Education, Inc.

40) Predict the specific rotation of the compound shown.

A) It is impossible to predict; it must be determined experimentally. B) Because both asymmetric centers are R, the compound is dextrorotatory. C) Because both asymmetric centers are S, the compound is levorotatory. D) Zero; the compound is achiral. E) Because this compound represents a racemic mixture, the compound is dextrorotatory. Answer: D Diff: 2 Section: 5.4 LO: 6.0.1 | 6.3.3 GO: G2 MCAT LO: MCAT5.4 41) Can one predict whether a compound with a single asymmetric carbon is dextro- or levorotatory based on the R/S assignment at this asymmetric carbon? Explain briefly. Answer: No. R/S assignment is purely a convention of nomenclature and is completely independent of the direction in which plane-polarized light is rotated by the compound. Diff: 2 Section: 6.4 LO: 6.3.3 GO: G2 42) Glucose has a specific rotation of +52.8°. Predict the concentration of a glucose aqueous solution contained in a 10 cm long polarimetry tube if a rotation of +15.8° was observed. A) 0.299 g/mL B) .0299 g/mL C) 3.34 g/mL D) .334 g/mL Answer: A Diff: 2 Section: 6.4 LO: 6.3.5 GO: G4 MCAT LO: MCAT5.4

43) A student measured the optical activity of an unknown sugar at two different concentrations. The results of his measurements are shown below. Given that the sample cell had a path length of 10.0 cm, calculate the specific rotation for the unknown sugar. (Hint: Consider each measurement of plane polarized light has a true reading and a "ghost" reading 180° from the true reading). concentration 2.00 g sugar in 10.0 mL water 5.00 g sugar in 10.0 mL water

observed rotation +159.1° +127.8°

A) -10.5° B) +25.6° C) +79.5° D) -105° E) +256° Answer: D Diff: 3 Section: 6.4 LO: 6.3.5 GO: G4 MCAT LO: MCAT5.4 44) A newly isolated natural product was shown to be optically active. If a solution of 2.0 g in 10 mL of ethanol in a 50 cm tube gives a rotation of +2.57°, what is the specific rotation of this natural product? Answer: +2.57° Diff: 3 Section: 6.4 LO: 6.3.5 GO: G4 MCAT LO: MCAT5.4

45) A mixture of equal amounts of two enantiomers ________. A) is called a racemic mixture B) is optically inactive C) implies that the enantiomers are meso forms D) both A and B E) none of the above Answer: D Diff: 2 Section: 6.4 LO: 6.3.4 GO: G1 46) If a mixture contains 75% of one compound and 25% of its enantiomer, what is the e.e. of the mixture? A) 100 B) 75 C) 50 D) 25 E) 3 Answer: C Diff: 2 Section: 6.4 LO: 6.3.4 GO: G4 MCAT LO: MCAT5.4 47) Calculate the e.e. of a mixture containing 8.0 g of (-)-glyceraldehyde and 2.0 g of (+)glyceraldehyde. Answer: 60% Diff: 2 Section: 6.4 LO: 6.3.4 GO: G4 MCAT LO: MCAT5.4

48) A mixture of two enantiomers with a composition of 65.0% R has an observed rotation of 25.3° in a polarimeter tube. If the mixture has a concentration of 2.038 g/mL at 25°C, what is the predicted of an optically pure sample of the S enantiomer? A) -25.3° B) -53.5° C) +12.4° D) +41.3° E) +53.5° Answer: D Diff: 3 Section: 6.4 LO: 6.3.5 GO: G4 MCAT LO: MCAT5.4 49) (-)-Lactic acid has a specific rotation of -3.8°. What is the specific rotation of a solution containing 7.5 g of (-)-lactic acid and 2.5 g of (+)-lactic acid? Answer: -1.9° Diff: 3 Section: 6.4 LO: 6.3.5 GO: G4 MCAT LO: MCAT5.4

50) How many enantiomers are there of the molecule shown below?

A) 0 B) 1 C) 2 D) 3 E) 6 Answer: B Diff: 1 Section:6.5 LO: 6.4.5 | 6.4.7 GO: G2 MCAT LO: MCAT5.5

51) Which of the following terms best describes the pair of compounds shown: enantiomers, diastereomers, or the same compound?

Answer: the same compound Diff: 1 Section:6.5 LO: 6.4.5 GO: G2 MCAT LO: MCAT5.6 52) Which of the following terms best describes the pair of compounds shown: enantiomers, diastereomers, or the same compound?

Answer: the same compound Diff: 1 Section:6.5 LO: 6.4.5 GO: G2 MCAT LO: MCAT5.6 53) How many asymmetric carbons are present in the compound below?

Answer: 2 Diff: 2 Section:6.5 LO: 6.4.1 | 6.4.7 GO: G2 MCAT LO: MCAT5.3

54) Which of the following terms best describes the pair of compounds shown: enantiomers, diastereomers, or the same compound?

Answer: enantiomers Diff: 3 Section: 6.5 LO: 6.4.5 GO: G2 MCAT LO: MCAT5.6 55) Circle all structures shown below that are chiral.

Answer:

Diff: 3 Section: 6.5 LO: 6.3.6 GO: G2 MCAT LO: MCAT5.2 56) Is the molecule shown below chiral or achiral?

Answer: achiral Diff: 3 Section: 6.5 LO: 6.0.3 GO: G2 MCAT LO: MCAT5.2

57) Which of the following structures are achiral and meso?

A) 1 B) 2 C) 3 D) 4 Answer: D Diff: 3 Section: 6.5 LO: 6.0.3 | 6.4.3 GO: G2 MCAT LO: MCAT5.2

58) Does the molecule shown below contain asymmetric carbon atoms? Is this molecule chiral?

Answer: Yes, the molecule contains 4 asymmetric carbon atoms. No, the molecule is not chiral since it is superimposable with its mirror image. Diff: 3 Section: 6.5 LO: 6.0.3 GO: G2

59) How many asymmetric carbons are present in the compound below?

Answer: 5 Diff: 3 Section: 6.5 LO: 6.4.1 GO: G2 MCAT LO: MCAT5.3 60) Label each asymmetric carbon in the compound below as R or S.

Answer:

Diff: 2 Section: 6.5 LO: 6.2.4 GO: G2 MCAT LO: MCAT5.3

61) Why is the following structure not a meso compound?

Answer: The functional group at the top (aldehyde) is different from the bottom (alcohol) and thus there is no internal reflective plane in the molecule. Diff: 1 Section: 6.5 LO: 6.4.3 GO: G2 62) How many diastereomers are there of the molecule shown below?

A) 0 B) 1 C) 2 D) 3 E) 6 Answer: C Diff: 1 Section: 6.5 LO: 6.4.5 GO: G2 MCAT LO: MCAT5.1

63) Stereoisomers which are not mirror image isomers are ________. Answer: diastereomers Diff: 1 Section: 6.5 LO: 6.4.6 GO: G1 MCAT LO: MCAT5.1 64) Which of the following terms best describes the stereochemical relationship of the two compounds shown below in Fischer notation?

A) enantiomers B) diastereomers C) constitutional isomers D) cis/trans - isomers E) meso - same structure Answer: B Diff: 2 Section: 5.11 LO: 6.4.5 | 6.4.7 GO: G2 MCAT LO: MCAT5.6

65) How many diastereomers are there of the molecule shown below?

A) 0 B) 1 C) 2 D) 3 E) 6 Answer: E Diff: 3 Section: 6.5 LO: 6.4.5 GO: G2 MCAT LO: MCAT5.1 Use the following three structures to answer the two questions below.

66) The relationship between I and III is: ________. A) same compound B) enantiomers C) diastereomers D) constitutional isomers Answer: C Diff: 3 Section: 6.5 LO: 6.4.5 GO: G2 MCAT LO: MCAT5.6

67) The relationship between I and II is: ________. A) same compound B) enantiomers C) diastereomers D) constitutional isomers Answer: C Diff: 3 Section: 6.5 LO: 6.4.5 GO: G2 MCAT LO: MCAT5.6 68) Which of the following terms best describes the pair of compounds shown: enantiomers, diastereomers, or the same compound?

Answer: diastereomers Diff: 3 Section: 6.5 LO: 6.4.5 GO: G2 MCAT LO: MCAT5.6 69) Which of the following terms best describes the pair of compounds shown: enantiomers, diastereomers, or the same compound?

Answer: the same compound Diff: 3 Section: 6.5 LO: 6.4.5 GO: G2 MCAT LO: MCAT5.6

70) Which of the following molecules, if isolated in its pure form, would demonstrate optical activity?

A) both IV and V B) both I and III C) only II D) both III and IV E) both I and V Answer: A Diff: 3 Section: 6.5 LO: 6.3.6 GO: G2 71) Can the molecule shown below be properly described as a meso compound?

Answer: Yes Diff: 1 Section: 6.5 LO: 6.4.3 GO: G2

72) How many enantiomers are there of the molecule shown below?

A) 0 B) 1 C) 2 D) 3 E) 6 Answer: A Diff: 2 Section: 6.5 LO: 6.4.5 GO: G2 73) If possible, draw the structure of the enantiomer of the molecule shown below.

Answer: The compound is an achiral, meso compound; it has no enantiomer. Diff: 2 Section: 6.5 LO: 6.4.5 GO: G2 MCAT LO: MCAT5.2

74) Is it theoretically possible to separate the pair of compounds below by distillation? Explain briefly.

Answer: Yes. The molecules are related as diastereomers and hence have different boiling points. Diff: 2 Section: 6.6 LO: 6.5.2 GO: G2 MCAT LO: MCAT5.7

75) The process by which enantiomers are separated is called ________. Answer: resolution Diff: 1 Section: 6.6 LO: 6.5.2 | 6.5.3 GO: G1 MCAT LO: MCAT5.7 76) Briefly describe how two enantiomers might be separated. Answer: The two compounds can be converted to diastereomers, separated based on different physical properties of these diastereomers, and subsequently returned to their original forms after separation. Another method involves the chromatographic separation using a chiral stationary phase. Diff: 2 Section: 6.6 LO: 6.5.3 GO: G2 MCAT LO: MCAT5.7 77) Can one separate a mixture of enantiomers by gas chromatography? Explain. Answer: Provided the compounds can be volatilized, a mixture of enantiomers can be separated by GC if an appropriate chiral column can be found. Enantiomers will be retained differently by the chiral stationary phase of the column. Diff: 2 Section: 6.6 LO: 6.5.3 GO: G2 MCAT LO: MCAT5.7 32 Copyright © 2021 Pearson Education, Inc.

78) Is the molecule shown below chiral or achiral?

Answer: achiral Diff: 3 Section: 6.7 LO: 6.0.3 GO: G2 MCAT LO: MCAT5.2 79) Can a molecule be chiral if it contains no asymmetric carbons? Explain briefly. Answer: Yes. The presence of asymmetric carbons is not required for a molecule to be chiral. The only requirement is that the molecule be nonsuperimposable with its mirror image. Structural features other than asymmetric carbons can lead to chirality. Diff: 2 Section: 6.7 LO: 6.01| 6.0.3 GO: G2 MCAT LO: MCAT5.2

80) Is the molecule shown below chiral or achiral? Explain what this means.

Answer: The molecule is chiral because its mirror image is nonsuperimposable. Diff: 2 Section: 6.7 LO: 6.0.3 GO: G2 MCAT LO: MCAT5.2 81) Which of the following terms best describes the pair of compounds shown: enantiomers, diastereomers, or the same compound?

Answer: enantiomers Diff: 3 Section: 6.7 LO: 6.4.5 GO: G2 MCAT LO: MCAT5.6

Chapter 7

There are no test bank questions in chapter 7.

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 8 Alkenes 1: Properties and Electrophilic Additions 1) Why is rotation about the carbon-carbon double bond in alkenes prohibited while relatively free rotation can occur about the carbon-carbon single bond in alkanes? Answer: Rotation about the C—C single bond in alkanes can occur without breaking the bond or disrupting the orbital overlap. For rotation to occur about a C C, the π bond would have to be broken since the p orbital overlap from which the bond is formed is disrupted by rotation. Diff: 2 Section: 8.1 LO: 8.0.2 GO: G2 MCAT LO: MCAT7.2

2) Consider molecules with the formula C10H16. Which of the following structural features are not possible within this set of molecules? A) 2 triple bonds B) 1 ring and 1 triple bond C) 2 rings and 1 double bond D) 2 double bonds and 1 ring E) 3 double bonds Answer: A Diff: 1 Section: 8.1 LO: 8.1.6 GO: G2

3) How many elements of unsaturation are implied by the molecular formula

A) 0 B) 1 C) 2 D) 3 E) 4 Answer: B Diff: 1 Section: 8.1 LO: 8.1.6 GO: G2

4) How many elements of unsaturation do molecules with a molecular formula of C6H6Cl6 have? A) 0 B) 1 C) 2 D) 3 E) 4 Answer: B Diff: 1 Section: 8.1 LO: 8.1.6 GO: G2

5) How many elements of unsaturation are implied by the molecular formula A) 0 B) 1 C) 2 D) 3 E) 4 Answer: E Diff: 3 Section: 8.1 LO: 8.1.6 GO: G2

6) Provide the proper IUPAC name for the alkene shown below. CH2 CHCH2CH2CH2CH3 Answer: hex-1-ene Diff: 1 Section: 8.1 LO: 8.1.1 GO: G2 MCAT LO: MCAT7.1

7) Provide the proper IUPAC name for the alkene shown below.

Answer: cyclopentene Diff: 1 Section: 8.1 LO: 8.1.1 GO: G2 MCAT LO: MCAT7.1

8) Draw an acceptable structure for 4-ethylhept-1-ene. Answer:

Diff: 1 Section: 8.1 LO: 8.1.2 GO: G2 MCAT LO: MCAT7.1

9) Provide an acceptable name for (CH3)2CHCH=C(CH3)CH2CH3. Answer: 2,4-dimethyl-3-hexene or 2,4-dimethylhex-3-ene Diff: 2 Section: 8.1 LO: 8.1.1 GO: G2 MCAT LO: MCAT7.1

10) Provide an acceptable name for (CH3CH2)2CHCH2CH=CH2. Answer: 4-ethyl-1-hexene or 4-ethylhex-1-ene Diff: 2 Section: 8.1 LO: 8.1.1 GO: G2 MCAT LO: MCAT7.1

11) Which of the following alkenes can show geometric isomerism: 2,3-dichloro-2-pentene, 4chloro-3-ethyl-3-hexene, 3-chloro-2-methyl-2-butene, and 3-chloro-2-methyl-1-butene? Answer: 2,3-dichloro-2-pentene Diff: 2 Section: 8.1 LO: 8.1.2 | 8.1.3 GO: G2

12) Name the compound shown below.

Answer: 2-propyl-1,3-cyclopentadiene or 2-propylcyclopenta-1,3-diene Diff: 2 Section: 8.1 LO: 8.1.1 GO: G2 MCAT LO: MCAT7.1

13) Provide the proper IUPAC name for the alkene shown below.

Answer: 6-bromo-1-methylcyclohexene Diff: 2 Section: 8.1 LO: 8.1.1 GO: G2 MCAT LO: MCAT7.1

14) Draw an acceptable structure for 4-phenylbut-1-ene. Answer:

Diff: 2 Section: 8.1 LO: 8.1.2 GO: G2 MCAT LO: MCAT7.1

15) Draw an acceptable structure for 1,2-dimethylcyclohexene. Answer:

Diff: 2 Section: 8.1 LO: 8.1.2 GO: G2 MCAT LO: MCAT7.1

16) Draw and name all alkenes which have the molecular formula C4H8. Answer:

Diff: 2 Section: 8.1 LO: 8.1.6 | 8.1.7 GO: G2 MCAT LO: MCAT7.1

17) Name the alkene shown. Be sure to include the appropriate E or Z label necessary.

Answer: 2,4-dichlorobut-1-ene Section: 8.1 LO: 8.1.1 | 8.1.5 GO: G2 MCAT LO: MCAT7.3

18) Draw and name the six alkenes which have the molecular formula C5H10. Answer:

Diff: 3 Section: 7.5 Section: 8.1 LO: 8.1.7 GO: G2 MCAT LO: MCAT7.3

19) Which of the following best describes the geometry about the carbon-carbon double bond in the alkene below?

A) E B) Z C) neither E nor Z Answer: C Diff: 2 Section: 8.1 LO: 8.1.4 GO: G2 MCAT LO: MCAT7.3

20) Provide the proper IUPAC name for the alkene shown below.

Answer: (E)-3,4-dimethylhept-3-ene Diff: 2 Section: 8.1 LO: 8.1.1 GO: G2 MCAT LO: MCAT7.3

21) Provide the proper IUPAC name for the alkene shown below.

Answer: (E)-2-ethylhexa-1,4-diene Diff: 2 Section: 8.1 LO: 8.1.1 | 8.1.4 GO: G2 MCAT LO: MCAT7.3

22) Name the alkene shown. Be sure to include the appropriate E or Z label necessary.

Answer: (E)-1-bromo-4-chlorohept-3-ene Diff: 2 Section: 8.1 LO: 8.1.1 | 8.1.4 GO: G2 MCAT LO: MCAT7.3

23) Provide the structure of the major organic product of the reaction below.

Answer:

Diff: 1 Section: 8.2 LO: 8.4.1 | 8.4.8 GO: G2 MCAT LO: MCAT8.1

24) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 1 Section: 8.2 LO: 8.4.1 | 8.4.8 GO: G2 MCAT LO: MCAT8.1

25) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 1 Section: 8.2 LO: 8.4.1 | 8.4.8 GO: G2 MCAT LO: MCAT8.1 26) HBr can be added to an alkene in the presence of peroxides (ROOR). What function does the peroxide serve in this reaction? A) nucleophile B) electrophile C) radical chain initiator D) acid catalyst E) solvent Answer: C Diff: 2 Section: 8.2 LO: 8.5.1 GO: G2 MCAT LO: MCAT8.1 27) Name the major product which results when HBr is added to 3-ethyl-3-hexene. Answer: 3-bromo-3-ethylhexane Diff: 2 Section: 8.2 LO: 8.4.1 | 8.4.8 GO: G2 MCAT LO: MCAT8.1

28) Provide the structure of the major organic product of the reaction below.

Answer:

Diff: 2 Section: 8.3 LO: 8.5.3 GO: G2 MCAT LO: MCAT8.1 29) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 8.2 LO: 8.4.1 | 8.4.8 GO: G2 MCAT LO: MCAT8.1

30) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 2 Section: 8.2 LO: 8.4.1 | 8.4.8 GO: G2 MCAT LO: MCAT8.1

31) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 2 Section: 8.2 LO: 8.4.1 | 8.4.8 GO: G2 MCAT LO: MCAT8.1 32) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

33) When propylene reacts with hydrogen bromide in the presence of a peroxide initiator, which of the following structures are formed during the mechanism? A) B) C) D) H∙ Answer: B Diff: 2 Section: 8.2 LO:8.4.5 | 8.5.1 GO: G2 MCAT LO: MCAT8.3 34) Draw the major regioisomeric product generated in the reaction below.

Answer:

Diff: 3 Section: 8.2 LO: 8.4.1 | 8.4.8 GO: G2 MCAT LO: MCAT8.1

35) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 8.2 LO: 8.4.8 | 8.5.3 GO: G2 MCAT LO: MCAT8.1 36) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 8.2 LO: 8.4.1 | 8.4.8 GO: G2 MCAT LO: MCAT8.1

37) Acid catalyzed hydration (H2SO4/water/△) of an unknown compound (A) with a chemical formula C6H12, yielded a racemic mixture of product C6H13OH. Which, if any, of the following compounds is/are possible structures for the initial compound (A)?

A) compound 1 only B) compounds 2 and 3 C) compound 2 only D) compounds 1 and 3 E) none of the above Answer: E Diff: 2 Section: 8.3 LO: 8.6.2 |8.6.5 GO: G2 MCAT LO: MCAT8.1

38) Name the major alcohol product which results when 3,3-dimethylbut-1-ene is treated with dilute acid. Answer: 2,3-dimethyl-2-butanol Diff: 2 Section: 8.3 LO: 8.6.2 GO: G2 MCAT LO: MCAT8.1

39) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 2 Section: 8.3 LO: 8.6.2 GO: G2 MCAT LO: MCAT8.1 40) What is the major product of the following reaction?

41) Draw the major organic product(s) generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 2 Section: 8.3 LO: 8.6.2 GO: G2 MCAT LO: MCAT8.1 42) Which of the following intermediates is thought to occur in the mechanism by which alkenes are hydrated in the presence of acid? A) carbanion B) carbocation C) free radical D) carbene E) alkyne Answer: B Diff: 2 Section: 8.3 LO: 8.6.1 GO: G1 MCAT LO: MCAT8.3

43) Complete the following reaction and provide a detailed, step-by-step mechanism for the process.

Answer:

Diff: 2 Section: 8.3 LO: 8.6.2 GO: G2 MCAT LO: MCAT8.3 44) Provide the structure of the major organic product of the reaction below.

Answer:

Diff: 3 Section: 8.3 LO: 8.6.2 GO: G2 MCAT LO: MCAT8.1

45) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 8.3 LO: 8.6.2 GO: G2 MCAT LO: MCAT8.1 46) Which of the following is the best reaction sequence to use if one wants to accomplish a Markovnikov addition of water to an alkene with minimal skeletal rearrangement? A) water + dilute acid B) water + concentrated acid C) oxymercuration-demercuration D) hydroboration-oxidation E) none of the above Answer: C Diff: 1 Section: 8.3 LO: 8.6.6 GO: G1 MCAT LO: MCAT8.1 47) What synthetic goal is achieved by subjecting an alkene to an oxymercuration-demercuration sequence? A) Markovnikov addition of H2O wherein skeletal rearrangement is promoted B) Markovnikov addition of H2O wherein skeletal rearrangement is prevented C) anti-Markovnikov addition of H2O wherein skeletal rearrangement is promoted D) anti-Markovnikov addition of H2O wherein skeletal rearrangement is prevented E) syn-hydroxylation Answer: B Diff: 2 Section: 8.3 LO: 8.6.6 GO: G1 MCAT LO: MCAT8.1

48) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 2 Section: 8.3 LO: 8.6.6 GO: G2 MCAT LO: MCAT8.1 49) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 2 Section: 8.3 LO: 8.6.6 GO: G2 MCAT LO: MCAT8.1

50) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 2 Section: 8.3 LO: 8.6.6 GO: G2 MCAT LO: MCAT8.1 51) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 8.3 LO: 8.6.6 GO: G2 MCAT LO: MCAT8.1

52) Treatment of 2-methylpropene with which of the following reaction conditions results in an anti-Markovnikov addition product? A) dry gaseous HBr with peroxides present B) BH3-THF, followed by alkaline H2O2 C) aqueous Hg(OAc)2, followed by alkaline NaBH4 D) dilute H2SO4 and heat E) both A and B Answer: E Diff: 1 Section: 8.3 LO: 8.6.7 GO: G2 MCAT LO: MCAT8.2 53) Provide the structure of the major organic product of the reaction below.

Answer:

Diff: 2 Section: 8.3 LO: 8.6.7 | 8.6.8 GO: G2 MCAT LO: MCAT8.1

54) Provide the structure of the major organic product of the reaction below.

Answer:

Diff: 2 Section: 8.3 LO: 8.6.7 | 8.6.8 GO: G2 MCAT LO: MCAT8.1 55) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 2 Section: 8.3 LO: 8.6.7 | 8.6.8 GO: G2 MCAT LO: MCAT8.1

56) Provide the structure of the major organic product of the reaction below.

Answer:

Diff: 3 Section: 8.3 LO: 8.6.7 | 8.6.8 GO: G2 MCAT LO: MCAT8.2 57) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 8.3 LO: 8.6.7 | 8.6.8 GO: G2

MCAT LO: MCAT8.2 58) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 8.3 LO: 8.6.7 | 8.6.8 GO: G2 MCAT LO: MCAT8.2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 9 Alkenes 2: Oxidation and Reduction 1) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 1 Section: 9.1 LO: 9.1.1 | 9.1.3 GO: G2 MCAT LO: MCAT8.2 2) Addition of Br2 to (E)-hex-3-ene produces ________. A) a meso dibromide B) a mixture of enantiomeric dibromides which is optically active C) a mixture of enantiomeric dibromides which is optically inactive D) (Z)-3,4-dibromo-3-hexene E) (E)-3,4-dibromo-3-hexene Answer: A Diff: 2 Section: 9.1 LO: 9.1.1 | 9.1.3 GO: G2 MCAT LO: MCAT8.2

3) Which of the following alkenes will yield a meso dihalide when reacted with Br2/CCl4 at room temperature? A)

E) both Band D Answer: B Diff: 2 Section: 9.1 LO: 9.1.1 | 9.1.3 GO: G2 MCAT LO: MCAT8.2

4) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 9.1 LO: 9.1.1 | 9.1.3 GO: G2 MCAT LO: MCAT8.2 5) Draw the major organic product(s) generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 2 Section: 9.1 LO: 9.1.1 | 9.1.3 GO: G2 MCAT LO: MCAT8.2

6) Provide a detailed, step-by-step mechanism for the reaction shown below.

Answer:

Diff: 2 Section: 9.1 LO: 9.1.1 | 9.1.3 GO: G2 MCAT LO: MCAT8.3 7) Provide the structure of the major organic product of the reaction below.

Answer:

Diff: 2 Section: 9.1 LO: 9.1.1 | 9.1.3 GO: G2 MCAT LO: MCAT8.2

8) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 9.1 LO: 9.1.1 | 9.1.3 GO: G2 MCAT LO: MCAT8.2

9) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 9.1 LO: 9.1.6 GO: G2 MCAT LO: MCAT8.1

10) Draw the major organic product(s) generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 2 Section: 9.1 LO: 9.1.6 GO: G2 MCAT LO: MCAT8.1 11) Provide the reagents necessary to complete the following transformation.

A) 1. BH3∙THF B) H2O, H2SO4 C) OsO4, H2O2 D) CH3CO3H E) 1. CH3CO3H Answer: D Diff: 2 Section: 9.1 LO: 9.1.6 GO: G2

2. H2O2, HO-

2. H+, H2O

12) Treatment of cyclopentene with peroxybenzoic acid ________. A) results in oxidative cleavage of the ring to produce an acyclic compound B) yields a meso epoxide C) yields an equimolar mixture of enantiomeric epoxides D) gives the same product as treatment of cyclopentene with OsO4 E) none of the above Answer: B Diff: 3 Section: 9.1 LO: 9.1.6 GO: G2 MCAT LO: MCAT8.1 13) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 9.1 LO: 9.1.6 GO: G2 MCAT LO: MCAT8.1 14) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 9.1 LO: 9.1.6 GO: G2

15) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 9.1 LO: 9.1.6 GO: G2 MCAT LO: MCAT8.1 16) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 9.1 LO: 9.1.8 GO: G2 MCAT LO: MCAT8.2

17) Provide the reagents necessary to complete the following transformation.

A) 1. BH3∙THF B) H2O, H2SO4 C) OsO4, H2O2 D) CH3CO3H E) 1. CH3CO3H Answer: C Diff: 2 Section: 9.1 LO: 9.1.8 GO: G2

2. H2O2, HO-

2. H+, H2O

18) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 9.1 LO: 9.1.7 GO: G2 MCAT LO: MCAT8.2

19) Give the structure of the alkene which would yield the following products upon ozonolysisreduction. CH3CH2CH2CH2CHO + CH2O Answer: CH3CH2CH2CH2CH CH2 Diff: 1 Section: 9.1 LO: 9.1.10a GO: G2 20) Give the structure of the alkene which would yield the following products upon ozonolysisreduction. CH3COCH3 + CH3CH2CHO Answer: (CH3)2C CHCH2CH3 Diff: 1 Section: 9.1 LO: 9.1.10a GO: G2 21) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 9.1 LO: 9.1.10a GO: G2 MCAT LO: MCAT8.1

22) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 9.1 LO: 9.1.10a GO: G2 MCAT LO: MCAT8.1 23) Provide the structure of the product which results when the alkene below is treated with O3 followed by (CH3)2S.

Answer:

Diff: 3 Section: 9.1 LO: 9.1.10a GO: G2 MCAT LO: MCAT8.1

24) The compound produced when 3-methylpent-2-ene undergoes hydrogenation in the presence of a platinum catalyst is ________. Answer: 3-methylpentane Diff: 1 Section: 9.2 LO: 9.2.1 GO: G2 MCAT LO: MCAT7.6 25) Circle the alkene below which has the smallest heat of hydrogenation.

Answer:

Diff: 2 Section: 9.2 LO: 9.3.2 GO: G2 MCAT LO: MCAT7.6 26) Which has the smaller heat of hydrogenation, (E)-2-pentene or (Z)-2-pentene? What is the structural origin of this difference? Answer: (E)-2-pentene has the smaller heat of hydrogenation. There is less steric strain between the alkyl substituents in the (E)-isomer than in the (Z)-isomer. Diff: 2 Section: 9.2 LO: 9.3.2 GO: G2 MCAT LO: MCAT7.6

27) Consider the constitutional isomers 2-methylbut-1-ene, 2-methylbut-2-ene, and 3-methylbut1-ene. When each of these alkenes is subjected to catalytic hydrogenation (H2, Pt), a single product results. Which of the following best describes the structural relationship among these products? A) The products are cis-trans isomers. B) The products are identical. C) The products are constitutional isomers. D) The products are enantiomers. E) The products are diastereomers. Answer: B Diff: 2 Section: 9.2 LO: 9.2.2 GO: G2 MCAT LO: MCAT7.3 28) Draw the alkene of formula C5H10 which evolves the most heat per mole upon hydrogenation. Answer: CH2 CHCH2CH2CH3 Diff: 2 Section: 9.2 LO: 9.2.1 | 9.3.2 GO: G2 MCAT LO: MCAT7.3

29) Circle the most stable alkene in the set of isomers below.

Answer:

Diff: 2 Section: 9.2 LO: 9.3.3 GO: G2 MCAT LO: MCAT7.3 30) There are three isomeric methylbutene structures. Draw each of them and then circle the isomer with the highest heat of hydrogenation. Answer:

31) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer: Diff: 1 Section: 9.2 LO: 9.2.1 GO: G2 MCAT LO: MCAT8.1

32) Both (E)- and (Z)-hex-3-ene can be treated with D2 in the presence of a platinum catalyst. How are the products from these two reactions related to each other? A) The (E)- and (Z)-isomers generate the same products but in differing amounts. B) The (E)- and (Z)-isomers generate the same products in exactly the same amounts. C) The products of the two isomers are related as constitutional isomers. D) The products of the two isomers are related as diastereomers. E) The products of the two isomers are related as enantiomers. Answer: D Diff: 2 Section: 9.2 LO: 9.2.1 | 9.2.2 GO: G2 MCAT LO: MCAT8.1

33) Draw the major organic product(s) generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 2 Section: 9.2 LO: 9.2.1 GO: G2 MCAT LO: MCAT8.1

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 10 Alkynes: Electrophilic Addition and Redox Reactions 1) Give the IUPAC name for HC CCH2CH2CH3. Answer: pent-1-yne Diff: 1 Section: 10.2 LO: 10.1.1 GO: G2 MCAT LO: MCAT9.1 2) Draw an acceptable structure for acetylene. Answer: H—C C—H Diff: 1 Section: 10.2 LO: 10.1.2 GO: G2 MCAT LO: MCAT9.1 3) Draw an acceptable structure for hex- 2-yne. Answer: Diff: 1 Section: 10.2 LO: 10.1.2 GO: G2 MCAT LO: MCAT9.1 4) Give the IUPAC name for Cl3CCH2CH2CH2C≡CH. Answer: 6,6,6-trichlorohex-1-yne Diff: 2 Section: 10.2 LO: 10.1.1 GO: G2 MCAT LO: MCAT9.1

5) Provide the IUPAC name for the compound below.

Answer: 3-ethylhex-4-yn-3-ol Diff: 2 Section: 10.2 LO: 10.1.1 GO: G2 MCAT LO: MCAT9.1 6) Provide the IUPAC name for Cl3C(CH2)2C≡CH. Answer: 5,5,5-trichloro-1-pentyne or 5,5,5-trichloropent-1-yne Diff: 2 Section: 10.2 LO: 10.1.1 GO: G2 MCAT LO: MCAT9.1 7) Provide the IUPAC name for (CH3)2CHCH2CH(OH)CH2C≡CCH3. Answer: 2-methyl-6-octyn-4-ol or 2-methyloct-6-yn-4-ol Diff: 2 Section: 10.2 LO: 10.1.1 GO: G2 MCAT LO: MCAT9.1 8) Name the compound shown below.

Answer: 6,6-dimethyl-3-heptyne or 6,6-dimethylhept-3-yne Diff: 2 Section: 10.2 LO: 10.1.1 GO: G2 MCAT LO: MCAT9.1

9) Draw and name all terminal alkynes with molecular formula C5H8. Answer: CH3CH2CH2C≡CH, 1-pentyne or pent-1-yne; (CH3)2CHC≡CH, 3-methyl-1-butyne or 3-methylbut-1-yne Diff: 2 Section: 10.2 LO: 10.0.2 GO: G2 MCAT LO: MCAT9.1 10) Give the IUPAC name for CH3CH2C CCH(OH)CH3. Answer: hex-3-yn-2-ol Diff: 2 Section: 10.2 LO: 10.1.1 GO: G2 MCAT LO: MCAT9.1 11) Draw an acceptable structure for 3-sec-butylhept-1-yne. Answer:

Diff: 2 Section: 10.2 LO: 10.1.2 GO: G2 MCAT LO: MCAT9.1 12) Draw an acceptable structure for hepta-3,6-dien-1-yne. Answer: HC CCH CHCH2CH CH2 Diff: 2 Section: 10.2 LO: 10.1.2 GO: G2 MCAT LO: MCAT9.1

13) What is the correct IUPAC name for the following compound?

