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Organic Chemistry with Biological Topics

Sixth Edition

Janice Gorzynski Smith University of Hawai‘i at Mānoa

ORGANIC CHEMISTRY WITH BIOLOGICAL TOPICS, SIXTH EDITION

Published by McGraw-Hill Education, 2 Penn Plaza, New York, NY 10121. Copyright © 2021 by McGraw-Hill Education. All rights reserved. Printed in the United States of America. Previous edition © 2018. No part of this publication may be reproduced or distributed in any form or by any means, or stored in a database or retrieval system, without the prior written consent of McGraw-Hill Education, including, but not limited to, in any network or other electronic storage or transmission, or broadcast for distance learning.

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ISBN 978-1-260-32529-4 (bound edition)

MHID 1-260-32529-6 (bound edition)

ISBN 978-1-260-51642-5 (loose-leaf edition)

MHID 1-260-51642-3 (loose-leaf edition)

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All credits appearing on page or at the end of the book are considered to be an extension of the copyright page. Spectra in Chapters 9, 10, 11, 12, Spectroscopy A–C, 13, 14, 15, 17, 19, 20, and 22 courtesy of the Chemistry Department at Rutgers University.

Library of Congress Cataloging-in-Publication Data

Names: Smith, Janice Gorzynski, author.

Title: Organic chemistry with biological topics / Janice Gorzynski Smith, University of Hawai‘i at Manoa.

Description: Sixth edition. | New York, NY : McGraw-Hill Education, [2021] | Includes index.

Identifiers: LCCN 2019031885 | ISBN 9781260325294 (hardcover) | ISBN 9781260516425 (spiral bound) | ISBN 9781260516395 (ebook)

Subjects: LCSH: Chemistry, Organic—Textbooks.

Classification: LCC QD253.2 .S6325 2021 | DDC 547—dc23 LC record available at https://lccn.loc.gov/2019031885

The Internet addresses listed in the text were accurate at the time of publication. The inclusion of a website does not indicate an endorsement by the author or McGraw-Hill Education, and McGraw-Hill Education does not guarantee the accuracy of the information presented at these sites.

About the Author

Janice Gorzynski Smith was born in Schenectady, New York. She received an A.B. degree summa cum laude in chemistry from Cornell University, and a Ph.D. in Organic Chemistry from Harvard University under the direction of Nobel Laureate E. J. Corey. During her tenure with the Corey group, she completed the total synthesis of the plant growth hormone gibberellic acid.

Following her postdoctoral work as a National Science Foundation National Needs Postdoctoral Fellow at Harvard, Jan joined the faculty of Mount Holyoke College, where she was employed for 21 years. During this time she was active in teaching organic chemistry lecture and lab courses, conducting a research program in organic synthesis, and serving as department chair. Her organic chemistry class was named one of Mount Holyoke’s “Don’t-miss courses” in a survey by Boston magazine. After spending two sabbaticals amidst the natural beauty and diversity in Hawai‘i in the 1990s, Jan and her family moved there permanently in 2000. She has been a faculty member at the University of Hawai‘i at Mānoa, where she has taught the two-semester organic chemistry lecture and lab courses. In 2003, she received the Chancellor’s Citation for Meritorious Teaching.

Jan resides in Hawai‘i with her husband Dan, an emergency medicine physician, pictured with her in Cambodia in 2018. She has four children and six grandchildren. When not teaching, writing, or enjoying her family, Jan bikes, hikes, snorkels, and scuba dives in sunny Hawai‘i, and time permitting, enjoys travel and Hawaiian quilting.

