Benzoyl bromide (BzBr) by Asch

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Date

54 reactions in Reaxys

2017-09-27 12h:12m:16s (EST)

1. Query Br

Search as: As drawn, No salts, No mixtures, No isotopes, No charges, No radicals

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Rx-ID: 758064 View in Reaxys 1/54 Yield 90 %

Conditions & References With bromine, triphenylphosphine in dichloromethane, Time= 0.25h, Ambient temperature Aizpurua, Jesus Mari; Palomo, Claudio; Synthesis; nb. 8; (1982); p. 684 - 686 View in Reaxys

78 %

With bromocyane, triphenylphosphine in 1,4-dioxane Froeyen, Paul; Phosphorus, Sulfur and Silicon and the Related Elements; vol. 102; nb. 1-4; (1995); p. 253 - 260 View in Reaxys

65 %

With aluminum oxide, boron tribromide in benzene, Time= 20h, T= 60 °C Bains; Green; Tan; Pagni; Kabalka; Tetrahedron Letters; vol. 33; nb. 49; (1992); p. 7475 - 7476 View in Reaxys

60 %

With 2,4,4,6-Tetrabromo-2,5-cyclohexadien-1-one, triphenylphosphine in dichloromethane, Time= 1h, T= 0 - 10 °C Matveeva; Podrugina; Sandakova; Zefirov; Russian Journal of Organic Chemistry; vol. 40; nb. 10; (2004); p. 1469 - 1472 View in Reaxys With phosphorus pentabromide, benzene Adams; Ulich; Journal of the American Chemical Society; vol. 42; (1920); p. 607 View in Reaxys With phosphorus tribromide Claisen; Chemische Berichte; vol. 14; (1881); p. 2475 View in Reaxys With phosphorus tribromide, Ambient temperature Miller, Joseph; Ying, Oi-Ling; Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999); (1985); p. 323 - 328 View in Reaxys With Oxalyl bromide Nagasawa, Kazuo; Ohhashi, Keiko; Yamashita, Asami; Ito, Keiichi; Chemistry Letters; nb. 2; (1994); p. 209 - 212 View in Reaxys With carbon tetrabromide, polymer-bound triphenylphosphine in dichloromethane, Time= 3h, T= 20 °C Thomas, Gemma L.; Boehner, Christine; Ladlow, Mark; Spring, David R.; Tetrahedron; vol. 61; nb. 51; (2005); p. 12153 - 12159 View in Reaxys With ethyl tribromoacetate, triphenylphosphine in dichloromethane, Time= 3h, T= 20 °C Kang, Dong Ho; Joo, Tae Young; Lee, Eun Hwa; Chaysripongkul, Skaydaw; Chavasiri, Warinthorn; Jang, Doo Ok; Tetrahedron Letters; vol. 47; nb. 32; (2006); p. 5693 - 5696 View in Reaxys Reaction Steps: 2 1: triethylamine / CH2Cl2 / 0.5 h / Ambient temperature 2: triphenylphosphine dibromide / CH2Cl2 / 0.17 h / Ambient temperature With triethylamine, dibromotriphenylphosphorane in dichloromethane Aizpurua, Jesus Mari; Palomo, Claudio; Synthesis; nb. 8; (1982); p. 684 - 686 View in Reaxys General procedure for esterification of carboxylic acidspromoted by TBCA/triphenylphosphine

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General procedure: To a stirred solution of TBCA (0.37 mmol) andtriphenylphosphine (1 mmol) in CH2Cl2 (6 cm3) was addedthe carboxylic acid (1 mmol) at room temperature. Theprogress of the reaction was monitored by GC-MS (time1 inTable 1) and, then, alcohol (1 mmol) was added. After time2(Table 1), cyanuric acid was filtered off and the liquid wasevaporated on a rotatory evaporator under reduced pressure.The producs were purified by column chromatography (silicagel 70-230 mesh) using diethyl ether/pentane as eluent. Isopropyl benzoate27Colorless liquid; 1H NMR (200 MHz, CDCl3) d 1.35(d, 6H, J 6.3), 5.16-5.36 (hept, 1H, J 6.2), 7.38-7.52 (m,3H), 8.05 (m, 2H); 13C NMR (50 MHz, CDCl3) d 22.0,68.4, 128.3, 129.6, 131.0, 132.8, 166.2; MS (70 eV) m/z164 (M+), 123, 105 (100percent), 77, 59, 51, 43. With TBCA, triphenylphosphine in dichloromethane, Time= 1.5h, T= 20 °C , Appel Halogenation, Time Da Cunha Sindra, Haryadylla; De Mattos, Marcio C.S.; Journal of the Brazilian Chemical Society; vol. 27; nb. 6; (2016); p. 1129 - 1136 View in Reaxys

O H HO

OH O

O O

Rx-ID: 41685640 View in Reaxys 2/54 Yield

Conditions & References 3 : Preparation of (2R,3R,4S,5R,6R)-2-bromo-6-(benzoyloxymethyl)tetrahydro-2H-pyran-3,4,5-triyl tribenzoate Example 3 Preparation of (2R,3R,4S,5R,6R)-2-bromo-6-(benzoyloxymethyl)tetrahydro-2H-pyran-3,4,5-triyl tribenzoate D-glucose (1.01 g, 5.61 mmol) was added to a mixture comprising benzoyl bromide (10.30 g, 55.67 mmol), zinc bromide (252.2 mg, 1.12 mmol) and dichloromethane (10 mL) under ice-cooling, and the resulting mixture was stirred at room temperature for 4 days. Under ice-cooling, the reaction mixture was distributed and washed with water and dichloromethane, and the organic layer was washed twice with a 10percent aqueous sodium hydrogencarbonate solution. The obtained organic layer was dried over magnesium sulfate, filtered and then concentrated. The concentrated residue was purified by column chromatography (SH silica gel, hexane/ethyl acetate) to obtain the title compound (2.34 g, Yield: 64percent). Patent; MITSUBISHI TANABE PHARMA CORPORATION; UEDA, Keita; HATSUDA, Masanori; HYODO, Isao; TANIMOTO, Kouichi; (13 pag.); US2016/2276; (2016); (A1) English View in Reaxys