A) 4-(1-bromopropyl)-1-hexen-5-yne B) 4-allyl-5-bromo-1-hexyne C) 3-(1-bromopropyl)-5-hexen-1-yne D) 5-bromo-4-ethynyl-1-heptene Answer: C Diff: 3 Section: 10.2 LO: 10.1.1 GO: G2 MCAT LO: MCAT9.1 14) Give the IUPAC name for CH3CH CHCH CHC CCH3. Answer: octa-2,4-dien-6-yne Diff: 3 Section: 10.2 LO: 10.1.1 GO: G2 MCAT LO: MCAT9.1 15) The pi bond of an alkyne is ________ and ________ than the pi bond of an alkene. A) shorter; stronger B) shorter; weaker C) longer; stronger D) longer; weaker Answer: B Diff: 2 Section: 10.4 LO: 10.2.1 GO: G1 MCAT LO: MCAT9.3

16) The carbon-carbon triple bond of an alkyne is composed of ________. A) three σ bonds B) three π bonds C) two σ bonds and one π bond D) one σ bond and two π bonds Answer: D Diff: 1 Section: 10.4 LO: 10.2.1 GO: G1 MCAT LO: MCAT9.3 17) In trans-hept-4-en-2-yne the shortest carbon-carbon bond is between carbons ________. A) 1 and 2 B) 2 and 3 C) 3 and 4 D) 4 and 5 E) 6 and 7 Answer: B Diff: 1 Section: 10.4 LO: 10.2.4 GO: G2 MCAT LO: MCAT9.1

18) Circle the shortest bond in the compound below.

Answer:

Diff: 2 Section: 10.4 LO: 10.2.4 GO: G2 MCAT LO: MCAT9.4 19) Among the compounds water, but-1-yne, but-2-yne, and ethane, which are stronger acids than ammonia? A) but-1-yne and ethane B) water and but-1-yne C) water and ethane D) but-1-yne and but-2-yne Answer: B Diff: 2 Section: 10.4 LO: 10.2.3 GO: G2

20) Provide the structure of the major organic product(s) in the reaction sequence below. CH3CH2C CH

→

Answer: CH3CH2C CCH2Ph Diff: 1 Section: 10.5 LO: 10.7.2 GO: G2 21) Provide the structure of the major organic product(s) in the reaction below.

Answer:

Diff: 2 Section: 10.5 LO: 10.7.2 GO: G2 MCAT LO: MCAT9.2 22) Complete the short synthesis below by providing the necessary reagents.

Answer: 1) Br2 2) CH3C≡CNa 3) Na / NH3 Diff: 3 Section: 10.6 LO: 10.4.2 GO: G2

23) Which of the following reagents will convert 1 mole of 3-methylpent-1-yne into 3methylpentane? A) 1 mole of Br2 in CCl4 B) 2 moles of Cl2 in CCl4 C) 2 moles of HCl D) 2 moles H2, Ni and heat E) 1 mole H2, Ni and heat Answer: D Diff: 1 Section: 10.6 LO: 10.4.2 | 10.5.2 GO: G2 MCAT LO: MCAT9.2 24) Describe a sequence of reactions by which trans-pent-2-ene can be straightforwardly prepared from propyne. Answer: 1) NaNH2 2) CH3CH2Br 3) Na, NH3 Diff: 1 Section: 10.6 LO: 10.4.2 | 10.5.2 GO: G2 25) Which of the following reagents should be used to convert A) H2, Pt B) Na, NH3 C) H2, Lindlar's catalyst D) H2SO4, H2O E) HgSO4, H2O Answer: B Diff: 2 Section: 10.6 LO: 10.4.2 | 10.5.2 GO: G2

26) Which of the following reagents should be used to convert A) H2, Pt B) Na, NH3 C) H2, Lindlar's catalyst D) H2SO4, H2O E) HgSO4, H2O Answer: C Diff: 2 Section: 10.6 LO: 10.4.2 GO: G2

27) A mixture of hept-1-yne, hept-2-yne, and hept-3-yne was hydrogenated in the presence of a platinum catalyst until hydrogen uptake ceased. If one assumes that the hydrogenation went to completion, how many different seven-carbon hydrocarbons were produced? A) 1 B) 2 C) 3 D) 6 E) 8 Answer: A Diff: 2 Section: 10.6 LO: 10.5.1 GO: G2 MCAT LO: MCAT9.2 28) Name the compound which results when pent-1-yne is treated with sodium in liquid ammonia. Answer: pent-1-ene Diff: 2 Section: 10.6 LO: 10.5.1 | 10.5.4 GO: G2 MCAT LO: MCAT9.2

29) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 10.6 LO: 10.5.1 | 10.5.2 GO: G2 MCAT LO: MCAT9.2 30) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 10.6 LO: 10.5.1 | 10.5.4 GO: G2 MCAT LO: MCAT9.2

31) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 10.6 LO: 10.5.1 GO: G2 MCAT LO: MCAT9.2 32) Provide the major organic product of the reaction below.

Answer: (CH3)2CHCH2CH2CH=CH2 Diff: 2 Section: 10.6 LO: 10.5.1 | 10.5.2 GO: G2 MCAT LO: MCAT9.2 33) Provide the structure of the major organic product(s) in the reaction below.

Answer:

Diff: 2 Section: 10.6 LO: 10.5.1 | 10.5.4 GO: G2 MCAT LO: MCAT9.2

34) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 10.6 LO: 10.5.1 GO: G2 MCAT LO: MCAT9.2

35) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 10.6 LO: 10.5.1 | 10.5.4 | 10.7.2 GO: G2

36) In the reduction of alkynes using sodium in liquid ammonia, which of the species below is not thought to be an intermediate in the commonly accepted mechanism? A) vinyl anion B) vinyl radical C) radical anion D) vinyl cation Answer: D Diff: 3 Section: 10.6 LO: 10.5.4 | 10.5.5 GO: G2 37) Which of the following describes an unsymmetrical addition reaction? A) propyne with 1 mole H2, Ni and heat B) propyne with 2 moles Cl2 in CCl4 C) propyne with 1 mole Br2 in CCl4 D) propyne with Na/NH3 E) propyne with 1 mole HBr Answer: E Diff: 1 Section: 10.8 LO: 10.7.2 GO: G2 MCAT LO: MCAT9.2 38) Which of the alkyne addition reactions below involve(s) an enol intermediate? A) hydroboration/oxidation B) treatment with HgSO4 in dilute H2SO4 C) hydrogenation D) both A and B E) none of the above Answer: D Diff: 2 Section: 10.8 LO: 10.7.6 GO: G1

39) What is the major organic product that results when 1-heptyne is treated with 2 equivalents of HBr? A) 2,3-dibromo-1-heptene B) 2,3-dibromo-2-heptene C) 1,2-dibromoheptane D) 2,2-dibromoheptane E) 1,1-dibromoheptane Answer: D Diff: 2 Section: 10.8 LO: 10.7.4 GO: G2 MCAT LO: MCAT9.2 40) What class of organic product results when 1-heptyne is treated with a mixture of mercuric acetate in aqueous sulfuric acid? A) aldehyde B) ketone C) diol D) ether E) carboxylic acid Answer: B Diff: 2 Section: 10.8 LO: 10.7.6 GO: G2 MCAT LO: MCAT9.2 41) What class of organic product results when 1-heptyne is reacted with disiamylborane followed by treatment with basic hydrogen peroxide? A) aldehyde B) ketone C) diol D) ether E) carboxylic acid Answer: A Diff: 2 Section: 10.8 LO: 10.7.6 GO: G2 MCAT LO: MCAT9.2

42) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 10.8 LO: 10.7.2 GO: G2 MCAT LO: MCAT9.2 43) Provide the major organic product of the reaction below.

Answer: (CH3)2CHCH2CH2CH2CHO Diff: 2 Section: 10.8 LO: 10.7.6 GO: G2 MCAT LO: MCAT9.2

44) Provide the structure of the major organic product(s) in the reaction below.

Answer:

45) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 10.8 LO: 10.7.2 GO: G2 MCAT LO: MCAT9.2 46) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 10.8 LO: 10.7.6 GO: G2 MCAT LO: MCAT9.2

47) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 10.8 LO: 10.7.6 GO: G2 MCAT LO: MCAT9.2

48) Provide the structure of the major organic product(s) in the reaction below.

Answer:

Diff: 3 Section: 10.8 LO: 10.7.6 GO: G2 MCAT LO: MCAT9.2 49) Provide the structure of the major organic product(s) in the reaction sequence below.

Answer:

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 11 Properties and Synthesis of Alkyl Halides: Radical Reactions 1) Provide the name of the compound below.

Answer: 3-fluoro-2,2-dimethylhexane Diff: 1 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1

2) Name the haloalkane shown.

Answer: 3,4-dibromoheptane Diff: 1 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1

3) Provide an acceptable name for the following compound.

Answer: 4,4-dichloro-6-isopropyl-3-methylnonane Diff: 2 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT3.1

4) Identify the correct IUPAC name for the following structures.

A) 4-(2-iodo-1-methylethyl)-3-methylheptane B) 3-s-butyl-1-iodo-2-methylhexane C) 1-iodo-2,4-dimethyl-3-propylhexane D) 2,4-dimethyl-1-iodo-3-propylhexane Answer: A Diff: 2 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1 2 Copyright © 2021 Pearson Education, Inc.

5) Name the haloalkane shown.

CH3CH2C(CH3)2CH2CH2I Answer: 1-iodo-3,3-dimethylpentane Diff: 2 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1

6) Identify the correct IUPAC name for each compound shown below.

A) 2-bromo-3-sec-butyl-4-ethylhexane B) 2-bromo-4-ethyl-3-sec-butylhexane C) 3-(1-bromoethyl)-2,4-diethylhexane D) 4-(1-bromoethyl)-3-ethyl-5-methylheptane E) 4-(1-bromoethyl)-5-ethyl-3-methylheptane Answer: D Diff: 3 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1

7) Provide the name of the compound shown.

Answer: 2,2,7-trichloro-4-ethyl-6-isobutyl-7,10-dimethyldodecane Diff: 3 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1

8) Identify the correct IUPAC name for the structure shown below.

A) 1-tert-butyl-2-chloro-5-bromocycloheptane B) 5-bromo-1-tert-butyl-2-chlorocycloheptane C) 1-bromo-4-chloro-5-tertbutylcycloheptane D) 1-bromo-4-tert-butyl-5-chlorocycloheptane E) 1-tert-butyl-4-bromo-7-chlorocycloheptane Answer: B Diff: 3 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1 4 Copyright © 2021 Pearson Education, Inc.

9) Provide the name of the bromoalkane shown below.

Answer: 3-bromo-4-ethylheptane Diff: 1 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1

10) Draw the structure of cis-1,3-dichlorocyclopentane. Answer:

Diff: 1 Section: 11.2 LO: 11.0.3 GO: G2 MCAT LO: MCAT6.1

11) Provide an acceptable name for CHCl3. Answer: chloroform or trichloromethane Diff: 1 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1

12) Provide an acceptable name for CH3CH2CH2C(CH3)2I. Answer: 2-iodo-2-methylpentane Diff: 1 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1

13) Provide an acceptable name for the compound shown below.

Answer: cis-1, 2-dichlorocyclopentane Diff: 1 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1 14) Provide the structure of isopropyl iodide. Answer: (CH3)2CHI Diff: 1 Section: 11.2 LO: 11.0.3 GO: G2 MCAT LO: MCAT6.1

15) Provide an acceptable name for the compound shown below.

Answer: 4-bromo-1,1-dimethylcyclohexane Diff: 2 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1 16) Provide the structure of 1-bromo-3-methylhexane. Answer: CH3CH2CH2CH(CH3)CH2CH2Br Diff: 2 Section: 11.2 LO: 11.0.3 GO: G2 MCAT LO: MCAT6.1

17) Name the haloalkane shown. Be sure to include the appropriate R or S description if needed.

Answer: (S)- 3-chloro-1,1-dimethylcyclohexane Diff: 2 Section: 11.2 LO: 11.0.2 GO: G2 MCAT LO: MCAT6.1

18) Among the following alkyl halides, choose the one with the lowest boiling point. A) t-butyl chloride B) n-butyl chloride C) t-butyl bromide D) n-butyl iodide E) t-butyl iodide Answer: A Diff: 2 Section: 11.3 LO: 11.1.1 GO: G2 MCAT LO: MCAT6.1

19) Arrange the following alkyl halides in order of increasing boiling point: CH3CH2Br, CH3CH2CH2Br, (CH3)2CHBr, CH3CH2F. Answer: CH3CH2F < CH3CH2Br < (CH3)2CHBr < CH3CH2CH2Br Diff: 2 Section: 11.3 LO: 11.1.1 GO: G2 MCAT LO: MCAT6.1 20) When water is shaken with dichloromethane, a two-phase system results. Which compound forms the upper phase? Explain. Answer: Water is less dense than dichloromethane and therefore forms the upper phase. Diff: 2 Section: 11.3 LO: 11.1.2 | 11.1.3 GO: G2 MCAT LO: MCAT6.1

21) When 2,2-dimethylbutane is subjected to free-radical chlorination, ________ distinct monochlorinated products are possible and ________ of these contain asymmetric carbon atoms. A) 4; 2 B) 5; 0 C) 3; 0 D) 5; 2 E) 4; 0 Answer: A Diff: 2 Section: 11.5 LO: 11.2.1 | 11.2.3 GO: G2 8 Copyright © 2021 Pearson Education, Inc.

22) Draw two reasonable resonance structures and the hybrid of the intermediate formed in the following reaction.

Answer: Free Radical mechanism at the allylic C's

Diff: 2 Section: 11.5 LO: 11.2.1 GO: G2 MCAT LO: MCAT6.5 23) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 11.5 LO: 11.2.1 GO: G2

24) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 11.5 LO: 11.2.1 GO: G2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 12 Substitution and Elimination: Reactions of Haloalkanes 1) Consider the reaction of (CH3)3CO- with iodomethane. Will the reaction rate increase, decrease, or remain the same if the concentration of iodomethane is increased? Explain. Answer: This is an SN2 reaction with a The reaction rate will increase as [CH3I] increases. Diff: 1 Section: 12.2 LO: 12.1.1 GO: G2 MCAT LO: MCAT6.3 2) What type of intermediate is present in the SN2 reaction of cyanide with bromoethane? A) carbocation B) free radical C) carbene D) carbanion E) This reaction has no intermediate. Answer: E Diff: 2 Section: 12.2 LO: 12.0.5 GO: G2 3) Provide the structure of the major organic product in the following reaction. (CH3)3N + CH3CH2CH2I → Answer: [(CH3)3NCH2CH2CH3]+ IDiff: 2 Section: 12.2 LO: 12.1.2 GO: G2 MCAT LO: MCAT6.2

4) Which of the following species is the least nucleophilic? A) H2O B) BF3 C) (CH3)3N D) CH3OE) CNAnswer: B Diff: 2 Section: 12.3 LO: 12.1.4 GO: G2 5) Which of the following compounds is the most nucleophilic? A) CH3SH B) CH3OH C) H2O D) CH3CO2H E) BF3 Answer: A Diff: 2 Section: 12.3 LO: 12.1.4 GO: G2 6) Arrange the following species in order of increasing nucleophilicity: CH3CH2S-, CH3CH2O-, (CH3)3CO-, (CH3)3COH. Answer: (CH3)3COH < (CH3)3CO- < CH3CH2O- < CH3CH2SDiff: 2 Section: 12.3 LO: 12.1.4 GO: G2 7) What type of solvent is best for SN2 reactions which employ anionic nucleophiles: polar, protic solvents; polar, aprotic solvents; or nonpolar solvents? Explain. Answer: Polar, aprotic solvents are best. These solvents have strong dipole moments to enhance solubility of the anionic species but lack the ability to solvate the anion by hydrogen bonding. Diff: 3 Section: 12.3 LO: 12.1.7 | 12.1.8 GO: G2 2 Copyright © 2021 Pearson Education, Inc.

8) Which of the following compounds will undergo an SN2 reaction most readily? A) (CH3)3CCH2I B) (CH3)3CCl C) (CH3)2CHI D) (CH3)2CHCH2CH2CH2I E) (CH3)2CHCH2CH2CH2Cl Answer: D Diff: 2 Section: 12.3 LO: 12.1.9 GO: G2 9) Which of the following alkyl chlorides will undergo SN2 reaction most readily? A) 1-chloro-4-methylpentane B) 2-chloro-4-methylpentane C) 2-chloro-3-methylpentane D) 3-chloro-2-methylpentane E) 2-chloro-2-methylpentane Answer: A Diff: 2 Section: 12.3 LO: 12.1.9 GO: G2 10) Arrange the following substrates in order of their increasing SN2 reactivity with NaCN: bromoethane, 1-chloro-3,3-dimethylpentane, 1-chloro-2,2-dimethylpentane, and 2-bromo-2methylpentane. Answer: 2-bromo-2-methylpentane < 1-chloro-2,2-dimethylpentane < 1-chloro-3,3dimethylpentane < bromoethane Diff: 2 Section: 12.3 LO: 12.1.9 GO: G2

11) Do all primary iodides react with N3- at the same rate via the SN2 mechanism? Explain. Answer: No, not all primary alkyl react with N3- at the same rate via the SN2 mechanism. Some primary iodides are more hindered than others. (CH3)3CCH2I and CH3CH2I are both primary, but (CH3)3CCH2I is significantly more hindered. Additionally, some primary iodides have increased activity due to a benzylic or allylic positioning. Diff: 2 Section: 12.3 LO: 12.1.1 GO: G2 12) Do all primary alkyl iodides undergo SN2 reactions with sodium cyanide in DMSO at identical rates? Explain. Answer: No. All primary iodides are not equally accessible to attack by the CN-. Steric hindrance varies among primary iodides. Diff: 2 Section: 12.3 LO: 12.1.1 GO: G2

13) Which of the following statements describe a favorable attribute of a leaving group? (More than one answer is possible.) A) The leaving group should be highly polarizable. B) The lower the electronegativity of the leaving group the better. C) Good leaving groups need to have low steric hindrance. D) The departed leaving group should have low basicity. Answer: A, D Diff: 2 Section: 12.3 LO: 12.1.6 GO: G2

14) Which of the following alkyl halides reacts most rapidly via an SN2 reaction with NaCN? A) 1-iodohexane B) 1-fluorohexane C) (R)-2-bromohexane D) iodocyclohexane E) 1-iodo-1-methylcyclohexane Answer: A Diff: 2 Section: 12.3 LO: 12.1.1 GO: G2 15) Which of the compounds below undergoes solvolysis in aqueous ethanol most rapidly? A) cyclohexyl bromide B) methyl iodide C) isopropyl chloride D) 3-chloropentane E) 3-iodo-3-methylpentane Answer: E Diff: 2 Section: 12.3 LO: 12.1.1 | 12.1.7 GO: G2

16) Which of the following alkyl bromides undergoes solvolysis in aqueous methanol most rapidly? A) PhCHBrCH3 B) (CH3)2CHCH2CH2Br C) (CH3)2CHCH2CHBrCH3 D) CH3CH2CH2CH2Br E) PhBr Answer: A Diff: 2 Section: 12.3 LO: 12.1.1 | 12.1.7 GO: G2

17) Arrange the following compounds in order of increasing reactivity toward ethanol solvolysis: t-butyl bromide, t-butyl iodide, isopropyl chloride, methyl iodide. Answer: methyl iodide < isopropyl chloride < t-butyl bromide < t-butyl iodide Diff: 2 Section: 12.3 LO: 12.1.1 | 12.1.7 GO: G2 18) List the following bromides in order of their increasing reactivity as substrates in SN1 reactions: 2-chlorobutane, 2-iodobutane, and 1-iodobutane. Answer: 1-iodobutane < 2-chlorobutane < 2-iodobutane Diff: 2 Section: 6.13 LO: 12.1.9 GO: G2 19) List the following bromides in order of their increasing reactivity as substrates in SN1 reactions: 1-iodo-1-ethylcyclopentane, chlorocyclopentane, and iodocyclopentane. Answer: chlorocyclopentane < iodocyclopentane < 1-iodo-1-ethylcyclopentane Diff: 2 Section: 6.13 LO: 12.1.9 GO: G2 20) When t-butyl chloride undergoes solvolysis in a solvent mixture composed of 70% water/30% acetone, the reaction rate is slower than when the same compound is solvolyzed in 80% water/20% acetone. Explain. Answer: This is purely a solvent effect. The greater the percentage of water in this solvent mixture, the more polar the solvent. The more polar the solvent, the more easily solvated the developing carbocation and the more rapidly it is formed. Diff: 3 Section: 6.13 LO: 12.1.7 GO: G2 21) Why does CH2 CHCHBrCH3 undergo solvolysis much more rapidly than 2-bromobutane? Answer: The intermediate carbocation is resonance stabilized. Diff: 3 Section: 12.3 LO: 12.1.1 | 12.1.7 6 Copyright © 2021 Pearson Education, Inc.

GO: G2 MCAT LO: MCAT6.5 22) SN2 reactions take place with ________ of stereochemistry at the center undergoing substitution. Answer: inversion Diff: 1 Section: 12.4 LO: 12.2.1 GO: G1 23) Complete the following SN2 reaction by providing structures for the necessary starting materials.

Answer:

Diff: 2 Section: 12.4 LO: 12.2.1 GO: G2 MCAT LO: MCAT6.2 24) Provide the major organic product of the SN2 reaction below.

Answer:

25) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 12.4 LO: 12.2.1 GO: G2 MCAT LO: MCAT6.3 26) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 12.4 LO: 12.2.1 GO: G2 MCAT LO: MCAT6.3

27) Provide the structure of the major organic product which results when (S)-2-iodopentane is treated with KCN in DMF. Answer:

Diff: 2 Section: 12.4 LO: 12.2.1 GO: G2 MCAT LO: MCAT6.2 28) Provide the structure of the major organic product in the following reaction.

Answer:

Diff: 2 Section: 12.4 LO: 12.2.1 GO: G2 MCAT LO: MCAT6.2 29) If the absolute configuration at an asymmetric carbon does not change during the course of a reaction, the reaction is said to occur with ________ of stereochemistry. Answer: retention Diff: 1 Section: 12.4 LO: 12.2.1 GO: G1 MCAT LO: MCAT6.2

30) When trans-1-iodo-4-methylcyclohexane is heated in methanol, the product mixture is primarily ________. A) a single, chiral compound B) a mixture of diasteromeric ethers C) a mixture of diasteromeric alcohols D) a single, chiral alcohol E) a single, chiral ether Answer: B Diff: 2 Section: 12.4 LO: 12.2.1 GO: G2 MCAT LO: MCAT6.2 31) Provide the structure of the major organic products which result in the reaction below.

Answer:

Diff: 2 Section: 12.4 LO: 12.2.1 GO: G2 MCAT LO: MCAT6.2

32) SN1 reactions usually proceed with ________. A) equal amounts of inversion and retention at the center undergoing substitution B) slightly more inversion than retention at the center undergoing substitution C) slightly more retention then inversion at the center undergoing substitution D) complete inversion at the center undergoing substitution E) complete retention at the center undergoing substitution Answer: B Diff: 3 Section: 12.4 LO: 12.2.1 GO: G1 MCAT LO: MCAT6.2

33) Provide two circumstances under which solvolysis of a chiral alkyl halide would not result in the generation of a mixture of enantiomeric products. Answer: Choose two from among: (i) leaving group not bound to stereocenter (ii) rearrangement yields a carbocation in which two groups bound to the cationic center are the same (iii) the molecule contains at least one additional stereocenter which is unaffected by the ionization (iv) rearrangement ultimately results in a meso compound Diff: 3 Section: 12.4 LO: 12.2.2 GO: G2 34) Which of the cations below would be subject to a structural rearrangement?

A) 1 B) 3 C) 1, 2, & 3 D) 2 & 3 Answer: B Diff: 2 Section: 12.4 LO: 12.2.2 GO: G2

35) Which of the following alkyl halides is most likely to undergo rearrangement in an SN1 reaction? A) 3-bromopentane B) 2-chloro-3,3-dimethylpentane C) 3-chloropentane D) bromocyclohexane E) 1-bromo-4-methylcyclohexane Answer: B Diff: 2 Section: 12.4 LO: 12.2.2 GO: G2 36) Which of the following alkyl chlorides is least likely to undergo rearrangement during a solvolysis reaction? A) 2-chloro-4-methylpentane B) 2-chloro-3-methylpentane C) 2-chloro-2-methylpentane D) cis-1-chloro-2-ethylcyclohexane E) trans-1-chloro-2-ethylcyclohexane Answer: C Diff: 2 Section: 12.4 LO: 12.2.2 GO: G2

37) A sample of 1-chloro-1-phenylethane with an [α]25D of -94.8° is reacted with NH3 in methanol/water solvent. The major substitution product of the reaction is 1-phenyl-1-ethylamine with an [α]25D of -8.6°. Given that optically pure (R) 1-chloro-1-phenylethane has a specific rotation of -109.0° and that optically pure (R) 1-phenyl-1-ethylamine has a specific rotation of +39.3°, which of the following statements best describes this reaction?

A) Net inversion 25% with 75% racemization — SN1 mechanism B) Net inversion 12% with 88% racemization — SN1 mechanism C) Net inversion 75% with 25% racemization — SN2 mechanism D) Net inversion 12% with 88% racemization — SN2 mechanism E) Net inversion 88% with 12% racemization — SN2 mechanism Answer: A Diff: 3 Section: 12.4 LO: 12.2.1 GO: G2 MCAT LO: MCAT5.3 38) Predict the structure of the expected product for the following reaction.

Answer:

Diff: 3 Section: 12.4 LO: 12.1.2 GO: G2

39) Provide the major organic product of the reaction below and a detailed, stepwise mechanism which accounts for its formation.

Answer:

Diff: 3 Section: 12.4 LO: 12.2.1 GO: G2 40) Provide the structure of the major organic product which results in the following reaction.

Answer:

Diff: 3 Section: 12.4 LO: 12.2.1 GO: G2 MCAT LO: MCAT6.2

41) Which of the alkyl chlorides listed below undergoes dehydrohalogenation in the presence of a strong base to give pent-2-ene as the only alkene product? A) 1-chloropentane B) 2-chloropentane C) 3-chloropentane D) 1-chloro-2-methylbutane E) 1-chloro-3-methylbutane Answer: C Diff: 1 Section: 12.5 LO: 12.4.1 | 12.4.5 GO: G2 42) Which of the following statements correctly describe(s) E1 reactions of alkyl halides (RX)? I. Rate = k[base] II. Rate = k[base][RX] III. Rate = k[RX] IV. The reactions occur in two or more distinct steps. V. Rearrangements are sometimes seen. A) II and IV B) III and V C) I, IV, and V D) I only E) III, IV, and V Answer: E Diff: 2 Section: 12.6 LO: 12.4.3 GO: G2 MCAT LO: MCAT6.3

43) Dehydrohalogenation of 2-bromobutane in the presence of a strong base proceeds via which of the following mechanistic pathways? A) SN1 B) SN2 C) E1 D) E2 E) none of the above Answer: D Diff: 1 Section: 12.6 LO: 12.4.5 GO: G2 MCAT LO: MCAT6.2

44) Dehydrohalogenation of an alkyl halide by treating it with a strong base to yield an alkene product typically occurs by what reaction mechanism? A) SN1 B) SN2 C) E1 D) E2 E) free radical Answer: D Diff: 1 Section: 12.6 LO: 12.4.5 GO: G2 MCAT LO: MCAT6.2 45) Which of the following alkenes is the major product when 2-bromo-2-methylpentane is treated with sodium ethoxide in ethanol? A) 2-methylpent-1-ene B) 2-methylpent-2-ene C) (E)-4-methylpent-2-ene D) (Z)-4-methylpent-2-ene E) 4-methylpent-1-ene Answer: B Diff: 2 Section: 12.6 LO: 12.4.5 | 12.5.1 GO: G2 MCAT LO: MCAT6.2

46) When 1-bromo-2, 2-dimethylcyclopentane is heated in ethanol, one of the products which results is shown below. Provide a detailed, stepwise mechanism for the production of this compound, and give the name of the mechanism by which it is produced.

Answer:

Diff: 3 Section: 12.7 LO: 12.4.5 GO: G2

47) What is Zaitsev's rule? Answer: In elimination reactions, the most highly substituted alkene product is the major product. Diff: 2 Section: 12.7 LO: 12.5.1 GO: G1

48) Which of the following alkyl halides can produce only a single alkene product from when treated with sodium methoxide? A) 2-chloro-2-methylpentane B) 3-chloro-3-ethylpentane C) 3-chloro-2-methylpentane D) 2-chloro-4-methylpentane E) 2-chloro-3-ethylpentane Answer: B Diff: 2 Section: 12.7 LO: 12.3.1 | 12.4.5 GO: G2 MCAT LO: MCAT6.2 49) How many distinct alkene products results when 1-bromo-1-ethylcyclopentane is treated with NaOCH3? A) 1 B) 2 C) 3 D) 4 Answer: B Diff: 2 Section: 12.7 LO: 12.5.1 GO: G2 MCAT LO: MCAT6.2

50) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 12.7 LO: 12.3.1 | 12.4.5 GO: G2 MCAT LO: MCAT6.2

51) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 12.7 LO: 12.3.1 | 12.4.5 GO: G2 MCAT LO: MCAT6.2

52) Provide a series of synthetic steps by which (CH3)2C CH2 could be prepared from 2methylpropane. Answer: 1) Br2, hν 2) NaOCH3, CH3OH Diff: 2 Section: 12.7 LO: 12.3.1 | 12.4.5 GO: G2 53) Provide the structure of the major organic product which results when 2-bromo-2methylbutane is treated with sodium ethoxide. Answer:

Diff: 2 Section: 12.7 LO: 12.3.1 | 12.4.5 GO: G2 MCAT LO: MCAT6.2

54) Which of the following statements applies to the E2 mechanism? A) It occurs with inversion of stereochemistry. B) It occurs with racemization of stereochemistry. C) It proceeds through the more stable carbocation intermediate. D) The C-H and C-X bonds that break must be anti. E) Use of a bulky base gives the more highly substituted alkene product. Answer: D Diff: 2 Section: 12.7 LO: 12.5.1 GO: G1 MCAT LO: MCAT6.2 55) Provide the structure of the major organic product of the reaction below.

Answer:

Diff: 2 Section: 12.7 LO: 12.5.1 GO: G2 MCAT LO: MCAT7.4

56) Provide the structure of the major organic product of the reaction below.

Answer:

Diff: 2 Section: 12.7 LO: 12.5.1 GO: G2 MCAT LO: MCAT6.2

57) Provide the structure of the major organic product of the reaction below.

Answer:

Diff: 2 Section: 12.7 LO: 12.5.1 GO: G2 MCAT LO: MCAT6.2 58) Provide the reagents necessary for carrying out the transformation of cyclopentane to cyclopentene. Answer: 1) Br2, hν 2) NaOH, acetone Diff: 2 Section: 12.7 LO: 12.4.3 GO: G2 59) Provide the reagents necessary for carrying out the transformation of 2-methylheptane to 2methylhept-2-ene. Answer: 1) Br2, hν 2) NaOH, acetone Diff: 3 Section: 12.7 LO: 12.4.3 GO: G2

60) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 12.8 LO: 12.5.1 GO: G2 MCAT LO: MCAT6.2 61) Provide the structure of the major organic product which results in the following reaction.

Answer:

Diff: 2 Section: 12.8 LO: 12.5.1 GO: G2 MCAT LO: MCAT6.2

62) Provide the structure of the major organic product which results in the following reaction.

Answer:

Diff: 2 Section: 12.8 LO: 12.1.2 | 12.5.1 | 12.6.1 GO: G2 MCAT LO: MCAT6.2

63) Provide a structure for the major substitution and elimination product of the following reaction.

Answer:

Diff: 3 Section: 12.8 LO: 12.3.1 | 12.4.5 GO: G2 MCAT LO: MCAT6.2

64) Provide the structure of the major organic product of the reaction below.

Answer:

Diff: 2 Section: 12.8 LO: 12.3.1 | 12.4.5 GO: G2 MCAT LO: MCAT7.4 65) Provide the major organic product in the reaction shown below.

Answer:

Diff: 2 Section: 12.8 LO: 12.3.1 | 12.4.5 GO: G2 MCAT LO: MCAT6.2

66) Provide the major organic product in the reaction shown below.

Answer:

Diff: 2 Section: 12.8 LO: 12.3.1 | 12.4.5 GO: G2 MCAT LO: MCAT7.4 67) Draw all likely alkene products in the following reaction and circle the product you expect to predominate.

Answer:

Diff: 2 Section: 12.8 LO: 12.3.1 | 12.4.5 GO: G2

68) Which base, ammonia (NH3) or triethylamine [(CH3CH2)3N], would be a better choice for use in converting 1-chlorohexane to hex-1-ene? Explain briefly. Answer: Triethylamine. Amines can serve as both nucleophiles and as bases in reactions with alkyl halides. Increasing the steric bulk about the nitrogen diminishes the nucleophilicity while allowing the amine to continue to function effectively as a base. Diff: 2 Section: 12.8 LO: 12.4.1 GO: G2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 13 Alcohols, Ethers and Related Compounds: Substitution and Elimination 1) Which molecule below is an ether? A) CH3CH2OCH2CH3 B) (CH3)2CHCH2OH C) (CH3)2CHCH2NH2 D) (CH3)2C=CH2 E) CH3CH2CH2CO2H Answer: A Diff: 1 Section: 13.1 LO: 13.7.1 GO: G2

2) What term is given to the sulfur analogues of ethers? Answer: sulfides or thioethers Diff: 1 Section: 13.1 LO: 13.7.1 GO: G2

3) 2-Methylbutan-1-ol is classified as ________. A) a primary alcohol B) a secondary alcohol C) a tertiary alcohol D) a phenol E) an enol Answer: A Diff: 1 Section: 13.2 LO: 13.0.3 | 13.0.5 1 Copyright © 2021 Pearson Education, Inc.