or Megan Sarah

©Daniel C. Smith

Contents in Brief

Prologue 1

1 Structure and Bonding 7

2 Acids and Bases 58

3 Introduction to Organic Molecules and Functional Groups 91

4 Alkanes 132

5 Stereochemistry 176

6 Understanding Organic Reactions 219

7 Alkyl Halides and Nucleophilic Substitution 254

8 Alkyl Halides and Elimination Reactions 302

9 Alcohols, Ethers, and Related Compounds 337

10 Alkenes and Alkynes 384

11 Oxidation and Reduction 434

12 Conjugation, Resonance, and Dienes 473

Spectroscopy A Mass Spectrometry 508

Spectroscopy B Infrared Spectroscopy 528

Spectroscopy C Nuclear Magnetic Resonance Spectroscopy 553

13 Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation and Reduction 598

14 Aldehydes and Ketones—Nucleophilic Addition 646

15 Carboxylic Acids and Nitriles 695

16 Carboxylic Acids and Their Derivatives—Nucleophilic Acyl Substitution 733

17 Substitution Reactions of Carbonyl Compounds at the α Carbon 779

18 Carbonyl Condensation Reactions 812

19 Benzene and Aromatic Compounds 849

20 Reactions of Aromatic Compounds 885

21 Radical Reactions 935

22 Amines 969

23 Amino Acids and Proteins 1021

24 Carbohydrates 1069

25 Lipids 1114

26 Nucleic Acids and Protein Synthesis 1144

27 Metabolism 1169

28 Carbon–Carbon Bond-Forming Reactions in Organic Synthesis (Available Online) 1197

29 Pericyclic Reactions (Available Online) 1226

30 Synthetic Polymers (Available Online) 1255 Appendices A-1

Glossary G-1

Preface xviii

Acknowledgments xxi

Prologue 1

What Is Organic Chemistry? 1

Some Representative Organic Molecules 2 Marine Natural Products 4

1 Structure and Bonding 7

1.1 The Periodic Table 8

1.2 Bonding 10

1.3 Lewis Structures 12

1.4 Isomers 17

1.5 Exceptions to the Octet Rule 17

1.6 Resonance 18

1.7 Determining Molecular Shape 24

1.8 Drawing Organic Structures 28

1.9 Hybridization 34

1.10 Ethane, Ethylene, and Acetylene 37

1.11 Bond Length and Bond Strength 42

1.12 Electronegativity and Bond Polarity 43

1.13 Polarity of Molecules 45

1.14 Oxybenzone—A Representative Organic Molecule 46 Chapter Review 48 Problems 51

2 Acids and Bases 58

2.1 Brønsted–Lowry Acids and Bases 59

2.2 Reactions of Brønsted–Lowry Acids and Bases 60

2.3 Acid Strength and p Ka 63

2.4 Predicting the Outcome of Acid–Base Reactions 66

2.5 Factors That Determine Acid Strength 67

2.6 Common Acids and Bases 76

2.7 Aspirin 77

2.8 Lewis Acids and Bases 78

Chapter Review 81 Problems 84

Buttchi 3 Sha Life/ Shutterstock Comstock/PunchStock

Purestock/SuperStock

3 Introduction to Organic Molecules and Functional Groups 91

3.1 Functional Groups 92

3.2 An Overview of Functional Groups 93

3.3 Intermolecular Forces 101

3.4 Physical Properties 104

3.5 Application: Vitamins 111

3.6 Application of Solubility: Soap 112

3.7 Application: The Cell Membrane 113

3.8 Functional Groups and Reactivity 116

3.9 Biomolecules 117

Chapter Review 123 Problems 126

4 Alkanes 132

4.1 Alkanes—An Introduction 133

4.2 Cycloalkanes 135

4.3 An Introduction to Nomenclature 136

4.4 Naming Alkanes 137

4.5 Naming Cycloalkanes 142

4.6 Common Names 144

4.7 Natural Occurrence of Alkanes 145

4.8 Properties of Alkanes 145

4.9 Conformations of Acyclic Alkanes—Ethane 147

4.10 Conformations of Butane 150

4.11 An Introduction to Cycloalkanes 153

4.12 Cyclohexane 154

4.13 Substituted Cycloalkanes 157

4.14 Oxidation of Alkanes 163 Chapter Review 166 Problems 170

5 Stereochemistry 176

5.1 Starch and Cellulose 177

5.2 The Two Major Classes of Isomers 179

5.3 Looking Glass Chemistry—Chiral and Achiral Molecules 179

5.4 Stereogenic Centers 182

5.5 Stereogenic Centers in Cyclic Compounds 186

5.6 Labeling Stereogenic Centers with R or S 189

5.7 Diastereomers 194

5.8 Meso Compounds 196

5.9 R and S Assignments in Compounds with Two or More Stereogenic Centers 198

5.10 Disubstituted Cycloalkanes 198

5.11 Isomers—A Summary 200

5.12 Physical Properties of Stereoisomers 201

5.13 Chemical Properties of Enantiomers 206 Chapter Review 208 Problems 212

Narongsak Nagadhana/ Shutterstock
George Ostertag/Alamy Stock Photo

Ninikas/Getty Images

6 Understanding Organic Reactions 219

6.1 Writing Equations for Organic Reactions 220

6.2 Kinds of Organic Reactions 221

6.3 Bond Breaking and Bond Making 223

6.4 Bond Dissociation Energy 227

6.5 Thermodynamics 231

6.6 Enthalpy and Entropy 234

6.7 Energy Diagrams 236

6.8 Energy Diagram for a Two-Step Reaction Mechanism 238

6.9 Kinetics 240

6.10 Catalysts 243

6.11 Enzymes 244 Chapter Review 245 Problems 248

Source: Claire Fackler/ CINMS/NOAA

7 Alkyl Halides and Nucleophilic Substitution 254

7.1 Introduction to Alkyl Halides 255

7.2 Nomenclature 256

7.3 Properties of Alkyl Halides 257

7.4 Interesting Alkyl Halides 258

7.5 The Polar Carbon–Halogen Bond 259

7.6 General Features of Nucleophilic Substitution 260

7.7 The Leaving Group 261

7.8 The Nucleophile 263

7.9 Possible Mechanisms for Nucleophilic Substitution 267

7.10 Two Mechanisms for Nucleophilic Substitution 267

7.11 The SN2 Mechanism 268

7.12 The SN1 Mechanism 273

7.13 Carbocation Stability 277

7.14 The Hammond Postulate 279

7.15 When Is the Mechanism SN1 or SN2? 282

7.16 Biological Nucleophilic Substitution 287

7.17 Vinyl Halides and Aryl Halides 289

7.18 Organic Synthesis 290 Chapter Review 292 Problems 295

Source: Forest & Kim Starr

8 Alkyl Halides and Elimination Reactions 302

8.1 General Features of Elimination 303

8.2 Alkenes—The Products of Elimination Reactions 304

8.3 The Mechanisms of Elimination 308

8.4 The E2 Mechanism 308

8.5 The Zaitsev Rule 312

8.6 The E1 Mechanism 314

8.7 SN1 and E1 Reactions 317

8.8 Stereochemistry of the E2 Reaction 318

8.9 When Is the Mechanism E1 or E2? 321

8.10 E2 Reactions and Alkyne Synthesis 322

8.11 When Is the Reaction SN1, SN2, E1, or E2? 323

Chapter Review 327 Problems 331

9 Alcohols, Ethers, and Related Compounds 337

9.1 Introduction 338

9.2 Structure and Bonding 339

9.3 Nomenclature 339

9.4 Properties of Alcohols, Ethers, and Epoxides 343

9.5 Interesting Alcohols, Ethers, and Epoxides 344

9.6 Preparation of Alcohols, Ethers, and Epoxides 346

9.7 General Features—Reactions of Alcohols, Ethers, and Epoxides 348

9.8 Dehydration of Alcohols to Alkenes 350

9.9 Carbocation Rearrangements 352

9.10 Dehydration Using POCl3 and Pyridine 355

9.11 Conversion of Alcohols to Alkyl Halides with HX 356

9.12 Conversion of Alcohols to Alkyl Halides with SOCl2 and PBr3 359

9.13 Tosylate—Another Good Leaving Group 361

9.14 Reaction of Ethers with Strong Acid 364

9.15 Thiols and Sulfides 366

9.16 Reactions of Epoxides 368

9.17 Application: Epoxides, Leukotrienes, and Asthma 373 Chapter Review 374 Problems 378

10 Alkenes and Alkynes 384

10.1 Introduction 385

10.2 Calculating Degrees of Unsaturation 386

10.3 Nomenclature 387

10.4 Properties of Alkenes and Alkynes 391

10.5 Interesting Alkenes and Alkynes 392

10.6 Fatty Acids and Triacylglycerols 393

10.7 Preparation of Alkenes and Alkynes 395

10.8 Introduction to the Reactions of Alkenes and Alkynes 396

10.9 Hydrohalogenation—Electrophilic Addition of HX to Alkenes 399

10.10 Markovnikov’s Rule 400

10.11 Stereochemistry of Electrophilic Addition of HX 401

10.12 Hydration—Electrophilic Addition of Water 403

10.13 Halogenation—Addition of Halogen 404

10.14 Stereochemistry of Halogenation 405

10.15 Halohydrin Formation 407

10.16 Hydroboration–Oxidation 408

10.17 Addition of Hydrogen Halides and Halogens to Alkynes 412

10.18 Addition of Water to Alkynes 414

10.19 Hydroboration–Oxidation of Alkynes 416

Stephen Orsillo/ Shutterstock
Michael Sewell/ Photolibrary/ Getty Images

10.20 Reaction of Acetylide Anions 417

10.21 Synthesis 421

Chapter Review 423 Problems 427

11 Oxidation and Reduction 434

11.1 Introduction 435

11.2 Reducing Agents 436

11.3 Reduction of Alkenes 436

11.4 Application: Hydrogenation of Oils 440

11.5 Reduction of Alkynes 442

11.6 The Reduction of Polar C–X σ Bonds 445

11.7 Oxidizing Agents 446

11.8 Epoxidation 447

11.9 Dihydroxylation 451

11.10 Oxidative Cleavage of Alkenes 453

11.11 Oxidative Cleavage of Alkynes 455

11.12 Oxidation of Alcohols 456

11.13 Biological Oxidation 458

11.14 Sharpless Epoxidation 460

Chapter Review 463 Problems 466

12 Conjugation, Resonance, and Dienes 473

12.1 Conjugation 474

12.2 Resonance and Allylic Carbocations 476

12.3 Common Examples of Resonance 477

12.4 The Resonance Hybrid 479

12.5 Electron Delocalization, Hybridization, and Geometry 481

12.6 Conjugated Dienes 482

12.7 Interesting Dienes and Polyenes 483

12.8 The Carbon–Carbon σ Bond Length in Buta-1,3-diene 484

12.9 Stability of Conjugated Dienes 485

12.10 Electrophilic Addition: 1,2- Versus 1,4-Addition 486

12.11 Kinetic Versus Thermodynamic Products 488

12.12 The Diels–Alder Reaction 490

12.13 Specific Rules Governing the Diels–Alder Reaction 492

12.14 Other Facts About the Diels–Alder Reaction 496 Chapter Review 498 Problems 501

Amarita/Shutterstock
Rene Dulhoste/ Science Source

Spectroscopy A Mass Spectrometry 508

A.1 Mass Spectrometry and the Molecular Ion 509

A.2 Alkyl Halides and the M + 2 Peak 514

A.3 Fragmentation 516

A.4 Fragmentation Patterns of Some Common Functional Groups 518

A.5 Other Types of Mass Spectrometry 520 Chapter Review 523 Problems 524

Spectroscopy B Infrared Spectroscopy 528

B.1 Electromagnetic Radiation 529

B.2 The General Features of Infrared Spectroscopy 531

B.3 IR Absorptions 532

B.4 Infrared Spectra of Common Functional Groups 539

B.5 IR and Structure Determination 544 Chapter Review 546 Problems 548

Spectroscopy C Nuclear Magnetic Resonance

Spectroscopy 553

C.1 An Introduction to NMR Spectroscopy 554

C.2 1 H NMR: Number of Signals 557

C.3 1 H NMR: Position of Signals 562

C.4 The Chemical Shift of Protons on sp2 and sp Hybridized Carbons 565

C.5 1 H NMR: Intensity of Signals 567

C.6 1 H NMR: Spin–Spin Splitting 568

C.7 More-Complex Examples of Splitting 572

C.8 Spin–Spin Splitting in Alkenes 575

C.9 Other Facts About 1 H NMR Spectroscopy 577

C.10 Using 1 H NMR to Identify an Unknown 579

C.11 13C NMR Spectroscopy 581

C.12 Magnetic Resonance Imaging (MRI) 584 Chapter Review 585 Problems 589

13 Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation and Reduction 598

13.1 Introduction 599

13.2 General Reactions of Carbonyl Compounds 600

13.3 A Preview of Oxidation and Reduction 603

13.4 Reduction of Aldehydes and Ketones 604

13.5 The Stereochemistry of Carbonyl Reduction 606

13.6 Enantioselective Biological Reduction 607

13.7 Reduction of Carboxylic Acids and Their Derivatives 608

Adam Bailleaux/ Atomazul/123RF
T.Daly/Alamy Stock Photo
Daniel C. Smith
AS Food studio/ Shutterstock

