611-17-6

Basic information

• Product Name: 2-Chlorobenzyl bromide
• Synonyms: Toluene, alpha-bromo-o-chloro-;Toluene,α-bromo-o-chloro-;2-CHLOROBENZYL BROMIDE;1-(BROMOMETHYL)-2-CHLOROBENZENE;ALPHA-BROMO-2-CHLOROTOLUENE;2-CHLOROBENZYL BROMIDE 95% (GC);2-Chlorobenzylbromide,97%;Benzene, 1-(bromomethyl)-2-chloro-
• CAS NO: 611-17-6
• Molecular Formula: C₇H₆BrCl
• Molecular Weight: 205.48
• EINECS: 210-257-2
• Product Categories: Benzyl
• Mol File: 611-17-6.mol
• Article Data: 36

Chemical Properties

• Melting Point: 83-84 °C
• Boiling Point: 103-104 °C (10 mmHg)
• Flash Point: 108 °C
• Appearance: Clear yellow/Liquid
• Density: 1.586
• Vapor Pressure: 0.0777mmHg at 25°C
• Refractive Index: 1.591-1.593
• Sensitive: Lachrymatory
• BRN: 386264
• CAS DataBase Reference: 2-Chlorobenzyl bromide(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Chlorobenzyl bromide(611-17-6)
• EPA Substance Registry System: 2-Chlorobenzyl bromide(611-17-6)

Safety Data

• Hazard Codes: C
• Statements: 34-36/37
• Safety Statements: 45-36/37/39-26-28-27
• RIDADR: 1760
• WGK Germany: 3
• HazardClass: 6.1
• PackingGroup: III
• Hazardous Substances Data: 611-17-6(Hazardous Substances Data)

Usage

Chemical Properties

Clear yellow liquid

Synthesis Reference(s)

Synthetic Communications, 6, p. 109, 1976 DOI: 10.1080/00397917608072618

General Description

2-Chlorobenzyl bromide participates in Hass-Bender oxidation as well as the Henry reaction.

InChI:InChI=1/C7H6BrCl/c8-5-6-3-1-2-4-7(6)9/h1-4H,5H2

Synthetic route

2-Chlorobenzyl alcohol (17849-38-6) → 1-bromomethyl-2-chlorobenzene (611-17-6)

Conditions	Yield
With 1,1,1,2,2,2-hexamethyldisilane In chloroform for 1.5h; Reflux;	96%
With phosphorus pentoxide; potassium bromide In acetonitrile at 20℃; for 0.5h;	89%
With hydrogen bromide; benzene

2-methylchlorobenzene (95-49-8) → 2-chloro-benzaldehyde (89-98-5) + 1-bromomethyl-2-chlorobenzene (611-17-6) + ortho-chlorobenzoic acid (118-91-2)

Conditions	Yield
With oxygen; cobalt(II) acetate; sodium bromide In acetic acid at 95℃; for 0.666667h; Kinetics; Mechanism; Rate constant; other time; other temperature; various concentrations of Co(OAc)2 and NaBr;	A n/a B n/a C 96%
With oxygen; cobalt(II) acetate; sodium bromide In acetic acid at 95℃; for 0.666667h;	A n/a B n/a C 95%

2-methylchlorobenzene (95-49-8) → 1-bromomethyl-2-chlorobenzene (611-17-6)

Conditions	Yield
With dihydrogen peroxide; bromine In dichloromethane; water for 4h; Reflux;	94%
With N-Bromosuccinimide In acetonitrile at 40℃; for 0.216667h; Flow reactor; Irradiation;	88%
With sodium bromate; 2,2'-azobis(isobutyronitrile); sulfuric acid; sodium bromide; dibenzoyl peroxide In water; 1,2-dichloro-ethane Reflux;	80%

2-chloro-benzaldehyde (89-98-5) → 1-bromomethyl-2-chlorobenzene (611-17-6)

Conditions	Yield
With Dichloromethylsilane; phosphorus tribromide; iron(III) chloride In acetonitrile for 4h; Heating;	93%
With chloro-trimethyl-silane; 1,1,3,3-Tetramethyldisiloxane; lithium bromide In acetonitrile at 80℃; for 0.25h;	64%
With chloro-trimethyl-silane; 1,1,3,3-Tetramethyldisiloxane; lithium bromide 1.) acetonitrile, room temperature, 10 min, 2.) 15 min, 80 deg C; Yield given. Multistep reaction;

1-chloro-2-(chloromethyl)benzene (611-19-8) → 2-bromo-2’-chlorodiethyl ether (51070-66-7) + 1-bromomethyl-2-chlorobenzene (611-17-6)

Conditions	Yield
With sodium bromide; 1,2-dibromomethane In N,N-dimethyl-formamide at 100℃; for 6h;	A n/a B 93%