GO: G2 MCAT LO: MCAT10.1 4) 1-Methylcyclopentanol is classified as ________. A) a primary alcohol B) a secondary alcohol C) a tertiary alcohol D) a phenol E) an enol Answer: C Diff: 1 Section: 13.2 LO: 13.0.3 | 13.0.5 GO: G2 MCAT LO: MCAT10.1 5) Consider the alcohol 3-methylpentan-3-ol. Is this alcohol primary, secondary, or tertiary? Answer: tertiary Diff: 1 Section: 13.2 LO: 13.0.3 | 13.0.5 GO: G2 MCAT LO: MCAT10.1 6) Provide an acceptable name for the compound below. HOCH2CH2OH Answer: ethylene glycol or ethane-1,2-diol Diff: 1 Section: 13.2 LO: 13.01 GO: G2 MCAT LO: MCAT10.1 7) Provide an acceptable name for the compound below. (CH3)2CHCH2OH Answer: isobutyl alcohol or 2-methylpropan-1-ol Diff: 1 Section: 13.2 LO: 13.01 GO: G2 MCAT LO: MCAT10.1

8) 2-Methylpentan-3-ol is classified as ________. A) a primary alcohol B) a secondary alcohol C) a tertiary alcohol D) a phenol E) an enol Answer: B Diff: 2 Section: 13.2 LO: 13.0.3 | 13.0.5 GO: G2 MCAT LO: MCAT10.1 9) Give the IUPAC name for (CH3)2C CHCH2CH2OH. Answer: 4-methylpent-3-en-1-ol Diff: 2 Section: 13.2 LO: 13.0.1 GO: G2 MCAT LO: MCAT10.1 10) Provide the IUPAC name for the compound below.

Answer: 3,4,5-triethyloctan-3-ol Diff: 2 Section: 13.2 LO: 13.0.1 | 13.0.2 | 13.0.4 GO: G2 MCAT LO: MCAT10.1

11) Provide the IUPAC name for the following compound.

Answer: (E)-4,5,5-trimethyl-3-hexen-1-ol or (E)-4,5,5-trimethylhex-3-en-1-ol Diff: 2 Section: 13.2 LO: 13.0.1 | 13.0.2 | 13.0.4 GO: G2 MCAT LO: MCAT10.1 12) Provide an acceptable name for the compound below.

Answer: 3-methylcyclopent-3-enol Diff: 2 Section: 13.2 LO: 13.0.1 | 13.0.2 | 13.0.4 GO: G2 MCAT LO: MCAT10.1 13) Provide an acceptable name for the compound below.

Answer: cis-cyclopentane-1,3-diol Diff: 2 Section: 13.2 LO: 13.0.1 | 13.0.2 GO: G2 MCAT LO: MCAT10.1

14) What is the correct IUPAC name of the compound below?

A) 3-(2-bromopropyl)-6,6-dimethylheptan-2-ol B) 5-bromo-3-(3,3-dimethylbutyl)hexan-2-ol C) 5-(2-bromopropyl)-2,2-dimethylheptan-6-ol D) 7-bromo-5-(1-hydroxyethyl)-2,2-dimethyloctane Answer: A Diff: 2 Section: 13.2 LO: 13.0.1 | 13.0.2 | 13.0.4 GO: G2 MCAT LO: MCAT10.1 15) Name the compound shown below.

Answer: 3-ethyl-6-methyl-2-heptanol or 3-ethyl-6-methylheptan-2-ol Diff: 2 Section: 13.2 LO: 13.0.1 | 13.0.2 | 13.0.4 GO: G2 MCAT LO: MCAT10.1 16) Draw (2R, 3S) 2-bromopentan-1,3-diol in a Fischer projection. Answer:

MCAT LO: MCAT10.1

17) Provide an acceptable name for the compound below.

Answer: cis-3-chlorocyclohexan-1-ol Diff: 3 Section: 13.2 LO: 13.0.1 | 13.0.2 | 13.0.4 GO: G2 MCAT LO: MCAT10.1

18) Provide an acceptable name for the compound below.

Answer: 4-bromo-2-propylhexan-1-ol Diff: 3 Section: 13.2 LO: 13.0.1 | 13.0.2 | 13.0.4 GO: G2 MCAT LO: MCAT10.1 19) Provide an acceptable name for the compound below.

Answer: (E)-4-chloro-3-methylpent-3-en-1-ol Diff: 3 Section: 13.2 LO: 13.0.1 | 13.0.2 | 13.0.4 GO: G2 MCAT LO: MCAT10.1

20) Provide an acceptable name for the compound below.

Answer: (Z)-4-methylhex-3-ene-1-thiol Diff: 3 Section: 13.2 LO: 13.0.1 | 13.0.2 | 13.0.4 GO: G2 MCAT LO: MCAT10.1

21) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 13.11 LO:13.8.5 GO: G2

22) Provide the structure of the major organic product in the reaction below. PhCH2CH2OH

→

Answer: PhCH2CH2CN Diff: 2 Section: 13.7 LO: 13.4.3 GO: G2 MCAT LO: MCAT11.2

23) Provide the structure of the major organic product in the reaction below. (CH3)2CHCH2OH Answer: (CH3)2CHCH2Br Diff: 2 Section: 13.7 LO: 13.4.4 GO: G2 MCAT LO: MCAT11.1 24) Provide the structure of the major organic product that results when 4-methyl-1-pentanol is treated with PBr3. Answer: (CH3)2CHCH2CH2CH2Br Diff: 2 Section: 13.7 LO: 13.4.4 GO: G2 MCAT LO: MCAT11.1 25) Which of the following reagents or sequences do not produce an alcohol or diol from an alkene starting material? A) H+, H2O B) HCO3H C) BH3.THF followed by H2O2, NaOH D) Hg(OAc)2, H2O followed by NaBH4 E) OsO4, H2O2 Answer: B Diff: 1 Section: 13.5 LO: 13.2.1 GO: G2 26) Provide the name of the major organic product that results when 1-pentene is treated with aqueous acid. Answer: 2-pentanol Diff: 2 Section: 13.5 LO: 13.2.1 GO: G2

27) Provide the name of the major organic product that results when 1-pentene is subjected to hydroboration/oxidation. Answer: 1-pentanol Diff: 2 Section: 13.5 LO: 13.2.1 GO: G2 28) Provide the major organic product of the following reaction.

Answer:

Diff: 3 Section: 13.5 LO: 13.2.1 GO: G2 29) What gaseous byproduct is evolved when sodium metal is added to ethanol? Answer: H2, molecular hydrogen Diff: 2 Section: 13.6 LO: 13.2.6 GO: G2 MCAT LO: MCAT10.2

30) Given the set of reactants below, complete the acid-base reaction, and indicate whether the equilibrium favors reactants or products. CH3O- + HCl → Answer: CH3OH + Cl-, products are favored at equilibrium Diff: 2 Section: 13.6 LO: 13.2.4 GO: G2 MCAT LO: MCAT10.2 31) When (R)-butan-2-ol is treated with TsCl in pyridine, the product formed is ________. A) a single enantiomer B) a racemic mixture C) a mixture of diastereomers D) an achial compound E) none of the above Answer: A Diff: 2 Section: 13.7 LO: 13.4.3 GO: G2 MCAT LO: MCAT11.2 32) What compound is produced when (R)-pentan-2-ol is treated with TsCl followed by NaI? A) sodium (R)-pent-3-oxide B) sodium (S)-pent-2-oxide C) (R)-2-iodopentane D) (S)-2-iodopentane E) none of the above Answer: D Diff: 2 Section: 13.7 LO: 13.4.3 GO: G2 MCAT LO: MCAT11.2

33) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 13.7 LO: 13.4.3 GO: G2 MCAT LO: MCAT11.2 34) Provide the major organic product of the reaction shown.

Answer:

Diff: 2 Section: 13.7 LO: 13.4.3 GO: G2 MCAT LO: MCAT11.2

35) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 13.7 LO: 13.4.3 GO: G2 MCAT LO: MCAT11.2 36) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 1 Section: 13.7 LO: 13.4.4 GO: G2 MCAT LO: MCAT11.1

37) Provide the major organic product of the reaction shown.

Answer:

Diff: 2 Section: 13.7 LO: 13.4.4 GO: G2 MCAT LO: MCAT11.1

38) Provide the major organic product of the following.

Answer:

Diff: 2 Section: 13.7 LO: 13.4.4 GO: G2 MCAT LO: MCAT11.1 39) Through what basic mechanism is 1-methylcyclohexanol converted to 1-bromo-1methylcyclohexane upon treatment with HBr? A) SN1 B) SN2 C) E1 D) E2 E) radical chain Answer: A Diff: 2 Section: 13.7 LO: 13.4.4 14 Copyright © 2021 Pearson Education, Inc.

GO: G2 40) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 13.7 LO: 13.4.7 GO: G2 MCAT LO: MCAT11.1 41) Provide the major organic product of the reaction shown.

Answer:

Diff: 2 Section: 13.7 LO: 13.4.7 GO: G2 MCAT LO: MCAT11.1

42) Provide the major organic product of the reaction shown.

Answer:

Diff: 2 Section: 13.7 LO: 13.4.7 GO: G2 MCAT LO: MCAT11.1 43) Provide the structure of the major organic product in the reaction below. PhCH2CH(OH)CH3 Answer: PhCH2CHClCH3 Diff: 1 Section: 13.7 LO: 13.4.5 GO: G2 MCAT LO: MCAT11.1 44) With close attention to stereochemistry, provide the major organic product for the reaction shown below.

45) Provide the major organic product of the following.

Answer:

Diff: 2 Section: 13.7 LO: 13.4.5 GO: G2 MCAT LO: MCAT11.1 46) In the group shown below, which of the following alcohols is (are) likely to yield a product where skeletal rearrangement has occurred when treated with sulfuric acid? 3-methyl-3-pentanol, 3,3-dimethyl-2-butanol, 2,2-dimethylcyclohexanol A) 3-methyl-3-pentanol only B) 3,3-dimethyl-2-butanol only C) 2,2-dimethylcyclohexanol only D) both 3,3-dimethyl-2-butanol and 2,2-dimethylcyclohexanol E) None of these three alcohols is prone to rearrangement. Answer: D Diff: 2 Section: 13.8 LO: 13.5.6 GO: G2

47) Provide the major organic product in the reaction shown below.

Answer:

Diff: 2 Section: 13.8 LO: 13.5.4 | 13.5.6 GO: G2 48) Dehydration of an unknown alcohol with concentrated H2SO4 results in the formation of all of the following alkene products. What is/are the possible structures of the original alcohol?

E) Both B and C are possible structures for the original alcohol. Answer: B Diff: 3 Section: 13.8 LO: 13.5.5 | 13.5.6 GO: G2 49) Predict the major product of the reaction shown below.

A) 2,3-dimethyl-2-butene B) 2,3-dimethyl-1-butene C) 3,3-dimethyl-1-butene D) None of the above Answer: A Diff: 3 Section: 13.8 LO: 13.5.4 GO: G2 50) Draw all likely products of the following reaction and circle the product you expect to predominate.

Answer:

GO: G2

51) Draw all likely products of the following reaction and circle the product you expect to predominate.

Answer:

Diff: 3 Section: 13.8 LO: 13.5.4 | 13.5.6 GO: G2 52) Draw the major product of the following reaction.

Answer: Diff: 3 Section: 13.8 LO: 13.5.4 GO: G2 53) Provide the major organic product of the following.

Answer:

54) Provide the structure of the major organic product in the reaction below.

Answer: Diff: 1 Section: 13.8 LO: 13.5.4 GO: G2 MCAT LO: MCAT11.1

55) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 13.8 LO: 13.5.4 GO: G2 MCAT LO: MCAT11.1 56) Provide the major organic product of the following.

Answer: Diff: 2 Section: 13.8 LO: 13.5.4 GO: G2 MCAT LO: MCAT11.1

57) Which of the following alcohols undergoes dehydration upon heating with concentrated H2SO4 without carbocation rearrangement? A) 3,3-dimethylpentan-2-ol B) 3-methylpentan-3-ol C) 2-methylhexan-3-ol D) 2-methyl-2-phenylpropan-1-ol E) both A and B Answer: E Diff: 2 Section: 13.8 LO: 13.5.6 GO: G2 58) Which of the following reaction series will result in the formation of a new secondary (2°) alcohol from the beginning alcohol listed at the top? A) Ethanol 1. Na° 2. CH3CH2I B) t-butyl alcohol 1. K2Cr2O7/acetic acid 2. CH3-MgBr 3. H3O+ C) 2-propanol 1. K2Cr2O7/acetic acid 2. CH3-MgBr 3. H3O+ D) n-butanol 1. H2SO4/heat 2. Hg(OAc)2 (aq) 3. NaBH4 E) 2-methylcycloxexanol 1. H2SO4/heat 2. OsO4/H2O2 3. H2SO4/heat Answer: D Diff: 3 Section: 13.8 LO: 13.5.5 GO: G2

59) What is the expected product of the reaction below?

D) Answer: B Diff: 2 Section: 13.8 LO: 13.5.7 | 13.5.8 GO: G2 MCAT LO: MCAT11.1 60) Predict the outcome of the following reaction.

Answer:

Diff: 3 Section: 13.8 LO: 13.5.7 | 13.5.8 GO: G2 MCAT LO: MCAT11.1

61) Predict the major product of the following dehydration reaction.

Answer:

This is a pinacol rearrangement reaction where the most stable carbocation would be formed at the tertiary position in the ring. Diff: 3 Section: 13.8 LO: 13.5.7 | 13.5.8 GO: G2 MCAT LO: MCAT11.1 62) Classify the reaction below as an oxidation, a reduction, or neither. (CH3)2CHCH2OH → (CH3)2CHCHO A) oxidation B) reduction C) neither Answer: A Diff: 1 Section: 13.9 LO: 13.6.1 GO: G1 63) In the chromic acid oxidation of alcohols, the chromium is ________. A) oxidized from Cr+3 to Cr+6 B) reduced from Cr+6 to Cr+3 C) oxidized from Cr+6 to Cr+3 D) reduced from Cr+3 to Cr+6 E) none of the above Answer: B Diff: 1 Section: 13.9 LO: 13.6.4 GO: G1 25 Copyright © 2021 Pearson Education, Inc.

64) Which of the following alcohols will give a positive chromic acid test? A) tert-butanol B) cyclohexanol C) pentan-3-ol D) both A and B E) both B and C Answer: E Diff: 2 Section: 13.9 LO: 13.6.4 GO: G1 MCAT LO: MCAT11.1 65) Which of the following reagents is the best choice for oxidizing a primary alcohol to an aldehyde? A) H2CrO4 B) pyridinium chlorochromate C) Na2Cr2O7, H2SO4 D) KMnO4 E) LiAlH4 Answer: B Diff: 2 Section: 13.9 LO: 13.6.5 GO: G1 66) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 13.9 LO: 13.6.4 | 13.6.5 GO: G2 MCAT LO: MCAT11.1

67) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 13.9 LO: 13.6.4 | 13.6.5 GO: G2 MCAT LO: MCAT11.1 68) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 13.9 LO: 13.6.4 | 13.6.5 GO: G2 MCAT LO: MCAT11.1

69) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 13.9 LO: 13.6.4 | 13.6.5 GO: G2 MCAT LO: MCAT11.1 70) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 13.9 LO: 13.6.4 | 13.6.5 GO: G2 MCAT LO: MCAT11.1

71) Provide the major organic product of the reaction shown.

Answer:

Diff: 2 Section: 13.9 LO: 13.6.4 | 13.6.5 GO: G2 MCAT LO: MCAT11.1

72) Provide the major organic product of the following.

Answer:

Diff: 2 Section: 13.9 LO: 13.6.4 | 13.6.5 GO: G2 MCAT LO: MCAT11.1

73) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 13.9 LO: 13.6.6 GO: G2 MCAT LO: MCAT11.1 74) Provide the major organic product of the reaction shown.

Answer:

Diff: 2 Section: 13.9 LO: 13.6.8 GO: G2

75) Provide the major organic product of the following.

Answer:

Diff: 3 Section: 13.8 LO: 13.5.4 GO: G2 MCAT LO: MCAT11.1 76) Provide the structure of the major organic product that results when 3-hexanol is treated with sodium dichromate. Answer: CH3CH2COCH2CH2CH3 Diff: 2 Section: 13.9 LO: 13.6.4 GO: G2 MCAT LO: MCAT11.1 77) Provide the structure of the major organic product that results when 1-octanol is treated with pyridinium chlorochromate. Answer: CH3(CH2)6CHO Diff: 2 Section: 13.9 LO: 13.6.4 GO: G2 MCAT LO: MCAT11.1 78) Provide the major organic product in the reaction below. CH3CH2CH2OH

→

GO: G2 79) Provide the major organic product in the reaction below.

Answer:

Diff: 1 Section: 13.11 LO: 13.8.5 GO: G2

80) Provide the major organic product of the following.

Answer:

Diff: 2 Section: 13.11 LO: 13.8.5 GO: G2

81) Provide the necessary reagents to complete the following reaction.

Answer:

Diff: 3 Section: 13.11 LO: 13.8.5 GO: G2

82) Which of the following reactions or series of reactions will lead to the formation of methoxycyclohexane? A)

Answer: D Diff: 2 Section: 13.11 LO: 13.8.4 GO: G2

83) Predict the products of the following reaction and give a reasonable mechanism for their formation.

Answer:

Diff: 2 Section: 13.12 LO: 13.9.2 GO: G2 84) Provide the major organic product of the following.

Answer:

Diff: 2 Section: 13.12 LO: 13.9.2 GO: G2

85) Provide the major organic product in the reaction below.

Answer:

Diff: 2 Section: 13.13 LO: 13.10.4 GO: G2 86) Provide the major organic product in the reaction below.

Answer:

Diff: 3 Section: 13.13 LO: 13.10.3 GO: G2 87) Show the reagents necessary to prepare trans-1,2-cyclopentanediol from cyclopentene. Answer: 1) PhCO3H 2) H3O+ Diff: 1 Section: 13.13 LO: 13.10.4 GO: G2

88) When an alkene is subjected to treatment with Hg(OAc)2 in alcohol followed by reaction with NaBH4, what new class of compound is formed? A) ether B) epoxide C) alkane D) syn diol E) alkyne Answer: A Diff: 2 Section: 13.11 LO: 13.8.5 GO: G2 MCAT LO: MCAT8.1 89) Provide the structure of the major organic product of the reaction below.

Answer:

Diff: 2 Section: 13.11 LO: 13.8.5 GO: G2 MCAT LO: MCAT8.1

90) Draw the major organic product generated in the reaction below. Pay particular attention to regio- and stereochemical detail.

Answer:

Diff: 3 Section: 13.11 LO: 13.8.5 GO: G2 MCAT LO: MCAT8.1 91) The Williamson ether synthesis proceeds via an ________ mechanism. A) SN1 B) SN2 C) E1 D) E2 E) none of the above Answer: B Diff: 1 Section: 13.11 LO: 13.8.3 GO: G1 92) Provide the structure of the major organic product in the reaction below.

Answer:

GO: G2 MCAT LO: MCAT11.1

93) Provide the name of the major organic product that results when cyclopentanol is subjected to the following sequence of reactions: 1. NaH; 2. CH3CH2Br. Answer: ethoxycyclopentane Diff: 2 Section: 13.11 LO: 13.8.3 GO: G2 MCAT LO: MCAT11.1 94) Provide the major organic product of the reaction shown.

Answer:

Diff: 2 Section: 13.11 LO: 13.8.3 GO: G2 MCAT LO: MCAT11.1

95) In the formation of the following ether, which reaction is preferred and why?

A) Reaction B is preferred because the oxidation step works best for primary alcohols. B) Reaction A is preferred over reaction B because the smaller methyl iodide would make a better nucleophilic target. C) Reaction A is preferred because the the formation of the carbocation would be stabilized in the benzylic position. D) Reaction B would be preferred because Iodine is a better leaving group for the SN1 reaction. E) There is no difference in these two reactions — they would give approximately the same yields. Answer: B Diff: 3 Section: 13.11 LO: 13.8.2 | 13.8.3 GO: G2 96) The Williamson ether synthesis occurs by the ________ mechanistic pathway. Answer: SN2 Diff: 1 Section: 13.11 LO: 13.8.3 GO: G1

97) Show the best method for preparing methoxycyclopentane via the Williamson ether synthesis. Answer:

Diff: 1 Section: 13.11 LO: 13.8.2 | 13.8.3 GO: G2 98) Which of the following reactions is classified as a Williamson ether synthesis? A)

Answer: B Diff: 2 Section: 13.11 LO: 13.8.2 GO: G1

99) Show the best method for preparing 4-propoxytoluene via the Williamson ether synthesis. Answer:

Diff: 2 Section: 13.11 LO: 13.8.2 | 13.8.3 GO: G2

100) Provide the sequence of reactions by which propoxycyclohexane can be prepared through a Williamson ether synthesis. Answer:

Diff: 2 Section: 13.11 LO: 13.8.2 | 13.8.3 GO: G2

101) Provide the major organic product of the following reactions.

Answer:

102) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 13.11 LO: 13.8.3 GO:G2 103) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 13.11 LO: 13.8.3 GO:G2

104) Show the best Williamson ether synthesis for the following target molecule.

Answer: Diff: 2 Section: 13.11 LO: 13.8.2 | 13.8.3 GO: G2 105) When cyclohexene is subjected to mercuration in methanol and the resulting mixture is reduced with sodium borohydride, the major organic product is ________. A) a meso ether B) a 1:1 mixture of enantiomeric ethers C) a meso diol D) a 1:1 mixture of enantiomeric diols E) methoxycyclohexane Answer: E Diff: 2 Section: 13.11 LO: 13.8.5 GO: G2 106) When pent-1-ene is treated with mercury(II) acetate in methanol and the resulting product is reacted with NaBH4, what is the primary organic compound which results? A) 3-ethoxypentane B) 1-methoxypentane C) 1-ethoxypentane D) 2-ethoxypentane E) 2-methoxypentane Answer: E Diff: 2 Section: 13.11 LO: 13.8.5 GO: G2

107) Provide the major organic product in the reaction below. CH3CH2CH CH2

→

Answer: CH3CH2CHCH3 ∣ OCH2CH3 Diff: 2 Section: 13.11 LO: 13.8.5 GO: G2 108) Provide the major organic product of the following.

Answer:

Diff: 2 Section: 13.11 LO: 13.8.5 GO: G2

109) Provide the major organic product of the following.

Answer:

Diff: 2 Section: 13.11 LO: 13.8.3 GO: G2 110) Which of the following is produced by the reaction of (CH3CH2)2S with CH3CH2I? A) CH3CH2CH2CH2I B) (CH3CH2)3S+ IC) (CH3CH2)3S D) CH3SCH2CH2CH3 E) CH3CH2SCH2CH2I Answer: B Diff: 2 Section: 13.11 LO: 13.8.3 GO: G2 111) Provide the major organic product of the reaction shown below.

Answer:

112) Provide the major organic product in the reaction below. HOCH2(CH2)2CH2Br Answer:

Diff: 3 Section: 13.11 LO: 13.8.3 GO: G2

113) What are the expected products of the reaction of PhOCH3 with concentrated HI? A) phenol and methanol B) phenol and iodomethane C) iodobenzene and methanol D) iodobenzene and iodomethane Answer: B Diff: 1 Section: 13.12 LO: 13.9.2 GO: G2 114) Provide the major organic product(s) in the reaction below.

Answer:

Diff: 1 Section: 13.12 LO: 13.9.2 GO: G2

115) Di-n-pentyl ether can be converted to 1-bromopentane by treatment with HBr through essentially a(n) ________ mechanism. A) SN2 B) SN1 C) E2 D) E1 E) ring opening Answer: A Diff: 1 Section: 13.12 LO: 13.9.2 GO: G2 116) Treatment of tetrahydrofuran with excess HBr results in the formation of what major organic product? A) 1-bromobutane B) 1,2-dibromobutane C) 1,4-dibromobutane D) 1-bromopentane E) 1,5-dibromopentane Answer: C Diff: 2 Section: 13.12 LO: 13.9.2 GO: G2 117) Provide the major organic product of the following reactions.

Answer:

118) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 13.12 LO: 13.9.2 GO: G2

119) Provide the major organic product of the reaction shown below.

Answer: Br(CH2)6Br Diff: 2 Section: 13.12 LO: 13.9.2 GO: G2 120) Provide the major organic product in the reaction below.

Answer: Diff: 3 Section: 13.12 LO: 13.9.2 GO: G2

121) Draw all likely products of the following reaction and circle the product you expect to predominate. CH3CH(OH)CH2CH2CH3 Answer:

Diff: 2 Section: 13.8 LO: 13.5.4 GO: G2

122) What series of synthetic steps could be used to carry out the transformation shown below?

Answer: 1) BH3 2) H2O2, -OH 3) PCC Diff: 1 Section: 13.9 LO: 13.6.4 GO: G2 123) Provide the structure of the major organic product in the reaction below.

Answer: No reaction. Tertiary alcohols are not oxidized by PCC. Diff: 2 Section: 13.9 LO: 13.6.4 GO: G2 MCAT LO: MCAT11.1

124) Provide the major organic product in the reaction below.

Answer:

Diff: 1 Section: 13.13 LO: 13.10.1 GO: G2 125) Provide the major organic product of the following reactions.

Answer:

plus enantiomer Diff: 2 Section: 13.13 LO: 13.10.1 GO: G2 126) Provide the major organic product in the reaction below.

Answer:

Section: 13.13 LO: 13.10.1 GO: G2 127) Identify all of the following reagents that could be used to accomplish the following transformation. (More than one answer is possible.)

A) mCPBA B) DMD C) cold KMnO4 D) 1) Br2 / H2O, 2) NaH Answer: A, B, D Diff: 2 Section: 13.13 LO: 13.10.1 GO: G2

128) Provide the major organic product of the following.

Answer:

Diff: 2 Section: 13.13 LO: 13.10.1 GO: G2

129) Through what mechanism can a 1,2-halohydrin be converted into an epoxide? A) SN1 B) SN2 C) E2 D) electrophilic addition E) polymerization Answer: B Diff: 2 Section: 13.13 LO: 13.10.5 GO: G2

130) Which of the following reactions or series of reactions will lead to formation of trans-2methoxycyclohexanol? A)

Answer: D Diff: 2 Section: 13.13 LO: 13.10.1 GO: G2

131) Draw the correct structure of the expected product of the following reaction.

Answer:

Diff: 2 Section: 13.13 LO: 13.10.4 GO: G2 132) Provide the major organic product in the reaction below.

Answer:

Diff: 2 Section: 13.13 LO: 13.10.1 GO: G2 133) Provide the major organic product in the reaction below.

Answer: Diff: 2 Section: 13.13 LO: 13.10.4 GO: G2

134) Provide the major organic product in the reaction below.

Answer:

Diff: 3 Section: 13.13 LO: 13.10.4 GO: G2 135) What compound is formed when 2,2-dimethyloxirane is treated with ethanol containing a trace of HCl? A) 2-ethoxy-2-methyl-1-propanol B) 1-ethoxy-2-methyl-2-propanol C) 2-ethoxy-2-methyl-2-propanol D) 2-ethoxy-1-butanol E) 1-ethoxy-2-butanol Answer: A Diff: 2 Section: 13.13 LO: 13.10.4 GO: G2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 14 Structural Identification 1: Infrared Spectroscopy and Mass Spectrometry 1) Which sequence correctly ranks the regions of the electromagnetic spectrum in order of increasing energy? 1) infrared

2) ultraviolet

3) radio wave

A) 3 < 1 < 2 B) 3 < 2 < 1 C) 2 < 1 < 3 D) 1 < 3 < 2 Answer: A Diff: 1 Section: 14.1 LO: 14.0.1 GO: G2 2) The energy of a photon is ________ proportional to its wavelength. Answer: inversely Diff: 1 Section: 14.1 LO: 14.0.1 GO: G1 3) The energy of a photon is ________ proportional to its frequency. Answer: directly Diff: 1 Section: 14.1 LO: 14.0.1 GO: G1 4) In what units are frequency values typically given? Answer: Hertz or cycles/sec or sec-1 Diff: 1 Section: 14.1 LO: 14.0.1 GO: G1 5) Arrange the following regions of the electromagnetic spectrum in order of increasing energy: microwave, UV, visible, and IR. Answer: microwave < IR < visible < UV Diff: 1 Section: 14.1 1 Copyright © 2021 Pearson Education, Inc.

LO: 14.0.1 GO: G2 6) Arrange the following regions of the electromagnetic spectrum in order of increasing wavelength: X ray, radio, UV, and IR. Answer: X ray < UV < IR < radio Diff: 1 Section: 14.1 LO: 14.0.1 GO: G2

7) Absorption of what type of electromagnetic radiation results in ionization? A) X-rays B) radio waves C) microwaves D) ultraviolet light E) infrared light Answer: A Diff: 2 Section: 14.1 LO: 14.0.3 GO: G1 8) Absorption of what type of electromagnetic radiation results in electronic transitions? A) X-rays B) radio waves C) microwaves D) ultraviolet light E) infrared light Answer: D Diff: 2 Section: 14.1 LO: 14.0.3 GO: G1 9) Absorption of what type of electromagnetic radiation results in transitions among allowed rotational motions? A) X-rays B) radio waves C) microwaves D) ultraviolet light E) infrared light Answer: C Diff: 2 Section: 14.1 2 Copyright © 2021 Pearson Education, Inc.

LO: 14.0.3 GO: G1 10) Absorption of what type of electromagnetic radiation results in transitions among allowed nuclear magnetic spin states? A) X-rays B) radio waves C) microwaves D) ultraviolet light E) infrared light Answer: B Diff: 2 Section: 14.1 LO: 14.0.3 GO: G1 11) Which has the higher speed in a vacuum, ultraviolet or infrared light? Answer: They have the same speed. Diff: 2 Section: 14.1 LO: 14.0.1 GO: G1 12) The wavelength and frequency of a given wave of electromagnetic radiation are ________ proportional. Answer: inversely Diff: 2 Section: 14.1 LO: 14.0.1 GO: G2 13) Which region of the electromagnetic spectrum, IR or UV, contains photons of the higher energy? Answer: UV Diff: 2 Section: 14.1 LO: 14.0.1 GO: G1

14) Which region of the electromagnetic spectrum, radio or visible, is characterized by waves of shorter wavelength? Answer: visible Diff: 2 Section: 14.1 LO: 14.0.1 GO: G1 15) Which region of the electromagnetic spectrum, IR or X-ray, is characterized by waves of lower frequency? Answer: IR Diff: 2 Section: 14.1 LO: 14.0.1 GO: G1 16) Absorption of what type of electromagnetic radiation results in transitions among allowed vibrational motions? A) X-rays B) radio waves C) microwaves D) ultraviolet light E) infrared light Answer: E Diff: 2 Section: 14.1 LO: 14.0.3 GO: G1 17) An infrared wavelength of 4.48μm is equivalent to a wavenumber of ________ cm-1. Answer: 2230 Diff: 2 Section: 14.3 LO: 14.0.2 GO: G4 18) An infrared wavelength of 5.81μm is equivalent to a wavenumber of ________ cm-1. Answer: 1720 Diff: 2 Section: 14.3 LO: 14.0.2 GO: G4 4 Copyright © 2021 Pearson Education, Inc.

19) What wavenumber corresponds to the wavelength of 4 μm? Answer: 2500 cm-1 Diff: 2 Section: 14.3 LO: 14.0.2 GO: G4 20) What wavelength in mm is equivalent to a wavenumber of 1750 cm-1? Answer: 5.71 mm Diff: 2 Section: 14.3 LO: 14.0.2 GO: G4 21) The frequency of the stretching vibration of a bond in IR spectroscopy depends on what two quantities? A) the stiffness of the bond and the electronegativity of the atoms B) the electronegativity of the atoms and the nuclear charges of the atoms C) the masses of the atoms and the stiffness of the bond D) the nuclear charges of the atoms and the atomic radii E) the electronegativity of the atoms and the masses of the atoms Answer: C Diff: 2 Section: 14.3 LO: 14.1.1 GO: G1 22) In IR spectroscopy, the C—O bond has a ________ frequency than the C—N bond because ________. A) higher; an O atom has more mass than an N atom B) lower; an O atom has more mass than an N atom C) higher; an O atom has more electronegativity than an N atom D) lower; an O atom has more electronegativity than an N atom E) higher; an O atom has an even number of neutrons Answer: B Diff: 2 Section: 14.3 LO: 14.2.3 GO: G2 23) Which of the following stretches tends to be the least intense? A) O-H (alcohol) B) O-H (carboxylic acid) 5 Copyright © 2021 Pearson Education, Inc.

C) C-H D) C=O E) C=C Answer: E Diff: 2 Section: 14.3 LO: 14.2.6 GO: G2 24) A nonlinear molecule with n atoms generally has ________ fundamental vibrational modes. A) 2n B) 2n - 2 C) 3n D) 3n - 3 E) 3n - 6 Answer: E Diff: 3 Section: 14.3 LO: 14.2.1 GO: G1 MCAT LO: MCAT12.3 25) Which has a lower characteristic stretching frequency, the C—H or C—D bond? Explain briefly. Answer: C—D; heavier atoms vibrate more slowly Diff: 3 Section: 14.3 LO: 14.2.3 GO: G2 26) Which has a lower characteristic stretching frequency, the C O bond or the C—O bond? Explain briefly. Answer: Stronger bonds are generally stiffer, thus requiring more force to stretch or compress them. The C-O bond is the weaker of the two and hence has the lower stretching frequency. Diff: 3 Section: 14.3 LO: 14.2.4 GO: G2 27) In order for a vibration mode to be observable in the IR, the vibration must change the ________ of the molecule. Answer: dipole moment Diff: 2 Section: 14.3 LO: 14.2.6 6 Copyright © 2021 Pearson Education, Inc.