13.8 Oxidation of Aldehydes 613

13.9 Organometallic Reagents 613

13.10 Reaction of Organometallic Reagents with Aldehydes and Ketones 617

13.11 Retrosynthetic Analysis of Grignard Products 620

13.12 Protecting Groups 622

13.13 Reaction of Organometallic Reagents with Carboxylic Acid Derivatives 624

13.14 Reaction of Organometallic Reagents with Other Compounds 627

13.15 α,β -Unsaturated Carbonyl Compounds 629

13.16 Summary—The Reactions of Organometallic Reagents 631

13.17 Synthesis 632 Chapter Review 634 Problems 639

1 4 Aldehydes and Ketones—Nucleophilic Addition 646

14.1 Introduction 647

14.2 Nomenclature 648

14.3 Properties of Aldehydes and Ketones 652

14.4 Interesting Aldehydes and Ketones 654

14.5 Preparation of Aldehydes and Ketones 655

14.6 Reactions of Aldehydes and Ketones—General Considerations 656

14.7 Nucleophilic Addition of H and R —A Review 659

14.8 Nucleophilic Addition of CN 660

14.9 The Wittig Reaction 662

14.10 Addition of 1° Amines 666

14.11 Addition of 2° Amines 668

14.12 Imine and Enamine Hydrolysis 669

14.13 Imines in Biological Systems 671

14.14 Addition of H2O—Hydration 673

14.15 Addition of Alcohols—Acetal Formation 675

14.16 Acetals as Protecting Groups 679

14.17 Cyclic Hemiacetals 680

14.18 An Introduction to Carbohydrates 682 Chapter Review 683 Problems 686

15 Carboxylic Acids and Nitriles 695

15.1 Structure and Bonding 696

15.2 Nomenclature 697

15.3 Physical and Spectroscopic Properties 700

15.4 Interesting Carboxylic Acids and Nitriles 702

15.5 Aspirin, Arachidonic Acid, and Prostaglandins 703

15.6 Preparation of Carboxylic Acids 704

15.7 Carboxylic Acids—Strong Organic Brønsted–Lowry Acids 705

15.8 The Henderson–Hasselbalch Equation 708

15.9 Inductive Effects in Aliphatic Carboxylic Acids 710

15.10 Extraction 711

Valentyn Volkov/ Shutterstock + ––
Sarka Babicka/Getty Images

15.11 Organic Acids That Contain Phosphorus 714

15.12 Amino Acids 715

15.13 Nitriles 719

Chapter Review 723 Problems 725

16 Carboxylic Acids and Their Derivatives—Nucleophilic Acyl Substitution

733

16.1 Introduction 734

16.2 Structure and Bonding 736

16.3 Nomenclature 737

16.4 Physical and Spectroscopic Properties 741

16.5 Interesting Esters and Amides 743

16.6 Introduction to Nucleophilic Acyl Substitution 745

16.7 Reactions of Acid Chlorides 749

16.8 Reactions of Anhydrides 750

16.9 Reactions of Carboxylic Acids 751

16.10 Reactions of Esters 756

16.11 Application: Lipid Hydrolysis 758

16.12 Reactions of Amides 760

16.13 Application: The Mechanism of Action of β -Lactam Antibiotics 762

16.14 Summary of Nucleophilic Acyl Substitution Reactions 762

16.15 Acyl Phosphates—Biological Anhydrides 763

16.16 Reactions of Thioesters—Biological Acylation Reactions 766

Chapter Review 768 Problems 771

17 Substitution Reactions of Carbonyl Compounds at the α Carbon 779

17.1 Introduction 780

17.2 Enols 780

17.3 Enolates 783

17.4 Enolates of Unsymmetrical Carbonyl Compounds 788

17.5 Racemization at the α Carbon 790

17.6 A Preview of Reactions at the α Carbon 790

17.7 Halogenation at the α Carbon 791

17.8 Direct Enolate Alkylation 793

17.9 Malonic Ester Synthesis 796

17.10 Acetoacetic Ester Synthesis 800

17.11 Biological Decarboxylation 802

Chapter Review 803 Problems 806

Likit Supasai/ Shutterstock
Surachetkhamsuk/ iStock/Getty Images

18 Carbonyl Condensation Reactions 812

18.1 The Aldol Reaction 813

18.2 Crossed Aldol Reactions 818

18.3 Directed Aldol Reactions 821

18.4 Intramolecular Aldol Reactions 822

18.5 The Claisen Reaction 825

18.6 The Crossed Claisen and Related Reactions 827

18.7 The Dieckmann Reaction 829

18.8 Biological Carbonyl Condensation Reactions 830

18.9 The Michael Reaction 833

18.10 The Robinson Annulation 835 Chapter Review 839 Problems 841

19 Benzene and Aromatic Compounds 849

19.1 Background 850

19.2 The Structure of Benzene 851

19.3 Nomenclature of Benzene Derivatives 853

19.4 Spectroscopic Properties 855

19.5 Interesting Aromatic Compounds 856

19.6 Benzene’s Unusual Stability 857

19.7 The Criteria for Aromaticity—Hückel’s Rule 859

19.8 Examples of Aromatic Compounds 861

19.9 Aromatic Heterocycles 864

19.10 What Is the Basis of Hückel’s Rule? 869

19.11 The Inscribed Polygon Method for Predicting Aromaticity 872

19.12 Aromatase Inhibitors for Estrogen-Dependent Cancer Treatment 874 Chapter Review 876 Problems 878

20 Reactions of Aromatic Compounds 885

20.1 Electrophilic Aromatic Substitution 886

20.2 The General Mechanism 887

20.3 Halogenation 888

20.4 Nitration and Sulfonation 890

20.5 Friedel–Crafts Alkylation and Friedel–Crafts Acylation 891

20.6 Substituted Benzenes 898

20.7 Electrophilic Aromatic Substitution of Substituted Benzenes 901

20.8 Why Substituents Activate or Deactivate a Benzene Ring 904

20.9 Orientation Effects in Substituted Benzenes 905

20.10 Limitations on Electrophilic Substitution Reactions with Substituted Benzenes 908

20.11 Disubstituted Benzenes 910

20.12 Synthesis of Benzene Derivatives 912

20.13 Nucleophilic Aromatic Substitution 913

Corbis
Jill Braaten
Pasieka/Science Photo Library/Getty Images

20.14 Reactions of Substituted Benzenes 917

20.15 Multistep Synthesis 921

Chapter Review 924 Problems 928

21 Radical Reactions 935

21.1 Introduction 936

21.2 General Features of Radical Reactions 937

21.3 Halogenation of Alkanes 939

21.4 The Mechanism of Halogenation 940

21.5 Chlorination of Other Alkanes 943

21.6 Chlorination Versus Bromination 943

21.7 The Stereochemistry of Halogenation Reactions 946

21.8 Application: The Ozone Layer and CFCs 949

21.9 Radical Halogenation at an Allylic Carbon 950

21.10 Application: Oxidation of Unsaturated Lipids 953

21.11 Application: Antioxidants 954

21.12 Radical Addition Reactions to Double Bonds 955

21.13 Polymers and Polymerization 957

Chapter Review 959 Problems 962

22 Amines 969

22.1 Introduction 970

22.2 Structure and Bonding 970

22.3 Nomenclature 971

22.4 Physical and Spectroscopic Properties 974

22.5 Interesting and Useful Amines 975

22.6 Preparation of Amines 979

22.7 Reactions of Amines—General Features 985

22.8 Amines as Bases 985

22.9 Relative Basicity of Amines and Other Compounds 987

22.10 Amines as Nucleophiles 993

22.11 Hofmann Elimination 995

22.12 Reaction of Amines with Nitrous Acid 997

22.13 Substitution Reactions of Aryl Diazonium Salts 999

22.14 Coupling Reactions of Aryl Diazonium Salts 1004

22.15 Application: Synthetic Dyes and Sulfa Drugs 1005

Chapter Review 1008 Problems 1013

23 Amino Acids and Proteins 1021

23.1 Amino Acids 1022

23.2 Separation of Amino Acids 1026

23.3 Enantioselective Synthesis of Amino Acids 1029

Hin255/Getty Images
Werner Arnold
Daniel C. Smith

23.4 Peptides 1031

23.5 Peptide Sequencing 1035

23.6 Peptide Synthesis 1038

23.7 Automated Peptide Synthesis 1043

23.8 Protein Structure 1045

23.9 Important Proteins 1051

23.10 Enzymes 1054

Chapter Review 1058 Problems 1063

24 Carbohydrates 1069

24.1 Introduction 1070

24.2 Monosaccharides 1071

24.3 The Family of d -Aldoses 1077

24.4 The Family of d -Ketoses 1078

24.5 Physical Properties of Monosaccharides 1079

24.6 The Cyclic Forms of Monosaccharides 1079

24.7 Glycosides 1087

24.8 Reactions of Monosaccharides at the OH Groups 1090

24.9 Reactions at the Carbonyl Group—Oxidation and Reduction 1091

24.10 Reactions at the Carbonyl Group—Adding or Removing One Carbon Atom 1094

24.11 Disaccharides 1098

24.12 Polysaccharides 1100

24.13 Other Important Sugars and Their Derivatives 1103

Chapter Review 1105 Problems 1108

Iconotec/Glowimages

25 Lipids 1114

25.1 Introduction 1115

25.2 Waxes 1116

25.3 Triacylglycerols 1116

25.4 Phospholipids 1120

25.5 Fat-Soluble Vitamins 1123

25.6 Eicosanoids 1124

25.7 Terpenes 1126

25.8 Steroids 1132

Chapter Review 1137 Problems 1139

26 Nucleic Acids and Protein Synthesis 1144

26.1 Nucleosides and Nucleotides 1145

26.2 Nucleic Acids 1148

26.3 The DNA Double Helix 1150

26.4 Replication 1153

26.5 Ribonucleic Acids and Transcription 1154

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Daniel C. Smith

26.6 The Genetic Code, Translation, and Protein Synthesis 1156

26.7 DNA Sequencing 1159

26.8 The Polymerase Chain Reaction 1161

26.9 Viruses 1162

Chapter Review 1163 Problems 1165

27 Metabolism 1169

27.1 Overview of Metabolism 1170

27.2 Key Oxidizing and Reducing Agents in Metabolism 1173

27.3 The Catabolism of Triacylglycerols by β -Oxidation 1176

27.4 The Catabolism of Carbohydrates—Glycolysis 1179

27.5 The Fate of Pyruvate 1184

27.6 The Citric Acid Cycle and ATP Production 1186

Chapter Review 1191 Problems 1193

28 Carbon–Carbon Bond-Forming Reactions in Organic Synthesis (Available Online) 1197

28.1 Coupling Reactions of Organocuprate Reagents 1198

28.2 Suzuki Reaction 1200

28.3 Heck Reaction 1205

28.4 Carbenes and Cyclopropane Synthesis 1207

28.5 Simmons–Smith Reaction 1210

28.6 Metathesis 1211

Chapter Review 1216 Problems 1218

29 Pericyclic Reactions (Available Online) 1226

29.1 Types of Pericyclic Reactions 1227

29.2 Molecular Orbitals 1228

29.3 Electrocyclic Reactions 1231

29.4 Cycloaddition Reactions 1236

29.5 Sigmatropic Rearrangements 1240

29.6 Summary of Rules for Pericyclic Reactions 1246

Chapter Review 1247 Problems 1249

30 Synthetic Polymers (Available Online) 1255

30.1 Introduction 1256

30.2 Chain-Growth Polymers—Addition Polymers 1257

30.3 Anionic Polymerization of Epoxides 1263

30.4 Ziegler–Natta Catalysts and Polymer Stereochemistry 1264

30.5 Natural and Synthetic Rubbers 1265

Samuel Borges Photography/ Shutterstock
DEA/M. GIOVANOLI/De Agostini Picture Library/ Getty Images
Premaphotos/Alamy Stock Photo

30.6 Step-Growth Polymers—Condensation Polymers 1267

30.7 Polymer Structure and Properties 1272

30.8 Green Polymer Synthesis 1274

30.9 Polymer Recycling and Disposal 1277 Chapter Review 1279 Problems 1281

Appendix A Periodic Table of the Elements A-1

Appendix B Common Abbreviations, Arrows, and Symbols A-2

Appendix C p Ka Values for Selected Compounds A-4

Appendix D Nomenclature A-6

Appendix E Bond Dissociation Energies for Some Common Bonds [A B → A• + •B] A-10

Appendix F Reactions That Form Carbon–Carbon Bonds A-11

Appendix G Characteristic IR Absorption Frequencies A-12

Appendix H Characteristic NMR Absorptions A-13

Appendix I General Types of Organic Reactions A-15

Appendix J How to Synthesize Particular Functional Groups A-17

Glossary G-1

Index I-1

Preface

Since the publication of Organic Chemistry in 2005, chemistry has witnessed a rapid growth in its understanding of the biological world. The molecular basis of many complex biological processes is now known with certainty, and can be explained by applying the basic principles of organic chemistry. Because of the close relationship between chemistry and many biological phenomena, Organic Chemistry with Biological Topics presents an approach to traditional organic chemistry that incorporates the discussion of biological applications that are understood using the fundamentals of organic chemistry.