Rx-ID: 42642077 View in Reaxys 3/54 Yield

Conditions & References General procedure: To a clean and dry small vial, a solution of substrate 1 (15.0 μmol, 1.0 equivalent) was added using an aqueous cyclodextrin solution (1.0 mL) of the specified concentration in D2O. DBDMH 3 (4.3 mg, 15.0 μmol, 1.0 equivalent) was added to the reaction mixture and sonicated to make sure that the reagents were well suspended. The reaction mixture was heated at 60 °C with occasional shaking to maintain the homogeneity of the solution. After the desired period of time, the 1H NMR spectrum of the reaction mixture was recorded to determine the percent conversion. With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione, water-d2, alpha cyclodextrin, Time= 1h, T= 60 °C , Green chemistry, Catalytic behavior

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Chaudhuri, Sauradip; Zaki, Hossam; Levine, Mindy; Synthetic Communications; vol. 46; nb. 7; (2016); p. 636 644 View in Reaxys O O

Rx-ID: 37335008 View in Reaxys 4/54 Yield

Conditions & References General procedure: Just as outlined in Scheme 1, the compound 1a (20 mmol) or 1b (20 mmol) and catalytic amount of AlCl3 was added to a three-necked flask containing THF (40 mL). Then the mixture was cooled to 0 °C and Br2 (20 mmol) stored in the constant pressure funnel was slowly and cautiously added to the mixture in 20 min. After the dropwise add completed, the mixture was evaporated under reduced pressure immediately. Then, precipitation crystallization was washed with mixed solvent of water and petroleum ether to get 2a, 2b. Freshly prepared 2a (20 mmol) or 2b (20 mmol) and thiourea (22 mmol) in anhydrous EtOH (30 mL) was refluxed for 30 min. After that, the solvent was evaporated under reduced pressure and then the saturated aqueous NaHCO3 was added tomake the mixture basic (pH 8-9). Then the mixture was extractedwith CH2Cl2 (3 30 mL). The combined organic phases were dried with anhydrous Na2SO4. After removal of all the solvent, the residue was purified by recrystallization from anhydrous EtOH to afford product 3a or 3b, 91percent and 93percent, respectively. With AlCl3, aluminium chloride, bromine in tetrahydrofuran, Time= 0.333333h, T= 0 °C Li, Jing-Ran; Li, Dong-Dong; Wang, Rong-Rong; Sun, Jian; Dong, Jing-Jun; Du, Qian-Ru; Fang, Fei; Zhang, Wei-Ming; Zhu, Hai-Liang; European Journal of Medicinal Chemistry; vol. 75; (2014); p. 438 - 447 View in Reaxys

(v4)

(v5)

O Pt P

(v4)

(v5)

Pt SP-4

(v4)

Rx-ID: 35274484 View in Reaxys 5/54 Yield

Conditions & References in benzene-d6, T= 35 °C , Glovebox, Equilibrium constant Kuniyasu, Hitoshi; Sanagawa, Atsushi; Nakane, Daisuke; Iwasaki, Takanori; Kambe, Nobuaki; Bobuatong, Karan; Lu, Yunpeng; Ehara, Masahiro; Organometallics; vol. 32; nb. 6; (2013); p. 2026 - 2032 View in Reaxys O Br

Rx-ID: 7018534 View in Reaxys 6/54 Yield 59%

Conditions & References 4.b : b b tert-Butyl 4-fluoro-3-(methylaminomethyl)benzoate A mixture of tert-butyl 4-fluoro-3-methylbenzoate (9.85 g, 46.9 mmole), N-bromosuccinimide (10 g, 56 mmole), benzoyl peroxide (0.6 g, 2.5 mmole), and CCl4 (100 mL) was heated to reflux with the aid of a 150 W tungsten flood lamp. After refluxing for 24 h, the reaction was cooled to RT and filtered, and the filter pad was washed with CCl4 (25 mL). The filtrate was concentrated to give the crude benzylic bromide (15.11 g, 59percent pure by GC, containing 32percent dibromide) as a yellow oil. Patent; SmithKline Beecham Corporation; US6503903; (2003); (B1) English View in Reaxys Lee,K.H.; Tetrahedron; vol. 24; (1968); p. 4793 - 4803