GO: G2

28) Ethyne (HC CH) does not show IR absorption in the region 2000-2500 cm-1 because ________. A) C—H stretches occur at lower energies B) C C stretches occur at about 1640 cm-1 C) there is no change in the dipole moment when the C C bond in ethyne stretches D) there is a change in the dipole moment when the C C bond in ethyne stretches Answer: C Diff: 2 Section: 14.3 LO: 14.2.4 | 14.2.6 GO: G2 MCAT LO: MCAT12.1 29) In an IR spectrometer, the ________ uses prisms or diffraction gratings to allow only one frequency of light to enter the detector at a time. Answer: monochromator Diff: 2 Section: 14.3 LO: 14.0.3 GO: G1

30) At approximately what wavenumber does one expect to find the carbon-carbon triple bond stretch in the IR spectrum of an alkyne? Answer: 2100 - 2200 cm-1 Diff: 2 Section: 14.4 LO: 14.3.3 GO: G2 31) What IR absorption is characteristic of the C-H stretch in alkanes? A) 3500 cm-1 B) 3300 cm-1 C) 2950 cm-1 D) 2250 cm-1 E) 1710 cm-1 Answer: C Diff: 1 Section: 14.4 LO: 14.3.3 7 Copyright © 2021 Pearson Education, Inc.

GO: G2 MCAT LO: MCAT12.1

32) Which compound would be expected to show an IR absorption at 3300 cm-1? A) CH3C CCH3 B) butane C) but-1-ene D) CH3CH2C CH Answer: D Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1 33) The IR spectrum of a sample contains absorptions at 3050, 2950, and 1620 cm-1. To what class of organic compound does this sample most likely belong? A) alkane B) alkene C) alkyne D) ester E) alcohol Answer: B Diff: 2 Section: 14.4 LO: 14.3.1 | 14.3.2 GO: G2 MCAT LO: MCAT12.1 34) Which of the following compounds would contain characteristic IR stretches at 3300 and 2200 cm-1? A) CH3CH2CHO B) CH3CH=CHCH2OH C) (CH3)2CHCN D) CH3CH2CH2C≡CH E) CH3C≡CCH2CH3 Answer: D Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1 8 Copyright © 2021 Pearson Education, Inc.

35) What IR absorption is characteristic of the terminal C-H stretch in terminal alkynes? A) 3500 cm-1 B) 3300 cm-1 C) 2400 cm-1 D) 2250 cm-1 E) 1710 cm-1 Answer: B Diff: 2 Section: 14.4 LO: 14.3.3 GO: G2 MCAT LO: MCAT12.

36) Which of the following would not have a C-H stretch at about 3050 cm-1? A) 1-pentene B) 2-pentene C) 2-methyl-2-pentene D) 2,3-dimethyl-2-pentene E) 2,4-dimethyl-2-pentene Answer: D Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1 37) Which compound has a strong and broad IR absorption centered at 3400 cm-1? A) 1-butanol B) octane C) diethyl ether D) 2-hexyne E) benzene Answer: A Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1

38) Which compound lacks a strong, characteristic IR absorption near 1700 cm-1? A) CH3CH2CO2H B) CH3CH2CHO C) (CH3CH2)2C=O D) (CH3CH2)2O E) H3CH2CO2CH3 Answer: D Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1 39) What IR absorption is characteristic of the O-H stretch in alcohols? A) 4000 cm-1 B) 3300 cm-1 C) 2950 cm-1 D) 2250 cm-1 E) 1710 cm-1 Answer: B Diff: 2 Section: 14.4 LO: 14.3.3 GO: G2 MCAT LO: MCAT12.1 40) Which compound would be expected to show intense IR absorption at 1715 cm-1? A) (CH3)2CHNH2 B) hex-1-yne C) 2-methylhexane D) (CH3)2CHCO2H Answer: D Diff: 1 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1

41) Which compound would be expected to show intense IR absorption at 1746 cm-1? A) CH3CH2OCH2CH3 B) CH3CH2CN C) CH3CO2CH2CH3 D) CH3CH2SCH3 Answer: C Diff: 1 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1

42) Which compound would be expected to show intense IR absorption at 2820, 2710 and A) CH3COCH2CH3 B) PhCOCH3 C) PhCHO D) CH2 CHCOCH3 Answer: C Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1 43) In addition to a carbonyl stretch, which of the following molecules exhibits two characteristic stretches at 2700 and 2800 cm-1? A) (CH3CH2)2CO B) CH3CH2CH2CHO C) CH3CH2CO2CH3 D) CH3CH2CH2CO2H E) CH3CH2CH2COCl Answer: B Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1 11 Copyright © 2021 Pearson Education, Inc.

44) Which of the following compounds has the lowest carbonyl stretching frequency?

Answer:

Diff: 2 Section: 14.4 LO: 14.2.7 | 14.2.8 GO: G2

45) Which statement best explains why a carbonyl absorbs infrared radiation at a higher frequency than an alkene absorption? A) Oxygen has a higher molecular mass than carbon. B) A carbonyl bond is more polarized than an alkene bond. C) Resonance delocalization of electrons invokes greater single bond character in a carbonyl bond. D) A carbonyl π bond is much stronger than an alkene π bond. Answer: D Diff: 2 Section: 14.4 LO: 14.2.7 GO: G2 46) What IR absorption is characteristic of the C=O stretch in aldehydes? A) 3500 cm-1 B) 3300 cm-1 C) 2950 cm-1 D) 2250 cm-1 E) 1710 cm-1 Answer: E 12 Copyright © 2021 Pearson Education, Inc.

Diff: 2 Section: 14.4 LO: 14.3.3 GO: G2 MCAT LO: MCAT12.1 47) Which compound would be expected to show intense IR absorption at 2250 cm-1? A) CH3CH2CH2CO2H B) (CH3)2CHCH2OH C) (CH3)2CHCN D) CH3CH2CH2CONH2 Answer: C Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1

48) Which of the following bonds, C—N, C N, or C N, has an IR stretch around 1600 cm-1? Answer: C N Diff: 2 Section: 14.4 LO: 14.2.3 | 14.3.3 GO: G2 MCAT LO: MCAT12.1 49) Which compound would be expected to show intense IR absorption at 1640 cm-1? A) hex-1-ene B) 2-methylheptane C) CH3CH2CH2OH D) CH3CH2COCH3 Answer: A Diff: 1 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1 50) Which of the following does not have a broad absorption with one or more spikes that is centered about 3300 cm-1 in the IR? A) (CH3CH2CH2)3N B) (CH3CH2CH2)2NH C) CH3CH2CH2NH2 D) (CH3)3CNH2 13 Copyright © 2021 Pearson Education, Inc.

E) (CH2=CHCH2)2NH Answer: A Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1 51) Rank the following bonds in order of increasing stretching frequency (cm-1) in IR spectroscopy:

Answer: C—O < C=O < C C < C—H Diff: 2 Section: 14.4 LO: 14.2.4 | 14.2.6 | 14.3.3 GO: G2 52) Rank the following bonds in order of increasing stretching frequency (cm-1) in IR spectroscopy:

Answer: C—N < C=O < C N < O—H Diff: 2 Section: 14.4 LO: 14.2.4 | 14.2.6 | 14.3.3 GO: G2 53) Arrange the following IR bond stretches in order of increasing wavenumber: C-O, C C, O-H, and C=C. Answer: C—O < C C < C C < O—H Diff: 2 Section: 14.4 LO: 14.2.4 | 14.2.6 | 14.3.3 GO: G2 54) Deduce a possible structure for the compound with the IR absorptions below. C3H5N: 2950, 2250 cm-1 Answer: CH3CH2CN Diff: 2 Section: 14.4 LO: 14.3.1 14 Copyright © 2021 Pearson Education, Inc.

GO: G2 MCAT LO: MCAT12.1

55) Deduce a possible structure for the compound with the IR absorptions below. C5H8O: 2950, 1750 cm-1 Answer: cyclopentanone Diff: 3 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1 56) Deduce a possible structure for the compound with the IR absorptions below. C4H8O: 2950, 2820, 2715, 1715 cm-1 Answer: CH3CH2CH2CHO Diff: 3 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1

57) Which of the following structures is consistent with the IR spectra shown below?

Answer: A Diff: 1 Section: 14.4 LO: 14.3.1 GO: G2 MCAT LO: MCAT12.1 58) Which compound would be expected to show intense IR absorption at 3363, 3185, 1660 cm1? A) CH3CH2CH2OH B) (CH3)2CHNH2 C) CH3CH2CONH2 D) but-1-ene Answer: C Diff: 2 Section: 14.4 LO: 14.3.1 GO: G3 MCAT LO: MCAT12.1

59) What two functional groups are represented in the following IR spectrum?

Answer: aromatic ring and nitrile Diff: 2 Section: 14.4 LO: 14.3.3 GO: G3 MCAT LO: MCAT12.1 60) Which of the following molecules has a characteristic stretch at 2200 cm-1? A) (CH3)2CHCH2OH B) (CH3)3CH C) (CH3)2CHCCCH3 D) (CH3)2CHCH=CH2 E) (CH3)2CHCO2CH3 Answer: C Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2 18 Copyright © 2021 Pearson Education, Inc.

61) Which of the following molecules has a characteristic stretch at 2250 cm-1? A) (CH3)2CHCH2OH B) (CH3)3CH C) (CH3)2CHCCN D) (CH3)2CHCH=CH2 E) (CH3)2CHCO2CH3 Answer: C Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2 62) Which of the following molecules has a characteristic stretch at 1750 cm-1? A) (CH3)2CHCH2OH B) (CH3)3CH C) (CH3)2CHCCCH3 D) (CH3)2CHCH=CH2 E) (CH3)2CHCO2CH3 Answer: E Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2 63) Which of the following molecules has a characteristic stretch at 3300 cm-1? A) (CH3)2CHCH2NHCH3 B) (CH3)3CH C) (CH3)2CHCCCH3 D) (CH3)2CHCH=CH2 E) (CH3)2CHCO2CH3 Answer: C Diff: 2 Section: 14.4 LO: 14.3.1 GO: G2

64) Which of the following structures is consistent with the IR spectra shown below?

Answer: E Diff: 3 Section: 14.4 LO: 14.3.1 GO: G3 MCAT LO: MCAT12.1

65) How might one distinguish an aldehyde from a ketone using IR data alone? Answer: The aldehyde has two C-H stretches at 2700 and 2800 cm-1. Diff: 2 Section: 14.4 LO: 14.2.7 | 14.2.8 GO: G2 MCAT LO: MCAT18.2 66) Describe the fate of a molecule from introduction to detection in a mass spectrometer. Answer: Upon introduction, sample molecules are ionized by an electron beam passing through a vacuum chamber. The resulting radical cation and fragment cations are accelerated into the flight tube of the magnet by a negatively charged plate. In the flight tube, the path of the ions is bent by the existing magnetic field. For a given magnetic field strength, only one m/z will be bent in such a way that its path matches the curvature of the tube and reaches the detector. The entire m/z range is scanned by varying the strength of the magnetic field. Diff: 2 Section: 14.6 LO: 14.5.5 GO: G2

67) An ________ molecular ion peak usually indicates the presence of an odd number of nitrogen atoms in the molecule. A) even B) odd C) intense D) absent Answer: B Diff: 1 Section: 14.6 LO: 14.5.2 GO: G2

68) The presence of which element is indicated by a peak at m/z 127 and a characteristic 127-unit gap in the mass spectrum? A) Br B) Cl C) I D) N E) S Answer: C Diff: 1 Section: 14.6 LO: 14.5.1 GO: G2

69) The two most abundant isotopes of boron are 10B and 11B, with 11B being about 4 times more abundant. In the mass spectrum of trimethylborate [(CH3O)3B], ________. A) the peaks at m/z 103 and m/z 104 have equivalent intensities B) the peak at m/z 103 has an intensity which is 4 times that of the m/z 104 peak C) the peak at m/z 103 has an intensity which is 1/4 the intensity of the peak at m/z 104 D) none of the above Answer: C Diff: 2 Section: 14.6 LO: 14.5.1 GO: G2 70) What spectroscopic technique can be used to determine the molecular formula of a compound? Answer: high resolution mass spectrometry Diff: 2 Section: 14.6 LO: 14.4.2 GO: G1 71) What m/z characterizes a strong peak in the mass spectrum of cyclopentanol? A) 86 B) 85 C) 84 D) 70 E) 68 Answer: E Diff: 2 Section: 14.7 LO: 14.5.4 22 Copyright © 2021 Pearson Education, Inc.

GO: G2 72) In a mass spectrum, the peak of greatest abundance is referred to as the ________. Answer: base peak Diff: 1 Section: 14.7 LO: 14.5.4 GO: G2 73) When a high energy electron impacts molecule M in the ionization chamber, what type of species is initially produced? A) cation B) anion C) radical D) radical cation E) radical anion Answer: D Diff: 2 Section: 14.7 LO: 14.5.2 GO: G1 74) Which compound would show a larger than usual M+2 peak in the mass spectrum? A) CH3CH2SCH3 B) (CH3)2CHNH2 C) CH3CH2CO2H D) CH3(CH2)2CH3 Answer: A Diff: 1 Section: 14.7 LO: 14.5.3 GO: G2

75) Which of the following structures is consistent with the mass spectrum shown below?

Answer: E Diff: 2 Section: 14.7 LO: 14.5.3 GO: G3 76) Which of the following fragment peaks would not be present in the mass spectrum of nhexane? A) 87 B) 71 C) 57 D) 43 E) 29 Answer: A Diff: 1 Section: 14.7 LO: 14.5.4 GO: G2 77) 2-Methylhexane shows an intense peak in the mass spectrum at m/z = 43. Propose a likely structure for this fragment. Answer: (CH3)2CH+ Diff: 1 Section: 14.7 LO: 14.5.4 GO: G2

78) Provide the structure of the fragment in the mass spectrum of dipropyl ether that results from a cleavage. Answer: Diff: 2 Section: 14.7 LO: 14.5.4 GO: G2 MCAT LO: MCAT14.2

79) In the mass spectrum of isobutylbenzene, the base peak occurs at m/z ________. A) 134 B) 133 C) 119 D) 105 E) 91 Answer: E Diff: 2 Section: 14.7 LO: 14.5.4 GO: G2 MCAT LO: MCAT16.6 80) Which compound will show an intense peak in the mass spectrum at m/z 58? A) CH3COCH2CH2CH3 B) (CH3)2CHCOCH3 C) CH3CH2COCH2CH3 D) (CH3)3CCHO E) (CH3)3CCOCH3 Answer: A Diff: 2 Section: 14.7 LO: 14.5.4 GO: G2 MCAT LO: MCAT18.2

81) In the mass spectrum of 3,3-dimethyl-2-butanone, the base peak will occur at m/z ________. A) 43 B) 58 C) 84 D) 85 E) 100 Answer: A Diff: 2 Section: 14.7 LO: 14.5.4 GO: G2 MCAT LO: MCAT18.2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 15 Structural Identification 2: Nuclear Magnetic Resonance Spectroscopy 1) What three-word term is abbreviated NMR? Answer: nuclear magnetic resonance Diff: 1 Section: 15.1 LO: 15.1.1 GO: G1 2) A nucleus with an ________ atomic number or an ________ mass number has a nuclear spin that can be observed by the NMR spectrometer. A) even; odd B) odd; even C) odd; odd D) even; even Answer: C Diff: 1 Section: 15.2 LO: 15.1.1 GO: G1 MCAT LO: MCAT13.3 3) How many nuclear spin states are allowed for the 1H nucleus? A) 1 B) 2 C) 3 D) 4 E) 10 Answer: B Diff: 1 Section: 15.2 LO: 15.1.2 GO: G1 MCAT LO: MCAT13.3 4) Any process faster than ________ will be recorded as an average by NMR spectroscopy. A) 0.0005 seconds B) 0.1 seconds C) 0.01 seconds D) 0.001 seconds E) 1 minute Answer: C Diff: 2 Section: 15.2 1 Copyright © 2021 Pearson Education, Inc.

LO: 15.1.1 GO: G1 MCAT LO: MCAT13.3 5) The energy difference between the allowed spin states for an 1H nucleus is ________ the strength of the external magnetic field in which it is placed. A) independent of B) directly proportional to C) inversely proportional to D) exponentially related to E) logarithmically related to Answer: B Diff: 2 Section: 15.4 LO: 15.1.2 GO: G1 MCAT LO: MCAT13.3 6) 1H nuclei located near electronegative atoms tend to be ________ relative to 1H nuclei which are not. A) shielded B) deshielded C) resonanced D) split E) none of the above Answer: B Diff: 1 Section: 15.4 LO: 15.2.6 GO: G2 MCAT LO: MCAT13.3 7) If a molecule contains 4 elements of unsaturation and signals in the 1H NMR spectrum between δ 7.0 and 8.0 ppm, what structural group is likely to be present? A) a carbonyl group B) an aromatic ring C) a hydroxyl group D) a cyclohexyl ring E) a carbon-carbon triple bond Answer: B Diff: 1 Section: 15.4 LO: 15.2.6 GO: G2 2 Copyright © 2021 Pearson Education, Inc.

8) Which of the following functional groups has the most deshielded proton and would be predicted to show an NMR signal that is the farthest downfield? A) benzylic - H B) allylic - H C) aldehyde - H D) aromatic - H E) acetylenic - H Answer: C Diff: 1 Section: 15.4 LO: 15.2.6 GO: G2 9) Which of the following reasons best explains why aromatic protons have a larger chemical shift than protons one carbon removed from a halogen? A) An aromatic ring is more electron withdrawing than a halogen. B) A halogen is more electron withdrawing than an aromatic ring. C) Electron movement induces a magnetic field opposing the external field. D) Electron movement induces a magnetic field reinforcing the external field. Answer: D Diff: 2 Section: 15.4 LO: 15.2.6 GO: G2 10) Predict the number of signals expected (disregarding splitting) in the 1H NMR spectrum of the compound shown below.

Answer: 4 Diff: 2 Section: 15.4 LO: 15.2.4 GO: G2 MCAT LO: MCAT13.1

11) Predict the number of signals expected (disregarding splitting) in the 1H NMR spectrum of the compound shown below.

Answer: 6 Diff: 2 Section: 15.4 LO: 15.2.4 GO: G2 MCAT LO: MCAT13.1 12) Predict the number of signals expected (disregarding splitting) in the 1H spectrum of mxylene (1,3-dimethylbenzene). Answer: 4 Diff: 2 Section: 15.4 LO: 15.2.4 GO: G2 MCAT LO: MCAT13.1 13) Predict the number of signals expected (disregarding splitting) in the 1H spectrum of 1,1dimethylcyclobutane. Answer: 3 Diff: 2 Section: 15.4 LO: 15.2.4 GO: G2 MCAT LO: MCAT13.1

14) How many unique NMR signals (disregard splitting) would be predicted in the 1H spectrum of the following compound?

A) 2 B) 3 C) 4 D) 5 E) 6 F) 7 Answer: F Diff: 3 Section: 15.4 LO: 15.2.4 GO: G2 MCAT LO: MCAT13.1 15) A compound (C5H8O) shows IR absorptions at 3600 and 3300 cm-1. Its 1H NMR spectrum contained singlets at and 2.9 (broad) (ppm) in a ratio of 6:1:1. Name this compound. Answer: 2-methylbut-3-yn-2-ol Diff: 1 Section: 15.4 LO: 15.0.1 GO: G2 16) What is the relative area of each peak in a quartet spin-spin splitting pattern? A) 1:2:1 B) 1:2:2:1 C) 1:1:1:1 D) 1:4:4:1 E) 1:3:3:1 Answer: E Diff: 2 Section: 15.4 LO: 15.3.5 GO: G2 MCAT LO: MCAT13.1

17) What compound exhibits only two signals in its 1H NMR spectrum, a triplet and a quintet? A) BrCH2CH2CH2Br B) BrCH2CH2CH2Cl C) (CH3)2CHCH(CH3)2 D) CH3CH2CH2CH3 E) (CH3)2CHOCH(CH3)2 Answer: A Diff: 2 Section: 15.4 LO: 15.2.2 GO: G2 MCAT LO: MCAT13.1 18) What 1H NMR spectral data is expected for the compound shown?

A) 3.8 (1H, septet), 2.1 (3H, s), 1.0 (6H, d) B) 3.8 (1H, septet), 3.3 (3H, s), 1.0 (6H, d) C) 3.3 (3H, s), 2.6 (3H, septet), 1.0 (6H, d) D) 2.6 (1H, septet), 2.1 (3H, s), 1.0 (6H, d) Answer: A Diff: 2 Section: 15.4 LO: 15.2.2 GO: G2 MCAT LO: MCAT13.1

19) Deduce the identity of the following compound from the 1H NMR data given. C8H10O: δ 3.4 (3H, singlet), 4.5 (2H, singlet), 7.2 (5H, apparent singlet) (ppm) Answer: PhCH2OCH3 Diff: 1 Section: 15.4 LO: 15.0.1 GO: G2 MCAT LO: MCAT13.2

20) Deduce the identity of the compound whose molecular formula is C8H14 from the spectral data provided: IR (cm-1): 2950, 2180; 1H NMR (δ): 0.9 (3H, t), 1.0 (9H, s), 2.3 (2H, q) (ppm). Answer: 2,2-dimethylhex-3-yne Diff: 2 Section: 15.4 LO: 15.0.1 GO: G2 21) Propose a structure for the ether of formula C4H10O with the following 1H NMR signals: δ 1.20 (triplet, 6H), δ 3.45 (quartet, 4H) (ppm). Answer: CH3CH2OCH2CH3 Diff: 2 Section: 15.4 LO: 15.0.1 GO: G2 MCAT LO: MCAT14.2 22) In the proton NMR spectra of aldehydes and ketones, the protons bonded to carbons adjacent to the carbonyl group typically fall into which of the chemical shift ranges below? A) 1.0-2.0 ppm B) 2.0-3.0 ppm C) 4.0-4.5 ppm D) 7.0-8.0 ppm E) 9.0-10.0 ppm Answer: B Diff: 2 Section: 15.4 LO: 15.2.6 GO: G1 MCAT LO: MCAT18.2 23) The proton NMR spectrum of an unknown compound contains a triplet at the following could be this unknown? A) (CH3)3CCHO B) CH3CH2CH2CO2H C) CH3CH2CH2CHO D) CH3CO CH2Ph E) PhCHO Answer: C Diff: 2 7 Copyright © 2021 Pearson Education, Inc.

Which of

Section: 15.4 LO: 15.0.1 | 15.3.5 GO: G2 MCAT LO: MCAT18.2

24) The protons marked Ha and Hb in the molecule below are ________.

A) chemically equivalent or homotopic B) enantiotopic C) diastereotopic D) endotopic E) none of the above Answer: A Diff: 2 Section: 15.5 LO: 15.3.1 GO: G2 MCAT LO: MCAT13.1 25) What is the relationships between Ha and Hb in the following structure?

A) homeotopic B) enantiotopic C) diastereotopic D) none of the previous Answer: C Diff: 3 Section: 15.5 LO: 15.5.1 GO: G2 MCAT LO: MCAT13.1

26) The protons marked Ha and Hb in the molecule below are ________.

A) chemically equivalent B) enantiotopic C) diastereotopic D) endotopic E) none of the above Answer: C Diff: 3 Section: 15.5 LO: 15.5.1 GO: G2 MCAT LO: MCAT13.1 27) The protons marked Ha and Hb in the molecule below are ________.

A) chemically equivalent B) enantiotopic C) diastereotopic D) endotopic E) none of the above Answer: B Diff: 3 Section: 15.5 LO: 15.3.1 GO: G2 MCAT LO: MCAT13.1

28) Use the structure below to state the relationship between the indicated protons as equivalent, enantiotopic, diastereotopic, or unrelated.

Ha & Hb: Ha & Hc: Hb & Hc: Answer: Ha & Hb: Diastereotopic Ha & Hc: Enantiotopic Hb & Hc: Diastereotopic Diff: 3 Section: 15.5 LO: 15.3.1 | 15.5.1 GO: G2 MCAT LO: MCAT13.1 29) Deduce the identity of the following compound from the 1H NMR data given. C7H7NO3: δ 3.9 (3H, singlet), 6.9 (2H, doublet), 8.1 (2H, doublet) (ppm) Answer: p-nitroanisole (p-O2NC6H4OCH3) Diff: 3 Section: 15.5 LO: 15.0.1 GO: G2 MCAT LO: MCAT13.2

30) Propose a structure for the ether of formula C4H10O with the following 1H NMR signals: δ 0.95 (triplet, 3H), 1.52 (multiplet, 2H), 3.30 (singlet, 3H), 3.40 (triplet, 2H) (ppm). Answer: CH3CH2CH2OCH3 Diff: 2 Section: 15.5 LO: 15.0.1 GO: G2 MCAT LO: MCAT14.2

31) Propose a structure for the ether of formula C4H10O with the following 1H NMR signals: δ 1.13 (doublet, 6H), 3.30 (singlet, 3H), 3.65 (septet, 1H) (ppm). Answer: (CH3)2CHOCH3 Diff: 2 Section: 15.5 LO: 15.0.1 GO: G2 MCAT LO: MCAT14.2 32) In the proton NMR, in what region of the spectrum does one typically observe hydrogens bound to the aromatic ring? A) 1.0-1.5 ppm B) 2.0-3.0 ppm C) 4.5-5.5 ppm D) 7.0-8.0 ppm E) 9.0-10.0 ppm Answer: D Diff: 2 Section: 15.5 LO: 15.2.6 GO: G2 MCAT LO: MCAT16.6 33) An NMR spectrometer that operates at a frequency of 60 MHz for 13C NMR spectra, operates at what frequency for 1H NMR spectra? A) 15 MHz B) 30 MHz C) 60 MHz D) 120 MHz E) 240 MHz Answer: E Diff: 2 Section: 15.7 LO: 15.6.7 GO: G1

34) What is the approximate chemical shift of an alkynyl carbon in 13C NMR spectroscopy? A) 10 ppm B) 30 ppm C) 70 ppm D) 120 ppm E) 200 ppm Answer: C Diff: 2 Section: 15.7 LO: 15.6.3 GO: G2

35) Which of the structures shown below is consistent with the C-13 NMR (off resonance splitting for each peak is shown as a table within the figure) and H-NMR spectra? (formula = C9H11OBr)

Answer: B Diff: 2 Section: 15.7 LO: 15.6.5 GO: G2

36) Compound I has a molecular formula of C7H16. In 13C NMR, compound I gave 3 peaks and in 1H NMR it also gave 3 peaks, a doublet, a triplet and a multiplet. Provide a structure for compound I. Answer: Diff: 2 Section: 15.7 LO: 15.6.5 GO: G2 MCAT LO: MCAT13.2

37) Given that compound X has a molecular formula of C6H8O2, gave two peaks in its 13C NMR spectrum (37 ppm and 208 ppm) but just one in its 1H NMR spectrum (2.5 ppm), provide a structure for compound X. Answer: Diff: 3 Section: 15.7 LO: 15.6.5 GO: G2 MCAT LO: MCAT13.2 38) What is the chemical shift of the carbon bound to oxygen in ethers in 13C NMR? Answer: δ 65 to δ 90 Diff: 3 Section: 15.7 LO: 15.6.3 GO: G2 39) In carbon NMR, the carbon atom of the carbonyl group in aldehydes and ketones has a chemical shift of about ________. A) 20 ppm B) 40 ppm C) 60 ppm D) 120 ppm E) 200 ppm Answer: E Diff: 1 Section: 15.7 LO: 15.6.3 GO: G2 MCAT LO: MCAT18.2 40) Predict the number of signals expected in the proton spin decoupled 13C spectrum of cyclopentane. Answer: 1 Diff: 1 Section: 15.8 LO: 15.6.2 GO: G2

41) What type of carbon environment does not generate a signal in the DEPT-90 spectrum and gives a positive peak in the DEPT-135 spectrum? A) quaternary B) methine C) methylene D) methyl E) carbonyl Answer: D Diff: 2 Section: 15.8 LO: 15.7.1 GO: G2 42) What type of carbon environment does not generate a signal in the DEPT-90 spectrum and gives a negative signal in the DEPT-135 spectrum? A) quaternary B) methine C) methylene D) methyl E) carbonyl Answer: C Diff: 2 Section: 15.8 LO: 15.7.1 GO: G2 43) Which compound generates positive peaks for the carbonyl in both its DEPT-90 and DEPT135 spectra? A) CH3CH2CHO B) CH3CH2COCH3 C) CH3CO2CH2CH3 D) CH3CH2CONH2 E) H2CO Answer: A Diff: 2 Section: 15.8 LO: 15.7.1 GO: G2

44) What compound exhibits three singlets in its proton spin decoupled 13C NMR spectrum? A) BrCH2CH2CH2Br B) BrCH2CH2CH2Cl C) (CH3)2CHCH(CH3)2 D) CH3CH2CH2CH3 E) (CH3)2CHOCH(CH3)2 Answer: B Diff: 2 Section: 15.8 LO: 15.6.5 GO: G2 45) How many peaks appear in the proton spin decoupled 13 C NMR spectrum of the compound below?

A) 1 B) 2 C) 3 D) 4 E) 5 Answer: E Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2

46) How many peaks appear in the proton spin decoupled 13 C NMR spectrum of the compound below?

A) 2 B) 3 C) 4 D) 5 E) 6 Answer: B Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2 47) What multiplicities are observed in the off-resonance decoupled 13C spectrum of 2,3dimethyl-but-2-ene? Answer: a singlet and a quartet Diff: 2 Section: 15.8 LO: 15.6.6 GO: G2 48) Predict the number of signals expected in the proton spin decoupled 13C NMR spectrum of the compound shown below.

Answer: 4 Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2

49) Predict the number of distinct quartets expected in the off-resonance decoupled spectrum of the compound shown below.

Answer: 2 Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2 50) Predict the number of signals expected in the proton spin decoupled 13C NMR spectrum of the compound shown below.

Answer: 5 Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2 51) Predict the number of signals expected in the proton spin decoupled 13C NMR spectrum of o-diethylbenzene (1,2-diethylbenzene). Answer: 5 Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2 52) Predict the number of signals expected in the proton spin decoupled 13C NMR spectrum of p-diethylbenzene (1,4-diethylbenzene). Answer: 4 Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2

53) How many peaks appear in the proton spin decoupled 13C NMR spectrum of the compound below?

Answer: 5 Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2 54) How many peaks appear in the proton spin decoupled 13C NMR spectrum of the compound below?

Answer: 3 Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2 55) How many peaks appear in the proton spin decoupled 13C NMR spectrum of the compound below?

Answer: 4 Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2

56) How many peaks appear in the proton spin decoupled 13C NMR spectrum of the compound below?

Answer: 3 Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2 57) How many peaks appear in the proton spin decoupled 13C NMR spectrum of the compound below?

Answer: 2 Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2 58) How many peaks appear in the proton spin decoupled 13C NMR spectrum of the compound below?

Answer: 2 Diff: 3 Section: 15.8 LO: 15.6.2 GO: G2

59) How many peaks appear in the proton spin decoupled 13C NMR spectrum of the compound below?

Answer: 3 Diff: 3 Section: 15.8 LO: 15.6.2 GO: G2 60) Deduce the identity of the following compound from the 13C NMR data given. C4H8O: δ 11.97 (triplet), 33.54 (triplet), 67.03 (doublet) (ppm) Answer: cyclobutanol Diff: 2 Section: 15.8 LO: 15.6.5 GO: G2 61) Deduce the identity of the following compound from the spectral data given. C9H10O2: 13C NMR, δ 18.06 (quartet), 45.40 (doublet), 127.32 (doublet), 127.55 (doublet), 128.61 (doublet), 139.70 (singlet) (ppm), 180.98 (singlet); IR, broad 3500-2800, Answer: PhCH(CH3)CO2H Diff: 3 Section: 15.8 LO: 15.6.5 GO: G2 MCAT LO: MCAT13.2

62) What multiplicities are observed for the signals in the off-resonance decoupled 13C spectrum of 2-chloropropene? A) 3 singlets B) 2 singlets and a doublet C) a singlet and 2 doublets D) a singlet, a doublet and a triplet E) a singlet, a triplet, and a quartet Answer: E Diff: 1 Section: 15.8 LO: 15.6.5 GO: G2 63) Provide a structure that is consistent with the data below. C6H10 IR (cm-1): 2950, 2230 1H NMR ( d): 2.0 (1H, septet), 1.8 (3H, s), 0.9 (6H, d) 13C NMR (d ): 78 (s), 72 (s), 45 (d), 18 (q), 15 (q) Answer: (CH3)2CHC≡CCH3 Diff: 2 Section: 15.8 LO: 15.6.5 GO: G2

64) Provide a structure that is consistent with the data below. C5H8Cl2 IR (cm-1): 2950 1H NMR ( d): 1.4 (4H, t), 1.2 (4H, t) 13C NMR (d ): 62 (s), 26 (t), 23 (t) Answer:

Diff: 3 Section: 15.8 LO: 15.6.5 GO: G2

65) Provide a structure that is consistent with the data below. C7H14O2 IR (cm-1): 2950, 1740 1H NMR ( d): 2.3 (2H, q), 1.0 (3H, t), 0.9 (9H, s) 13C NMR (d ): 185 (s), 78 (s), 29 (t), 14 (q), 12 (q) Answer:

Diff: 3 Section: 15.8 LO: 15.6.5 GO: G2 66) Provide a structure that is consistent with the data below. C9H7Cl IR (cm-1): 3050, 2950, 2220, 1620 1H NMR ( d): 7.8 (2H, d), 7.2 (2H, d), 2.1 (3H, s) 13C NMR (d ): 140 (s), 132, (s), 125 (d), 122 (d), 88 (s), 83 (s), 18 (q) Answer:

Diff: 3 Section: 15.8 LO: 15.6.5 GO: G2 67) Deduce the identity of the following compound from the NMR data given. C4H6O2: 1H NMR, δ 2.28 (2H, multiplet), 2.50 (2H, triplet), 4.35 (2H, triplet); 13C NMR, δ 177.81 (singlet), 68.58 (triplet), 27.70 (triplet), 22.17 (triplet) (ppm) Answer: γ-butyrolactone Diff: 3 Section: 15.8 LO: 15.6.5 GO: G2 MCAT LO: MCAT13.2

68) Deduce the identity of the following compound from the spectral data given. C7H10O2: 1H NMR, δ 1.16 (3H, singlet), 2.21 (2H, singlet); 13C NMR, δ 216.25 (singlet), 52.57 (singlet), 34.51 (triplet), 20.22 (quartet) (ppm) Answer: 2,2-dimethylcyclopentane-1,3-dione Diff: 3 Section: 15.8 LO: 15.6.5 GO: G2 MCAT LO: MCAT13.2 69) Which of the following compounds has the most signals in the proton-decoupled 13C NMR spectrum? A) o-dibromobenzene B) m-dibromobenzene C) p-dibromobenzene D) 1,3,5-tribromobenzene E) 1,2,3,4-tetrabromobenzene Answer: B Diff: 2 Section: 15.8 LO: 15.6.6 GO: G2 MCAT LO: MCAT16.6 70) How many peaks are in the proton spin decoupled 13C NMR spectrum of 1,3,5trinitrobenzene? A) 1 B) 2 C) 3 D) 4 E) 6 Answer: B Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2 MCAT LO: MCAT16.6

71) How many peaks are in the proton spin decoupled 13C NMR spectrum of the compound shown?