The Basic Features

Organic Chemistry with Biological Topics continues the successful student-oriented approach used in Organic Chemistry by Janice Gorzynski Smith. This text uses less prose and more diagrams and bulleted summaries for today’s students, who rely more heavily on visual imagery to learn than ever before. Each topic is broken down into small chunks of information that are more manageable and easily learned. Sample Problems illustrate stepwise problem solving, and relevant examples from everyday life are used to illustrate topics. New concepts are introduced one at a time so that the basic themes are kept in focus.

The organization of Organic Chemistry with Biological Topics provides the student with a logical and accessible approach to an intense and fascinating subject. The text begins with a healthy dose of review material in Chapters 1 and 2 to ensure that students have a firm grasp of the fundamentals. Stereochemistry, the three-dimensional structure of molecules, is introduced early (Chapter 5) and reinforced often. Certain reaction types with unique characteristics and terminology are grouped together. These include acid–base reactions (Chapter 2), oxidation and reduction (Chapters 11 and 13), reactions of organometallic reagents (Chapter 13), and radical reactions (Chapter 21). Because of its importance in biological molecules, the chemistry of carbonyl-containing compounds has been moved much earlier than traditional organic chemistry texts and is now described in Chapters 13–18. Each chapter ends with a Chapter Review, end-of-chapter summaries that succinctly organize the main concepts and reactions.

New to This Edition

Students sometimes ask me if the facts of organic chemistry have significantly changed since the last edition. While the basic principles remain the same—carbon forms four bonds in stable compounds and oppositely charged species attract each other—organic chemistry is a dynamic subject that is continually refined as new facts are determined, and new editions reflect current understanding. Each year, novel compounds are discovered and new drugs are marketed, and these compounds replace older examples to illustrate particular concepts. Also of significance is how the material in the text is presented. I continue to endeavor to make this difficult subject as student-friendly as possible, by redesigning sample problems and end-ofchapter material, and rewriting sentences and paragraphs for improved clarity.

General

Expanded Problem-Solving Approach A central component of each chapter of Organic Chemistry with Biological Topics is the Sample Problems, which illustrate how to solve key elements of the chapter. In this edition, Sample Problems are always paired with a follow-up Problem to allow students to apply what they have just learned. The Problems are followed by “More Practice,” a list of end-of-chapter problems that are similar in concept. Students can find detailed solutions and verify their answers to all of the Problems from the book with the Student Study Guide/Solutions Manual for Organic Chemistry with Biological Topics

Chapter Review The end-of-chapter summary sections have been expanded into parts: Key Concepts, Key Skills, Key Reactions, and Key Mechanism Concepts, with structures and examples to illustrate each part, providing students with a broader and more detailed overview of each chapter’s important concepts and skills. Extensive cross-referencing has also been added to connect this material with relevant Sample Problems, Problems, Figures, and Tables within the body of the chapter.

New Chapters

In addition to the six chapters that contained new biological material in the fifth edition— Chapters 3, 6, 15, 16, 18, and 19—two new chapters have been added:

∙ Chapter 26 provides an in-depth discussion of the structure and properties of the nucleic acids DNA and RNA. Three key processes are also presented: replication—how DNA makes copies of itself; transcription—how the genetic information in DNA is passed onto RNA; and translation—how the coded genetic information in RNA is used to synthesize proteins. The chapter concludes with discussions of manipulating DNA in the laboratory and how viruses act.

∙ Chapter 27 focuses on the biochemical reactions involved in metabolism. The discussion centers on three components: the breakdown of fats, the metabolism of the carbohydrate glucose to the three-carbon unit pyruvate by glycolysis, and the citric acid cycle, a key cyclic metabolic pathway used for amino acids, carbohydrates, and fats.

Spectroscopy

The revisions to the spectroscopy coverage are designed to allow for more flexibility, making these chapters more portable to accommodate various lecture and lab arrangements. Three new spectroscopy chapters have been created for the sixth edition: Spectroscopy A Mass Spectrometry; Spectroscopy B Infrared Spectroscopy; and Spectroscopy C Nuclear Magnetic Resonance Spectroscopy. The coverage and problem sets for these chapters have also been expanded to include material previously covered in other sections of earlier editions. Extensive crossreferencing has been added so that whether spectroscopy is covered early or late in an organic chemistry course, students can readily find the material they need.

Other New Coverage

Examples of biomolecules are sprinkled throughout the chapters to illustrate common organic structural features and reactions, such as Lewis structures (Chapter 1), Lewis acids and bases (Chapter 2), stereochemistry (Chapter 5), and elimination reactions (Chapters 8 and 9). Other changes include the following:

∙ Section 11.13 on biological oxidation has been expanded to include the treatment of prochirality.

∙ New material has been added to Sections 13.6 and 13.7, including the biological reduction of acyl phosphates to aldehydes.

∙ The role of imines in the deamination of amino acids is discussed in Section 14.13B, and a detailed mechanism that illustrates the role of pyridoxal phosphate, vitamin B6, is presented.

∙ The coverage of nitriles has been moved to the chapter on carboxylic acids, forming Chapter 15, Carboxylic Acids and Nitriles. This chapter is now placed after Chapter 14, Aldehydes and Ketones, and this move offers two advantages. The chapter places the chemistry of carboxylic acids closer to similar chemistry seen with the acyl derivatives that is covered in Chapter 16. It also places the nucleophilic addition reactions of nitriles in closer proximity to related reactions in Chapter 14.

∙ A new Section 17.11 on biological decarboxylation has been added to Chapter 17.

∙ A new Section 23.8D on protein denaturation has been added to Chapter 23.

∙ Section 23.10 on enzymes illustrates how enzymes work with a specific example, how the serine proteases hydrolyze peptide bonds in proteins. The section concludes with a discussion of how enzymes are used to diagnose and treat diseases.

∙ The importance of human milk oligosaccharides in breast milk is discussed in Section 24.12D.

Learning Resources for Instructors and Students

The following items may accompany this text. Please consult your McGraw-Hill representative for policies, prices, and availability as some restrictions may apply.

Presentation Tools

Within the Instructor’s Resources, instructors have access to editable, accessible PowerPoint lecture outlines, which appear as ready-made presentations that combine art and lecture notes for each chapter of the text. For instructors who prefer to create their lecture notes from scratch, all illustrations, photos, tables, How To’s, and Sample Problems are pre-inserted by chapter into a separate set of PowerPoint slides. They are also available as individual .jpg files. Photos, artwork, and other media types can be used to create customized lectures, visually enhanced tests and quizzes, compelling course websites, or attractive printed support materials. All assets are copyrighted by McGraw-Hill Higher Education, but can be used by instructors for classroom purposes. The visual resources in this collection include:

∙ Art Full-color digital files of all illustrations in the book can be readily incorporated into lecture presentations, exams, or custom-made classroom materials.

∙ Photos The photo collection contains digital files of photographs from the text, which can be reproduced for multiple classroom uses.

∙ Tables Every table that appears in the text has been saved in electronic form for use in classroom presentations and/or quizzes.

Student Study Guide/Solutions Manual

Written by Janice Gorzynski Smith and Erin R. Smith, the Student Study Guide/Solutions Manual provides step-by-step solutions to all in-chapter and end-of-chapter problems. Each chapter begins with an overview of key concepts and includes a short-answer practice test on the fundamental principles and new reactions.

Acknowledgments

Although I have been an author for many years, this edition of Organic Chemistry with Biological Topics reflects recent advances in our understanding of organic chemistry, as well as new advances in digital media that allow this work to be better understood by a larger student audience. To produce a high quality text and ancillary materials requires not only my insights as an author, but also the expertise of a group of individuals with whom I work, beginning with the generation of a manuscript, progressing through the publication of the finished product both in print and digital form, and bringing the text to the larger chemistry community by the sales and marketing team.

My special thanks in this edition go out to two individuals who are integral to success of the project. Mary Hurley, Senior Developmental Editor, with whom I have worked for several years, is a master at supervising all the details of this large project and heading off problems before they become crises. I feel that Mary has been key in keeping my projects on a smooth trajectory even when many of the other personnel involved have changed. Amy Gehl, Production Manager, although new to the team, has skillfully and seamlessly managed the conversion of this text from paper manuscript to printed edition. Thanks so much to both of you and my sincere appreciation goes out to the entire chemistry group.

I especially thank my husband Dan and the other members of my immediate family, who have experienced the dayto-day demands of living with a busy author. The joys and responsibilities of the family have always kept me grounded during the rewarding but sometimes all-consuming process of writing a textbook. This book, like the prior edition of Organic Chemistry with Biological Topics, is dedicated to my wonderful daughter Megan, who passed away after a nine-year battle with cystic fibrosis.

Among the many others that go unnamed but who have profoundly affected this work are the thousands of students I have been lucky to teach over many years. I have learned so much from my daily interactions with them, and I hope that the wider chemistry community can benefit from this experience.

This edition has evolved based on the helpful feedback of many people who reviewed past editions and digital products, class-tested the book, and attended focus groups or symposiums. These many individuals have collectively provided constructive improvements to the project.