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View in Reaxys Sheinkman et al.; Chemistry of Heterocyclic Compounds (New York, NY, United States); vol. 6; (1970); p. 1413; Khimiya Geterotsiklicheskikh Soedinenii; vol. 6; (1970); p. 1515 View in Reaxys Seyferth; Shih; Journal of the American Chemical Society; vol. 95; (1973); p. 8464 View in Reaxys Fumarola; Orio; Anales de la Asociacion Quimica Argentina (1921-2001); vol. 60; (1972); p. 61 View in Reaxys Clark-Lewis; Skingle; Australian Journal of Chemistry; vol. 21; (1968); p. 2077,2083 View in Reaxys Anders; Synthesis; (1978); p. 586 View in Reaxys Jones; Ritchie; Journal of the Chemical Society; (1960); p. 4141,4151 View in Reaxys Bestmann; Mott; Justus Liebigs Annalen der Chemie; vol. 693; (1966); p. 132 View in Reaxys Semenyuk et al.; Zhurnal Organicheskoi Khimii; vol. 10; (1974); p. 2150,2166,2167 View in Reaxys Saraf; Zaki; Synthesis; (1973); p. 612 View in Reaxys Jagupol'skii; Kondratenko; J. Gen. Chem. USSR (Engl. Transl.); vol. 37; (1967); p. 1770,1686 View in Reaxys Yamase; Goto; Nippon Kagaku Zasshi; vol. 81; (1960); p. 1906,1909; ; vol. 56; nb. 3397; (1962) View in Reaxys Patent; Nat.Distillers Chem.; NL6614185; (1967); ; vol. 67; nb. 64066 View in Reaxys Ol'dekop; Kalinina; J. Gen. Chem. USSR (Engl. Transl.); vol. 34; (1964); p. 3473,3515 View in Reaxys Ol'dekop et al.; Doklady Chemistry; vol. 139; (1961); p. 862; Doklady Akademii Nauk SSSR; vol. 139; (1961); p. 1383 View in Reaxys Majer; Patrick; Transactions of the Faraday Society; vol. 59; (1963); p. 1274,1275 View in Reaxys Patent; Chemische Fabrik Kalk G.m.b.H.; FR1556480; (1969); ; vol. 72; nb. 42844v; (1970) View in Reaxys Anderson; Kono; Tetrahedron Letters; (1973); p. 5121,5122 View in Reaxys Gloede; Gross; Chemische Berichte; vol. 100; (1967); p. 1770 View in Reaxys Mukai et al.; Tetrahedron Letters; (1968); p. 1695 View in Reaxys A : Method A Method A Cinnamic ester 1 is treated with a brominating agent such as NBS in a refluxing inert solvent such as CCl4, with the use of an initiator like benzoyl peroxide. or light. The resulting benzylic bromide is reacted in a Suzuki coupling reaction with the appropriate boronic acid or ester, a catalyst such as tetrakis(triphenylphosphine) palladium and cesium fluoride or Na2CO3 or a base in an inert refluxing solvent such as DME at 80-90° C. The new cinnamic ester 3 is hydrolyzed with aqueous sodium hydroxide to afford the acid 4 that is converted to the cinnamic sulfonamide 5 with a coupling reagent such as DCC or DCI in CH2Cl2 at r.t. Patent; CHAN, CHI CHUNG; LABELLE, MARC; METTERS, KATHLEEN; US2001/12845; (2001); (A1) English View in Reaxys 20.3 : N-Hydroxy-6,6-dimethyl-7-(4-methoxybenzoyl)heptanamide (58) A mixture of ester 55 (190 mg, 0.65 mmol) and N-bromosuccinimide(150 mg, 0.85 mmol) in CCl1 was heated at reflux overnight in the presence of a catalytic amount of AIBN (7mg). The reaction mixture was cooled to ambient temperature, and the floating solid was filtered off. The filtrate was then concentrated to give the crude benzylic bromide: 1H NMR (300 MHz, CDCl3) δ7.28 (d, J=8.7 Hz, 2H), 6.81(d, J=8.7 Hz, 2H), 4.89 (s, 1H), 4.13 (q, J=7.2 Hz, 2H), 3.80 (s, 3H), 2.31 (t, J=7.5 Hz, 2H), 1.60 (m, 2H), 1.26 (t, J=7.2 Hz, 3H), 1.10-1.40 (m, 4H), 1.05 (s, 3H), 0.93 (s, 3H).

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Patent; Delorme, Daniel; Woo, Soon Hyung; Vaisburg, Arkadii; US2002/115826; (2002); (A1) English View in Reaxys 2-(4-Methoxy-benzenesulfonyl)-octyl-aminol-3-(4-methyl-piperazin-1-ylmethyl)-benzoic acid methyl ester 2-(4-Methoxy-benzenesulfonyl)-octyl-aminol-3-(4-methyl-piperazin-1-ylmethyl)-benzoic acid methyl ester To a solution of 0.515 g (1.112 mmol) of the product of Example 323 in dichloromethane was added 0.438 g (1.668 mmol) of triphenylphosphine and 0.461 g (1.390 mmol) of carbon tetrabromide. The mixture was stirred for 1 h at room temperature and then concentrated in vacuo. The residue was filtered through a pad of silica gel eluding with EtOAc/hexanes (1:10) to provide the benzylic bromide. Patent; American Cyanamid Company; US5929097; (1999); (A1) English View in Reaxys 2-{5-Bromo-2-[(4-methoxy-benzenesulfonyl)-methyl-amino]-3-methoxycarbonyl-benzyl}-malonic acid dimethyl ester 2-{5-Bromo-2-[(4-methoxy-benzenesulfonyl)-methyl-amino]-3-methoxycarbonyl-benzyl}-malonic acid dimethyl ester To a solution of 1.50 g (3.505 mmol) of the product of Example 202 in 65 mL of carbon tetrachloride was added 0.749 g (4.206 mmol) of N-bromosuccinimide and 0.06 g of dibenzoyl peroxide. The reaction was heated to reflux for 15 h, cooled and washed with water. The organics were dried over MgSO4, filtered and concentrated in vacuo. The residue was chromatographed on silica gel eluding with EtOAc/Hiexanes (1:3) to provide 1.46 g of the benzylic bromide. Patent; American Cyanamid Company; US5929097; (1999); (A1) English View in Reaxys 1.51 g (80%)

1 : 2-(tert-Butyl)dimethylsilyloxy-4-bromo-5-methoxybenzyl bromide (6): Purification by trituration at 0° C. (2*30 mL ea. hexanes) to remove residual triphenylphosphine oxide, followed by flash column chromatography (silica gel, hexanes/ethyl acetate, gradient elution) afforded 1.51 g (80percent) of the benzylic bromide as a colorless, viscous oil, which solidified upon standing. 1 H NMR (400 MHz, CDCl3) δ0.27 s, 6H, Si(CH3)2!, 1.04 s, 9H, SiC(CH3)3!, 3.84 (s, 3H, OCH3), 4.46 (s, 2H CH2 Br), 6.87 and 7.01 ppm (2s, 2*1H, Ar--H). Patent; Ligand Pharmaceuticals Incorporated; US5677336; (1997); (A1) English View in Reaxys