1-chloro-2-(chloromethyl)benzene (611-19-8) → 1-bromomethyl-2-chlorobenzene (611-17-6)

Conditions	Yield
With 1,1'-[1,2-phenylenebis(nitrilomethylylidene)dinaphthalen-2-olato]uranyl(VI); bromine In dichloromethane at 20℃; for 0.583333h;	82%

2-chloro-1-(methoxymethoxy)methyl benzene (1058649-12-9) → 1-bromomethyl-2-chlorobenzene (611-17-6)

Conditions	Yield
With tetrabutylammomium bromide; 1-(n-butyl)-3-methylimidazolium tetrachloroindate at 135 - 140℃; for 0.0833333h; Microwave irradiation; Neat (no solvent); chemoselective reaction;	81%

2-chloro-1-[(ethoxymethoxy)methyl]benzene (1058649-16-3) → 1-bromomethyl-2-chlorobenzene (611-17-6)

Conditions	Yield
With tetrabutylammomium bromide; 1-(n-butyl)-3-methylimidazolium tetrachloroindate at 135 - 140℃; for 0.0833333h; Microwave irradiation; Neat (no solvent); chemoselective reaction;	79%

2-methylchlorobenzene (95-49-8) → 1-bromomethyl-2-chlorobenzene (611-17-6) + ortho-chlorobenzoic acid (118-91-2)

Conditions	Yield
With tert.-butylhydroperoxide; copper(ll) bromide In acetic anhydride	A 72% B 12%

bromocyane (506-68-3) + 1-(2-chlorophenyl)-N,N-dimethylmethanamine (10175-31-2) → 1-bromomethyl-2-chlorobenzene (611-17-6)

bromocyane (506-68-3) + (2-chloro-benzyl)-methyl-(4-nitro-benzyl)-amine (65763-39-5) → methyl-(4-nitro-benzyl)-carbamonitrile (52245-37-1) + 1-bromomethyl-2-chlorobenzene (611-17-6)

bromocyane (506-68-3) + (2-chloro-benzyl)-(3-iodo-benzyl)-methyl-amine → (2-chloro-benzyl)-methyl-carbamonitrile + (3-iodo-benzyl)-methyl-carbamonitrile + 1-bromomethyl-2-chlorobenzene (611-17-6) + 3-iodobenzyl bromide (49617-83-6)

bromocyane (506-68-3) + (2-bromo-benzyl)-(2-chloro-benzyl)-methyl-amine (876476-07-2) → (2-bromo-benzyl)-methyl-carbamonitrile + 1-bromomethyl-2-chlorobenzene (611-17-6)

bromocyane (506-68-3) + (2-chloro-benzyl)-methyl-(2-nitro-benzyl)-amine (854392-01-1) → methyl-(2-nitro-benzyl)-carbamonitrile + 1-bromomethyl-2-chlorobenzene (611-17-6)

bromocyane (506-68-3) + 1-(2-chlorophenyl)-N,N-dimethylmethanamine (10175-31-2) → 1-bromomethyl-2-chlorobenzene (611-17-6) + NCNMe2 (1467-79-4) + dimethyl-bis-<2-chloro-benzyl>-ammonium bromide

chlorobenzene (108-90-7) + 1,1-dibromomethane (74-95-3) → 1-bromomethyl-2-chlorobenzene (611-17-6) + 4-chlorobenzyl bromide (622-95-7)

Conditions	Yield
Stage #1: chlorobenzene With sodium hydride In N,N-dimethyl-formamide at 20℃; Stage #2: 1,2-dibromomethane In N,N-dimethyl-formamide at 60℃; for 2h;

ortho-chlorobenzoic acid (118-91-2) → 1-bromomethyl-2-chlorobenzene (611-17-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodium tetrahydroborate / methanol / 2 h / 0 - 20 °C 2: phosphorus tribromide / dichloromethane / 0.5 h / 0 - 5 °C View Scheme
Multi-step reaction with 2 steps 1: sodium tetrahydroborate; iodine / tetrahydrofuran / 12 h / 0 °C / Heating 2: acetic acid; hydrogen bromide / water / 2 h / 100 °C View Scheme

methyl 2-hydroxy-5-(tetrahydropyranyloxy)benzoate (94420-55-0) + 1-bromomethyl-2-chlorobenzene (611-17-6) → C20H21ClO5 (945989-82-2)

Conditions	Yield
With caesium carbonate In acetone at 40℃; for 4h;	100%

ethyl 4-bromo-2-nitro-6-(trifluoromethyl)phenylcarbamate (444901-29-5) + 1-bromomethyl-2-chlorobenzene (611-17-6) → ethyl 4-bromo-2-nitro-6-(trifluoromethyl)phenyl(2-chlorobenzyl)carbamate (444901-30-8)

Conditions	Yield
With potassium carbonate In DMF (N,N-dimethyl-formamide) at 50℃; for 1h;	100%