Answer: 6 Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2 MCAT LO: MCAT16.6 72) How many peaks are in the proton spin decoupled 13C NMR spectrum of the compound shown?

Answer: 3 Diff: 2 Section: 15.8 LO: 15.6.2 GO: G2 MCAT LO: MCAT16.6 73) Which of the following compounds would show only one triplet in its off resonance decoupled spectrum? A) acetone B) butanal C) pentanal D) 2-pentanone E) 3-pentanone Answer: E Diff: 2 Section: 15.8 LO: 15.6.6 GO: G2 MCAT LO: MCAT18.2 26 Copyright © 2021 Pearson Education, Inc.

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 16 Metals in Organic Chemistry 1) Which of the following terms best describes the reactive nature of a Grignard reagent? A) carbocation B) free radical C) electrophile D) nucleophile E) carbene Answer: D Diff: 1 Section: 16.2 LO: 4.5.7 GO: G2 MCAT LO: MCAT10.3 2) Complete the following reaction by providing a structure for the necessary starting material.

Answer:

Diff: 2 Section: 16.2 LO: 16.0.4 GO: G2 MCAT LO: MCAT10.3

3) Provide the structure of the major organic product in the reaction shown below.

Answer:

GO: G2

4) Provide the structure of the major organic product in the reaction shown below.

Answer:

Diff: 2 Section: 16.2 LO: 16.0.2 GO: G2 5) Identify the structure of the product of the following reaction.

Answer:

Diff: 3 Section: 16.2 LO: 16.0.1 | 16.0.3 GO: G2 MCAT LO: MCAT10.3 6) What Grignard reagent and carbonyl compound could be used to prepare 1ethylcyclohexanol? Answer:

7) The reaction of CH3CH2MgBr with CH3COCH2CH3 gives ________. A) an achiral product B) a mixture of diastereomers C) the racemate of a chiral product D) a single enantiomer E) none of the above Answer: A Diff: 2 Section: 16.2 LO: 16.0.1 GO: G2 MCAT LO: MCAT10.3 8) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 16.2 LO: 16.0.2 GO: G2 MCAT LO: MCAT10.3

9) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 16.2 LO: 16.0.1 GO: G2 MCAT LO: MCAT10.3 10) Provide the structure of the major organic product in the reaction shown below.

Answer:

Diff: 2 Section: 16.2 LO: 16.0.1 GO: G2 MCAT LO: MCAT10.3

11) Provide the structure of the major organic product in the reaction shown below.

Answer:

Diff: 2 Section: 16.2 LO: 16.0.1 GO: G2 MCAT LO: MCAT10.3 12) Provide the major organic product(s) of the reaction below.

Answer:

Diff: 2 Section: 16.2 LO: 16.0.1 GO: G2 MCAT LO: MCAT10.3 13) Provide the major organic product(s) of the reaction below.

Answer:

Section: 16.2 LO: 16.0.1 GO: G2 MCAT LO: MCAT10.3

14) Provide the major organic product(s) of the reaction below.

Answer:

Diff: 3 Section: 16.2 LO: 16.0.1 | 16.0.3 GO: G2 MCAT LO: MCAT10.3 15) Which of the following alkyl halides would be suitable to use when forming a Grignard reagent? A) BrCH2CH2CH2CN B) CH3COCH2CH2Br C) (CH3)2NCH2CH2Br D) H2NCH2CH2Br E) all of the above Answer: C Diff: 2 Section: 16.2 LO: 16.0.1 GO: G2 MCAT LO: MCAT10.3

16) Which of the following substrates will not form a Grignard reagent when treated with Mg/diethylether? A)

Answer: B Diff: 2 Section: 16.2 LO: 16.0.1 GO: G2 MCAT LO: MCAT10.3

17) Provide the major organic product of the following.

Answer:

Diff: 3 Section: 16.2 LO: 16.0.1 GO: G2 MCAT LO: MCAT11.1 18) Provide the major organic product of the following.

Answer:

Diff: 3 Section: 16.2 LO: 16.0.1 GO: G2 MCAT LO: MCAT11.1

19) Provide a structure for the expected product of the following reaction.

Answer:

Diff: 3 Section: 16.2 LO: 16.0.3 GO: G2 20) What is the major difference in the structure of the product formed in a Grignard reaction when an alkyl magnesium halide (Grignard reagent) is reacted with an epoxide rather than an aldehyde or ketone followed by work-up with H3O+? A) The alkyl group from the Grignard reagent will be bonded to the α-carbon of the alcohol product. B) The alkyl group from the Grignard reagent will be bonded to the β-carbon of the alcohol product. C) The alkyl group from the Grignard reagent will form an ether product rather than an alcohol product. D) Two equivalents of the Grignard will result in the bonding of two alkyl groups to the αcarbon of the alcohol product. E) The epoxide will protonate the Grignard reagent resulting an alkane product. Answer: B Diff: 1 Section: 16.2 LO: 16.0.3 GO: G2

21) What compound is formed when methyloxirane is reacted with ethylmagnesium bromide followed by treatment with aqueous acid? A) 1-pentanol B) 2-pentanol C) 2-methyl-1-butanol D) 2-methyl-2-butanol E) 3-methyl-1-butanol Answer: B Diff: 2 Section: 16.2 LO: 16.0.1 | 16.0.3 GO: G2 22) Provide the major organic product of the following reactions.

Answer:

Diff: 2 Section: 16.2 LO: 16.0.2 | 16.0.3 GO: G2 23) Provide the major organic product in the reaction below.

Answer:

24) What reagent is needed to complete the following transformation?

A) iPrMgBr B) iPrLi C) (iPr)2CuLi D) iPrBr Answer: C Diff: 2 Section: 16.5 LO: 16.0.5 GO: G2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 17 Carbonyl Addition Reactions: Aldehydes and Ketones 1) Acetone is a ketone that contains three carbon atoms. Provide its structure. Answer:

Diff: 1 Section: 17.1 LO: 17.0.2 GO: G2 2) Provide the structure of cyclohexanecarbaldehyde. Answer:

Diff: 1 Section: 17.1 LO: 17.0.2 GO: G2 MCAT LO: MCAT18.1 3) Provide the proper IUPAC name for PhCH2CH(CH3)CH2CH2CHO. Answer: 4-methyl-5-phenylpentanal Diff: 1 Section: 17.1 LO: 17.0.1 GO: G2 MCAT LO: MCAT18.1

MCAT LO: MCAT18.1 5) Provide the proper IUPAC name for CH3OCH2CH2CH(CH3)CHO. Answer: 4-methoxy-2-methylbutanal Diff: 1 Section: 17.1 LO: 17.0.1 GO: G2 MCAT LO: MCAT18.1 6) Provide the IUPAC name for the following compound.

Answer: 6-hydroxy-4-nonanone or 6-hydroxynonan-4-one Diff: 2 Section: 17.1 LO: 17.0.1 GO: G2 MCAT LO: MCAT18.1 7) Provide the IUPAC name for (CH3)3CCH2CHClCH2CHO. Answer: 3-chloro-5,5-dimethylhexanal Diff: 2 Section: 17.1 LO: 17.0.1 GO: G2 MCAT LO: MCAT18.1 8) Provide the proper IUPAC name for (CH3)2CHCH2CH2COCH CH2. Answer: 6-methylhept-1-en-3-one Diff: 2 Section: 17.1 LO: 17.0.1 GO: G2 MCAT LO: MCAT18.1 9) Provide the proper IUPAC name for CH3CHBrCH2COCH2CHO. Answer: 5-bromo-3-oxohexanal Diff: 2 Section: 17.1 LO: 17.0.1 GO: G2 2 Copyright © 2021 Pearson Education, Inc.

MCAT LO: MCAT18.1 10) What is the correct IUPAC name for the following compound?

A) 2-oxocyclohex-3-ene carbaldehyde B) 5-formylcyclohex-2-enone C) 2-formylcyclohex-5-enone D) 3-oxocyclohex-4-enal Answer: A Diff: 2 Section: 17.1 LO: 17.0.1 GO: G2 MCAT LO: MCAT18.1 11) Name the following compound.

Answer: 4,7,7-trimethyl2-octanone or 4,7,7,-trimethyloctan-2-one Diff: 2 Section: 17.1 LO: 17.0.1 GO: G2 MCAT LO: MCAT18.1

12) Name the following compound.

Answer: 5,5-difluoroheptanal Diff: 2 Section: 17.1 LO: 17.0.1 GO: G2 MCAT LO: MCAT18.1 13) Which of the following represents the correct ranking in terms of increasing boiling point? A) n-butane < 1-butanol < diethyl ether < 2-butanone B) n-butane < 2-butanone < diethyl ether < 1-butanol C) 2-butanone < n-butane < diethyl ether < 1-butanol D) n-butane < diethyl ether < 1-butanol < 2-butanone E) n-butane < diethyl ether < 2-butanone < 1-butanol Answer: E Diff: 2 Section: 17.1 LO: 17.0.1 GO: G2 MCAT LO: MCAT18.5 14) Which of the following compounds is most soluble in water? A) acetone B) cyclohexanone C) 2-butanone D) 3-octanone E) benzophenone Answer: A Diff: 2 Section: 17.1 LO: 17.0.1 GO: G2 MCAT LO: MCAT18.5

15) The positively polarized carbon atom of a carbonyl group acts as ________. A) an electrophile and a Lewis base B) a nucleophile and a Lewis base C) an electrophile and a Lewis acid D) a nucleophile and a Lewis acid E) both a Lewis acid and a Lewis base Answer: C Diff: 2 Section: 17.2 LO: 17.2.4 GO: G2 MCAT LO: MCAT18.5 16) When the carbonyl group of a neutral ketone is protonated ________. A) the resulting species becomes more electrophilic B) the resulting species is activated toward nucleophilic attack C) subsequent nucleophilic attack on the resulting species is said to occur under acid-catalyzed conditions D) the resulting species has a positive charge E) all of the above Answer: E Diff: 1 Section: 17.3 LO: 17.2.2 | 17.2.4 GO: G2 MCAT LO: MCAT18.3 17) Draw two major resonance forms of the cation which results when cyclohexanone's carbonyl group is protonated. Answer:

Diff: 2 Section: 17.3 LO: 17.1.3 GO: G2 MCAT LO: MCAT18.3

18) The following compound has been found effective in treating pain and inflammation (J. Med. Chem. 2007, 4222). Which sequence correctly ranks each carbonyl group in order of increasing reactivity toward nucleophilic addition?

A) 1 < 2 < 3 B) 2 < 3 < 1 C) 3 < 1 < 2 D) 1 < 3 < 2 Answer: B Diff: 2 Section: 17.4 LO: 17.2.5 GO: G2 MCAT LO: MCAT18.3 19) Rank the following compounds in order of their propensity to become a hydrate in water (i.e., start with the least easy to hydrate: CH3COCH2CH3, H2CO, Cl3CCHO, and CH3CH2CHO. Answer: CH3COCH2CH3 < CH3CH2CHO < H2CO < Cl3CCHO Diff: 2 Section: 17.4 LO: 17.2.5 GO: G2 MCAT LO: MCAT18.3

20) Which sequence ranks the following carbonyl compounds in order of increasing rate of nucleophilic addition?

A) 2 < 3 < 1 B) 3 < 2 < 1 C) 2 < 1 < 3 D) 1 < 3 < 2 Answer: A Diff: 2 Section: 17.4 LO: 17.2.5 GO: G2 MCAT LO: MCAT18.3

21) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 17.5 LO: 17.3.1 GO: G2 MCAT LO: MCAT18.3

22) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 17.5 LO: 17.3.1 GO: G2 MCAT LO: MCAT18.3 23) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 17.5 LO: 17.3.1 GO: G2 MCAT LO: MCAT18.3

24) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 17.5 LO: 17.3.1 GO: G2 MCAT LO: MCAT18.3 25) Provide the structure of the compound which results when HCN adds to pentanal. Answer:

Diff: 2 Section: 17.5 LO: 17.3.3 GO: G2 MCAT LO: MCAT18.3 26) Provide the major organic product of the reaction shown below.

Answer:

27) An ylide is a molecule that can be described as a ________. A) carbanion bound to a negatively charged heteroatom B) carbocation bound to a positively charged heteroatom C) carbocation bound to a carbon radical D) carbocation bound to a diazonium ion E) carbanion bound to a positively charged heteroatom Answer: E Diff: 1 Section: 17.6 LO: 17.5.1 GO: G2 MCAT LO: MCAT18.1 28) Provide the single reagent necessary for the conversion of cyclobutanone to the compound shown below.

Answer: CH3CH PPh3 Diff: 1 Section: 17.6 LO: 17.5.2 GO: G2 MCAT LO: MCAT18.4 29) Provide the structure of the major organic product which results when with PPh3 and the resulting salt is reacted with one equivalent of butyllithium. Answer: CH3CH PPh3 Diff: 1 Section: 17.6 LO: 17.5.1 GO: G2

is treated

30) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 17.6 LO: 17.5.1 GO: G2 MCAT LO: MCAT18.3 31) Provide the preferred reagent pair to synthesize 3-ethylpent-2-ene via a Wittig reaction. Answer: CH3CH2COCH2CH3 and CH3CH PPh3 Diff: 2 Section: 17.6 LO: 17.5.2 GO: G2 MCAT LO: MCAT18.3 32) Provide the structure of the hydrate of cyclopentanone. Answer:

Diff: 1 Section: 17.7 LO: 17.6.1 GO: G2 MCAT LO: MCAT18.1

33) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 17.7 LO: 17.6.5 GO: G2 MCAT LO: MCAT18.3 34) What product will result from the reaction shown?

A) acetal B) hydrazine C) ester D) ylide E) ketone Answer: A Diff: 2 Section: 17.7 LO: 17.6.1 GO: G2 MCAT LO: MCAT18.3

35) What would be the product of the following reaction?

36) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 17.7 LO: 17.6.1 GO: G2 MCAT LO: MCAT18.3 37) Provide the structure of the diethyl acetal of butanal. Answer: CH3CH2CH2CH(OCH2CH3)2 Diff: 2 Section: 17.7 LO: 17.6.1 GO: G2 MCAT LO: MCAT18.1 38) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 17.7 LO: 17.6.7 GO: G2 MCAT LO: MCAT18.3

39) Why do acetal-forming reactions that use ethylene glycol have more favorable equilibrium constants than those using methanol? A) Ethylene glycol reacts more rapidly. B) They are more favorable on entropy grounds. C) They are more favorable on enthalpy grounds. D) Ethylene glycol is acidic and catalyzes the reaction. E) The ethylene acetal can serve as a protecting group. Answer: B Diff: 3 Section: 17.7 LO: 17.6.5 GO: G2 MCAT LO: MCAT18.3 40) When HOCH2CH2CH2CH2COCH2CH2CH2CH2OH is heated in the presence of an acid catalyst, a reaction occurs. This product has the formula C9H16O2. Provide the structure of this product. Answer:

Diff: 3 Section: 17.7 LO: 17.6.5 GO: G2 MCAT LO: MCAT18.3

41) Which series of reactions described below will result in the formation of compound A, starting with compound B?

A) 1. HO-(CH2)2-OH /trace H3O+ 2. DMSO (COCl2)/Et3N, CH2Cl2 3. MgBr-(CH2)2-CH3/diethyl ether 4. work-up with H3O+ 5. PCC B) 1. PCC 2. SOCl2 3. LiCu-((CH2)2-CH3)2 4. work-up with H3O+ C) 1. Na2Cr2O7/H2SO4 2. SOCl2 3. 2 MgBr-(CH2)2-CH3/diethyl ether 4. work-up with H3O+ D) both A and B E) both B and C Answer: A Diff: 2 Section: 17.7 LO: 17.3.2 | 17.6.5 | 17.6.8GO: G2 MCAT LO: MCAT18.4

42) Give the structure of the acyclic compound from which the following imine was formed.

Answer:

Diff: 2 Section: 17.8 LO: 17.7.3 GO: G2 MCAT LO: MCAT18.4 43) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 17.8 LO: 17.7.3 GO: G2 MCAT LO: MCAT18.3 44) Provide the major organic product of the reaction of aniline with 3-pentanone. Answer:

MCAT LO: MCAT18.3 45) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 17.8 LO: 17.7.3 GO: G2 MCAT LO: MCAT18.3 46) What product will result from the reaction shown?

A) imine B) amino acid C) amino alcohol D) hydrazine E) hydroxylamine Answer: A Diff: 2 Section: 17.8 LO: 17.7.3 GO: G2 MCAT LO: MCAT18.3

47) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 17.8 LO: 17.7.3 GO: G2 MCAT LO: MCAT18.3 48) Provide the structure of cyclohexanone oxime. Answer:

Diff: 2 Section: 17.8 LO: 17.7.1 GO: G2 MCAT LO: MCAT18.1 49) Provide the structure of the major organic product which results when benzaldehyde reacts with hydroxylamine in the presence of acid. Answer:

50) When a ketone is treated with LiAlH4 followed by addition of H2O, what general class of product results? A) primary alcohol B) secondary alcohol C) tertiary alcohol D) ether E) aldehyde Answer: B Diff: 1 Section: 17.9 LO: 17.8.1 GO: G2 51) When an aldehyde is treated with LiAlH4 followed by addition of H2O, what general class of product results? A) primary alcohol B) secondary alcohol C) tertiary alcohol D) ether E) ketone Answer: A Diff: 1 Section: 17.9 LO: 17.8.1 GO: G2 52) Reduction of a ketone with NaBH4 will result in the formation of ________. A) a primary alcohol B) an alkene C) a secondary alcohol D) an alkane E) an aldehyde Answer: C Diff: 1 Section: 17.9 LO: 17.8.1 GO: G2

53) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 1 Section: 17.9 LO: 17.8.1 GO: G2 54) Provide the structure of the major organic product in the reaction below. (CH3)2CHCH2CH2CHO

→

Answer: (CH3)2CHCH2CH2CH2OH Diff: 1 Section: 17.9 LO: 17.8.1 GO: G2

55) Which of the following reactions will result in the formation of a secondary alcohol(s) in good yield? A)

E) both A and D Answer: E Diff: 2 Section: 17.9 LO: 17.8.1 GO: G2

56) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 17.9 LO: 17.8.1 GO: G2 57) In addition to the use of complex metal hydrides, what other reaction can be used to reduce aldehydes and ketones to alcohols? Answer: catalytic hydrogenation (H2, Raney Ni) Diff: 2 Section: 17.9 LO: 17.8.1 GO: G2 58) Provide the major organic product(s) of the reaction below.

Answer:

Diff: 2 Section: 17.9 LO: 17.8.1 GO: G2 59) Provide the major organic product(s) of the reaction below.

Answer:

60) What intermediate occurs when a ketone undergoes a Wolff-Kishner reduction? A) a cyanohydrin B) a hydrated aldehyde C) a carboxylate D) a semicarbazone E) a hydrazone Answer: E Diff: 2 Section: 17.9 LO: 17.8.3 GO: G2 MCAT LO: MCAT18.3 61) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 17.9 LO: 17.8.1 GO: G2 MCAT LO: MCAT18.3

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 18 Nucleophilic Acyl Substitution 1: Carboxylic Acids 1) What is the name of the characteristic functional group found in the molecule CH3CH2CONH2 Answer: It is an amide. Diff: 1 Section: 18.1 LO: 18.0.1 GO: G2

2) The combination of a carbonyl group and a hydroxyl group on the same carbon atom is called a ________ group. A) carbamate B) carbonate C) urethane D) carboxyl E) carboxylate Answer: D Diff: 1 Section: 18.1 LO: 18.0.1 GO: G2 MCAT LO: MCAT20.1 3) Provide the structure of 4-oxohexanoic acid. Answer:

Diff: 1 Section: 18.2 LO: 18.0.2 GO: G2 MCAT LO: MCAT18.1

4) Provide the IUPAC name for HO2CCH2C(CH3)2CH2CH2CO2H. Answer: 3,3-dimethylhexanedioic acid Diff: 1 Section: 18.2 LO: 18.0.1 GO: G2 MCAT LO: MCAT20.1 5) Provide the IUPAC name for the compound shown below.

Answer: E-2,5-dimethyloct-5-enoic acid Diff: 1 Section: 18.2 LO: 18.0.1 GO: G2 MCAT LO: MCAT20.1 6) Provide the IUPAC name for the compound shown below.

Answer: 3-hydroxyhexanoic acid Diff: 1 Section: 18.2 LO: 18.0.1 GO: G2 MCAT LO: MCAT20.1 7) Provide the structure of trans-1,3-cyclohexanedicarboxylic acid. Answer:

Diff: 1 Section: 18.2 LO: 18.0.2 GO: G2 MCAT LO: MCAT20.1

8) Provide the structure of pent-3-ynoic acid. Answer: CH3C CCH2CO2H Diff: 1 Section: 18.2 LO: 18.0.2 GO: G2 MCAT LO: MCAT20.1 9) Name the compound shown below.

Answer: 2,4-dimethylhexanoic acid Diff: 1 Section: 18.2 LO: 18.0.1 GO: G2 MCAT LO: MCAT20.1 10) Name the compound shown below.

Answer: 4-methylpentanoic acid Diff: 1 Section: 18.2 LO: 18.0.1 GO: G2 MCAT LO: MCAT20.1

11) Provide the name of the compound shown below.

Answer: 2,5-dimethyl-4-hexenoic acid or 2,5-dimethylhex-4-enoic acid Diff: 2 Section: 18.2 LO: 18.0.1 GO: G2 MCAT LO: MCAT20.1 12) What is the common name for the following compound?

A) γ-hydroxyvaleric acid B) γ-hydroxypentanoic acid C) γ-hydroxy-γ-methylbutyric acid D) δ-hydroxyvaleric acid Answer: A Diff: 2 Section: 18.2 LO: 18.0.1 GO: G2 MCAT LO: MCAT20.1 13) Name the compound shown below.

Answer: 3,3,6-trimethyl-6-heptenoic acid or 3,3,6-trimrthylhept-6-enoic acid Diff: 2 Section: 18.2 LO: 18.0.1 GO: G2 MCAT LO: MCAT20.1

14) Why are the OH groups of carboxylic acids more acidic than alcohols? A) resonance stabilization of the carboxylate ion B) inductive electron donating by the carbonyl oxygen C) reduced hydrogen bonding capacity D) because they have lower pKa values E) None of the above — carboxylic acids are not more acidic than alcohols. Answer: A Diff: 1 Section: 18.4 LO: 18.2.3 GO: G2 MCAT LO: MCAT20.8 15) List the following weak acids in order of increasing acidity (from lowest to highest.).

A) 4 < 3 < 2 < 1 < 5 B) 4 < 1 < 3 < 2 < 5 C) 5 < 2 < 3 < 1 < 4 D) 4 < 1 < 2 < 5 < 3 E) 1 < 2 < 4 < 3 < 5 Answer: B Diff: 1 Section: 18.4 LO: 18.2.2 GO: G2 MCAT LO: MCAT20.2 16) Which of the following is the strongest acid? A) acetic acid B) chloroacetic acid C) bromoacetic acid D) fluoroacetic acid Answer: D Diff: 2 Section: 18.4 LO: 18.2.2 | 18.2.3 GO: G2 MCAT LO: MCAT20.2 5 Copyright © 2021 Pearson Education, Inc.

17) Which of the following is the strongest acid? A) chloroacetic acid B) dichloroacetic acid C) trichloroacetic acid D) acetic acid Answer: C Diff: 2 Section: 18.4 LO: 18.2.2 | 18.2.3 GO: G2 MCAT LO: MCAT20.2 18) The strongest dichlorobutanoic acid is ________. A) 2,2-dichlorobutanoic acid B) 2,3-dichlorobutanoic acid C) 3,3-dichlorobutanoic acid D) 3,4-dichlorobutanoic acid E) 4,4-dichlorobutanoic acid Answer: A Diff: 2 Section: 18.4 LO: 18.2.2 | 18.2.3 GO: G2 MCAT LO: MCAT20.2 19) Which of the following compounds is the strongest acid? A) p-nitrobenzoic acid B) p-bromobenzoic acid C) m-methylbenzoic acid D) m-methoxybenzoic acid E) water Answer: A Diff: 2 Section: 18.4 LO: 18.2.2 | 18.2.3 GO: G2 MCAT LO: MCAT20.2

20) Which of the following sequences ranks the structures below in order of increasing acidity?

A) 1 < 2 < 3 B) 2 < 3 < 1 C) 3 < 1 < 2 D) 2 < 1 < 3 Answer: D Diff: 2 Section: 18.4 LO: 18.2.2 GO: G2 MCAT LO: MCAT20.2 21) Where would one expect to find the 1H NMR signal for the carboxyl group's hydrogen in propanoic acid? A) δ 4.1 - 5.6 ppm B) δ 10 - 13 ppm C) δ 8 - 9 ppm D) δ 6.1 - 7.8 ppm E) δ 9.5 - 10 ppm Answer: B Diff: 1 Section: 18.4 LO: 18.2.4 GO: G2 MCAT LO: MCAT20.4

22) Which of the following statements is true? A) The carbonyl carbon in a carboxylic acid does not give a 13C signal in a 13C-NMR spectrum. B) The carbonyl carbon in a carboxylic acid gives a 13C signal in the same region as a carbonyl carbon from a ketone or aldehyde — in the range of 200 ppm. C) The carbonyl carbon of a carboxylic acid splits a proton signal into a doublet in an H-NMR spectrum. D) The carbonyl carbon in a carboxylic acid gives a 13C signal in the same region as a carbonyl carbon from an ester or amide in the range of 150 to 180 ppm. E) The carbonyl carbon in a carboxylic acid cannot be distinguished from an aromatic carbon because they both give signals in the range of 110 to 130 ppm. Answer: D Diff: 1 Section: 18.4 LO: 18.2.4 GO: G2 MCAT LO: MCAT20.4 23) In the mass spectrum of pentanoic acid, the base peak occurs at m/z ________. A) 102 B) 101 C) 85 D) 73 E) 60 Answer: E Diff: 2 Section: 18.4 LO: 18.2.4 GO: G2 MCAT LO: MCAT20.4 24) In the mass spectrum of 3-methylhexanoic acid, predict the mass of the fragment resulting from a McLafferty rearrangement. Answer:

Diff: 2 Section: 18.4 LO: 18.2.4 GO: G2 MCAT LO: MCAT20.4

25) Carboxylic acids can be made from Grignards by treating the Grignard reagents with ________. A) carbon monoxide B) esters C) aldehydes D) diborane E) carbon dioxide Answer: E Diff: 1 Section: 18.5 LO: 18.3.1 | 18.3.2 GO: G2 26) 1-Hexanol reacts with chromic acid to yield what product? Answer: Hexanoic acid Diff: 1 Section: 18.5 LO: 18.3.1 | 18.3.3 GO: G2 27) 2-Phenylethanol yields what acid upon treatment with cold chromic acid? Answer: phenylacetic acid Diff: 1 Section: 18.5 LO: 18.3.1 | 18.3.3 GO: G2 28) An acid which could not be prepared by the reaction of an organic halide with cyanide ion followed by acid hydrolysis of the nitrile is ________. A) propanoic acid B) phenylacetic acid C) acetic acid D) (CH3)3CCO2H E) CH3(CH2)14CO2H Answer: D Diff: 2 Section: 18.5 LO: 18.3.1 GO: G2

29) An acid which could not be prepared from an organic halide by carboxylation of the Grignard reagent is ________. A) benzoic acid B) 2,2-dimethylpropanoic acid C) propanoic acid D) 4-oxocyclohexanecarboxylic acid E) 2-methylbutanoic acid Answer: D Diff: 2 Section: 18.5 LO: 18.3.1 | 18.3.2 GO: G2 30) What compound is produced when cyclohexene is treated with concentrated KMnO4? A) hexanoic acid B) adipic acid C) cyclohexanecarboxylic acid D) benzoic acid E) succinic acid Answer: B Diff: 2 Section: 18.5 LO: 18.3.1 | 18.3.3 GO: G2 31) Which of the following must be converted into a carboxylic acid through nitrile hydrolysis rather than through a Grignard synthesis with Mg/ether followed with dry CO2 and work-up with H3O+?

LO: 18.3.3 GO: G2

32) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 18.5 LO: 18.3.1 GO: G2

33) Provide the major organic product of the following reaction.

Answer: Diff: 2 Section: 18.5 LO: 18.3.1 GO: G2

34) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 18.5 LO: 18.3.1 GO: G2 35) Provide the major organic product of the following reaction sequence.

Answer:

Diff: 2 Section: 18.5 LO: 18.3.1 GO: G2 36) Provide the major organic product of the following reaction sequence.

Answer:

GO: G2

37) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 18.5 LO: 18.3.1 GO: G2 38) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 18.5 LO: 18.3.1 GO: G2 39) What two alkenes, which contain only one double bond, yield exclusively propanoic acid upon oxidation with hot concentrated KMnO4? Answer: E- and Z-hex-3-ene Diff: 2 Section: 18.5 LO: 18.3.3 GO: G2

40) Hept-3-yne yields what acids upon treatment with concentrated permanganate of ozone followed by water? Answer: propanoic and butanoic acids Diff: 2 Section: 18.5 LO: 18.3.1 GO: G2 41) Which sequence of steps below describes the best synthesis of 5-oxohexanoic acid starting with 1-methylcyclopentan-1-ol? A) 1. Conc. KMnO4 2. Dry gaseous HBr 3. mg/ether 4. CO2 B) 1. H2SO4 and heat 2. Conc. KMnO4 C) 1. Conc. KMnO4 2. CH3MgBr/ ether 3. H3O+ D) 1. H2SO4 and heat 2. O3 3. (CH3)2S 4. PCC E) 1. H2SO4 and heat 2. Conc. KMnO4 3. LiAlH4 4. H3O+ Answer: B Diff: 3 Section: 18.5 LO: 18.3.1 GO: G2

GO: G2

43) An unknown compound is insoluble in water but dissolves in an aqueous solution of sodium bicarbonate with a release of carbon dioxide bubbles. The compound is almost certainly ________. A) a carboxylic acid B) an amine C) an aldehyde D) an alkyl chloride E) an alcohol Answer: A Diff: 1 Section: 18.6 LO: 18.2.4 GO: G2 MCAT LO: MCAT20.3 44) An ether solution of PhCO2H (A), PhNH2 (B), and PhCH3 (C) is extracted with aqueous NaOH. The ether layer will contain what compound(s) after the extraction? A) A + B B) A + C C) B + C D) A + B + C E) A only Answer: C Diff: 1 Section: 18.6 LO: 18.4.1 GO: G2 MCAT LO: MCAT20.3 45) After completing the synthesis of 3-methylpentanoic acid, which of the following treatments will neutralize the mineral acids and facilitate the distribution of the organic acid from the organic layer to the aqueous extraction layer? A) extraction with aqueous NaCl B) extraction with ether C) extraction with aqueous NaHCO3 D) extraction with water E) extraction with dilute aqueous HCl Answer: C Diff: 1 Section: 18.6 LO: 18.4.1 GO: G2 16 Copyright © 2021 Pearson Education, Inc.

MCAT LO: MCAT20.3

46) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 18.6 LO: 18.5.1 GO: G2 47) What class of organic compound is the major product of the acid catalyzed reaction of an alcohol with a carboxylic acid? A) ether B) ester C) thiol D) nitrile E) sulfonate ester Answer: B Diff: 1 Section: 18.7 LO: 18.6.1 GO: G2 MCAT LO: MCAT11.1 48) Name the alcohol that would be used in the Fischer esterification synthesis of ethyl propanoate (CH3CH2O2CCH2CH3). Answer: ethanol Diff: 1 Section: 18.7 LO: 18.6.3 GO: G2

49) Draw the products formed in the Fischer esterification reaction between acetic acid (CH3CO2H) and cyclohexanol. Answer:

Diff: 2 Section: 18.7 LO: 18.6.1 GO: G2 50) Draw a structure for the expected product of the reaction below.