1.51 g (80%)

5 : 2-(tert-Butyl)dimethylsilyloxy-4-bromo-5-methoxybenzyl bromide (6) Purification by trituration at 0° C. (2*30 mL ea. hexane) to remove residual triphenylphosphine oxide, followed by flash column chromatography (silica gel, hexane/ethyl acetate, gradient elution) afforded 1.51 g (80percent) of the benzylic bromide as a colorless, viscous oil. 1 H NMR (400 MHz, CDCl3) δ 0.28 s, 6H, Si(CH3)2!, 1.05 s, 9H, SiC(CH3)3!, 387 (s, 3H, OCH3), 4.48 (s, 2H CH2 Br), 6.79 and 7.01 ppm (2s, 2*1H, Ar--H). Patent; Ligand Pharmaceuticals Incorporated; The Regents of the University of California; US5808139; (1998); (A1) English View in Reaxys 29.B.2 : Step 2 To the product of Step 1 and CBr4 (13.90 g, 1.3 equiv.) in CH2 Cl2 (160 mL) at 0° C., a solution of 1,2-bis(diphenylphosphino)ethane (DIPHOS, 8.37 g, 0.65 equiv.) in CH2 Cl2 (75 mL) was added and the resulting mixture was stirred at 0° C. for 45 min. and at r.t. for 30 min. Ether was then added and the mixture was filtered through a pad of silica and the silica was washed with EtOAc:toluene 20:80 to yield the pure benzylic bromide. 1 H NMR (CD COCD ) δ (ppm): 4.62 (s, 2H), 5.4 (s, 2H), 7.04 (d, 1H), 7.08 (d, 1H), 7.21 (s, 1H), 7.30 (t, 1H), 7.6 3 3 (dd, 1H), 7.76 (d, 1H), 8.02 (d, 1H), 8.05 (s, 1H), 8.42 (d, 1H). Patent; Merck Frosst Canada, Inc.; US5104882; (1992); (A1) English View in Reaxys Suitable acid halides include the following: ... phenoxyacetyl chloride, p-bromophenylacetyl chloride, p-nitrophenylacetyl chloride, ethyloxalyl chloride,

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benzoyl bromide, p-chlorobenzoyl chloride, p-octylbenzoyl chloride, 3,5-dinitrobenzoyl chloride, ... Patent; American Cyanamid Company; US4288592; (1981); (A1) English View in Reaxys Specific examples of these acid halides and acid anhydrides are shown below. Ii-1-a. acid Halides ... 4-methyl-2-pentenoic acid chloride, 10-undecenoyl chloride, oleyl chloride, benzoyl chloride, benzoyl bromide, phenylacetyl chloride, p-methylbenzoyl chloride, β-phenylpropionyl chloride, ... Patent; Teijin Limited; US4009196; (1977); (A1) English View in Reaxys Examples of an acid halide of the Formula III or IV are as follows: ... Butyryl chloride Isobutyryl chloride Cyclohexane carbonyl chloride Benzoyl chloride Benzoyl bromide p-Anisoyl chloride p-Chlorobenzoyl chloride m-Chlorobenzoyl chloride ... Patent; Sumitomo Chemical Company, Limited; US4055565; (1977); (A1) English View in Reaxys 2-[(4-Methoxy-benzenesulfonyl)-octyl-amino]-3-(4-methyl-piperazin-1-ylmethyl)-benzoic acid methyl ester 2-[(4-Methoxy-benzenesulfonyl)-octyl-amino]-3-(4-methyl-piperazin-1-ylmethyl)-benzoic acid methyl ester To a solution of 0.515g (1.112 mmol) of the product of Example 323 in dichloromethane was added 0.438g (1.668 mmol) of triphenylphosphine and 0.461g (1.390 mmol) of carbon tetrabromide. The mixture was stirred for 1h at room temperature and then concentrated in vacuo. The residue was filtered through a pad of silica gel eluding with EtOAc/hexanes (1:10) to provide the benzylic bromide. Patent; American Cyanamid Company; EP938471; (2001); (B1) English View in Reaxys 2-{5-Bromo-2-[(4-methoxy-benzenesulfonyl)-methyl-amino]-3-methoxycarbonyl-benzyl}-malonic acid dimethyl ester 2-{5-Bromo-2-[(4-methoxy-benzenesulfonyl)-methyl-amino]-3-methoxycarbonyl-benzyl}-malonic acid dimethyl ester To a solution of 1.50g (3.505 mmol) of the product of Example 202 in 65mL of carbon tetrachloride was added 0.749g (4.206 mmol) of N-bromosuccinimide and 0.06g of dibenzoyl peroxide. The reaction was heated to reflux for 15h, cooled and washed with water. The organics were dried over MgSO4, filtered and concentrated in vacuo. The residue was chromatographed on silica gel eluding with EtOAc/Hexanes (1:3) to provide 1.46g of the benzylic bromide. Patent; American Cyanamid Company; EP938471; (2001); (B1) English View in Reaxys