Listed below are the reviewers of Organic Chemistry with Biological Topics, fifth edition:

Steven Castle, Brigham Young University

Manashi Chatterjee, Hunter College

Emma Chow, Palm Beach State College

Jeff Corkill, Eastern Washington University

Andrew Frazer, University of Central Florida

Bob Kane, Baylor University

Donna J. Nelson, University of Oklahoma

Joshua L. Price, Brigham Young University

Elizabeth Walters, University of North Carolina at Wilmington

Lisa Whalen, University of New Mexico

Alexander Wurthmann, University of Vermont

The following individuals helped write and review learning goal-oriented content for SmartBook for Organic Chemistry with Biological Topics: David Jones, St. David’s School in Raleigh, NC; Adam Keller, Columbus State Community College; and Angela Perkins, University of Minnesota. Andrea Leonard of the University of Louisiana, Lafayette, revised the PowerPoint Lectures, and Ryan Simon also of the University of Louisiana, Lafayette, revised the Test Bank for Organic Chemistry with Biological Topics, sixth edition.

Although every effort has been made to make this text and its accompanying Student Study Guide/Solutions Manual as error-free as possible, some errors undoubtedly remain. Please feel free to email me about any inaccuracies, so that subsequent editions may be further improved.

With much aloha,

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Prologue

What is organic chemistry?

Some representative organic molecules

Marine natural products

Some compounds that contain the element carbon are not organic compounds. Examples include carbon dioxide (CO2), sodium carbonate (Na2CO3), and sodium bicarbonate (NaHCO3).

Organic chemistry. You might wonder how a discipline that conjures up images of eccentric old scientists working in basement laboratories is relevant to you, a student in the twenty-first century.

Consider for a moment the activities that occupied your past 24 hours. You likely showered with soap, drank a caffeinated beverage, ate at least one form of starch, took some medication, and traveled in a vehicle that had rubber tires and was powered at least partly by fossil fuels. If you did any one of these, your life was touched by organic chemistry.

What Is Organic Chemistry?

• Organic chemistry is the chemistry of compounds that contain the element carbon.

It is one branch in the entire field of chemistry, which encompasses many classical subdisciplines including inorganic, physical, and analytical chemistry, and newer fields such as bioinorganic chemistry, physical biochemistry, polymer chemistry, and materials science.

Organic chemistry was singled out as a separate discipline for historical reasons. Originally, it was thought that compounds in living things, termed organic compounds, were fundamentally different from those in nonliving things, called inorganic compounds. Although we have known for more than 150 years that this distinction is artificial, the name organic persists. Today the term refers to the study of the compounds that contain carbon, many of which, incidentally, are found in living organisms.

It may seem odd that a whole discipline is devoted to the study of a single element in the periodic table, when more than 100 elements exist. It turns out, though, that there are far more organic compounds than any other type. Organic chemicals affect virtually every facet of our lives, and for this reason, it is important and useful to know something about them.

Clothes, foods, medicines, gasoline, refrigerants, and soaps are composed almost solely of organic compounds. Some, like cotton, wool, and silk, are naturally occurring; that is, they can be isolated directly from natural sources. Others, such as nylon and polyester, are synthetic, meaning they are produced by chemists in the laboratory. By studying the principles and concepts of organic chemistry, you can learn more about compounds such as these and how they affect the world around you.

Realize, too, what organic chemistry has done for us. Organic chemistry has made available both comforts and necessities that were previously nonexistent, or reserved for only the wealthy. We have seen an enormous increase in life span, from 47 years in 1900 to over 70 years currently. To a large extent this is due to the isolation and synthesis of new drugs to fight infections and the availability of vaccines for childhood diseases. Chemistry has also given us the tools to control insect populations that spread disease, and there is more food for all because

of fertilizers, pesticides, and herbicides. Our lives would be vastly different today without the many products that result from organic chemistry (Figure 1).

• Organic chemistry has given us contraceptives, plastics, antibiotics, and the knitted material used in synthetic heart valves.

Some Representative Organic Molecules

Perhaps the best way to appreciate the variety of organic molecules is to look at a few. Three simple organic compounds are methane, ethanol, and trichlorofluoromethane.

∙ Methane, the simplest of all organic compounds, contains one carbon atom. Methane—the main component of natural gas—occurs widely in nature. Like other hydrocarbons organic compounds that contain only carbon and hydrogen—methane is combustible; that is, it burns in the presence of oxygen. Methane is the product of the anaerobic (without air) decomposition of organic matter by bacteria. The natural gas we use today was formed by the decomposition of organic material millions of years ago. Hydrocarbons such as methane are discussed in Chapter 4.

Figure 1
Products of organic chemistry used in medicine
a. Oral contraceptives
b. Plastic syringes
c. Antibiotics
Comstock Images/PictureQuest
Tom Grill/Corbis Premium/Alamy Stock Photo
Julian Claxton/Alamy Stock Photo
d. Synthetic heart valves
Layne Kennedy/Corbis NX/Getty Images

Complex organic structures are drawn with shorthand conventions described in Chapter 1.

∙ Ethanol, the alcohol present in beer, wine, and other alcoholic beverages, is formed by the fermentation of sugar, possibly the oldest example of organic synthesis. Ethanol can also be made in the lab by a totally different process, but the ethanol produced in the lab is identical to the ethanol produced by fermentation. Alcohols including ethanol are discussed in Chapter 9.

∙ Trichlorofluoromethane is a member of a class of molecules called chlorofluorocarbons, or CFCs, which contain one or two carbon atoms and several halogens. Trichlorofluoromethane is an unusual organic molecule in that it contains no hydrogen atoms. Because it has a low molecular weight and is easily vaporized, trichlorofluoromethane has been used as an aerosol propellant and refrigerant. It and other CFCs have been implicated in the destruction of the stratospheric ozone layer, a topic discussed in Chapter 21.

Three complex organic molecules that are important medications are amoxicillin, fluoxetine, and AZT.

∙ Amoxicillin is one of the most widely used antibiotics in the penicillin family. The discovery and synthesis of such antibiotics in the twentieth century made routine the treatment of infections that were formerly fatal. You were likely given some amoxicillin to treat an ear infection when you were a child. The penicillin antibiotics are discussed in Chapter 16.

∙ Fluoxetine is the generic name for the antidepressant Prozac. Prozac was designed and synthesized by chemists in the laboratory, and is now produced on a large scale in chemical factories. Because it is safe and highly effective in treating depression, Prozac is widely prescribed. Over 40 million individuals worldwide have used Prozac since 1986.

∙ AZT, azidodeoxythymidine, is a drug that treats human immunodeficiency virus (HIV), the virus that causes acquired immune deficiency syndrome (AIDS). Also known by its generic name zidovudine, AZT represents a chemical success to a different challenge: synthesizing agents that combat viral infections.

Other complex organic compounds with interesting properties are capsaicin and DDT.

∙ Capsaicin, one member of a group of compounds called vanilloids, is responsible for the characteristic spiciness of hot peppers. It is the active ingredient in pepper sprays used for personal defense and topical creams used for pain relief.

∙ DDT, dichlorodiphenyltrichloroethane, is a pesticide once called “miraculous” by Winston Churchill because of the many lives it saved by killing disease-carrying mosquitoes. DDT use is now banned in the United States and many developed countries because it is a nonspecific insecticide that persists in the environment.

What are the common features of these organic compounds?

• All organic compounds contain carbon atoms and most contain hydrogen atoms.

• All the carbon atoms have four bonds. A stable carbon atom is said to be tetravalent.

• Other elements may also be present. Any atom that is not carbon or hydrogen is called a heteroatom. Common heteroatoms include N, O, S, P, and the halogens.

• Some compounds have chains of atoms and some compounds have rings.

These features explain why there are so many organic compounds: Carbon forms four strong bonds with itself and other elements. Carbon atoms combine together to form rings and chains.

Marine Natural Products

Nature has generously supplied the organic chemist with a wide variety of complex compounds that have promising therapeutic potential. In the last 40 years, the largely unexplored marine environment has been recognized as a vast resource of unique compounds with novel chemical properties, but the challenges in discovering drug leads among such expansive biodiversity are many. Organisms are often found in waters offshore remote islands, and structure determination must be carried out on minute quantities of material. Even when potential targets are identified, supplying enough compound for preclinical and clinical trials often means that the compound must then be synthesized in the laboratory. Nonetheless, new compounds with useful bioactivity are routinely discovered and synthesized. Among the first available anticancer drugs with origins in the world of marine natural products are eribulin mesylate and trabectedin.

Eribulin mesylate is a synthetic analogue of the more complex natural product halichondrin B, which is isolated from the black sponge Halichondria okadai. Sold under the trade name Halaven, it was approved in the United States in 2010 for the treatment of metastatic breast cancer.

Trabectedin, also known as ecteinascidin 743 or ET-743, is obtained from the sea squirt Ecteinascidia turbinata. Sold under the trade name Yondelis, it was approved in the European Union in 2007 for the treatment of advanced soft tissue sarcoma. In 2015, the U.S. Food and Drug Administration approved trabectedin for the treatment of specific soft tissue cancers that cannot be removed by surgery.

trabectedin, ET-743

Ecteinascidia turbinata

Florent Charpin 2004-2016. All Rights Reserved

Because isolation of enough trabectedin for clinical trials was not feasible—one ton of organisms yielded one gram of compound—trabectedin was synthesized in the laboratory of Nobel Laureate E. J. Corey in 1996. Now it is readily available by a shorter synthesis from a starting material obtained by a fermentation process.

Halichondria okadai
halichondrin
eribulin mesylate
Guido & Philippe Poppe

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may still all come out right. You know how shrewd and resourceful I am.”

“I know what a numbskull you are! A dolt, a nincompoop, my dear friend! Will you have the goodness to tell me what your resourcefulness can accomplish at this stage? Perhaps there is a bank somewhere in the wide world that will lend you a shilling? Or another father-in-law? Ah, no; you have already played your best card. You can’t play it twice.—With all due respect, my dear fellow, and my highest regards.”

“Speak lower, devil take you!”