Answer:

Diff: 2 Section: 18.7 LO: 18.5.1 GO: G2 MCAT LO: MCAT11.1 51) Provide the major organic product of the reaction shown below.

Answer:

MCAT LO: MCAT20.5

52) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 18.7 LO: 18.6.1 GO: G2 MCAT LO: MCAT20.5 53) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 18.7 LO: 18.6.1 GO: G2 MCAT LO: MCAT20.5

54) What reagent is needed to complete the following transformation?

Answer:

Diff: 2 Section: 18.7 LO: 18.6.3 GO: G2 MCAT LO: MCAT20.5 55) Which of the following conditions will drive the equilibrium of the Fischer esterification towards ester formation? A) addition of water B) removal of water as it is formed C) addition of an inorganic acid as a catalyst D) addition of alcohol E) both B and D Answer: E Diff: 3 Section: 18.7 LO: 18.6.2 GO: G2 MCAT LO: MCAT20.6

56) Which of the following would be the preferred reagents used in the following synthesis?

A) 1. NaBH3-THF 2. H3O+ B) 1. Mg/ether 2. dry CO2 3. H3O+ C) 1. LiAlH4-THF 2. H3O+ D) 1. Hot KMnO4 2. H3O+ E) 1. LiAlH[O(CH3)3]3-THF 2. H3O+ Answer: C Diff: 2 Section: 18.7 LO: 18.5.5 GO: G2 MCAT LO: MCAT20.7 57) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 18.7 LO: 18.5.1 GO: G2 MCAT LO: MCAT20.5

58) Provide the major organic product for the following reaction.

Answer:

Diff: 2 Section: 18.7 LO: 18.5.1 GO: G2 MCAT LO: MCAT20.5 59) Provide the major organic product for the following reaction.

Answer:

Diff: 2 Section: 18.7 LO: 18.5.1 GO: G2 MCAT LO: MCAT20.5 60) Lithium aluminum hydride reduces carboxylic acids to primary alcohols via what intermediate? A) a ketone B) a methyl ester C) an aldehyde D) a secondary alcohol E) an acid chloride Answer: C Diff: 3 Section: 18.7 LO: 18.5.2 GO: G2 MCAT LO: MCAT20.5 22 Copyright © 2021 Pearson Education, Inc.

61) The conversion of butanoic acid to 2-pentanone is best accomplished with ________. A) 1. thionyl chloride; 2. methylmagnesium bromide. B) methyllithium. C) 1. methanol, sulfuric acid; 2. methyllithium. D) 1. thionyl chloride; 2. methanol. E) 1. sulfuric acid; 2. methanol. Answer: B Diff: 2 Section: 18.7 LO: 18.5.7 GO: G2 MCAT LO: MCAT20.7 62) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 18.7 LO: 18.5.1 | 18.5.7 GO: G2 MCAT LO: MCAT20.5 63) Provide the structure of the major organic product of the reaction sequence shown.

Answer:

MCAT LO: MCAT20.5 64) What alkyllithium would react with acetic acid to form 2-butanone? A) methyllithium B) vinyllithium C) ethyllithium D) propyllithium E) phenyllithium Answer: C Diff: 3 Section: 18.7 LO: 18.5.1 | 18.5.7 GO: G2 MCAT LO: MCAT20.7 65) Provide the major organic product of the following reaction.

Answer:

Diff: 1 Section: 18.7 LO: 18.5.1 GO: G2 MCAT LO: MCAT20.5

66) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 18.7 LO: 18.5.1 GO: G2 MCAT LO: MCAT20.5 67) Provide the major organic product of the following reaction sequence.

Answer:

Diff: 2 Section: 18.7 LO: 18.5.1 GO: G2 MCAT LO: MCAT20.5

68) Provide the major organic product of the following reaction sequence.

Answer:

Diff: 2 Section: 18.7 LO: 18.5.1 GO: G2 MCAT LO: MCAT20.5

69) Provide the major organic product of the following reaction sequence.

Answer:

Diff: 2 Section: 18.7 LO: 18.5.1 GO: G2 MCAT LO: MCAT20.5

70) What are the products of the reaction of benzoic acid with thionyl chloride? Answer: benzoyl chloride, SO2(g), and HCl(g) Diff: 2 Section: 18.7 LO: 18.5.1 GO: G2 MCAT LO: MCAT20.5 71) The methyl ester of a carboxylic acid can be synthesized directly using ________. A) SOCl2 B) PCl5 C) C2O2Cl2 D) CH2N2 E) CH3NH2 Answer: D Diff: 1 Section: 18.8 LO: 18.5.1 GO: G2 MCAT LO: MCAT20.7 72) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 18.8 LO: 18.5.1 GO: G2 MCAT LO: MCAT20.5

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 19 Nucleophilic Acyl Substitution 2: Carboxylic Acid Derivatives 1) Which of the molecules below is an ester? A) CH3CH2CH(CH3)2 B) CH3OCH2CH2CH3 C) CH3COOH D) CH3COOCH3 E) HC≡CCH3 Answer: D Diff: 1 Section: 19.1 LO: 19.01.1 GO: G2

2) N-Methylacetamide is an example of ________. A) a primary amide B) a secondary amide C) a tertiary amide D) an N, N-disubstituted amide E) an imine Answer: B Diff: 1 Section: 19.1 LO: 19.01.1 GO: G2 MCAT LO: MCAT21.1

3) Which of the following structures are carboxylic acid derivatives?

Answer: 1 & 3 Diff: 2 Section: 19.1 LO: 19.01.1 GO: G2 MCAT LO: MCAT21.1 4) Provide the proper IUPAC name for the compound below.

Answer: trans-5-octenoyl chloride Diff: 1 Section: 19.2 LO: 19.0.2 GO: G2 MCAT LO: MCAT21.1 5) Provide the structure of propanoic anhydride. Answer: (CH3CH2CO)2O Diff: 1 Section: 19.2 LO: 19.0.3 GO: G2 MCAT LO: MCAT21.1 6) Provide the structure of cyclohexyl formate. Answer:

LO: 19.0.3 GO: G2 MCAT LO: MCAT21.1 7) Provide the structure of (R)-4-ethoxypentanenitrile. Answer:

Diff: 2 Section: 19.2 LO: 19.0.3 GO: G2 MCAT LO: MCAT21.1 8) Provide the structure of trifluoroacetic anhydride. Answer: (CF3CO)2O Diff: 2 Section: 19.2 LO: 19.0.3 GO: G2 MCAT LO: MCAT21.1

9) Provide the IUPAC name of the following compound.

Answer: N-ethyl-N-methylpentanamide Diff: 2 Section: 19.2 LO: 19.0.2 GO: G2 MCAT LO: MCAT21.1 10) Provide the name of the compound shown below.

GO: G2 MCAT LO: MCAT21.1 11) Provide the proper IUPAC name for the compound below.

Answer: isopropyl cyclohexanecarboxylate Diff: 2 Section: 19.2 LO: 19.0.2 GO: G2 MCAT LO: MCAT21.1 12) Provide the proper IUPAC name for ClCH2CH2CONHCH3. Answer: N-methyl-3-chloropropanamide Diff: 2 Section: 19.2 LO: 19.0.2 GO: G2 MCAT LO: MCAT21.1 13) Provide the proper IUPAC name for the compound below.

Answer: 3,3-dimethylcyclobutanecarbonitrile Diff: 2 Section: 19.2 LO: 19.0.2 GO: G2 MCAT LO: MCAT21.1 14) Provide the proper IUPAC name for NCCH2CH2CH2CH2CO2CH3. Answer: methyl 5-cyanopentanoate Diff: 2 Section: 19.2 LO: 19.0.2 GO: G2 MCAT LO: MCAT21.1

15) Provide the structure of N,N-diethylbutanamide. Answer: CH3CH2CH2CON(CH2CH3)2 Diff: 2 Section: 19.2 LO: 19.0.3 GO: G2 MCAT LO: MCAT21.1 16) Provide the structure of 3-oxobutanenitrile. Answer: CH3COCH2CN Diff: 2 Section: 19.2 LO: 19.0.3 GO: G2 MCAT LO: MCAT21.1 17) Provide the structure of 2-bromo-2-methylbutanoyl chloride. Answer: CH3CH2CBr(CH3)COCl Diff: 2 Section: 19.2 LO: 19.0.3 GO: G2 MCAT LO: MCAT21.1

18) Provide the IUPAC name for HCONHCH2CH2CH3. Answer: N-propylmethanamide Diff: 2 Section: 19.2 LO: 19.0.2 GO: G2 MCAT LO: MCAT21.1 19) Provide the name of the compound shown below.

GO: G2 MCAT LO: MCAT21.1 20) Provide the name of CH3O2CH2CH2CH2CH3. Answer: methyl butanoate Diff: 2 Section: 19.2 LO: 19.0.2 GO: G2 MCAT LO: MCAT21.1

21) What is the common name for the following carboxylic acid derivative?

A) β-hydroxybutyronitrile B) 1-cyano-2-butanol C) β-hydroxyvaleronitrile D) γ-hydroxyvaleronitrile E) 2-hydroxypentane nitrile Answer: C Diff: 3 Section: 19.2 LO: 19.0.2 GO: G2 MCAT LO: MCAT21.1

22) Which of the following are strongly hydrogen bonded in the liquid phase? A) nitriles B) esters C) secondary amides D) tertiary amides E) acid chlorides Answer: C Diff: 2 Section: 19.4 LO: 19.1.1 GO: G2 MCAT LO: MCAT21.2

23) Arrange the following compounds in order of increasing boiling point: acetic acid, propanenitrile, butane, and acetamide. Answer: butane < propanenitrile < acetic acid < acetamide Diff: 2 Section: 19.4 LO: 19.1.1 GO: G2 MCAT LO: MCAT21.2 24) List the following five compounds, ethanamide, 1-propanol, methyl formate, acetic acid, and propanenitrile, in order of increasing boiling point. Start with the lowest boiling compound. Answer: methyl formate < propanenitrile < 1-propanol < acetic acid < ethanamide Diff: 2 Section: 19.4 LO: 19.1.1 GO: G2 MCAT LO: MCAT21.2 25) While the carbonyl stretching frequency for simple aldeydes, ketones, and carboxylic acids is about 1710 cm-1, the carbonyl stretching frequency for esters is about ________. A) 1660 cm-1 B) 1700 cm-1 C) 1735 cm-1 D) 1800 cm-1 E) 2200 cm-1 Answer: C Diff: 2 Section: 19.4 LO: 19.1.1 GO: G2 MCAT LO: MCAT21.3

26) While the carbonyl stretching frequency for simple aldehydes, ketones, and carboxylic acids is about 1710 cm-1, the carbonyl stretching frequency for acid chlorides is about ________. A) 1700 cm-1 B) 1735 cm-1 C) 1800 cm-1 D) 1660 cm-1 E) 2200 cm-1 Answer: C Diff: 2 Section: 19.4 LO: 19.1.1 GO: G2 MCAT LO: MCAT21.3 27) While the carbonyl stretching frequency for simple aldehydes, ketones, and carboxylic acids is about 1710 cm-1, the carbonyl stretching frequency for amides is about ________. A) 1700 cm-1 B) 1735 cm-1 C) 1800 cm-1 D) 1660 cm-1 E) 2200 cm-1 Answer: D Diff: 2 Section: 19.4 LO: 19.1.1 GO: G2 MCAT LO: MCAT21.3 28) In 1H NMR, the chemical shifts for protons α to a carbonyl group ________. A) are similar for all acid derivatives B) are farthest downfield for carboxylic acids C) are farther downfield than those α to a nitrile D) fall between δ 3.1 and δ 4.2 (ppm) E) fall between δ 1.3 and δ 1.8 (ppm) Answer: A Diff: 2 Section: 19.4 LO: 19.1.1 GO: G2 MCAT LO: MCAT21.3

29) The most characteristic IR stretch of butanenitrile occurs at approximately what wavenumber? A) 3500 cm-1 B) 3100 cm-1 C) 2600 cm-1 D) 2200 cm-1 E) 1750 cm-1 Answer: D Diff: 2 Section: 19.4 LO: 19.1.1 GO: G2 MCAT LO: MCAT21.3 30) ) Propose a synthesis of PhNHCHO from benzene. Answer: 1) HNO3, H2SO4 2) H2, Ni 3) (HCO)2O Diff: 3 Section: 19.5 LO: 19.2.3 GO: G2 MCAT LO: MCAT21.6

31) Predict the correct product of the following reaction.

Answer:

Diff: 2 Section: 19.6 LO: 19.5.1 GO: G2 MCAT LO: MCAT10.3

32) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 19.6 LO: 19.5.1 GO: G2 MCAT LO: MCAT10.3 33) Provide the major organic product of the reaction below.

Answer:

Diff: 2 Section: 19.6 LO: 19.5.1 GO: G2 MCAT LO: MCAT10.3

34) Provide the structure of the major organic product in the reaction shown below.

Answer:

Diff: 2 Section: 19.6 LO: 19.5.1 GO: G2 MCAT LO: MCAT10.3 35) Provide the major organic product(s) of the reaction below.

Answer:

Diff: 2 Section: 19.6 LO: 19.5.1 GO: G2 MCAT LO: MCAT10.3

36) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 19.6 LO: 19.5.1 GO: G2 MCAT LO: MCAT11.1 37) Provide the name of the major organic product that results when cyclopentanol is treated with acetyl chloride. Answer: cyclopentyl acetate Diff: 3 Section: 19.6 LO: 19.5.1 GO: G2 MCAT LO: MCAT11.1 38) Which of the following is the most reactive carboxylic acid derivative? A) ester B) anhydride C) nitrile D) acid chloride E) amide Answer: D Diff: 1 Section: 19.6 LO: 19.2.3 GO: G2 MCAT LO: MCAT21.8 12 Copyright © 2021 Pearson Education, Inc.

39) In nucleophilic acyl substitution ________. A) protonation of the carbonyl is followed immediately by loss of the leaving group B) loss of the leaving group is followed by rearrangement of the carbocation C) addition to the carbonyl by a nucleophile is followed by loss of the leaving group D) ester hydrolysis is followed by deprotonation E) an SN2 reaction occurs Answer: C Diff: 2 Section: 19.6 LO: 19.2.1 GO: G2 MCAT LO: MCAT21.5 40) Arrange the carboxylic acid derivatives below in order of increasing reactivity towards nucleophilic acyl substitution.

A) 1 < 2 <3 B) 1 < 3 < 2 C) 2 < 1 < 3 D) 2 < 3 < 1 E) 3 < 2 < 1 Answer: A Diff: 2 Section: 19.6 LO: 19.2.3 GO: G2 MCAT LO: MCAT21.8 41) List the following four carboxylic acid derivatives, ester, anhydride, amide, and acid halide, in order of increasing reactivity in nucleophilic acyl substitution reactions. Start with the least reactive derivative. Answer: amide < ester < anhydride < acid halide Diff: 2 Section: 19.6 LO: 19.2.3 GO: G2 MCAT LO: MCAT21.8

42) Which of the following reactions is favorable, in the direction indicated, under fairly "normal" laboratory conditions? A)

Answer: A Diff: 2 Section: 19.7 LO: 19.2.2 GO: G2 MCAT LO: MCAT21.5

43) Name the compound which results when propyl benzoate is heated in a large excess of ethanol in the presence of catalytic acid. Answer: ethyl benzoate Diff: 1 Section: 19.7 LO: 19.3.1 GO: G2 MCAT LO: MCAT21.5 44) Draw the product resulting from the following reaction. Indicate any relevant stereochemistry.

Answer:

Diff: 3 Section: 19.7 LO: 19.3.5 GO: G2 MCAT LO: MCAT21.5 45) Predict the major product of the following reaction.

Answer:

Diff: 3 Section: 19.7 LO: 19.3.1 GO: G2 MCAT LO: MCAT21.5

46) The hydrolysis of esters in base is called ________. A) the Fischer esterification B) the Hunsdiecker reaction C) the Dieckmann condensation D) transesterification E) saponification Answer: E Diff: 1 Section: 19.7 LO: 19.3.3 GO: G2 47) Provide the major organic product in the reaction of CH3CH2CONH2 with hot aqueous acid. Answer: CH3CH2CO2H Diff: 1 Section: 19.7 LO: 19.3.3 GO: G2 MCAT LO: MCAT21.4 48) Which of the following compounds is(are) hydrolyzed to butanoic acid upon heating in A) ethyl butanoate B) butyl acetate C) N-methylbutanamide D) both A and B E) both A and C Answer: E Diff: 2 Section: 19.7 LO: 19.3.1 GO: G2 MCAT LO: MCAT21.4 49) Provide the major organic product in the reaction shown below.

50) Provide the major organic product in the reaction shown below.

Answer: HO2CCH2CH2CH2CH2CO2H Diff: 2 Section: 19.7 LO: 19.3.1 GO: G2 MCAT LO: MCAT21.4 51) Which sequence ranks the following carboxylic acid derivatives in order of increasing rate of hydrolysis?

A) 2 < 3 < 1 B) 3 < 2 < 1 C) 2 < 1 < 3 D) 1 < 3 < 2 Answer: A Diff: 2 Section: 19.7 LO: 19.3.1 GO: G2 MCAT LO: MCAT21.8

52) Predict the major product of the following reaction.

Answer:

Diff: 2 Section: 19.7 LO: 19.3.1 GO: G2 MCAT LO: MCAT21.4 53) Predict the major product of the following reaction.

Answer:

Diff: 2 Section: 19.7 LO: 19.3.1 GO: G2 MCAT LO: MCAT21.4

54) Which of the following are intermediates in the acid hydrolysis of an amide?

A) 1 B) 2 C) 2 & 3 D) 4 E) 1, 2, & 3 Answer: C Diff: 3 Section: 19.7 LO: 19.3.1 GO: G2 GO: G2 55) Predict the major product of the following reaction.

Answer:

Diff: 2 Section: 19.7 LO: 19.3.5 GO: G2 MCAT LO: MCAT21.5 56) What are the major organic products when 1 equivalent of acetic formic anhydride reacts with 1 equivalent of methanol? Answer: acetic acid and methyl formate Diff: 2 Section: 19.7 LO: 19.3.5 GO: G2 MCAT LO: MCAT21.5 19 Copyright © 2021 Pearson Education, Inc.

57) Provide the major organic product in the reaction shown below.

Answer:

Diff: 2 Section: 19.7 LO: 19.3.8 GO: G2 MCAT LO: MCAT21.5 58) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 19.7 LO: 19.3.5 GO: G2 MCAT LO: MCAT21.5 59) What type of compound results from the reaction of an acid chloride and a 2° amine? A) amide B) 1° amine C) ester D) nitrile E) carboxylate Answer: A Diff: 2 Section: 19.7 LO: 19.3.7 GO: G2 20 Copyright © 2021 Pearson Education, Inc.

MCAT LO: MCAT21.5 60) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 19.7 LO: 19.3.7 GO: G2 MCAT LO: MCAT21.5 61) What type of compound results from the reaction of ethyl formate with cyclohexylamine? A) amide B) 1° amine C) acid anhydride D) nitrile E) carboxylate Answer: A Diff: 2 Section: 19.7 LO: 19.3.7 GO: G2 MCAT LO: MCAT21.5

62) Provide the reagents necessary to carry out the transformation shown below.

LO: 19.4.2 GO: G2 63) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 19.8 LO: 19.5.1 GO: G2 MCAT LO: MCAT10.3 64) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 3 Section: 19.8 LO: 19.4.2 GO: G2

65) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 3 Section: 19.8 LO: 19.4.2 GO: G2 GO: G2 66) What reagent(s) are needed to complete the following reaction?

A) 1) LiAlH4, 2) H3O+ B) 1) NaBH4, 2) H3O+ C) H2, Pd D) 1) DIBAL-H, 2) H3O+ Answer: A Diff: 2 Section: 19.8 LO: 19.4.2 GO: G2 67) Provide the major organic product which results when Answer: (CH3)2CHCH2CH2CHO Diff: 2 Section: 19.8 LO: 19.4.2 GO: G2 23 Copyright © 2021 Pearson Education, Inc.

is treated with

68) What organic compound is generated when PhCOCl is treated with Answer: PhCOCH2CH2CH3 Diff: 2 Section: 19.8 LO: 19.5.1 GO: G2

69) Lithium aluminum hydride reduces carboxylic acids, acid chlorides, and esters to ________. A) aldehydes B) primary alcohols C) secondary alcohols D) tertiary alcohols E) ketones Answer: B Diff: 1 Section: 19.8 LO: 19.4.2 GO: G2 70) What compound is produced when N,N-dimethylpropanamide is treated with LiAlH4? A) CH3CH2CONH2 B) CH3CH2CH2NH2 C) CH3CH2CH2OH D) CH3CH2CH2N(CH3)2 E) CH3CH2N(CH3)2 Answer: D Diff: 2 Section: 19.8 LO: 19.4.2 GO: G2

71) Predict the major product of the following reaction.

Answer:

Diff: 2 Section: 19.8 LO: 19.4.2 GO: G2 72) Predict the major product of the following reaction.

Answer:

Diff: 3 Section: 19.8 LO: 19.4.2 GO: G2 73) What reagent is used to convert pentanamide to 1-pentanamine? A) POCl3 B) CuCN C) CH3MgBr D) SOCl2 E) LiAlH4 Answer: E Diff: 2 Section: 19.8 LO: 19.4.4 GO: G2 MCAT LO: MCAT21.6 25 Copyright © 2021 Pearson Education, Inc.

74) Two equivalents of methyl magnesium bromide will add to ________. A) lactones B) aldehydes C) ketones D) imines E) secondary amines Answer: A Diff: 2 Section: 19.9 LO: 19.5.1 GO: G2

75) Which of the following statements is/are true? A) Two equivalents of Grignard reagent react with acid chlorides to yield tertiary alcohols after hydrolysis. B) LiAlH4 reacts with acid chlorides to yield secondary alcohols after hydrolysis. C) LiAlH[OC(CH3)3]3 reacts with acid chlorides to yield primary alcohols after hydrolysis. D) both A and B E) both B and C Answer: A Diff: 2 Section: 19.9 LO: 19.5.1 GO: G2 76) Which of the following reagents convert(s) benzoyl chloride to phenyl propyl ketone? A) CH3CH2CH2MgBr B) CH3CH2CH2Li C) (CH3CH2CH2)2CuLi D) both A and B E) both A and C Answer: C Diff: 2 Section: 19.9 LO: 19.5.1 GO: G2 77) What are the products from the reaction of excess methyl magnesium bromide with ethyl acetate followed by H3O+? Answer: t-butanol and ethanol Diff: 2 Section: 19.9 LO: 19.5.1 GO: G2 26 Copyright © 2021 Pearson Education, Inc.

78) Provide the major organic product in the reaction shown below.

Answer:

Diff: 2 Section: 19.9 LO: 19.5.1 GO: G2 79) Predict the major product of the following reaction.

Answer:

Diff: 2 Section: 19.9 LO: 19.5.1 GO: G2

80) What is the predicted major product of the following reaction?

Answer: A Diff: 3 Section: 19.9 LO: 19.5.1 GO: G2

81) Provide the major organic product in the reaction shown below.

Answer:

Diff: 2 Section: 19.9 LO: 19.5.1 GO: G2 82) Predict the major product of the following reaction.

Answer:

Diff: 2 Section: 19.9 LO: 19.5.1 GO: G2 MCAT LO: MCAT21.5 83) Acids can be converted to primary amines by ________. A) conversion to the nitrile followed by treatment with LiAlH4 B) conversion to the diazonium salt followed by treatment with NaBH4 C) conversion to the primary amide followed by treatment with LiAlH4 D) both A and B E) both A and C Answer: E Diff: 2 Section: 19.10 29 Copyright © 2021 Pearson Education, Inc.

LO: 19.4.2 GO: G2 84) Provide the major organic product in the reaction shown below.

Answer:

Diff: 2 Section: 19.10 LO: 19.4.2 GO: G2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 20 Enolates: Carbonyl Addition and Substitution 1) Which of the following compounds will not undergo reaction with an enolate? A) 1-pentene B) bromine C) propanal D) 1-bromobutane E) benzoyl chloride Answer: A Diff: 2 Section: 20.2 LO: 20.1.1 GO: G2 MCAT LO: MCAT22.1 2) The relationship between ketones and their corresponding enols is one of ________. A) allotropes B) tautomers C) enantiomers D) diastereomers E) cis-trans isomers Answer: B Diff: 1 Section: 20.2 LO: 20.1.1 GO: G1 MCAT LO: MCAT22.1 3) Provide the structure of the more stable enol tautomer of 1-phenyl-2-octanone. Answer:

Diff: 2 Section: 20.2 LO: 20.1.1 GO: G2

4) Provide the structure of the enol of 2,2,4-trimethyl-3-pentanone. Answer:

Diff: 2 Section: 20.2 LO: 20.1.1 GO: G2 5) When a ketone and its enol are in equilibrium, under most conditions the concentration of the enol is ________ the concentration of the ketone. A) slightly higher than B) equal to C) much higher than D) much lower than E) exactly half of Answer: D Diff: 2 Section: 20.2 LO: 20.1.1 GO: G1 6) (S)-2-Methylbutanal ________ upon sitting in an acidic or a basic aqueous solution. A) racemizes B) esterifies C) inverts completely to the R configuration D) hydrolyzes E) irreversibly forms the hydrate Answer: A Diff: 3 Section: 20.2 LO: 20.1.1 GO: G2 MCAT LO: MCAT22.1

7) What compound is produced in the reaction of cyclopentanone with Br2 in acetic acid? Answer: 2-bromocyclopentanone Diff: 1 Section: 20.2 LO: 20.1.1 GO: G2 8) What is the carbon nucleophile which attacks molecular bromine in the acid-catalyzed αbromination of a ketone? A) an enolate B) a Grignard reagent C) an acetylide D) a carbocation E) an enol Answer: E Section: 20.2 LO: 20.1.1 GO: G2 9) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 20.2 LO: 20.1.1 GO: G2

10) What product results when an aldol is dehydrated? A) conjugated alkyne B) β-diketone C) β-ketoester D) α,β-unsaturated aldehyde E) β,γ-unsaturated aldehyde Answer: D Diff: 2 Section: 20.2 LO: 20.1.1 GO: G2 MCAT LO: MCAT22.4 11) Which of the following reagents will quantitatively convert an enolizable ketone to its enolate salt? A) lithium hydroxide B) lithium diisopropylamide C) methyllithium D) diethylamine E) pyridine Answer: B Diff: 1 Section: 20.3 LO: 20.2.7 GO: G2 MCAT LO: MCAT22.1

12) When 2-methylcyclohexanone is treated with catalytic base in excess D2O, how many deuterium atoms become incorporated in the organic compound? A) 0 B) 1 C) 2 D) 3 E) 5 Answer: D Diff: 2 Section: 20.3 LO: 20.1.1 GO: G2 MCAT LO: MCAT22.1

13) Provide the structure of lithium diisopropylamide. Answer: [(CH3)2CH]2N- Li+ Diff: 2 Section: 20.3 LO: 20.1.1 GO: G2 14) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 20.3 LO: 20.2.4 GO: G2 15) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 20.3 LO: 20.2.4 GO: G2

16) An enolate attacks an aldehyde and the resulting product is subsequently protonated. What type of reaction is this? A) a Fischer esterification B) an acid-catalyzed aldol condensation C) a base-mediated aldol condensation D) a Hell-Volhard-Zelinsky reaction E) a Selman-Jones reaction Answer: C Diff: 1 Section: 20.3 LO: 20.2.4 GO: G2 MCAT LO: MCAT22.4 17) The aldol condensation is ________. A) an irreversible reaction B) an equilibrium reaction C) a tautomerization D) an isomerization E) a type of esterification Answer: B Diff: 1 Section: 20.3 LO: 20.2.4 GO: G1 MCAT LO: MCAT22.4 18) Provide the structure of the major organic product which results when PhCH2CHO is treated with NaOH. Answer:

Diff: 2 Section: 20.3 LO: 20.2.4 GO: G2 MCAT LO: MCAT22.4

19) Provide the structure of the aldol product that results when 5-methylhexanal is treated with hydroxide. Answer:

Diff: 2 Section: 20.3 LO: 20.2.4 GO: G2 MCAT LO: MCAT22.4 20) The following compound isolated from a marine sponge has been found to have antitubercular activity (Tet. Lett. 2007, 8851). Show how it may be constructed by an aldol reaction by drawing a structure of the starting material.

Answer:

Diff: 3 Section: 20.3 LO: 20.2.5 GO: G2 MCAT LO: MCAT22.4 21) What two organic starting materials are required to produce cinnamaldehyde via a crossed aldol condensation followed by dehydration? Answer: PhCHO and CH3CHO Diff: 2 Section: 20.3 7 Copyright © 2021 Pearson Education, Inc.

LO: 20.3.5 GO: G2 MCAT LO: MCAT22.4 22) Provide the structure of the product which results from the base-catalyzed condensation followed by dehydration between benzophenone and propanal. Answer:

Diff: 2 Section: 20.3 LO: 20.3.2 GO: G2 MCAT LO: MCAT22.4

23) What two molecules were condensed in an aldol reaction to produce Answer: (CH3)3CCHO and CH3COCH3 Diff: 2 Section: 20.3 LO: 20.3.5 GO: G2 MCAT LO: MCAT22.4 24) What two molecules were condensed in an aldol reaction to produce Answer: PhCHO and PhCOCH3 Diff: 2 Section: 20.3 LO: 20.3.5 GO: G2 MCAT LO: MCAT22.4

25) Provide the structure of the intramolecular aldol condensation/dehydration product that results when 2,6-heptanedione is heated in base. Answer:

Diff: 2 Section: 20.3 LO: 20.3.5 GO: G2 MCAT LO: MCAT22.4 26) Name the aldol produced when butanal is treated with NaOH. Answer: 2-ethyl-3-hydroxyhexanal Diff: 2 Section: 20.3 LO: 20.3.2 GO: G2 MCAT LO: MCAT22.4 27) Predict the outcome of the following reaction.

Answer:

Diff: 3 Section: 20.3 LO: 20.3.2 GO: G2 MCAT LO: MCAT22.4

28) Provide the major organic product of the following reaction.

Answer:

Diff: 3 Section: 20.3 LO: 20.3.2 GO: G2 MCAT LO: MCAT22.4

29) Provide the structure of the ester that would undergo self-condensation to yield the shown below.

Answer:

Diff: 2 Section: 20.4 LO: 20.5.1 GO: G2 30) Provide the structure of the Claisen product in the self condensation of methyl phenylacetate. Answer:

Diff: 2 Section: 20.4 LO: 20.5.1 GO: G2 31) Name the product which results when ethyl butanoate is treated with sodium ethoxide followed by neutralization. Answer: Ethyl 2-ethyl-3-oxohexanoate Diff: 3 Section: 20.4 LO: 20.5.1 GO: G2

32) Provide the major organic product of the following reactions.

Answer:

33) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 20.4 LO: 20.5.1 | 20.5.5 GO: G2 34) Predict the structure of the expected product of the following reaction.

Answer:

Diff: 3 Section: 20.4 LO: 20.5.1 | 20.5.5 GO: G2 35) Which of the following is least likely to undergo a smooth crossed Claisen condensation with methyl pentanoate? A) (CH3)3CCO2CH3 B) PhCH2CO2CH3 C) PhCO2CH3 D) HCO2CH3 E) (CH3O)2CO Answer: B Diff: 2 12 Copyright © 2021 Pearson Education, Inc.

Section: 20.4 LO: 20.5.4 GO: G2

36) What additional starting material is needed to complete the following transformation?

Answer: methyl propanoate Diff: 2 Section: 20.4 LO: 20.5.4 GO: G2 37) What two starting materials yield OHCCH2CO2CH2CH3 as the crossed Claisen condensation product? Answer: HCO2CH2CH3 and CH3CO2CH2CH3 Diff: 2 Section: 20.4 LO: 20.5.4 GO: G2 38) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 20.5 LO: 20.2.4 GO: G2 MCAT LO: MCAT22.2

39) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 20.5 LO: 20.2.4 GO: G2 MCAT LO: MCAT22.2 40) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 20.5 LO: 20.2.4 GO: G2 MCAT LO: MCAT22.2

41) What product results when malonic ester is treated with the following sequence of reagents:

Answer: PhCH2CH2CO2H Diff: 2 Section: 20.5 LO: 20.6.1 GO: G2 MCAT LO: MCAT22.5 42) Provide the major organic product of the following reaction sequence.

Answer:

Diff: 2 Section: 20.5 LO: 20.2.4 GO: G2 MCAT LO: MCAT22.5 43) Provide the major organic product of the following reaction.

MCAT LO: MCAT22.5 44) Which of the following will react most slowly with an enamine? A) isopropyl chloride B) methyl bromide C) acetyl chloride D) benzyl chloride E) allyl bromide Answer: A Diff: 1 Section: 20.6 LO: 20.7.1 GO: G2 MCAT LO: MCAT22.2 45) What type of product results when 3-pentanone reacts with dimethylamine? A) enolate B) enol C) amide D) imine E) enamine Answer: E Diff: 2 Section: 20.6 LO: 20.7.2 GO: G2 MCAT LO: MCAT22.2

46) What iminium salt is produced in the reaction shown below?

Answer:

Diff: 2 Section: 20.6 LO: 20.7.3 GO: G2 MCAT LO: MCAT22.2 47) Provide the major organic product of the reaction shown below.