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73 : 4-[(4-Hydroxy-benzenesulfonyl)-methyl-amino]-5-(4-methyl-piperazin-1-ylmethyl)-biphenyl-3-carboxylic acid methyl ester EXAMPLE 73 4-[(4-Hydroxy-benzenesulfonyl)-methyl-amino]-5-(4-methyl-piperazin-1-ylmethyl)-biphenyl-3-carboxylic acid methyl ester A mixture of 1.84 g (3.5 mmol) of the product of Example 72 and 0.748 g (4.2 mmol) of N-bromosuccinimide in 35 mL of carbon tetrachloride was refluxed with sun lamp under nitrogen for 2.5 h. The reaction was cooled, washed with water and brine, dried over Na2SO4 and concentrated in vacuo to give 2.33 g of the benzylic bromide. Patent; American Cyanamid Company; US6277885; (2001); (B1) English View in Reaxys 32 : Synthesis of benzoyl bromide EXAMPLE 32 Synthesis of benzoyl bromide To a reaction vessel, 0.24 g (2.0 m mol) of benzoic acid, 1.60 g of a 25.91 wt percent DMFB solution in acetonitrile (0.414 g, 2.1 m mol as DMFB), and 3.86 g of acetonitrile were charged and reacted at room temperature for 43 hours in a nitrogen atmosphere. The results of the reaction by GC analysis were 11.0percent in benzoyl bromide, 31.5percent in benzoyl fluoride, 26.0percent in benzoic anhydride, and 16.0percent in unreacted benzoic acid. Patent; Mitsui Chemicals, Inc.; US6329529; (2001); (B1) English View in Reaxys O : K. O. (R)- and (RS)-1-Bromo-1-(2-bromophenyl)ethane, 7b, from 1-(2-Bromophenyl)ethanol (8b) The preparation of (R)-7b from (S)-8b, diphos and bromine was done essentially as for the 2-naphthyl analogue, (S)-8a, using a 20percent excess of the diphosibromine reagent. Patent; Richman, Jack E.; US2009/181462; (2009); (A1) English View in Reaxys O Br

Rx-ID: 11215523 View in Reaxys 7/54 Yield

Conditions & References With trihexyl(tetradecyl) phosphonium bromide, 1,1'-bis-(diphenylphosphino)ferrocene, palladium diacetate, Time= 8h, T= 60 °C , p= 760.051Torr McNulty, James; Nair, Jerald J.; Robertson, Al; Organic Letters; vol. 9; nb. 22; (2007); p. 4575 - 4578 View in Reaxys O

Rx-ID: 9260376 View in Reaxys 8/54 Yield

Conditions & References With oxygen in 1,2,2-trifluoro-trichloroethane, T= 20 °C , Kinetics Makihara, Taiki; Nojima, Takayuki; Ishiguro, Katsuya; Sawaki, Yasuhiko; Tetrahedron Letters; vol. 44; nb. 4; (2003); p. 865 - 868 View in Reaxys O

(5-Bromomethyl-pyrazin-2-yl)-carbatic acid tert-butyl ester Br

Rx-ID: 23969117 View in Reaxys 9/54 Yield 51%

Conditions & References 1 : 1-[5-(1,3-Dioxo-1,3-dihydro-isoindol-2-ylmethyl)-pyrazin-2-yl]-3-(2-methoxy-5-methyl-phenyl)-urea

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Step 1: (5-Bromomethyl-pyrazin-2-yl)-carbatic acid tert-butyl ester. To a stirred solution of 2-Boc-amino-5-methyl pyrazine (1.34 gm, 6.4 mmol), in 20 mL CCl4 at room temperature under nitrogen was added N-bromosuccinimide (1.14 gm, 6.4 mmol) followed by benzoyl peroxide (125 mg). The solution was irradiated with a 100 watt flood lamp, which caused the reaction to reflux vigorously. After 2 hours, the reaction was cooled to room temperature, diluted to 125 mL with CH2Cl2 and washed 1*125 mL with 10percent sodium bisulfite solution and 1*125 mL with saturated NaCl. The organics were dried (MgSO4), filtered and concentrated to a brown oil, which was directly loaded onto a Biotage 40S column with CH2Cl2 and eluted with 15/85 EtOAc/hexane to give the desired benzylic bromide as a yellow solid (954 mg, 51percent). 1H-NMR (400 MHz, CDCl ) δ9.22 (s, 1H), 8.29 (s, 1H), 7.37 (br s, 1H), 4.54 (s, 2H), 1.55 (s, 9H). 3 Patent; Keegan, Kathleen S.; Kesicki, Edward A.; Gaudino, John Joseph; Cook, Adam Wade; Cowen, Scott Douglas; Burgess, Laurence Edward; US2003/69284; (2003); (A1) English View in Reaxys O C O

Rx-ID: 2057700 View in Reaxys 10/54 Yield

Conditions & References With trichloromonobromomethane, T= 24 °C , Rate constant Neville; Brown; Rayner; Lusztyk; Ingold; Journal of the American Chemical Society; vol. 113; nb. 5; (1991); p. 1869 - 1870 View in Reaxys With trichloromonobromomethane in hexane, T= 22.9 °C , Rate constant Brown, Carl E.; Neville, Anthony G.; Rayner, David M.; Ingold, Keith U.; Lusztyk, Janusz; Australian Journal of Chemistry; vol. 48; nb. 2; (1995); p. 363 - 380 View in Reaxys With trichloromonobromomethane in acetonitrile, T= 24.85 °C , Kinetics Colley, Christopher S.; Grills, David C.; Besley, Nicholas A.; Jockusch, Steffen; Matousek, Pavel; Parker, Anthony W.; Towrie, Michael; Turro, Nicholas J.; Gill, Peter M. W.; George, Michael W.; Journal of the American Chemical Society; vol. 124; nb. 50; (2002); p. 14952 - 14958 View in Reaxys O

Br Br

Rx-ID: 24074587 View in Reaxys 11/54 Yield 3.10 g (98%)

Conditions & References 1 : Synthesis of 1,3-Bis-[3,4-dichlorophenyl)aminocarbonyl]-5-(benzyloxy)benzene (Exemplary Compound 43) 3,5-Bis(ethoxycarbonyl)benzyl bromide. A solution of 3,5-bis(ethoxycarbonyl) benzyl alcohol (2.53 g, 10 mmol) and PBr3 (0.95 mL, 10 mmol) in chloroform (50 mL) was stirred at room temperature overnight. Yellowish solution was washed with water (50 mL). The organic layer was separated, dried with Na2SO4 anhyd. and evaporated in vacuo to provide the benzylic bromide as a white solid, yield 3.10 g (98percent). NMR (CDCl3, 400 MHz), δ8.61 (s, 1H); 8.25 (s, 2H); 4.55 (s, 2H); 4.42 (q, J=7.0 Hz, 4H); 1.43 (t, J=7.0 Hz, 6H).