“You are a fool. Shrewd and resourceful, are you? Yes, to the other chap’s advantage. You’re not scrupulous, I’ll say that for you, but much good it’s done you! You have played tricks, and wormed capital out of people by hook or crook, just to pay me my twelve or sixteen per cent. You threw your honour overboard without getting any return. You have a conscience like a butcher’s dog, and yet you are nothing but a ninny, a scapegoat. There are always such people —they are too funny for words. Why is it you are so afraid to apply to the person we mean with the whole story? Isn’t it because there was crooked work four years ago? Perhaps it wasn’t all quite straight— what? Are you afraid that certain things—?”

“Very well, Kesselmeyer; I will write. But suppose he refuses? Suppose he lets me down?”

“Oh—ah, ha! Then we will just have a bankruptcy, a highly amusing little bankruptcy That doesn’t bother me at all. So far as I am concerned, I have about covered my expenses with the interest you have scratched together, and I have the priority with the assets. Oh, you wait; I shan’t come short. I know everything pretty well, my good friend; I have an inventory already in my pocket. Ah, ha! We shall see that no dressing-gown and no silver bread-basket gets away.”

“Kesselmeyer, you have sat at my table—”

“Oh, be quiet with your table! In eight days I’ll be back for the answer. I shall walk in to town—the fresh air will do me good. Good morning, my friend, good morning!”

And Herr Kesselmeyer seemed to depart—yes, he went. She heard his odd, shuffling walk in the corridor, and imagined him rowing along with his arms....

Herr Grünlich entered the “pensée-room” and saw Tony standing there with the little watering-can in her hand. She looked him in the face.

“What are you looking at? Why are you staring like that?” he said to her. He showed his teeth, and made vague movements in the air with his hands, and wiggled his body from side to side. His rosy face could not become actually pale; but it was spotted red and white like a scarlet-fever patient’s.

CHAPTER VII

C J B arrived at the villa at two o’clock in the afternoon. He entered the Grünlich salon in a grey travellingcloak and embraced his daughter with painful intensity. He was pale and seemed older. His small eyes were deep in their sockets, his large pointed nose stuck out between the fallen cheeks, his lips seemed to have grown thinner, and the beard under his chin and jaws half-covered by his stiff choker and high neck-band,—he had lately ceased to wear the two locks running from the temples halfway down the cheeks—was as grey as the hair on his head.

The Consul had hard, nerve-racking days behind him. Thomas had had a haemorrhage; the Father had learned of the misfortune in a letter from Herr van der Kellen. He had left his business in the careful hands of his clerk and hurried off to Amsterdam. He found nothing immediately dangerous about his son’s illness, but an openair cure was necessary, in the South, in Southern France; and as it fortunately happened that a journey of convalescence had been prescribed for the young son of the head of the firm, the two young men had left for Pau as soon as Thomas was able to travel.

The Consul had scarcely reached home again when he was attacked by a fresh misfortune, which had for the moment shaken his firm to its foundations and by which it had lost eighty thousand marks at one blow. How? Discounted cheques drawn on Westfall Brothers had come back to the firm, liquidation having begun. He had not failed to cover them. The firm had at once showed what it could do, without hesitation or embarrassment. But that could not prevent the Consul from experiencing all the sudden coldness, the reserve, the mistrust at the banks, with “friends,” and among firms abroad, which such an event, such a weakening of working capital, was sure to bring in its train.

Well, he had pulled himself together, and had reviewed the whole situation; had reassured, reinforced, made head. And then, in the midst of the struggle, among telegrams, letters, and calculations, this

last blow broke upon him as well: B. Grünlich, his daughter’s husband, was insolvent. In a long, whining, confused letter he had implored, begged, and prayed for an assistance of a hundred to a hundred and twenty thousand marks. The Consul replied curtly and non-committally that he would come to Hamburg to meet Herr Grünlich and Kesselmeyer the banker, made a brief, soothing explanation to his wife, and started off.

Tony received him in the salon. She was fond of receiving visits in her brown silk salon, and she made no exception now; particularly as she had a very profound impression of the importance of the present occasion, without comprehending in the least what it was about. She looked blooming and yet becomingly serious, in her pale grey frock with its laces at breast and wrists, its bell-shaped sleeves and long train, and little diamond clasp at the throat. “How are you, Papa? At last you have come to see us again. How is Mamma? Is there good news from Tom? Take off your things, Father dear. Will you dress? The guest-room is ready for you. Grünlich is dressing.”

“Don’t call him, my child. I will wait for him here. You know I have come for a talk with your husband—a very, very serious talk, my dear Tony. Is Herr Kesselmeyer here?”

“Yes, he is in the pensée-room looking at the album.”

“Where is Erica?”

“Up in the nursery with Tinka. She is very well. She is bathing her doll—of course, not in real water; I mean—she is a wax-doll, she only—”

“Of course.” The Consul drew a deep breath and went on: “Evidently you have not been informed as to—to the state of affairs with your husband.”

He had sat down in an arm-chair near the large table, and Tony placed herself at his feet on a little seat made of three cushions on top of one another. The finger of her right hand toyed gently with the diamond at her throat.

“No, Papa,” answered Tony. “I must confess I know nothing. Heavens, I am a goose!—I have no understanding at all. I heard

Kesselmeyer talking lately to Grünlich—at the end it seemed to me he was just joking again—he always talks so drolly. I heard your name once or twice—”

“You heard my name? In what connection?”

“Oh, I know nothing of the connection, Papa. Grünlich has been insufferably sulky ever since that day, I must say. Until yesterday— yesterday he was in a good mood, and asked me a dozen times if I loved him, and if I would put in a good word for him with you if he had something to ask you.”

“Oh!”

“Yes, he told me he had written you and that you were coming here. It is good you have. Everything is so queer. Grünlich had the cardtable put in here. There are a lot of paper and pencils on it—for you to sit at, and hold a council together.”

“Listen, my dear child,” said the Consul, stroking her hair. “I want to ask you something very serious. Tell me: you love your husband with your whole heart, don’t you?”

“Of course, Papa,” said Tony with a face of childlike hypocrisy— precisely the face of the child Tony when she was asked: “You won’t tease the old doll-woman again, Tony?” The Consul was silent a minute.

“You love him so much,” he asked again, “that you could not live without him, under any circumstances, even if by God’s will your situation should alter so that he could no longer surround you with all these things?” And his hand described a quick movement over the furniture and portières, over the gilt clock on the étagère, and finally over her own frock.

“Certainly, Papa,” repeated Tony, in the soothing tone she nearly always used when any one spoke seriously to her. She looked past her father out of the window, where a heavy veil of rain was silently descending. Her face had the expression children wear when some one tells them a fairy story and then tactlessly introduces a generalization about conduct and duty—a mixture of embarrassment and impatience, piety and boredom.

The Consul looked at her without speaking for a minute. Was he satisfied with her response? He had weighed everything thoroughly, at home and during the journey.

It is comprehensible that Johann Buddenbrook’s first impulse was to refuse his son-in-law any considerable payment. But when he remembered how pressing—to use a mild word—he had been about this marriage; when he looked back into the past, and recalled the words: “Are you satisfied with me?” with which his child had taken leave of him after the wedding, he gave way to a burdensome sense of guilt against her and said to himself that the thing must be decided according to her feelings. He knew perfectly that she had not made the marriage out of love, but he was obliged to reckon with the possibility that these four years of life together and the birth of the child had changed matters; that Tony now felt bound body and soul to her husband and would be driven by considerations both spiritual and worldly to shrink from a separation. In such a case, the Consul argued, he must accommodate himself to the surrender of whatever sum was necessary. Christian duty and wifely feeling did indeed demand that Tony should follow her husband into misfortune; and if she actually took this resolve, he did not feel justified in letting her be deprived of all the ease and comfort to which she had been accustomed since childhood. He would feel himself obliged to avert the catastrophe, and to support B. Grünlich at any price. Yet the final result of his considerations was the desire to take his daughter and her child home with him and let Grünlich go his own way. God forbid that the worst should happen!

In any case, the Consul invoked the pronouncement of the law that a continued inability to provide for wife and children justified a separation. But, before everything, he must find out his daughter’s real feelings.

“I see,” he said, “my dear child, that you are actuated by good and praiseworthy motives. But—I cannot believe that you are seeing the thing as, unhappily, it really is—namely, as actual fact. I have not asked what you would do in this or that case, but what you to-day, now, will do. I do not know how much of the situation you know or suspect. It is my painful duty to tell you that your husband is obliged

to call his creditors together; that he cannot carry on his business any longer. I hope you understand me.”

“Grünlich is bankrupt?” Tony asked under her breath, half rising from the cushions and seizing the Consul’s hand quickly.

“Yes, my child,” he said seriously. “You did not know it?”

“My suspicions were not definite,” she stammered. “Then Kesselmeyer was not joking?” she went on, staring before her at the brown carpet. “Oh, my God!” she suddenly uttered, and sank back on her seat.

In that minute all that was involved in the word “bankrupt” rose clearly before her: all the vague and fearful hints which she had heard as a child. “Bankrupt”—that was more dreadful than death, that was catastrophe, ruin, shame, disgrace, misery, despair. “He is bankrupt,” she repeated. She was so cast down and shaken by the fatal word that the idea of escape, of assistance from her father, never occurred to her. He looked at her with raised eyebrows, out of his small deep-set eyes, which were tired and sad and full of an unusual suspense. “I am asking you,” he said gently, “my dear Tony, if you are ready to follow your husband into misery?” He realized at once that he had used the hard word instinctively to frighten her, and he added: “He can work himself up again, of course.”

“Certainly, Papa,” answered she. But it did not prevent her from bursting into tears. She sobbed into her batiste handkerchief, trimmed with lace and with the monogram A. G. She still wept just like a child; quite unaffectedly and without embarrassment. Her upper lip had the most touching expression.

Her father continued to probe her with his eyes. “That is your serious feeling, my child?” he asked. He was as simple as she.

“I must, mustn’t I?” she sobbed. “Don’t I have to—?”