Answer: 2-acetylcyclohexanone Diff: 2 Section: 20.6 LO: 20.7.3 GO: G2 MCAT LO: MCAT22.2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 21 Conjugated Systems 1: Stability and Addition Reactions 1) What descriptive term is applied to the type of diene represented by 2,4-hexadiene? A) conjugated diene B) cumulated diene C) isolated diene D) alkynyl diene E) none of the above Answer: A Diff: 1 Section: 21.1 LO: 21.0.1 GO: G2 2) What descriptive term is applied to the type of diene represented by 1,5-octadiene? A) conjugated diene B) cumulated diene C) isolated diene D) alkynyl diene E) none of the above Answer: C Diff: 1 Section: 21.1 LO: 21.0.1 GO: G2 3) What descriptive term is applied to the type of diene shown?

A) conjugated diene B) cumulated diene C) isolated diene D) alkynyl diene E) none of the above Answer: C Diff: 1 Section: 21.1 LO: 21.0.1 GO: G2

4) Rank the following dienes in order of increasing stability: trans-1,3-pentadiene, cis-1,3pentadiene, 1,4-pentadiene, and 1,2-pentadiene. Answer: 1,2-pentadiene < 1,4-pentadiene < cis-1,3-pentadiene < trans-1,3-pentadiene Diff: 2 Section: 21.2 LO: 21.1.2 GO: G2 MCAT LO: MCAT7.6 5) When (S)-3-bromopent-1-ene is heated in water, which of the following compounds is not produced? A) (S)-pent-1-en-3-ol B) (R)-pent-1-en-3-ol C) pent-4-en-1-ol D) (E)-pent-2-en-1-ol E) (Z)-pent-2-en-1-ol Answer: C Diff: 2 Section: 21.2 LO: 21.5.1 GO: G2 MCAT LO: MCAT15.2 6) Which of the following alkyl halides yields the most stable carbocation intermediate during solvolysis in hot ethanol? A) methyl iodide B) (S)-2-bromopentane C) (R)-2-bromopentane D) (S)-3-bromopent-1-ene E) 1-chlorobutane Answer: D Diff: 2 Section: 21.2 LO: 21.1.2 GO: G2 MCAT LO: MCAT15.2 7) When 3-bromobut-1-ene is heated in a good ionizing solvent, reactions occur through a carbocation intermediate. Draw all reasonable resonance contributors of this cation and indicate which is the major contributor. Answer:

GO: G2 MCAT LO: MCAT15.2 8) When 3-bromo-1-methylcyclohexene is heated in a good ionizing solvent, reactions occur through a carbocation intermediate. Draw all reasonable resonance contributors of this cation and indicate which is the major contributor. Answer:

Diff: 3 Section: 21.2 LO: 21.1.2 GO: G2 MCAT LO: MCAT15.2 9) Name the two major products which are formed when solvolysis in hot methanol. Answer: 3-methoxy-1-methylcyclohexene and 3-methoxy-3-methylcyclohexene Diff: 3 Section: 21.2 LO: 21.1.2 GO: G2 MCAT LO: MCAT15.2 10) Provide the two major organic products of the following reaction.

Answer:

Diff: 2 Section: 21.2 LO: 21.1.2 GO: G2 MCAT LO: MCAT15.2

undergoes

11) What is the major organic product which results when cycloheptene is irradiated in the presence of N-bromosuccinimide? A) 1-bromocycloheptene B) 2-bromocycloheptene C) 1,2-dibromocycloheptane D) 3-bromocycloheptene E) 4-bromocycloheptene Answer: D Diff: 1 Section: 21.2 LO: 21.1.2 GO: G2 MCAT LO: MCAT15.2 12) Including all possible stereoisomeric forms, how many distinct allylic bromides could be produced when 2-methylpent-1-ene is treated with NBS under irradiation by a sunlamp? A) 2 B) 3 C) 4 D) 5 E) 6 Answer: D Diff: 3 Section: 21.2 LO: 21.1.3 GO: G2 MCAT LO: MCAT15.2 13) How many nodes, other than the node coincident with the molecular plane, are found in the highest energy π MO of A) 0 B) 1 C) 2 D) 3 E) none of the above Answer: D Diff: 2 Section: 21.3 LO: 21.2.2 GO: G2 MCAT LO: MCAT15.1

14) In the allyl radical, which π molecular orbital is singly occupied? A) The bonding π molecular orbital. B) The nonbonding π molecular orbital. C) The antibonding π molecular orbital. D) None of the above. Answer: B Diff: 2 Section: 21.3 LO: 21.2.1 GO: G2 MCAT LO: MCAT15.1 15) How many electrons are present in the nonbonding π molecular orbital of the allyl anion? A) 0 B) 1 C) 2 D) 3 E) 4 Answer: C Diff: 2 Section: 21.3 LO: 21.2.1 GO: G2 MCAT LO: MCAT15.1

16) Absorption of UV-visible energy by a molecule results in ________. A) vibrational transitions B) electronic transitions C) rotational transitions D) nuclear transitions E) none of the above Answer: B Diff: 1 Section: 21.3 LO: 21.3.1 GO: G2

17) Which of the following compounds absorbs the longest wavelength of UV-visible light? A) (E)-but-2-ene B) (Z)-but-2-ene C) hex-1-ene D) (Z)-1,3-hexadiene E) (E)-1,3,5-hexatriene Answer: E Diff: 1 Section: 21.3 LO: 21.3.1 GO: G2 MCAT LO: MCAT15.3 18) UV spectroscopy measures the energy required to promote an electron from the ________ molecular orbital to the ________ molecular orbital. A) highest occupied, lowest unoccupied B) lowest occupied, lowest unoccupied C) lowest occupied, highest unoccupied D) highest occupied, highest unoccupied E) None of the above Answer: A Diff: 1 Section: 21.3 LO: 21.3.3 GO: G2 MCAT LO: MCAT15.6 19) How many nodes, other than the node coincident with the molecular plane, are present in the HOMO of 1,3,5-hexatriene? A) 1 B) 2 C) 3 D) 4 E) 5 Answer: B Diff: 2 Section: 21.3 LO: 21.2.2 GO: G2 MCAT LO: MCAT15.1

20) How many nodes, other than the node coincident with the molecular plane, are present in the LUMO of 1,3,5-hexatriene? A) 1 B) 2 C) 3 D) 4 E) 5 Answer: C Diff: 2 Section: 21.3 LO: 21.2.2 GO: G2 MCAT LO: MCAT15.1 21) In the UV-visible spectrum of (E)-1,3,5-hexatriene, the lowest energy absorption corresponds to a ________. A) σ to π transition B) σ to π* transition C) π to σ* transition D) σ to σ* transition E) π to π* transition Answer: E Diff: 2 Section: 21.3 LO: 21.3.3 GO: G2 MCAT LO: MCAT15.6 22) Given that 1,3-butadiene has a uv absorption of 217nm, predict the approximate absorption for the conjugated system in vitamin D3.

GO: G2 MCAT LO: MCAT15.3 23) Provide the structure of the major product which results from 1,4-addition of Br2 to the diene shown below.

Answer:

Diff: 1 Section: 21.4 LO: 21.5.1 GO: G2 MCAT LO: MCAT15.2 24) Provide the structure of the major product which results from 1,2-addition of HBr to the diene shown below.

Answer:

Diff: 2 Section: 21.4 LO: 21.5.1 GO: G2 MCAT LO: MCAT15.2

25) When 1 mole of anhydrous HCl is reacted with excess 1,3-pentadiene, both the 1,2 and the 1,4-addition products are formed. Which of the following structures shown below is the least likely to be one of these products? (Note: When a chiral carbon is formed in this reaction a racemic mixture results, only one of the two possible enantiomers is shown.) A)

26) Draw structures for the two major products of the following reaction.

Answer:

Diff: 3 Section: 21.4 LO: 21.5.1 GO: G2 MCAT LO: MCAT15.2 27) What name is given to the type of "control" which arises in a reaction which does not achieve equilibrium and in which the product distribution is determined by the relative activation energies of the pathways which produced them? Answer: kinetic control Diff: 1 Section: 21.4 LO: 21.5.3 GO: G1 MCAT LO: MCAT15.2 28) Draw the structure of the major product which results when the diene shown is treated with HBr at 40°C.

Answer:

Diff: 2 Section: 21.4 LO: 21.5.1 GO: G2 MCAT LO: MCAT15.2

29) Draw the structure of the major product which results when the diene shown is treated with HBr at -80°C.

Answer:

Diff: 2 Section: 21.4 LO: 21.5.1 GO: G2 MCAT LO: MCAT15.2 30) In the diene shown below, there are two possible double bonds that could react when 1 eq. of HBr is added. However, the double bond labeled "A" reacts preferentially to give the major product. Using resonance structures, justify this observation.

Answer:

When double bond A reacts, the carbocation is 2° and 3°, while when B reacts the resulting carbocation is less stable (2° and 2° only) Diff: 3 Section: 21.4 LO: 21.5.1 11 Copyright © 2021 Pearson Education, Inc.

GO: G2 MCAT LO: MCAT15.2 31) In the Michael reaction, addition to the α,β-unsaturated carbonyl occurs in a ________. A) 1,2-fashion B) 1,3-fashion C) 1,4-fashion D) 1,5-fashion E) Diels-Alder reaction Answer: C Diff: 1 Section: 21.5 LO: 21.6.1 GO: G2 32) Which of the following is a nucleophile that does conjugate additions? A) CH2 CHCHO B) CH2 CHCN C) CH2 CHCO2CH3 D) CH3CH2MgBr E) (CH3)2CuLi Answer: E Diff: 1 Section: 21.5 LO: 21.6.3 GO: G2 33) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 21.5 LO: 21.6.7 GO: G2

34) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 21.5 LO: 21.6.7 GO: G2 35) Complete the following reaction by filling in the necessary reagents.

Answer:

Diff: 3 Section: 21.5 LO: 21.6.7 GO: G2 36) Predict the starting materials necessary for the following Robinson annulation.

Answer:

37) The following structure was used in the synthesis of a complex natural product shown to have cytotoxic activity (Org. Lett. 2006, 5585). Show how this structure may be constructed by a Robinson annulation by indicating the necessary starting materials.

Answer:

Diff: 3 Section: 21.5 LO: 21.6.7 GO: G2

38) Draw a correct structure of the expected product for the following reaction.

Answer:

Diff: 3 Section: 21.5 LO: 21.6.7 GO: G2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 22 Conjugated Systems 2: Pericyclic Reactions 1) When the relative energies of the s-cis and s-trans conformers of 1,3-butadiene are compared, one finds that ________. A) the s-cis conformer is lower in energy than the s-trans B) the s-trans conformer is lower in energy than the s-cis C) the two conformers are of equal energy Answer: B Diff: 1 Section: 22.3 LO: 22.1.3 GO: G2

2) Draw (Z)-1,3-hexadiene in its s-trans conformation. Answer:

Diff: 2 Section: 22.3 LO: 22.1.3 GO: G2 3) When 1,3-butadiene reacts with CH2 CHCN, which of the terms below best describes the product mixture? A) a mixture of two diastereomers B) a single compound C) a racemic mixture D) optically active E) a mixture of bicyclic compounds Answer: C Diff: 1 Section: 22.3 LO: 22.1.2 GO: G2

4) Provide the structure of the major organic product in the following reaction.

Answer:

Diff: 1 Section: 22.3 LO: 22.1.6 GO: G2 5) What diene and dienophile would react to give the product below?

Answer:

Diff: 1 Section: 22.3 LO: 22.1.9 GO: G2

6) What diene and dienophile would react to give the product below?

Answer:

Diff: 1 Section: 22.3 LO: 22.1.9 GO: G2 7) The Diels-Alder reaction is a concerted reaction; this means ________. A) a mixture of endo and exo products are formed B) all bond making and bond breaking occurs simultaneously C) the products contain rings D) the reaction follows Markovnikov's rule E) the reaction is highly endothermic Answer: B Diff: 2 Section: 22.3 LO: 22.1.1 GO: G2 8) Which of the following compounds is the most reactive dienophile in a Diels-Alder reaction with 1,3-butadiene? A) CH2 CHOCH3 B) CH2 CHCHO C) CH3CH CHCH3 D) (CH3)2C CH2 E) CH2 CH2 Answer: B Diff: 2 Section: 22.3 LO: 22.1.4 GO: G2

9) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 22.3 LO: 22.1.6 GO: G2 10) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 22.3 LO: 22.1.6 GO: G2

11) What diene and dienophile are used in the Diels-Alder route to the compound shown?

Answer:

Diff: 2 Section: 22.3 LO: 22.1.9 GO: G2 12) What diene and dienophile are used in the Diels-Alder route to the compound shown?

Answer:

Diff: 2 Section: 22.3 LO: 22.1.9 GO: G2

13) Provide the structure of the major organic product in the following reaction.

Answer:

Diff: 2 Section: 22.3 LO: 22.1.6 GO: G2

14) Provide the structure of the major organic product in the following reaction.

Answer:

Diff: 2 Section: 22.3 LO: 22.1.6 GO: G2

15) What diene and dienophile would react to give the product below?

Answer:

Diff: 2 Section: 22.3 LO: 22.1.9 GO: G2

16) What diene and dienophile would react to give the product below?

Answer:

Diff: 2 Section: 22.3 LO: 22.1.9 GO: G2

17) What diene and dienophile would react to give the product below?

Answer:

Diff: 2 Section: 22.3 LO: 22.1.9 GO: G2 18) Which sequence correctly ranks the following dienes in order of increasing reactivity in the Diels-Alder reaction?

A) 1 < 2 < 3 B) 2 < 3 < 1 C) 3 < 1 < 2 D) 3 < 2 < 1 Answer: D Diff: 2 Section: 22.3 LO: 22.1.4 GO: G2

19) Provide the structure of the major organic product in the following reaction.

Answer:

Diff: 2 Section: 22.3 LO: 22.1.6 GO: G2 20) Provide the structure of the major organic product in the following reaction.

Answer:

Diff: 2 Section: 22.3 LO: 22.1.6 GO: G2

21) Provide the structure of the major organic product in the following reaction.

Answer:

Diff: 2 Section: 22.3 LO: 22.1.6 GO: G2 22) Provide the structure of the major organic product in the following reaction.

Answer:

LO: 22.1.6 GO: G2 23) According to the 1,3-butadiene structure below, which positions would be best to place methoxy groups to yield the most reactive dimethoxy-1,3-butadiene isomer in the Diels-Alder reaction?

A) c and d B) a and c C) b and c D) a and d E) a and f Answer: D Diff: 3 Section: 22.3 LO: 22.1.4 GO: G2 24) Provide the major organic product of the following reaction.

Answer:

Diff: 3 Section: 22.3 LO: 22.1.6 GO: G2

25) Provide the major organic product of the following reaction.

Answer:

Diff: 3 Section: 22.3 LO: 22.1.6 GO: G2

26) Provide the major organic product of the following reaction.

Answer:

Diff: 3 Section: 22.3 LO: 22.1.6 GO: G2

27) Provide the major organic product of the following reaction.

Answer:

Diff: 3 Section: 22.3 LO: 22.1.6 GO: G2 28) Provide the major organic product of the following reaction.

Answer:

Diff: 3 Section: 22.3 LO: 22.1.6 GO: G2

29) Provide the major organic product of the following reaction.

Answer:

Diff: 3 Section: 22.3 LO: 22.1.6 GO: G2 30) Assuming kinetic conditions, provide the correct stereochemistry and regiochemistry of the major product of the following reaction.

Answer:

Diff: 3 Section: 22.3 LO: 22.1.6 GO: G2 31) Provide the structure of the major organic product in the following reaction.

Answer:

32) Provide the structure of the major organic product in the following reaction.

Answer:

Diff: 3 Section: 22.3 LO: 22.1.6 GO: G2 33) Dicylopentadiene results when cyclopentadiene reacts with itself in a Diels-Alder reaction. Provide the structure of dicyclopentadiene. Pay particular attention to stereochemical detail. Answer:

Diff: 3 Section: 22.3 LO: 22.1.6 GO: G2 34) Which of the following terms best describes a Diels-Alder reaction? A) a [4+2] cycloaddition B) a [2+2] cycloaddition C) a sigmatropic rearrangement D) a 1,3-dipolar cycloaddition E) a substitution reaction Answer: A Diff: 1 Section: 22.4 LO: 22.2.3 GO: G2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 23 Benzene 1: Aromatic Stability and Substitution Reactions 1) Classify the following compound as aromatic, antiaromatic, or nonaromatic.

Answer: Aromatic Diff: 3 Section: 23.3 LO: 23.2.1 GO: G2 2) Classify the following compound as being aromatic, nonaromatic or antiaromatic.

Answer: antiaromatic (8 electrons) Diff: 3 Section: 23.3 LO: 23.2.1 GO: G2 3) Aromatic molecules contain ________ π electrons. A) no B) 4n + 1 (with n an integer) C) 4n + 2 (with n an integer) D) 4n (with n an integer) E) unpaired Answer: C Diff: 1 Section: 23.3 LO: 23.1.1 GO: G1

4) Classify 1,3,5-heptatriene as aromatic, antiaromatic, or nonaromatic. Assume planarity of the π network. Answer: nonaromatic Diff: 1 Section: 23.3 LO: 23.2.1 GO: G2

5) Classify cycloheptatriene as aromatic, antiaromatic, or nonaromatic. Assume planarity of the π network. Answer: nonaromatic Diff: 2 Section: 23.3 LO: 23.2.1 GO: G2 6) Classify cyclopentadiene as aromatic, antiaromatic, or nonaromatic. Assume planarity of the π network. Answer: nonaromatic Diff: 2 Section: 23.3 LO: 23.2.1 GO: G2

7) Which of the following structures, if flat, would be classified as antiaromatic? A)

Answer: C Diff: 2 Section: 23.3 LO: 23.2.1 GO: G2

8) Classify the compound below as aromatic antiaromatic, or nonaromatic. Assume planarity of the π network.

Answer: aromatic Diff: 3 Section: 23.3 LO: 23.2.1 GO: G2

9) Classify the compound below as aromatic, antiaromatic, or nonaromatic. Assume planarity of the π network.

Answer: aromatic Diff: 1 Section: 23.3 LO: 23.2.1 GO: G2

10) Which of the following structures is aromatic? A)

Answer: A Diff: 2 Section: 23.3 LO: 23.2.1 GO: G2

11) Provide the structure of sodium cyclopentadienide. Answer:

Diff: 2 Section: 23.3 LO: 8.1.7 | 23.2.1 GO: G2 MCAT LO: MCAT16.4 12) Provide the major resonance structures of the ion which results when the most acidic hydrogen of cyclopentadiene is lost. Answer:

Diff: 2 Section: 23.3 LO: 8.1.7 | 23.2.1 GO: G2 MCAT LO: MCAT16.5

13) Classify the compound below as aromatic, antiaromatic, or nonaromatic. Assume planarity of the π network.

Answer: aromatic Diff: 2 Section: 23.3 LO: 23.2.1 GO: G2 14) Classify the compound below as aromatic, antiaromatic, or nonaromatic. Assume planarity of the π network.

Answer: antiaromatic Diff: 2 Section: 23.3 LO: 23.2.1 GO: G2 15) Classify the compound below as aromatic, antiaromatic, or nonaromatic. Assume planarity of the π network.

Answer: antiaromatic Diff: 2 Section: 23.3 LO: 23.2.1 GO: G2

16) Which of the labeled H atoms (1 -5) in the following molecule would be predicted to be the most acidic?

A) 1 B) 2 C) 3 D) 4 E) 5 Answer: A Diff: 3 Section: 23.3 LO: 23.1.4 GO: G2 MCAT LO: MCAT16.5 17) Which sequence ranks the indicated protons in order of increasing acidity?

MCAT LO: MCAT16.5 18) Which sequence ranks the indicated protons in order of increasing acidity?

A) 1 < 2 < 3 B) 2 < 3 < 1 C) 3 < 1 < 2 D) 3 < 2 < 1 Answer: D Diff: 3 Section: 23.3 LO: 23.1.4 GO: G2 MCAT LO: MCAT16.5 19) Classify pyrrole as aromatic, antiaromatic, or nonaromatic. Assume planarity of the π network. Answer: aromatic Diff: 2 Section: 23.3 LO: 23.2.1 GO: G2

20) Classify the compound below as aromatic, antiaromatic, or nonaromatic. Assume planarity of the π network.

Answer: aromatic Diff: 3 Section: 23.3 LO: 23.2.1 GO: G2

21) Classify the compound below as aromatic, antiaromatic, or nonaromatic. Assume planarity of the π network.

Answer: aromatic Diff: 3 Section: 23.3 LO: 23.2.1 GO: G2 22) Classify the compound below as aromatic, antiaromatic, or nonaromatic. Assume planarity of the π network.

Answer: aromatic Diff: 2 Section: 23.3 LO: 23.2.1 GO: G2 23) Classify the compound below as aromatic, antiaromatic, or nonaromatic. Assume planarity of the π network.

Answer: aromatic Section: 23.3 LO: 23.2.1 GO: G2 Diff: 2

24) In the molecular orbital representation of benzene, how many π molecular orbitals are present? A) 1 B) 2 C) 4 D) 6 E) 8 Answer: D Diff: 1 Section: 23.4 LO: 23.2.1 GO: G2 MCAT LO: MCAT16.1 25) How many distinct nodal planes which are perpendicular to the molecular plane are present in the π4* orbital of benzene? A) 0 B) 1 C) 2 D) 4 E) 5 Answer: C Diff: 2 Section: 23.4 LO: 23.3.1 GO: G2 MCAT LO: MCAT16.1 26) How many pairs of degenerate π molecular orbitals are found in benzene? A) 6 B) 5 C) 4 D) 3 E) 2 Answer: E Diff: 2 Section: 23.4 LO: 23.3.1 GO: G2 MCAT LO: MCAT16.1

27) How many distinct trichlorobenzene isomers are possible? A) 2 B) 3 C) 4 D) 5 E) 6 Answer: B Diff: 1 Section: 23.5 LO: 8.1.7 | 23.4.3 GO: G2 MCAT LO: MCAT16.4 28) Which of the following is also an acceptable name for 3-nitrophenol? A) o-nitrophenol B) m-nitrophenol C) p-nitrophenol D) 3-cresol E) hydroquinone Answer: B Diff: 1 Section: 23.5 LO: 23.4.1 | 23.4.2 GO: G2 MCAT LO: MCAT16.4 29) Provide an acceptable name for the compound below.

Answer: 1,3,5-trinitrobenzene Diff: 1 Section: 23.5 LO: 23.4.1 GO: G2 MCAT LO: MCAT16.4

30) Provide an acceptable name for the compound below.

Answer: para-dichlorobenzene or 1,4-dichlorobenzene Diff: 1 Section: 23.5 LO: 23.4.1 | 23.4.2 GO: G2 MCAT LO: MCAT16.4 31) Provide an acceptable name for the compound below.

Answer: ortho-xylene or 1,2-dimethylbenzene Diff: 1 Section: 23.5 LO: 23.4.1 | 23.4.2 GO: G2 MCAT LO: MCAT16.4 32) Provide an acceptable name for the compound below.

Answer: aniline or aminobenzene or benzeneamine Diff: 2 Section: 23.5 LO: 23.4.1 GO: G2 MCAT LO: MCAT16.4

33) Provide an acceptable name for the compound below.

Answer: 2,4-dinitrotoluene Diff: 2 Section: 23.5 LO: 23.4.1 GO: G2 MCAT LO: MCAT16.4 34) Provide the structure of m-nitrophenol. Answer:

Diff: 2 Section: 23.5 LO: 23.4.3 GO: G2 MCAT LO: MCAT16.4 35) Provide the structure of anisole. Answer:

Diff: 2 Section: 23.5 LO: 23.4.3 GO: G2 MCAT LO: MCAT16.4 36) Provide the structure of 2-bromo-4-chlorobenzoic acid. Answer:

MCAT LO: MCAT16.4 37) Provide the structure of 4-isopropylbenzaldehyde. Answer:

Diff: 2 Section: 23.5 LO: 23.4.3 GO: G2 MCAT LO: MCAT16.4 38) Correctly name the following compound.

Answer: 2-bromo-5-nitrotoluene Diff: 2 Section: 23.5 LO: 23.4.1 GO: G2 MCAT LO: MCAT16.4 39) Which step in an electrophilic aromatic substitution reaction is typically rate determining, formation of the sigma complex or loss of H+ by the sigma complex to form the product? Explain. Answer: Formation of the sigma complex is typically rate determining. This endothermic step goes through a high energy transition state on the path from an aromatic starting material to a nonaromatic, carbocationic intermediate. Diff: 2 Section: 23.7 LO: 23.5.6 GO: G2

40) Under what reaction conditions does the electrophilic chlorination of aromatic compounds usually occur? A) Cl2, AlCl3 B) Cl2, H2O C) Cl2, CCl4 D) NaCl, H2O E) NaCl, CH3OH Answer: A Diff: 1 Section: 23.7 LO: 23.5.4 GO: G2 41) Which of the following is an incorrect statement about the bromination of benzene by Br2 and FeBr3? A) FeBr3 functions to increase the electrophilicity of Br2. B) Formation of the sigma complex is the rate-determining step of the mechanism. C) The carbanionic intermediate is resonance stabilized. D) There is one carbon-containing intermediates in the mechanism. E) The final step of the mechanism is loss of H+. Answer: C Diff: 2 Section: 23.7 LO: 23.5.6 GO: G2 42) Which of the following species is attacked by benzene in the electrophilic nitration reaction? A) HNO3 B) NO2+ C) NO2 D) NO+ E) N3Answer: B Diff: 1 Section: 23.7 LO: 23.5.1 GO: G2

43) Draw the two major resonance structures of the acylium ion which results when butanoyl chloride is treated with AlCl3. Answer: Diff: 2 Section: 23.7 LO: 23.5.6 GO: G2 44) Provide the structure of the major organic product(s) in the following reaction.

Answer:

Diff: 1 Section: 23.8 LO: 23.5.4 GO: G2 45) Which of the following compounds will react most rapidly when treated with CH3CH2Cl and AlCl3? A) benzene B) chlorobenzene C) nitrobenzene D) anisole E) toluene Answer: D Diff: 2 Section: 23.8 LO: 23.5.3 GO: G2

46) Which sequence correctly ranks the following aromatic rings in order of increasing rate of reactivity with chlorine and aluminum chloride?

A) 1 < 2 < 3 B) 2 < 3 < 1 C) 3 < 2 < 1 D) 2 < 1 < 3 E) 1 < 3 < 2 Answer: E Diff: 2 Section: 23.8 LO: 23.5.3 GO: G2 47) Which of the following is an intermediate in the bromination of toluene? A)

48) Which sequence correctly ranks the following aromatic rings in order of increasing rate of reactivity in an electrophilic aromatic substitution reaction?

A) 1 < 2 < 3 B) 2 < 3 < 1 C) 3 < 1 < 2 D) 2 < 1 < 3 Answer: D Diff: 2 Section: 23.8 LO: 23.5.3 GO: G2 49) Derivatives of the compound shown below are currently being examined for their effectiveness in treating drug addiction and metabolic syndrome (J. Med. Chem. 2006, 872). Which sequence ranks the following aromatic rings of this compound in order of increasing reactivity in an electrophilic aromatic substitution reaction (slowest to fastest reacting)?

A) 1 < 2 < 3 B) 2 < 3 < 1 C) 3 < 2 < 1 D) 3 < 1 < 2 E) 2 < 1 < 3 Answer: E Diff: 3 Section: 23.8 LO: 23.5.3 GO: G2

50) Draw the four major resonance structures of the sigma complex intermediate in the reaction of anisole with HNO3/H2SO4 to yield p-nitroanisole. Answer:

Diff: 3 Section: 23.8 LO: 23.5.6 GO: G2 MCAT LO: MCAT17.1 51) Provide the structure of the major organic product(s) in the following reaction.

Answer:

Diff: 1 Section: 23.8 LO: 23.5.4 GO: G2

52) Which of the following compounds will not undergo Friedel-Crafts acylation when treated with A) toluene B) p-xylene C) anisole D) ethoxybenzene E) benzophenone Answer: E Diff: 2 Section: 23.8 LO: 23.5.3 GO: G2

53) Rank the following compounds in order of increasing reactivity towards chlorination with Cl2/AlCl3 (slowest reacting to fastest).

A) 3 < 4 < 2 < 1 < 5 B) 2 < 4 < 1 < 3 < 5 C) 4 < 2 < 1 < 3 < 5 D) 2 < 4 < 5 < 1 < 3 E) 2 < 4 < 1 < 5 < 3 Answer: E Diff: 2 Section: 23.8 LO: 23.5.3 GO: G2 54) Provide the major organic product of the following reaction.

Answer:

GO: G2 55) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2 56) Provide the structure of the major mononitration product of the compound below.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2

57) Draw the three major resonance structures of the sigma complex intermediate in the reaction of acetophenone with HNO3/H2SO4 to yield o-nitroacetophenone. Circle the resonance form which is less stable than the other two. Answer:

Diff: 3 Section: 23.8 LO: 23.5.4 | 23.5.6 GO: G2 MCAT LO: MCAT17.1 58) Provide the structure of the major organic product(s) in the following reaction.

Answer:

Diff: 1 Section: 23.8 LO: 23.5.4 GO: G2 59) Which of the following compounds undergoes reaction with HNO3/H2SO4 at the fastest rate? A) ethylbenzene B) benzenesulfonic acid C) nitrobenzene D) chlorobenzene E) acetophenone Answer: A Diff: 2 Section: 23.8 LO: 23.5.3 GO: G2 23 Copyright © 2021 Pearson Education, Inc.

60) Provide the major organic product(s) of the reaction shown below.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2 61) Provide the major organic product(s) of the reaction shown below.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2

62) Provide the major organic product(s) of the reaction shown below.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2 63) Provide the major organic product(s) of the reaction shown below.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2

64) Rank the following groups in order of increasing activating power in electrophilic aromatic substitution reactions: -Br. Answer: -Br < -CH2CH3 < -OCOCH2CH3 < -OCH3 Diff: 2 Section: 23.8 LO: 23.5.3 GO: G2

65) Provide the structure of the major mononitration product(s) of the compound below.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2

66) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2 67) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2

68) Provide the major organic product that results when benzene is treated with the following sequence of reagents: 1. CH3COCl, AlCl3 2. Br2, FeBr3. Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2

69) Provide the major organic product(s) of the reaction shown below.

Answer:

Diff: 2 Section: 17.9 LO: 17.3

70) Provide the structure of the major monoitration product of the compound below.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2 71) Provide the structure of the major mononitration product(s) of the compound below.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2 72) Provide the structure of the major mononitration product of the compound below.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2

73) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2 74) Provide the major organic product of the following reaction.

Answer:

75) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2

76) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2

77) Provide the major organic product of the following reaction.

Answer:

Diff: 3 Section: 23.8 LO: 23.5.4 GO: G2

78) Show what reagents are needed to complete the transformation below.

Answer: 1) Cl2 / hν 2) AlCl3 Diff: 3 Section: 23.8 LO: 23.6.7 GO: G2

79) Provide the structure of the major organic product of the following reaction.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2 80) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2

81) Which of the following compounds would most likely be used in the preparation of isobutylbenzene from benzene? A) (CH3)2CHCOCl B) (CH3)2CHCH2Cl C) (CH3)2CHCH2Br D) CH3CH2CH2CH2Cl E) CH3CH2CH2COCl Answer: A Diff: 2 Section: 23.8 LO: 23.5.4 GO: G2 82) Which of the following compounds is least reactive in the nucleophilic aromatic substitution reaction with NaOH? A) 2,4-dinitrochlorobenzene B) m-nitrochlorobenzene C) o-nitrochlorobenzene D) p-nitrochlorobenzene E) 3,5-dinitrochlorobenzene Answer: B Diff: 2 Section: 23.9 LO: 23.7.5 GO: G2 83) When 2,4-dinitrochlorobenzene is treated with sodium hydroxide at 100°C followed by protonation ________. A) 2,4-dinitrophenol is formed via an addition-elimination nucleophilic aromatic substitution mechanism B) 2,4-dinitrophenol is formed via an elimination-addition nucleophilic aromatic substitution mechanism C) 3,5-dinitrophenol is formed via an elimination-addition nucleophilic aromatic substitution mechanism D) 3,5-dinitrophenol is formed via an electrophilic aromatic substitution mechanism E) 2,4-dinitrophenol is formed via an electrophilic aromatic substitution mechanism Answer: A Diff: 2 Section: 23.9 LO: 23.7.4 GO: G2

84) Provide the structures of the major organic products of the following reaction.

Answer:

Diff: 2 Section: 23.9 LO: 23.7.4 GO: G2

85) Provide the structures of the major organic products of the following reaction.

Answer:

Diff: 2 Section: 23.9 LO: 23.7.4 GO: G2 86) When o-fluorotoluene is treated with sodium amide, the product is ________. A) only o-toluidine B) only m-toluidine C) only p-toluidine D) a mixture of o- and p-toluidine E) a mixture of o- and m-toluidine. 35 Copyright © 2021 Pearson Education, Inc.

Answer: E Diff: 2 Section: 23.9 LO: 23.7.4 GO: G2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 24 Benzene 2: Reactions Influenced by the Aromatic Ring 1) Provide a common name for the following structure.

Answer: ortho-isopropylphenol Diff: 1 Section: 24.2 LO: 23.4.1 GO: G2 MCAT LO: MCAT10.1

2) Provide an acceptable name for the compound below.

Answer: meta-propylphenol or 3-propylphenol Diff: 2 Section: 24.2 LO: 23.4.1 GO: G2 MCAT LO: MCAT10.1

3) Explain why phenol is about 106 times more acidic than methanol. Use appropriate resonance structures as part of your explanation. Answer: The phenoxide ion is highly stabilized relative to methoxide through resonance delocalization of the negative charge into the aromatic ring. This stabilization makes phenoxide less reactive and a weaker base. The weaker the base, the stronger its conjugate acid.

Diff: 3 Section: 24.2 LO: 24.1.4 GO: G2 MCAT LO: MCAT10.2

4) Complete the following reaction by filling in the necessary reagents.