With phosphorus tribromide in chloroform Patent; Wu, Yong-Qian; Belyakov, Sergei; Hamilton, Gregory S.; Limburg, David; Steiner, Joseph P.; Vaal, Mark; Wei, Ling; Wilkinson, Douglas; US2002/165275; (2002); (A1) English

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View in Reaxys O

Rx-ID: 25589352 View in Reaxys 12/54 Yield

Conditions & References 1.a : EXAMPLE 1 The benzylic alcohol (99.8 g, 0.38 mol) is dissolved in 48percent HBr (500 ml) and heated to reflux temperature for 4 hours. The resulting benzylic bromide is isolated as a yellow solid by pouring the cooled mixture into a large volume (1.5 L) of water followed by filtration. in hydrogen bromide Patent; Novartis AG; US6291523; (2001); (B1) English View in Reaxys

Rx-ID: 2690773 View in Reaxys 13/54 Yield

Conditions & References

96 %

With thionyl bromide, Time= 3h, T= 80 - 90 °C Saraf, S. D.; Journal fuer Praktische Chemie (Leipzig); vol. 323; nb. 4; (1981); p. 673 - 676 View in Reaxys

78 %

With N-bromosuccinmide, 2,2'-azo-bisisobutyronitrile in tetrachloromethane, Time= 0.5h, Heating Marko; Mekhalfia; Tetrahedron Letters; vol. 31; nb. 49; (1990); p. 7237 - 7240 View in Reaxys

O O O

O O

Br O

O Br

Rx-ID: 2612694 View in Reaxys 14/54 Yield

Conditions & References With trichloromonobromomethane in tetrachloromethane, Irradiation Collins, P. M.; Premaratne, P.; Manro, A.; Hussain, A.; Tetrahedron Letters; vol. 30; nb. 35; (1989); p. 4721 - 4722 View in Reaxys

O O

O Br

Rx-ID: 2623222 View in Reaxys 15/54 Yield

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O O

Rx-ID: 2636999 View in Reaxys 16/54 Yield

O Br

Rx-ID: 2736653 View in Reaxys 17/54 Yield

O O

O Br

O O

Rx-ID: 2743944 View in Reaxys 18/54 Yield

Conditions & References With Bromotrichloromethane in tetrachloromethane, Time= 1.08333h, Irradiation Collins, P. M.; Premaratne, P.; Manro, A.; Hussain, A.; Tetrahedron Letters; vol. 30; nb. 35; (1989); p. 4721 - 4722 View in Reaxys

O O

O Br

O O

Rx-ID: 2743945 View in Reaxys 19/54 Yield

Conditions & References With Bromotrichloromethane in tetrachloromethane, Irradiation Collins, P. M.; Premaratne, P.; Manro, A.; Hussain, A.; Tetrahedron Letters; vol. 30; nb. 35; (1989); p. 4721 - 4722

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View in Reaxys

O O

O Br

O O

Rx-ID: 2743946 View in Reaxys 20/54 Yield

O O

O Br

O O

Rx-ID: 2743947 View in Reaxys 21/54 Yield

O P

(v4)

Pd SP-4 Cl (v4)

Rx-ID: 26515261 View in Reaxys 22/54 Yield

Conditions & References With bromine in dichloromethane, byproducts: (P(C6H5)3)2PdClBr; addition of Br2 to Pd(P(C6H5)3)2(C6H5CO)Cl in CH2Cl2; determination : IR Kubota, Mitsuru; Boegeman, Scott C.; Keil, Robert N.; Webb, Carl G.; Organometallics; vol. 8; (1989); p. 1616 1620 ; (from Gmelin) View in Reaxys

O (v5) (v4)

Pt Cl SP-4

(v5)

O Br

Rx-ID: 26631025 View in Reaxys 23/54 Yield

Conditions & References With bromine in dichloromethane, byproducts: (C8H12)PtClBr; addition of Br2 to Pt(C8H12)(C6H5CO)Cl in CH2Cl2; determination:IR

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Kubota, Mitsuru; Boegeman, Scott C.; Keil, Robert N.; Webb, Carl G.; Organometallics; vol. 8; (1989); p. 1616 1620 ; (from Gmelin) View in Reaxys

O (v4)

P (v4) SP-4 Pt (v4) P

Rx-ID: 26635266 View in Reaxys 24/54 Yield

Conditions & References With bromine in dichloromethane, byproducts: ((C6H5)2PCH2CH2P(C6H5)2)PtClBr; addition of Br2 to Pt((C6H5)2PCH2CH2P(C6H5)2)(C6H5CO)Cl in CH2Cl2; determination:IR Kubota, Mitsuru; Boegeman, Scott C.; Keil, Robert N.; Webb, Carl G.; Organometallics; vol. 8; (1989); p. 1616 1620 ; (from Gmelin) View in Reaxys

P (v4) Pt SP-4

(v4) (v4)

Rx-ID: 26635269 View in Reaxys 25/54 Yield

Conditions & References With bromine in dichloromethane, byproducts: (PPh)2PtBr2; addition of Br2 to trans-(Pt(PPh3)2(PhCO)Br) in CH2Cl2; determination:IR Kubota, Mitsuru; Boegeman, Scott C.; Keil, Robert N.; Webb, Carl G.; Organometallics; vol. 8; (1989); p. 1616 1620 ; (from Gmelin) View in Reaxys

(v4)

Pt SP-4

(v4)

Rx-ID: 26635322 View in Reaxys 26/54 Yield

Conditions & References With bromine in dichloromethane, byproducts: (PPh)2PtClBr; addition of Br2 to trans-(Pt(PPh3)2(PhCO)Cl) in CH2Cl2; determination:IR Kubota, Mitsuru; Boegeman, Scott C.; Keil, Robert N.; Webb, Carl G.; Organometallics; vol. 8; (1989); p. 1616 1620 ; (from Gmelin) View in Reaxys