“Certainly not,” he said. But with a guilty feeling he added: “I would not force you to it, my dear Tony. If it should be the case that your feelings did not bind you indissolubly to your husband—”

She looked at him with uncomprehending, tear-streaming eyes. “How, Papa?”

The Consul twisted and turned, and found a compromise. “My dear child, you can understand how painful it would be for me to have to tell you all the hardships and suffering that would come about through the misfortune of your husband, the breaking-up of the business and of your household. I desire to spare you these first unpleasantnesses by taking you and little Erica home with me. You would be glad of that, I think?”

Tony was silent a moment, drying her tears. She carefully breathed on her handkerchief and pressed it against her eyes to heal their inflammation. Then she asked tn a firm tone, without lifting her voice: “Papa, is Grünlich to blame? Is it his folly and lack of uprightness that has brought him to this?”

“Very probably,” said the Consul. “That is—no, I don’t know, my child. The explanation with him and the banker has not taken place yet.”

She seemed not to be listening. She sat crouched on her three silk cushions, her elbow on her knee, her chin in her hand, and with her head bowed looked dreamily into the room.

“Ah, Papa,” she said softly, almost without moving her lips, “wouldn’t it have been better—?”

The Consul could not see her face—but it had the expression it often wore those summer evenings at Travemünde, as she leaned at the window of her little room. One arm rested on her Father’s knee, the hand hanging down limply. This very hand was expressive of a sad and tender abandonment, a sweet, pensive longing, travelling back into the past.

“Better?” asked Consul Buddenbrook. “If what, my child?”

He was thoroughly prepared for the confession that it would have been better had this marriage not taken place; but Tony only answered with a sigh: “Oh, nothing.”

She seemed rapt by her thoughts, which had borne her so far away that she had almost forgotten the “bankrupt.” The Consul felt himself

obliged to utter what he would rather only have confirmed.

“I think I guess your thoughts, Tony,” he said, “and I don’t on my side hesitate to confess that in this hour I regret the step that seemed to me four years ago so wise and advisable. I believe, before God, I am not responsible. I think I did my duty in trying to give you an existence suitable to your station. Heaven has willed otherwise. You will not believe that your Father played lightly and unreflectingly with your happiness in those days! Grünlich came to us with the best recommendations, a minister’s son, a Christian and a cosmopolitan man. Later I made business inquiries, and it all sounded as favourable as possible. I examined the connections. All that is still very dark; and the explanation is yet to come. But you don’t blame me—?”

“No, Papa—how can you say such a thing? Come, don’t take it to heart, poor Papa! You look pale. Shall I give you a little cordial?” She put her arm around his neck and kissed his cheek.

“Thank you, no,” he said. “There, there! It is all right. Yes, I have bad days behind me. I have had much to try me. These are all trials sent from God. But that does not help my feeling a little guilty toward you, my child. Everything depends on the question I have already asked you. Speak openly, Tony Have you learned to love your husband in these years of marriage?”

Tony wept afresh; and covering her eyes with both hands, in which she held the batiste handkerchief, she sobbed out: “Oh, what are you asking me, Papa? I have never loved him—he has always been repulsive to me. You know that.”

It would be hard to say what went on in Johann Buddenbrook. His eyes looked shocked and sad; but he bit his lips hard together, and great wrinkles came in his cheeks, as they did when he had brought a piece of business to a successful conclusion. He said softly: “Four years—”

Tony’s tears ceased suddenly. With her damp handkerchief in her hand, she sat up straight on her seat and said angrily: “Four years!

Yes! Sometimes, in those four years, he sat with me in the evening and read the paper.”

“God gave you a child,” said the Father, moved.

“Yes, Papa. And I love Erica very much, although Grünlich says I am not fond of children. I would not be parted from her, that is certain. But Grünlich—no! Grünlich, no. And now he is bankrupt. Ah, Papa, if you will take Erica and me home—oh, gladly.”

The Consul compressed his lips again. He was extremely well satisfied. But the main point had yet to be touched upon; though, by the decision Tony showed, he did not risk much by asking.

“You seem not to have thought it might be possible to do something, to get help. I have already said to you that I do not feel myself altogether innocent of the situation, and—in case you should expect —hope—I might intervene, to prevent the failure and cover your husband’s debts, the best I could, and float his business—”

He watched her keenly, and her bearing filled him with satisfaction. It expressed disappointment.

“How much is it?” she asked.

“What is that to the point, my child? A very large sum.” And Consul Buddenbrook nodded several times, as though the weight of the very thought of such a sum swung his head back and forth. “I should not conceal from you,” he went on, “that the firm has suffered losses already quite apart from this affair, and that the surrender of a sum like this would be a blow from which it would recover with difficulty. I do not in any way say this to—”

He did not finish. Tony had sprung up, had even taken a few steps backward, and with the wet handkerchief still in her hand she cried: “Good! Enough! Never!” She looked almost heroic. The words “the firm” had struck home. It is highly probable that they had more effect than even her dislike of Herr Grünlich. “You shall not do that, Papa,” she went on, quite beside herself. “Do you want to be bankrupt too? Never, never!”

At this moment the hall door opened a little uncertainly and Herr Grünlich entered.

Johann Buddenbrook rose, with a movement that meant: “That’s settled.”

CHAPTER VIII

H G’ face was all mottled with red; but he had dressed carefully in a respectable-looking black coat and pea-green trousers like those in which he had made his first visits in Meng Street. He stood still, with his head down, looking very limp, and said in a weak exhausted sort of voice: “Father?”

The Consul bowed, not too cordially, and straightened his neck-cloth with an energetic movement.

“Thank you for coming,” said Herr Grünlich.

“It was my duty, my friend,” replied the Consul. “But I am afraid it will be about all I can do for you.”

Herr Grünlich threw him a quick look and seemed to grow still more limp.

“I hear,” the Consul went on, “that your banker, Herr Kesselmeyer, is awaiting us—where shall the conference be held? I am at your service.”

“If you will be so good as to follow me,” Herr Grünlich murmured. Consul Buddenbrook kissed his daughter on the forehead and said, “Go up to your child, Antonie.”

Then he went, with Herr Grünlich fluttering in front of and behind him to open the portières, through the dining-room into the living-room.

Herr Kesselmeyer stood at the window, the black and white down softly rising and falling upon his cranium.

“Herr Kesselmeyer, Herr Consul Buddenbrook, my father-in-law,” said Herr Grünlich, meekly. The Consul’s face was impassive. Herr Kesselmeyer bowed with his arms hanging down, both yellow teeth against his upper lip, and said “Pleasure to meet you, Herr Consul.”

“Please excuse us for keeping you waiting, Kesselmeyer,” said Herr Grünlich. He was not more polite to one than to the other. “Pray sit down.”

As they went into the smoking-room, Herr Kesselmeyer said vivaciously: “Have you had a pleasant journey? Ah, rain? Yes, it is a bad time of year, a dirty time. If we had a little frost, or snow, now— but rain, filth—very, very unpleasant.”

“What a queer creature!” thought the Consul.

In the centre of the little room with its dark-flowered wall-paper stood a sizable square table covered with green baize. It rained harder and harder; it was so dark that the first thing Herr Grünlich did was to light the three candles on the table. Business letters on blue paper, stamped with the names of various firms, torn and soiled papers with dates and signatures, lay on the green cloth. There were a thick ledger and a metal inkstand and sand-holder, full of well-sharpened pencils and goose-quills.

Herr Grünlich did the honours with the subdued and tactful mien of a man greeting guests at a funeral. “Dear Father, do take the easychair,” he said. “Herr Kesselmeyer, will you be so kind as to sit here?”

At last they were settled. The banker sat opposite the host, the Consul presided on the long side of the table. The back of his chair was against the hall door.

Herr Kesselmeyer bent over, released his upper lip, disentangled a glass from his waistcoat and stuck it on his nose, which he wrinkled for the purpose, and opened his mouth wide. Then he scratched his stubbly beard with an ugly rasping noise, put his hands on his knees, and remarked in a sprightly tone, jerking his head toward the piles of papers: “Well, there we have the whole boiling.”

“May I look into matters a little more closely?” asked the Consul, taking up the ledger. But Herr Grünlich suddenly stretched out his hands over the table—long, trembling hands marked with high blue veins—and cried out in a voice that trembled too: “A moment, Father. Just a moment. Let me make just a few explanations. Yes, you will get an insight into everything—nothing will escape your glance; but, believe me, you will get an insight into the situation of an unfortunate, not a guilty man. You see in me a man who fought

unwearied against fate, but was finally struck down. I am innocent of all—”

“We shall see, my friend, we shall see,” said the Consul, with obvious impatience; and Herr Grünlich took his hands away and resigned himself to his fate.

Then there were long dreadful minutes of silence. The three gentlemen sat close together in the flickering candle-light, shut in by the four dark walls. There was not a sound but the rustling of the Consul’s papers and the falling rain outside.

Herr Kesselmeyer stuck his thumbs in the arm-holes of his waistcoat and played piano on his shoulders with his fingers, looking with indescribable jocosity from one to the other. Herr Grünlich sat upright in his chair, hands on the table, staring gloomily before him, and now and then stealing an anxious glance at his father-in-law out of the tail of his eye. The Consul examined the ledger, followed columns of figures with his finger, compared dates, and did indecipherable little sums in lead-pencil on a scrap of paper. His worn features expressed astonishment and dismay at the conditions into which he now “gained an insight.” Finally he laid his left arm on Herr Grünlich’s and said with evident emotion: “You poor man!”

“Father,” Herr Grünlich broke out. Two great tears rolled down his cheeks and ran into the golden whiskers. Herr Kesselmeyer followed their course with the greatest interest. He even raised himself a little, bent over, and looked his vis-à-vis in the face, with his mouth open. Consul Buddenbrook was moved. Softened by his own recent misfortunes, he felt himself carried away by sympathy; but he controlled his feelings.