Answer:

Section: 24.2 LO: 24.2.3 | 24.2.5 GO: G2

5) Provide the structure of the major organic product in the following reaction.

Answer:

Diff: 3 Section: 24.2 LO: 24.2.3 | 24.2.5 GO: G2

6) Predict the major product from the following reaction:

Answer: A Diff: 3 Section: 24.3 LO: 24.3.2 GO: G2 MCAT LO: MCAT17.2

7) Provide the structure of the major organic product in the following reaction.

Answer:

Diff: 1 Section: 24.4 LO: 24.4.2 GO: G2 MCAT LO: MCAT17.2

8) Provide the structure of the major organic product in the following reaction.

Answer:

Diff: 2 Section: 24.5 LO: 24.5.1 GO: G2 MCAT LO: MCAT17.2

9) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 24.5 LO: 24.5.1 GO: G2 MCAT LO: MCAT17.2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 25 Amines: Structure, Reactions, and Synthesis 1) Which of the molecules below can be properly called an amine? A) CH3CN B) CH3COOH C) CH3CH2CH2OH D) CH3CH2NHCH3 E) CH3CH2CH2NO2 Answer: D Diff: 1 Section: 25.1 LO: 25.0.4 GO: G2 2) Provide the condensed structures of two structurally isomeric amines that contain two carbons. Answer: (CH3)2NH and CH3CH2NH2 Diff: 2 Section: 25.1 LO: 25.0.5 GO: G2 MCAT LO: MCAT3.2 3) Provide the structure of N-ethyl-1-butanamine. Answer: CH3CH2CH2CH2NHCH2CH3 Diff: 1 Section: 25.2 LO: 25.0.3 GO: G2 MCAT LO: MCAT19.1

Answer:

Diff: 1 Section: 25.2 LO: 25.0.3 GO: G2 MCAT LO: MCAT19.1

5) Provide the systematic name for the compound below. (CH3)4N+ClAnswer: tetramethylammonium chloride Diff: 1 Section: 25.2 LO: 25.0.2 GO: G2 MCAT LO: MCAT19.1 6) Provide the IUPAC name for the compound shown below.

Answer: 3,3-dimethyl-1-butanamine Diff: 2 Section: 25.2 LO: 25.0.2 GO: G2 MCAT LO: MCAT19.

7) Provide the name of (CH3CH2)4N+ Cl-. Answer: tetraethylammonium chloride Diff: 2 Section: 25.2 LO: 25.0.2 GO: G2 MCAT LO: MCAT19.1

8) Provide the name of the compound shown below.

Answer: 6-amino-1-methylcyclohexene Diff: 2 Section: 25.2 LO: 25.0.2 GO: G2 MCAT LO: MCAT19.1 9) Draw the structure of 2,3-dimethyl-2-butanamine Answer:

Diff: 2 Section: 25.2 LO: 25.0.3 GO: G2 MCAT LO: MCAT19.1 10) Draw the structure of N-propyl-4-methyl-3-octanamine. Answer:

Diff: 2 Section: 25.2 LO: 25.0.3 GO: G2 MCAT LO: MCAT19.1

11) Provide the systematic name for the compound below.

Answer: 4-aminocyclohexanone Diff: 2 Section: 25.2 LO: 25.0.2 GO: G2 MCAT LO: MCAT19.1

12) Provide the systematic name for the compound below.

Answer: 2-bromo-N-methylaniline Diff: 2 Section: 25.2 LO: 25.0.2 GO: G2 MCAT LO: MCAT19.1

13) Name the compound shown below.

Answer: 1-heptanamine or heptan-1-amine Diff: 2 Section: 25.2 LO: 25.0.2 GO: G2 MCAT LO: MCAT19.1

14) Which of the following is a tertiary amine? A) cyclohexylamine B) 3-pentanamine C) methylamine D) N,N-dimethylaniline E) N-ethyl-1-propanamine Answer: D Diff: 1 Section: 25.2 LO: 25.0.4 GO: G2 MCAT LO: MCAT19.1 15) Which of the following is a secondary amine? A) cyclohexylamine B) 3-pentanamine C) methylamine D) N,N-dimethylaniline E) N-ethyl-1-propanamine Answer: E Diff: 1 Section: 25.2 LO: 25.0.4 GO: G2 MCAT LO: MCAT19.1 16) Which of the following compounds is a 2° amine? A) cyclohexylamine B) t-butylamine C) N-ethylaniline D) N,N-diethylaniline E) N-butylpyridinium bromide Answer: C Diff: 1 Section: 25.2 LO: 25.0.4 GO: G2 MCAT LO: MCAT19.1

17) Which of the following amines is most soluble in water? A) pyrrolidine B) PhNH2 C) (CH3)3N D) (CH3CH2CH2)2NH E) ethylamine Answer: E Diff: 1 Section: 25.4 LO: 25.1.6 GO: G2 MCAT LO: MCAT19.1 18) Arrange the following compounds in order of increasing boiling point: CH3NHCH2CH3, CH3OCH2CH3, (CH3)3N, and CH3CH2CH2OH. Answer: (CH3)3N < CH3OCH2CH3 < CH3NHCH2CH3 < CH3CH2CH2OH Diff: 2 Section: 25.4 LO: 25.1.1 GO: G2 MCAT LO: MCAT19.4 19) Rank the following compounds in order of increasing boiling point (lowest to highest): triethylamine, cyclohexylamine, di-n-propylamine. Answer: triethylamine < di-n-propylamine < cyclohexylamine Diff: 2 Section: 25.4 LO: 25.1.1 GO: G2 MCAT LO: MCAT19.4

20) Provide the product of the reaction shown below.

Answer:

Diff: 2 Section: 25.4 LO: 25.1.4 | 25.4.1 GO: G2 MCAT LO: MCAT19.3 21) Which of the following amines is most basic? A) aniline B) N-ethylaniline C) N,N-diethylaniline D) piperidine E) pyrrole Answer: D Diff: 2 Section: 25.4 LO: 25.1.4 GO: G2 MCAT LO: MCAT19.3 22) Which of the following amines is the strongest base? A) cyclohexylamine B) pyrrole C) p-iodoaniline D) piperidine E) imidazole Answer: D Diff: 2 Section: 25.4 LO: 25.1.4 GO: G2 MCAT LO: MCAT19.3

23) Physostigmine is used in the treatment of glaucoma. Within this structure, the atom indicated by ________ is most basic, while atom ________ is least basic.

A) 1 (most basic), 4 (least basic) B) 1 (most basic), 3 (least basic) C) 2 (most basic), 4 (least basic) D) 2 (most basic), 3 (least basic) E) None of the above Answer: A Diff: 2 Section: 25.4 LO: 25.1.4 GO: G2 MCAT LO: MCAT19.3 24) The α-carbon atom bonded to the nitrogen of an alkylamine usually appears in what chemical shift (δ) range? A) 5-20 B) 30-50 C) 80-100 D) 120-150 E) 180-220 Answer: B Diff: 2 Section: 25.4 LO: 25.1.2 GO: G2 MCAT LO: MCAT19.2

25) A three-carbon, nitrogen-containing compound exhibits 3 13C NMR peaks (d 11.2, 27.3, and 44.9). Which of the following compounds best matches this spectral data? A) H2NCH2CH2CH2OH B) (CH3)2CHNH2 C) CH3NHCH2CH3 D) CH3CH2CH2NH2 E) CH3CH2C≡N Answer: D Diff: 2 Section: 25.4 LO: 25.1.2 GO: G2 MCAT LO: MCAT19.2 26) Provide the major organic product of the following reaction.

Answer: Diff: 2 Section: 25.5 LO: 25.2.2 GO: G2 27) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 25.5 LO: 25.3.1 GO: G2

28) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 1 Section: 25.6 LO: 25.4.2 GO: G2 MCAT LO: MCAT19.5 29) Provide the major organic compound in the following reaction.

Answer:

Diff: 2 Section: 25.6 LO: 25.4.2 GO: G2 MCAT LO: MCAT19.5

30) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 25.6 LO: 25.4.2 GO: G2 MCAT LO: MCAT19.5 31) What compound results from the reaction below?

A) imine B) amide C) primary amine D) quaternary ammonium salt E) nitrous acid Answer: D Diff: 2 Section: 25.6 LO: 25.4.2 GO: G2 MCAT LO: MCAT19.5

32) Which of the following is an intermediate in the mechanism for amide synthesis through acylation of an amine?

Answer: D Diff: 2 Section: 25.6 LO: 25.4.2 GO: G2

33) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 25.6 LO: 25.4.2 GO: G2 MCAT LO: MCAT19.5

34) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 25.6 LO: 25.4.2 GO: G2 MCAT LO: MCAT19.5

35) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 25.6 LO: 25.4.2 GO: G2 MCAT LO: MCAT19.5

36) Draw a structure for the expected product of the following reaction.

Answer:

Diff: 3 Section: 25.6 LO: 25.4.2 GO: G2 MCAT LO: MCAT19.5

37) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 25.6 LO: 25.4.2 GO: G2 MCAT LO: MCAT19.5 38) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 25.6 LO: 25.3.1 GO: G2 MCAT LO: MCAT19.5

39) Which of the following amines could be formed by reduction of an amide? 1) benzylamine 2) isopropylamine 3) aniline 4) triethylamine A) 1 B) 3 & 4 C) 1 & 4 D) 2 & 3 E) 1, 3, & 4 Answer: C Diff: 3 Section: 25.6 LO: 25.3.2 GO: G2 40) The final product is a derivative of Amonafide, a drug used to treat breast cancer (J. Med. Chem. 2007, 4122). Complete each step of the synthesis by filling in the necessary reagents.

Answer:

Diff: 3 Section: 25.6 LO: 25.3.4 GO: G2

41) When pentanal reacts with ethylamine under conditions of acid catalysis, the major organic product is ________. A) a ketone B) a nitrile C) an imine D) an oxime E) a hydrazone Answer: C Diff: 2 Section: 25.7 LO: 25.4.2 GO: G2 MCAT LO: MCAT19.5 42) When CH3CH2CHO reacts with PhNHNH2 under conditions of acid catalysis, the major organic product is ________. A) a ketone B) a nitrile C) an imine D) an oxime E) a hydrazone Answer: E Diff: 2 Section: 25.7 LO: 25.4.2 GO: G2 MCAT LO: MCAT19.5 43) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 25.7 LO: 25.4.2 GO: G2 MCAT LO: MCAT19.5

44) The Hofmann elimination proceeds via a(n) ________ pathway. A) E2 B) E1 C) SN1 D) SN2 E) none of the above Answer: A Diff: 1 Section: 25.7 LO: 25.4.5 GO: G2 45) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 25.7 LO: 25.4.2 | 25.4.5 GO: G2 MCAT LO: MCAT19.5 46) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 25.7 LO: 25.4.2 | 25.4.5 GO: G2 MCAT LO: MCAT19.5

47) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 25.7 LO: 25.4.2 | 25.4.5 GO: G2 MCAT LO: MCAT19.5 48) Compound A, C9H17N, is an optically inactive alkaloid, containing a tertiary amine that is not located at the bridgehead of the structures fused bicyclic ring system. Exhaustive alkylation of A with methyl iodide, followed by a Hofmann elimination reaction resulted in a racemic mixture of chiral tertiary amine products B, C10H19N. Provide a structure for A and one of the enantiomeric products B. Answer:

Diff: 3 Section: 25.7 LO: 25.4.2 | 25.4.5 GO: G2 MCAT LO: MCAT19.5

49) Provide the structure of the major organic product in the reaction below.

Answer: Diff: 3 Section: 25.7 LO: 25.4.2 | 25.4.5 GO: G2 MCAT LO: MCAT19.5 50) The following substrate is a starting material in the synthesis of compounds having opiod activity (J. Med. Chem. 2011, 957). Show all products that would result from the reaction below.

Answer:

Diff: 3 Section: 19.14 LO: 19.7 GO: G2, G5 MCAT LO: MCAT19.5 51) Heating a(n) ________ results in a Cope elimination. A) amine oxide B) imine C) enamine D) oxime E) quaternary ammonium salt Answer: A Diff: 1 Section: 25.7 LO: 25.4.2 | 25.4.7 GO: G2 MCAT LO: MCAT19.5 20 Copyright © 2021 Pearson Education, Inc.

52) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 25.7 LO: 25.4.2 | 25.4.7 GO: G2 MCAT LO: MCAT19.5 53) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 3 Section: 25.7 LO: 25.4.2 | 25.4.7 GO: G2 MCAT LO: MCAT19.5

54) Provide the major organic compound in the following reaction.

Answer:

Diff: 2 Section: 25.7 LO: 25.4.2 | 25.4.8 GO: G2 MCAT LO: MCAT19.5

55) Provide the major organic compound in the following reaction.

Answer:

56) Provide the major organic product of the following reaction.

Answer:

Diff: 2 Section: 25.7 LO: 25.4.2 | 25.4.8 GO: G2 MCAT LO: MCAT19.5 57) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 25.7 LO: 25.4.2 | 25.4.8 GO: G2 MCAT LO: MCAT19.5

58) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 25.7 LO: 25.4.2 | 25.4.8 GO: G2 MCAT LO: MCAT19.5 59) Provide the structure of the major organic product in the reaction below.

Answer:

Diff: 2 Section: 25.7 LO: 25.4.2 | 25.4.8 GO: G2 MCAT LO: MCAT19.5

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 26 Amino Acids, Proteins, and Peptide Synthesis 1) Peptide bonds are ________. A) ester linkages B) imido linkages C) ether linkages D) amide linkages E) disulfide linkages Answer: D Diff: 1 Section: 26.1 LO: 26.01 GO: G1 2) Which of the standard amino acids is achiral? A) lysine B) proline C) valine D) alanine E) glycine Answer: E Diff: 1 Section: 26.2 LO: 26.01 GO: G2 MCAT LO: MCAT24.1 3) How many standard amino acids are there? A) 4 B) 12 C) 20 D) 30 E) 64 Answer: C Diff: 1 Section: 26.2 LO: 26.01 GO: G2

4) Which of the following amino acids has its α-carbon as part of a 5-membered ring? A) proline B) tryptophan C) histidine D) tyrosine E) phenylalanine Answer: A Diff: 1 Section: 26.2 LO: 26.02 GO: G2 MCAT LO: MCAT24.1 5) Which of the following amino acids has a nonpolar side chain? A) serine B) aspartic acid C) asparagine D) threonine E) leucine Answer: E Diff: 1 Section: 26.2 LO: 26.02 GO: G2 MCAT LO: MCAT24.1, MCAT24.3 6) Which amino acid has a phenol in its side chain? A) tyrosine B) tryptophan C) isoleucine D) asparagine E) histidine Answer: A Diff: 1 Section: 26.2 LO: 26.02 GO: G2 MCAT LO: MCAT24.1

7) Which amino acid has an amide group in its side chain? A) tyrosine B) tryptophan C) isoleucine D) asparagine E) histidine Answer: D Diff: 1 Section: 26.2 LO: 26.02 GO: G2 MCAT LO: MCAT24.1

8) Which amino acid has an imidazole ring in its side chain? A) tyrosine B) tryptophan C) isoleucine D) asparagine E) histidine Answer: E Diff: 1 Section: 26.2 LO: 26.02 GO: G2 MCAT LO: MCAT24.1 9) Which amino acid has an indole ring in its side chain? A) tyrosine B) tryptophan C) isoleucine D) asparagine E) histidine Answer: B Diff: 1 Section: 26.2 LO: 26.02 GO: G2 MCAT LO: MCAT24.1

10) Which of the following amino acids does not contain an aromatic R-group? A) tyrosine B) phenylalanine C) tryptophan D) histidine E) none of the above Answer: E Diff: 1 Section: 26.2 LO: 26.02 GO: G2 MCAT LO: MCAT24.1 11) Which of the following amino acids does not have an aromatic substructure within its side chain? A) tryptophan B) tyrosine C) phenylalanine D) histidine E) proline Answer: E Diff: 2 Section: 26.2 LO: 26.02 GO: G2 MCAT LO: MCAT24.1

12) What is the one letter symbol of the amino acid below?

A) G B) Q C) W D) R E) M Answer: B Diff: 2 Section: 26.2 LO: 26.02 GO: G2 MCAT LO: MCAT24.1

13) What is the one letter symbol of the amino acid below?

A) G B) Q C) W D) T E) F Answer: C Diff: 2 Section: 26.2 LO: 26.02 GO: G2 MCAT LO: MCAT24.1 14) Which of the following amino acids are classified as essential amino acids? (More than one answer is possible.) A) isoleucine B) proline C) tryptophan D) histidine Answer: A, C, D Diff: 2 Section: 26.2 LO: 26.02 GO: G2

15) Which of the following terms best describes the side chain of valine? A) acidic B) basic C) charged, polar D) uncharged, polar E) nonpolar Answer: E Diff: 2 Section: 26.3 LO: 26.1.1 GO: G2 MCAT LO: MCAT24.3 16) Provide the structure of the predominant form of alanine present in an aqueous solution at a pH of 2.0. Answer:

Diff: 2 Section: 26.3 LO: 26.1.3 GO: G2

17) Provide the structure of the predominant form of glutamine present in an aqueous solution at a pH of 12.0. Answer:

18) The isoelectric point is important in ________. A) the enzymatic resolution of amino acids B) electrophoresis C) determination of the C-terminal amino acid D) determination of the N-terminal amino acid E) the ninhydrin test Answer: B Diff: 1 Section: 26.3 LO: 26.1.6 GO: G2 19) What is the isoelectric point of lysine within in +/- 1 pH unit? A) 3 B) 6 C) 9 D) 12 Answer: C Diff: 2 Section: 26.3 LO: 26.1.2 GO: G2 20) What is the name of the amino acid produced when propanoic acid is subjected to the following sequence of reagents: A) alanine B) aspartic acid C) glutamic acid D) valine E) asparagine Answer: A Diff: 3 Section: 26.4 LO: 26.2.6 GO: G2 MCAT LO: MCAT24.4

21) What is the major end product of the following reaction series?

A) Ala B) Gly C) Leu D) Ile E) Val Answer: E Diff: 3 Section: 26.4 LO: 26.2.6 GO: G2 MCAT LO: MCAT24.4 22) Provide the single letter code for the following peptide Arg-Phe-Tyr-Cys-Asp-Trp-Gln-Ala-Glu-Glu-His-Lys Answer: RFYCDWQAEEHK Diff: 2 Section: 26.6 LO: 26.4.2 GO: G2 MCAT LO: MCAT24.1 23) The nonprotein part of a conjugated protein is called a ________ group. Answer: prosthetic Diff: 1 Section: 26.6 LO: 26.4.1 GO: G2 24) A protein bonded to a sugar residue would be classified as a ________. A) simple protein B) glycoprotein C) lipoprotein D) metalloprotein E) nucleoprotein Answer: B Diff: 1 Section: 26.6 LO: 26.4.3 9 Copyright © 2021 Pearson Education, Inc.

GO: G2 25) A protein bonded to a fat would be classified as a ________. A) simple protein B) glycoprotein C) lipoprotein D) metalloprotein E) nucleoprotein Answer: C Diff: 1 Section: 26.6 LO: 26.4.3 GO: G2 26) Disulfide linkages can form between ________. A) two cysteine residues B) two methionine residues C) a cysteine residue and a methionine residue D) two threonine residues E) a methionine residue and a threonine residue Answer: A Diff: 1 Section: 26.7 LO: 26.4.1 GO: G2 27) Draw the dipeptide Val-Tyr. Answer:

Diff: 2 Section: 26.7 LO: 26.4.2 GO: G2 MCAT LO: MCAT24.1

28) Draw the structure of the tetrapeptide Ser-Leu-Phe-Pro. Answer:

Diff: 2 Section: 26.7 LO: 26.4.2 GO: G2 MCAT LO: MCAT24.1 29) Provide the structure of Thr-Gln-Met. Answer:

Diff: 2 Section: 26.7 LO: 26.4.2 GO: G2 MCAT LO: MCAT24.1 30) The primary structure of a protein refers to ________. A) the sequence of its amino acids B) the orientation of α-helices C) the orientation of pleated sheets D) the orientation of peptide subunits within a complex protein E) the placement of the protein's active site Answer: A Diff: 1 Section: 26.7 LO: 26.5.1 GO: G2 MCAT LO: MCAT24.6

31) What is the major force responsible for the formation of an α-helix in protein secondary structure? Answer: hydrogen bonding Diff: 2 Section: 26.7 LO: 26.5.1 GO: G2 MCAT LO: MCAT24.6 32) A polypeptide was treated with a certain enzyme to yield the following amino acid sequences. What enzyme was used to induce the observed fragmentations? Val-Pro-Phe Leu-Ser-Lys-Glu-Trp Answer: Chymotrypsin Diff: 2 Section: 26.8 LO: 26.6.2 GO: G2

Arg-Ile-Ser-Ser-Leu-Tyr

33) Which of the following compounds would reduce a disulfide linkage in a peptide? A) urea B) concentrated NaOH C) dithiothreitol D) dilute HCl E) bromine Answer: C Diff: 1 Section: 26.8 LO: 26.6.1 GO: G2 34) The reagent used in the determination of the N-terminal amino acid residue of a peptide is ________. A) carboxypeptidase B) phenyl isothiocyanate C) dicyclohexylcarbodiimide D) ethyl chloroformate E) peroxyformic acid Answer: B Diff: 2 Section: 26.8 LO: 26.6.1 GO: G2

35) Show where trypsin would cleave the peptide shown below.

Answer:

Diff: 2 Section: 26.8 LO: 26.6.1 GO: G2 MCAT LO: MCAT24.3 36) Show where chymotrypsin would cleave the peptide shown below.

Answer:

Diff: 2 Section: 26.8 LO: 26.6.1 GO: G2 MCAT LO: MCAT24.3 37) What peptide remains after two sequential Edman degradations of the pentapeptide A) Pro-Gly-Phe B) Ser-Pro-Gly C) Gly-Phe-Arg D) Pro-Gly E) Phe-Arg Answer: C Diff: 3 Section: 26.8 LO: 26.6.1 GO: G2

38) What is the practical limit on the use of carboxypeptidase in providing sequence information? A) two residues on the C-terminal end B) two residues on the N-terminal end C) three residues on the N-terminal end D) three residues on the C-terminal end E) six residues on the N-terminal end Answer: A Diff: 3 Section: 26.8 LO: 26.6.4 GO: G2

39) Which of the following fragments would not result when the decapeptide Asn-Gly-Lys-PhePro-Arg-Gly-Leu-Lys-Ser is treated with trypsin? A) Gly-Leu-Lys B) Phe-Pro-Arg C) Asn-Gly-Lys D) Pro-Arg-Gly-Leu Answer: D Diff: 3 Section: 26.8 LO: 26.6.1 GO: G2 40) Complete hydrolysis of a hexapeptide gives 2 Gly, Leu, Phe, Pro, and Tyr. Reaction of the peptide with phenylisothiocyanate gave the phenylthiohydantoin of Pro. Partial hydrolysis of the peptide gave the following fragments: Phe-Gly-Tyr, Gly-Phe-Gly, Pro-Leu-Gly, Leu-Gly-Phe. What is the structure of the peptide? Answer: Pro-Leu-Gly-Phe-Gly-Tyr Diff: 3 Section: 26.8 LO: 26.7.2 GO: G2 MCAT LO: MCAT24.5

41) Bradykinin is a nonapeptide released by globulins in the blood in response to a wasp sting. Hydrolysis gives the following amino acids: 2 Arg, Gly, 2 Phe, 3 Pro, and Ser. Edman degradation gives phenylthiohydantoin of Arg. Cleavage with carboxypeptidase gives Arg. Partial hydrolysis gives the following di- and tripeptides: Phe-Ser, Pro-Gly-Phe, Pro-Pro, SerPro-Phe, Phe-Arg, and Arg-Pro. What is the amino acid sequence of bradykinin? Answer: Arg-Pro-Pro-Gly-Phe-Ser-Pro-Phe-Arg Diff: 3 Section: 26.8 LO: 26.6.2 GO: G2 MCAT LO: MCAT24.5 42) Chymotrypsin is an enzyme which cleaves a peptide chain at the carboxyl groups of three aromatic amino acid residues. Name these three. Answer: phenylalanine, tyrosine, and tryptophan Diff: 3 Section: 26.8 LO: 26.6.1 GO: G2 43) Which of the following reagents is used to protect the amino group of the N-terminal residue in solution-phase peptide synthesis? A) lithium diisopropyl amide B) benzyl chloroformate C) phenyl isothiocyanate D) dicyclohexylcarbodiimide E) trifluoroacetic acid Answer: B Diff: 2 Section: 26.8 LO: 26.7.1 GO: G2 44) What peptide coupling reagent is most commonly used in solid phase peptide synthesis? Answer: dicyclohexylcarbodiimide (DCC) Diff: 2 Section: 26.8 LO: 26.7.1 GO: G2

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 27 Carbohydrates, Nucleic Acids, and Lipids 1) Stereoisomeric aldohexoses that differ in configuration at only a single carbon are ________. A) meso compounds B) threo sugars C) enantiomers D) constitutional isomers E) epimers Answer: E Diff: 1 Section: 27.2 LO: 27.0.5 GO: G1

2) Identify the C3 epimer of the sugar below drawn in its open chain (acyclic) Fischer projection.

Section: 27.3 LO: 27.0.5 GO: G2 3) What is the major organic product of the following reaction?

Answer:

LO: 27.3.4 GO: G2 4) Provide the major organic product of the reaction shown below.

Answer:

Diff: 2 Section: 27.4 LO: 27.3.4 GO: G2

5) What nucleophilic carbon species is used in the Kiliani-Fischer synthesis? Answer: cyanide Diff: 1 Section: 27.5 LO: 27.4.3 GO: G2 6) Sucrose is hydrolyzed to what two monosaccharides? A) glucose and fructose B) glucose and galactose C) maltose and fructose D) galactose and lactose E) galactose and maltose Answer: A Diff: 1 Section: 27.6 LO: 27.5.2 GO: G2 MCAT LO: MCAT23.8

7) Which of the following nitrogens of adenine connects to ribose to form a nucleoside?

A) 1 B) 2 C) 3 D) 4 Answer: C Diff: 1 Section: 27.8 LO: 27.6.1 GO: G2 8) Provide the structure of cytidine. Answer:

Diff: 2 Section: 27.8 LO: 27.6.1 GO: G2

9) Provide the structure of adenosine monophosphate. Answer:

Diff: 2 Section: 27.8 LO: 27.6.1 GO: G2

10) Draw the structure of deoxyguanosine. Answer:

Diff: 2 Section: 27.8 LO: 27.6.2 GO: G2

11) Provide the structure of deoxythymidine. Answer:

Diff: 2 Section: 27.8 LO: 27.6.2 GO: G2 12) Which of the following terms best describes the compound below? CH3(CH2)7CH CH(CH2)7CO2H A) an unsaturated fatty acid B) a triglyceride C) a synthetic detergent D) a micelle E) isoprene Answer: A Diff: 1 Section: 27.11 LO: 27.8.1 GO: G2 MCAT LO: MCAT25.1

13) Which best describes the lipid shown below?

A) wax B) triglyceride C) saturated fatty acid D) unsaturated fatty acid E) lecithin Answer: B Diff: 2 Section: 27.11 LO: 27.8.1 GO: G2 MCAT LO: MCAT25.1 14) Which of the following statements correctly describe(s) the relationship between the structure of a fatty acid and its melting point? A) Saturated fatty acids have melting points that increase gradually with their molecular weights. B) The presence of a trans double bond in the fatty acid has a greater effect on its melting point than does the presence of a cis double bond. C) As the number of double bonds in a fatty acid increases, its melting point decreases. D) both A and C E) A, B, and C Answer: D Diff: 2 Section: 27.11 LO: 27.8.4 GO: G2 15) ________ is the base-promoted hydrolysis of fats and oils. Answer: Saponification Diff: 1 Section: 27.12 LO: 27.10.1 GO: G1 MCAT LO: MCAT25.3

16) Provide the structures of the major organic products which result when tristearin (shown below) is heated in aqueous solution of sodium hydroxide.

Answer: HOCH2CHOHCH2OH and CH3(CH2)16CO2-Na+ Diff: 2 Section: 27.12 LO: 27.10.1 GO: G2 MCAT LO: MCAT25.2, MCAT25.4 17) β-carotene is a naturally occurring compound containing 40 carbon atoms which has a significant extended system of conjugated double bonds. This compound is also a terpene. How many isoprene units are present in A) 2 B) 4 C) 6 D) 8 E) 10 Answer: D Diff: 2 Section: 27.13 LO: 27.11.1 GO: G2

18) Which of the following terms best describes the compound below?

A) a sesquiterpene B) a steroid C) a protein D) a cephalin E) an essential oil Answer: B Diff: 1 Section: 27.14 LO: 27.12.1 GO: G2 MCAT LO: MCAT25.1, MCAT25.5 19) Draw the basic 4-ring skeletal structure found in steroids. Answer:

Diff: 2 Section: 27.14 LO: 27.12.1 GO: G2 MCAT LO: MCAT25.1, MCAT25.5

20) Which of the following terms best describes the compound below?

A) a lecithin B) a diterpene C) a steroid D) a glyceride E) a prostaglandin Answer: E Diff: 2 Section: 27.15 LO: 27.12.1 GO: G2 MCAT LO: MCAT25.1

Organic Chemistry: A Learner-Centered Approach, 1e (Mullins) Chapter 28 Synthetic Polymers 1) Which of the following polymers can be classified as copolymers?

A) 1 & 2 B) 2 & 4 C) 1 & 4 D) 2 & 3 E) 1, 3, & 4 Answer: B Diff: 3 Section: 28.2 LO: 28.0.1 GO: G2

2) Is the polymer shown an addition polymer or a condensation polymer?

Answer: addition polymer Diff: 2 Section: 28.3 LO: 28.4.3 GO: G2

3) Which of the following is the best initiator for a cationic polymerization? A) BuLi B) PhOH C) (PhCO2)2 D) CH3CH(OCH3)2 E) BF3 Answer: E Diff: 1 Section: 28.4 LO: 28.3.1 GO: G2 4) Which of the following is the best initiator for an anionic polymerization? A) BuLi B) PhOH C) (PhCO2)2 D) CH3CH(OCH3)2 E) BF3 Answer: A Diff: 1 Section: 28.4 LO: 28.3.1 | 28.3.4 GO: G2 5) Provide the structure of the monomer from which polystyrene is formed. Answer:

Diff: 2 Section: 28.4 LO: 28.3.5 GO: G2

6) What monomer is needed to produce the polymer below?

Answer: acrylonitrile, Diff: 2 Section: 28.4 LO: 28.3.5 GO: G2 7) Which of the following is the monomer unit of the polymer shown below?

D) Answer: A Diff: 2 Section: 28.4 LO: 28.3.5 GO: G2

8) Which of the following is least readily formed by cationic polymerization? A) poly(acrylonitrile) B) poly(isobutylene) C) poly(propylene) D) polystyrene E) All of the above have equal propensity to undergo cationic polymerization. Answer: A Diff: 2 Section: 28.4 LO: 28.3.1 GO: G2 9) Which of the following monomers is least readily polymerized under conditions of anionic polymerization? A) isobutylene B) acrylonitrile C) methyl acrylate D) methyl α-cyanoacrylate E) methyl α-methacrylate Answer: A Diff: 2 Section: 28.4 LO: 28.3.4 GO: G2 10) Predict the monomer units that combine to form polyurethane.

Answer:

Diff: 3 Section: 28.5 LO: 28.4.1 GO: G2

11) Nylon 6 is a ________. A) polyurethane B) polyester C) polycarbonate D) polyamide E) none of the above Answer: D Diff: 1 Section: 28.5 LO: 28.4.6 GO: G2 12) What type of polymer is formed from ethylene glycol and a diester as monomer components? A) polyurethanes B) polyamides C) polyesters D) polycarbonates E) none of the above Answer: C Diff: 1 Section: 28.5 LO: 28.4.6 GO: G2

13) Which of the following is a condensation polymer? A) poly(ethylene terephthalate) B) poly(tetrafluoroethylene) C) polystyrene D) poly(vinyl chloride) E) poly(methyl α-methacrylate) Answer: A Diff: 2 Section: 28.5 LO: 28.4.3 GO: G2

14) Which of the following is not a condensation polymer? A) Dacron B) poly(propylene) C) nylon 6 D) Lexan polycarbonate E) Mylar Answer: B Diff: 2 Section: 28.5 LO: 28.4.3 GO: G2

15) What type of polymer is shown below?

A) polyester B) polyamide C) polyurethane D) polycarbonate E) polypropylene Answer: A Diff: 2 Section: 28.5 LO: 28.4.6 GO: G2

16) Is the polymer shown below an addition polymer or a condensation polymer?

Answer: Condensation polyner Diff: 2 Section: 28.5 LO: 28.4.3 GO: G2 17) What kind of polymer is produced in the following reaction?

A) a polycarbonate B) poly(acrylonitrile) C) a polyester D) polyurethane E) a synthetic rubber Answer: D Diff: 2 Section: 28.5 LO: 28.4.2 | 28.4.6 GO: G2

18) Which of the following represents a carbonate ester? A) RCO2R' B) ROCO2R' C) RCOR' D) (RO)3CR' E) RNHCO2R' Answer: B Diff: 2 Section: 28.5 LO: 28.4.6 GO: G2

19) What type of polymer uses phosgene as one of its monomer components? A) polyurethanes B) polyamides C) polyesters D) polycarbonates E) none of the above Answer: D Diff: 2 Section: 28.5 LO: 28.4.2 GO: G2 20) What type of polymer uses a diisocyanate as one of its monomer components? A) polyurethanes B) polyamides C) polyesters D) polycarbonates E) none of the above Answer: A Diff: 2 Section: 28.5 LO: 28.4.3 GO: G2