(v4)

Br Pd SP-4 (v4) P

(v4)

Rx-ID: 26529230 View in Reaxys 27/54

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Yield

Conditions & References

With 1,4-dimethyl-1,4-diazacyclohexane in not given, Absence of CO, tenfold excess of piperazine, 90°C, rate of reaction increases with basicity of the amine Moser, William R.; Wang, Andrew W.; Kildahl, Nicholas K.; Journal of the American Chemical Society; vol. 110; nb. 9; (1988); p. 2816 - 2820 ; (from Gmelin) View in Reaxys

With 2,6-dimethylpyridine in not given, Absence of CO, tenfold excess of butidine, 90°C, rate of reaction increases with basicity of the amine Moser, William R.; Wang, Andrew W.; Kildahl, Nicholas K.; Journal of the American Chemical Society; vol. 110; nb. 9; (1988); p. 2816 - 2820 ; (from Gmelin) View in Reaxys

With 4-methyl-morpholine in not given, Absence of CO, tenfold excess of morpholine, 90°C, rate of reaction increases with basicity of the amine Moser, William R.; Wang, Andrew W.; Kildahl, Nicholas K.; Journal of the American Chemical Society; vol. 110; nb. 9; (1988); p. 2816 - 2820 ; (from Gmelin) View in Reaxys

With 1-methyl-piperidine in not given, Absence of CO, tenfold excess of piperidine, 90°C, rate of reaction increases with basicity of the amine Moser, William R.; Wang, Andrew W.; Kildahl, Nicholas K.; Journal of the American Chemical Society; vol. 110; nb. 9; (1988); p. 2816 - 2820 ; (from Gmelin) View in Reaxys

With N-methyl-pyrrolidine in not given, Absence of CO, tenfold excess of pyrrolidine, 90°C, rate of reaction increases with basicity of the amine Moser, William R.; Wang, Andrew W.; Kildahl, Nicholas K.; Journal of the American Chemical Society; vol. 110; nb. 9; (1988); p. 2816 - 2820 ; (from Gmelin) View in Reaxys

With triethylamine in not given, Absence of CO, tenfold excess of NEt3, 90°C, rate of reaction increases with basicity of the amine Moser, William R.; Wang, Andrew W.; Kildahl, Nicholas K.; Journal of the American Chemical Society; vol. 110; nb. 9; (1988); p. 2816 - 2820 ; (from Gmelin) View in Reaxys

C O

Rx-ID: 1912463 View in Reaxys 28/54 Yield

Conditions & References in water, acetonitrile, T= 20 °C , Rate constant Timpe, Hans-Joachim; Wagner, Roland; Paleta, Oldrich; Zeitschrift fuer Chemie (Stuttgart, Germany); vol. 27; nb. 11; (1987); p. 410 - 411 View in Reaxys

O Si

O O

P Br

Rx-ID: 3868697 View in Reaxys 29/54 Yield

Conditions & References in dichloromethane, Ambient temperature

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Aizpurua, Jesus M.; Cossio, Fernando P.; Palomo, Claudio; Journal of Organic Chemistry; vol. 51; nb. 25; (1986); p. 4941 - 4943 View in Reaxys in dichloromethane, Time= 0.25h, Ambient temperature, other trialkylsilyl esters and trialkylsilyl ethers, var. time, Product distribution Aizpurua, Jesus M.; Cossio, Fernando P.; Palomo, Claudio; Journal of Organic Chemistry; vol. 51; nb. 25; (1986); p. 4941 - 4943 View in Reaxys

O N

S N

O S

Rx-ID: 2607642 View in Reaxys 30/54 Yield

Conditions & References With bromine in tetrachloromethane, Ambient temperature, Yield given Khripak, S. M.; Yakubets, V. I.; Dobosh, A. A.; Chemistry of Heterocyclic Compounds (New York, NY, United States); vol. 21; nb. 9; (1985); p. 1091 - 1094; Khimiya Geterotsiklicheskikh Soedinenii; vol. 21; nb. 9; (1985); p. 1333 - 1336 View in Reaxys

O S

Rx-ID: 2607653 View in Reaxys 31/54 Yield

S N

Rx-ID: 2615793 View in Reaxys 32/54 Yield

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S N

Rx-ID: 2615877 View in Reaxys 33/54 Yield

–S

Na + O

Rx-ID: 21329030 View in Reaxys 34/54 Yield

Conditions & References Reaction Steps: 2 1: 38.8 percent / neat (no solvent) / 2.7 h / 100 °C 2: Br2 / CCl4 / Ambient temperature With bromine in tetrachloromethane Khripak, S. M.; Yakubets, V. I.; Dobosh, A. A.; Chemistry of Heterocyclic Compounds (New York, NY, United States); vol. 21; nb. 9; (1985); p. 1091 - 1094; Khimiya Geterotsiklicheskikh Soedinenii; vol. 21; nb. 9; (1985); p. 1333 - 1336 View in Reaxys

O Cl

O 5-benzoyl-O 1,O 2-isopropyliden-β-D-arabinofuranose

Rx-ID: 21348513 View in Reaxys 35/54 Yield

Conditions & References Reaction Steps: 2 1: 77.5 percent / benzene / 6 h / Ambient temperature 2: Br2 / CCl4 / Ambient temperature With bromine in tetrachloromethane, benzene Khripak, S. M.; Yakubets, V. I.; Dobosh, A. A.; Chemistry of Heterocyclic Compounds (New York, NY, United States); vol. 21; nb. 9; (1985); p. 1091 - 1094; Khimiya Geterotsiklicheskikh Soedinenii; vol. 21; nb. 9; (1985); p. 1333 - 1336 View in Reaxys Reaction Steps: 2 1: 60.2 percent / benzene / 6 h / Ambient temperature 2: Br2 / CCl4 / Ambient temperature With bromine in tetrachloromethane, benzene Khripak, S. M.; Yakubets, V. I.; Dobosh, A. A.; Chemistry of Heterocyclic Compounds (New York, NY, United States); vol. 21; nb. 9; (1985); p. 1091 - 1094; Khimiya Geterotsiklicheskikh Soedinenii; vol. 21; nb. 9; (1985); p. 1333 - 1336 View in Reaxys Reaction Steps: 2 1: 57.6 percent / benzene / 2 h / 100 °C