“How is it possible?” he said, with a sad head-shake. “In so few years—”

“Oh, that’s simple,” answered Herr Kesselmeyer, good-temperedly. “One can easily ruin oneself in four years. When we remember that it took an even shorter time for Westfall Brothers in Bremen to go smash—” The Consul stared at him, but without either seeing or hearing him. He himself had not expressed his own actual thoughts,

his real misgivings. Why, he asked himself with puzzled suspicion, why was this happening now? It was as clear as daylight that, just where he stood to-day, B. Grünlich had stood two years, three years before. But his credit had been inexhaustible, he had had capital from the banks, and for his undertakings continual endorsement from sound houses like Senator Bock and Consul Goudstikker. His paper had passed as current as banknotes. Why now, precisely now—and the head of the firm of Johann Buddenbrook knew well what he meant by this “now”—had there come this crash on all sides, this complete withdrawal of credit as if by common consent, this unanimous descent upon B. Grünlich, this disregard of all consideration, all ordinary business courtesy? The Consul would have been naïve indeed had he not realized that the good standing of his own firm was to the advantage of his son-in-law. But had the son-in-law’s credit so entirely, so strikingly, so exclusively depended upon his own? Had Grünlich himself been nothing at all? And the information the Consul had had, the books he had examined—? Well, however the thing stood, his resolution was firmer than ever not to lift a finger. They had reckoned without their host.

Apparently B. Grünlich had known how to make it appear that he was connected with the firm of Buddenbrook—well, this widelycirculated error should be set right once for all. And this Kesselmeyer —he was going to get a shock too. The clown! Had he no conscience whatever? It was very plain how shamelessly he had speculated on the probability that he, Johann Buddenbrook, would not let his daughter’s husband be ruined; how he had continued to finance Grünlich long after he was unsound, and exacted from him an ever crueller rate of interest.

“Now,” he said shortly, “let us get to the point. If I am asked as a merchant to say frankly what I think, I am obliged to say that if the situation is that of an unfortunate man, it is also in a great degree that of a guilty one.”

“Father!” stammered Herr Grünlich.

“The name does not come well to my ears,” said the Consul, quickly and harshly. “Your demands on Herr Grünlich amount, sir”—turning

for a moment to the banker—“to sixty thousand marks, I believe?”

“With the back interest they come to sixty-eight thousand seven hundred and fifty-five marks and fifteen shillings,” answered Herr Kesselmeyer pleasantly.

“Very good. And you would not be inclined under any circumstances to be patient for a longer time?”

Herr Kesselmeyer simply began to laugh. He laughed with his mouth open, in spasms, without a trace of scorn, even good-naturedly, looking at the Consul as though he were inviting him to join in the fun.

Johann Buddenbrook’s little deep eyes clouded over and began to show red rims around them that ran down to the cheek-bones. He had only asked for form’s sake, being aware that a postponement on the part of one creditor would not materially alter the situation. But the manner of this man’s refusal was mortifying indeed. With a motion of the hand he pushed away everything from in front of him, laid the pencil down with a jerk on the table, and said, “Then I must express myself as unwilling to concern myself any further with this affair.”

“Ah, ha!” cried Herr Kesselmeyer, shaking his hands in the air. “That’s the way to talk. The Herr Consul will settle everything out of hand—we shan’t have any long speeches. Without more ado.” Johann Buddenbrook did not even look at him.

“I cannot help you, my friend.” He turned calmly to Herr Grünlich. “Things must go on as they have begun. Pull yourself together, and God will give you strength and consolation. I must consider our interview at an end.”

Herr Kesselmeyer’s face took on a serious expression which was vastly becoming to it. But then he nodded encouragingly to Herr Grünlich. The latter sat motionless at the table, only wringing his hands so hard that the fingers cracked.

“Father—Herr Consul,” he said, with a trembling voice. “You will not —you cannot desire my ruin. Listen. It is a matter of a hundred and twenty thousand marks in all—you can save me! You are a rich man.

Regard it as you like—as a final arrangement, as your daughter’s inheritance, as a loan subject to interest. I will work—you know I am keen and resourceful—”

“I have spoken my last word,” said the Consul.

“Permit me—may I ask whether you could if you would?” asked Herr Kesselmeyer, looking at him through his glasses, with his nose wrinkled up. “I suggest to the Consul that this would be a most advantageous time to display the strength of the firm of Buddenbrook.”

“You would do well, sir, to leave the good name of my house to me. I do not need to throw my money in the nearest ditch in order to show how good my credit is.”

“Dear me, no, of course not—ditch, ah, ha!—Ditch is very funny. But doesn’t the gentleman think the failure of his son-in-law places his own credit in a bad light—er—ah—?”

“I can only recommend you again to remember that my credit in the business world is entirely my own affair,” said the Consul.

Herr Grünlich looked at his banker helplessly and began afresh: “Father! I implore you again: think what you are doing. Is it a question of me alone? I—oh, I myself might be allowed to perish. But your daughter, my wife, whom I love, whom I won after such a struggle—and our child—both innocent children—are they to be brought low as well? No, Father, I will not bear it; I will kill myself. Yes, I would kill myself with this hand. Believe me—and may heaven pardon you if it will.”

Johann Buddenbrook leaned back in his arm-chair quite white, with a fast-beating heart. For the second time the emotions of this man played upon him, and their expression had the stamp of truth; again he heard, as when he told Herr Grünlich the contents of his daughter’s letter from Travemünde, the same terrible threat, and again there shuddered through him all the fanatical reverence of his generation for human feelings, which yet had always been in conflict with his own hard practical sense. But the attack lasted no longer than a moment. “A hundred thousand marks,” he repeated to

himself; and then he said quietly and decisively: “Antonie is my daughter. I shall know how to protect her from unmerited suffering.”

“What do you mean by that?” asked Herr Grünlich, slowly stiffening.

“That you will see,” answered the Consul. “For the present I have nothing to add.” And he got up, pushed back his chair, and turned toward the door.

Herr Grünlich sat silent, stiff, irresolute; his mouth opened and closed without a word coming out. But the sprightliness of Herr Kesselmeyer returned at this conclusive action of the Consul. Yes, it got the upper hand entirely, it passed all bounds, it became frightful. The glasses fell from his nose, which went skyward, while his little mouth, with the two triangular yellow teeth, looked as though it were splitting. He rowed with his little red hands in the air, the fuzz on his head waved up and down, his whole face, with its bristly white beard distorted and grotesque with uncontrolled hilarity—had grown the colour of cinnamon.

“Ah, ha, ha, ah, ha!” he yelled, his voice cracking. “I find that in the last—degree—funny! You ought to consider, Consul Buddenbrook, before you consign to the grave such a valuable—such a supreme specimen of a son-in-law. Anything so shrewd, so resourceful as he is, won’t be born upon God’s wide earth a second time. Aha! Four years ago—when the knife was at our throat, the rope around our neck—suddenly we made a match with Fräulein Buddenbrook, and spread the news on ’Change, even before it had actually come off! Congratulations, my dear friend; my best respects!”

“Kesselmeyer,” groaned Herr Grünlich, making spasmodic motions with his hands, as though waving off an evil spirit. He rushed into one corner of the room, where he sat down and buried his face in his hands. The ends of his whiskers lay on his shanks, and he rocked his knees up and down in his emotion.

“How did we do that?” went on Herr Kesselmeyer. “How did we actually manage to catch the little daughter and the eighty thousand marks? O-ho, ah, ha! That is easy. Even if one has no more shrewdness and resourcefulness than a tallow candle, it is easy! You

show the saviour Papa nice, pretty, clean books, in which everything is put in the right way—only that they don’t quite correspond with the plain fact—for the plain fact is that three-quarters of the dowry is already debts.”

The Consul stood at the door deathly pale, the handle in his hand. Shivers ran up and down his back. He seemed to be standing in this little room lighted by the flickering candles, between a swindler and an ape gone mad with spite.

“I despise your words, sir,” he brought out with uncertain emphasis. “I despise your wild utterances the more that they concern me as well. I did not hand my daughter over light-headedly to misfortune; I informed myself as to my son-in-law’s prospects. The rest was God’s will.”

He turned—he would not hear any more—he opened the door. But Herr Kesselmeyer shrieked after him: “Aha, inquiries? Where? Of Bock? Of Goudstikker? Of Petersen? Of Massmann and Timm? They were all in it. They were all in it up to their necks. They were all uncommonly pleased to be secured by the wedding—” The Consul slammed the door behind him.

CHAPTER IX

D the cook, about whose honesty Tony had had her doubts, was busy in the dining-room.

“Ask Madame Grünlich to come down,” ordered the Consul. “Get yourself ready, my child,” he said as Tony appeared. He went with her into the salon. “Get ready as soon as possible, and get Erica ready too. We are going to the city We shall sleep to-night in a hotel and travel home to-morrow.”

“Yes, Papa,” Tony said. Her face was red; she was distracted and bewildered. She made unnecessary and hurried motions about her waist, as if not knowing where to begin and not grasping the actuality of the occasion.

“What shall I take, Papa?” she asked distractedly. “Everything? All our clothes? One trunk or two? Is Grünlich really bankrupt? Oh, my God! But can I take my jewelry, then? Papa, the servants must leave —I cannot pay them. Grünlich was to have given me housekeeping money to-day or to-morrow.”

“Never mind, my child; things will all be arranged here. Just take what is necessary in a small trunk. They can send your own things after you. Hurry, do you hear?”

Just then the portières were parted and Herr Grünlich came into the salon. With quick steps, his arms outstretched, his head on one side, with the bearing of a man who says: “Here I am; kill me if you will,” he hurried to his wife and sank down on his knees right in front of her. His appearance was pitiable. His golden whiskers were dishevelled, his coat crumpled, his neck-cloth askew, his collar open; little drops stood upon his forehead.

“Antonie!” he said. “Have you a heart that can feel? Hear me. You see before you a man who will be utterly ruined, if—yes, who will die of grief, if you deny him your love. Here I lie; can you find it in your heart to say to me: ‘I despise you—I am leaving you’?”

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