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2: Br2 / CCl4 / Ambient temperature With bromine in tetrachloromethane, benzene Khripak, S. M.; Yakubets, V. I.; Dobosh, A. A.; Chemistry of Heterocyclic Compounds (New York, NY, United States); vol. 21; nb. 9; (1985); p. 1091 - 1094; Khimiya Geterotsiklicheskikh Soedinenii; vol. 21; nb. 9; (1985); p. 1333 - 1336 View in Reaxys O

Si O

Rx-ID: 1987090 View in Reaxys 36/54 Yield

Conditions & References With dibromotriphenyl-phosphorane in dichloromethane, Time= 0.166667h, Ambient temperature Aizpurua, Jesus Mari; Palomo, Claudio; Synthesis; nb. 8; (1982); p. 684 - 686 View in Reaxys

Rx-ID: 616034 View in Reaxys 37/54 Yield

Conditions & References With hydrogen bromide, T= 100 °C Staudinger; Anthes; Chemische Berichte; vol. 46; (1913); p. 1435 View in Reaxys With trimethylsilyl bromide, Yield given Schmidt, Arthur H.; Russ, Manuel; Grosse, Detlef; Synthesis; nb. 3; (1981); p. 216 - 218 View in Reaxys O

CS2

H Cl

Rx-ID: 5806193 View in Reaxys 38/54 Yield

Conditions & References T= 18 °C Baddeley; Voss; Journal of the Chemical Society; (1954); p. 418,422 View in Reaxys O

Br Al Br

CS2

Rx-ID: 5806194 View in Reaxys 39/54 Yield

Conditions & References T= 18 °C Baddeley; Voss; Journal of the Chemical Society; (1954); p. 418,422 View in Reaxys O

boiling benzyl bromide Br

Rx-ID: 5690734 View in Reaxys 40/54 Yield

Conditions & References Einleiten von Sauerstoff und HBr Barnett et al.; Industrial and Engineering Chemistry; vol. 41; (1949); p. 2612,2614

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View in Reaxys

Br Br

Rx-ID: 7029510 View in Reaxys 41/54 Yield

Conditions & References Wieland; Justus Liebigs Annalen der Chemie; vol. 514; (1934); p. 145,157 View in Reaxys

Rx-ID: 283148 View in Reaxys 42/54 Yield

Conditions & References With bromine Lachman; Journal of the American Chemical Society; vol. 45; (1923); p. 2359 View in Reaxys

Br Br

Rx-ID: 7441848 View in Reaxys 43/54 Yield

Conditions & References Lachman; Journal of the American Chemical Society; vol. 45; (1923); p. 2359 View in Reaxys

Na + O–

Rx-ID: 228706 View in Reaxys 44/54 Yield

Conditions & References With benzene Adams; Ulich; Journal of the American Chemical Society; vol. 42; (1920); p. 607 View in Reaxys

Na + O–

Rx-ID: 532610 View in Reaxys 45/54 Yield

Conditions & References With phosphorus pentabromide, benzene Adams; Ulich; Journal of the American Chemical Society; vol. 42; (1920); p. 607 View in Reaxys

Rx-ID: 5806191 View in Reaxys 46/54 Yield

Conditions & References T= 100 °C Staudinger; Anthes; Chemische Berichte; vol. 46; (1913); p. 1435

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View in Reaxys

α-bromo-d-camphor

Br Br

Rx-ID: 7156132 View in Reaxys 47/54 Yield

Conditions & References benzoate of/the/ enolform of d-camphor Lees; Journal of the Chemical Society; vol. 83; (1903); p. 152 View in Reaxys

Br Br

Rx-ID: 8258823 View in Reaxys 48/54 Yield

Conditions & References Nef; Justus Liebigs Annalen der Chemie; vol. 308; (1899); p. 325 View in Reaxys

Br Cl

O Br

Rx-ID: 7440336 View in Reaxys 49/54 Yield

Conditions & References Jobst; Hesse; Justus Liebigs Annalen der Chemie; vol. 199; (1879); p. 73 View in Reaxys Ciamician; Silber; Chemische Berichte; vol. 25; (1892); p. 1123 View in Reaxys

Br Br

Rx-ID: 7449998 View in Reaxys 50/54 Yield

Conditions & References Seelig; Journal fuer Praktische Chemie (Leipzig); vol. <2> 39; (1889); p. 175 View in Reaxys O

eso-dibromo-durol

x.x.x.x.x-pentabromo-benzoyl-durol

Rx-ID: 7089196 View in Reaxys 51/54 Yield

Conditions & References Friedel; Crafts; Ador; Annales de Chimie (Cachan, France); vol. <6> 1; (1884); p. 511

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View in Reaxys

O O

Z O

CS2

Rx-ID: 8258824 View in Reaxys 52/54 Yield

Conditions & References Klingel; Chemische Berichte; vol. 16; (1883); p. 996 View in Reaxys

Br P

Rx-ID: 5806192 View in Reaxys 53/54 Yield

Conditions & References Claisen; Chemische Berichte; vol. 14; (1881); p. 2475 View in Reaxys

Br Br

H O

Rx-ID: 7443667 View in Reaxys 54/54 Yield

Conditions & References Paterno; Chemische Berichte; vol. 5; (1872); p. 288 View in Reaxys

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