1,3-Dihydro-3,3-dimethyl-5-nitro-2H-indol-2-one (100511-00-0) + 1-bromomethyl-2-chlorobenzene (611-17-6) → C17H15ClN2O3 (925220-74-2)

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 80℃; for 12h;	100%

1-hydroxy-3,6,7-tris(methoxymethoxy)-9H-xanthen-9-one (1314917-55-9) + 1-bromomethyl-2-chlorobenzene (611-17-6) → C26H25ClO9 (1314917-82-2)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 50℃; for 6h;	100%

methyl 3-chloro-1H-indole-4-carboxylate + 1-bromomethyl-2-chlorobenzene (611-17-6) → C17H13Cl2NO2

Conditions	Yield
With sodium hydride at 0℃; for 5h;	100%

3,5-dibromo-4-hydroxybenzaldehyde (2973-77-5) + 1-bromomethyl-2-chlorobenzene (611-17-6) → (E)-2,6-dibromo-4-(2-chlorostyryl)phenol (1207104-21-9)

Conditions	Yield
Stage #1: 1-bromomethyl-2-chlorobenzene With triethyl phosphite at 150℃; for 3h; Horner-Wittig reaction; Inert atmosphere; Stage #2: With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; Horner-Wittig reaction; Inert atmosphere; Stage #3: 3,5-dibromo-4-hydroxybenzaldehyde In N,N-dimethyl-formamide; mineral oil at 0℃; Horner-Wittig reaction; Inert atmosphere;	99%

2-(N,N-dimethylamino)ethanol (108-01-0) + 1-bromomethyl-2-chlorobenzene (611-17-6) → 2-((2-chlorobenzyl)oxy)-N,N-dimethylethanamine hydrochloride

Conditions	Yield
Stage #1: 2-(N,N-dimethylamino)ethanol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 0.5h; Stage #2: 1-bromomethyl-2-chlorobenzene In N,N-dimethyl-formamide; mineral oil at 20℃; for 16h; Stage #3: With hydrogenchloride In 1,4-dioxane; methanol for 0.5h;	99%

de(3'-N-methyl)-9-dihydro-pseudoerythromycin A 6,9-epoxide + 1-bromomethyl-2-chlorobenzene (611-17-6) → de(3'-N-methyl)-3'-N-(o-chlorobenzyl)-9-dihydro-pseudoerythromycin A 6,9-epoxide

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In chloroform at 20℃; for 2.5h;	98%

t-butyl 3-(2-fluorospiro[4,5-dihydrothieno[2,3-c]pyran-7,4'-piperidine]-1'-yl)propanoate (1283095-51-1) + 1-bromomethyl-2-chlorobenzene (611-17-6) → tert-butyl 2-[(2-chlorophenyl)methyl]-3-(2-fluorospiro[4,5-dihydrothieno[2,3-c]pyran-7,4'-piperidine]-1'-yl)propanoate (1283095-53-3)

Conditions	Yield
Stage #1: t-butyl 3-(2-fluorospiro[4,5-dihydrothieno[2,3-c]pyran-7,4'-piperidine]-1'-yl)propanoate With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 1.5h; Stage #2: With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone In tetrahydrofuran at -78℃; for 0.5h; Stage #3: 1-bromomethyl-2-chlorobenzene In tetrahydrofuran at -78 - 0℃; for 1h;	98%

1-bromomethyl-2-chlorobenzene (611-17-6) + malonic acid dimethyl ester (108-59-8) → diethyl 2-(2-chlorobenzyl)malonate (77738-21-7)

Conditions	Yield
Stage #1: malonic acid dimethyl ester With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 0.25h; Stage #2: 1-bromomethyl-2-chlorobenzene In tetrahydrofuran; mineral oil at 60℃;	98%

1-bromomethyl-2-chlorobenzene (611-17-6) + potassium selenocyanate (3425-46-5) → (2-chlorophenyl)methaneselenenyl cyanide (57239-47-1)

Conditions	Yield
In ethanol for 0.166667h;	97%
In ethanol for 5h; Ambient temperature;	85%

2-(2-chloro-5-hydroxyphenyl)-2-isopropyl-3-methylbutanenitrile (1274905-18-8) + 1-bromomethyl-2-chlorobenzene (611-17-6) → 2-(2-chloro-((2-chlorobenzyl)oxy)phenyl)-2-isopropyl-3-methylbutanenitrile (1274905-20-2)

Conditions	Yield
With potassium carbonate In acetone at 50℃;	97%

1-bromomethyl-2-chlorobenzene (611-17-6) + (piperidin-4-yl)carbamic acid tert-butyl ester (73874-95-0) → C17H25ClN2O2 (1286273-10-6)

Conditions	Yield
With potassium carbonate In dichloromethane at 20℃;	97%
With triethylamine In ethanol
With sodium hydride In tetrahydrofuran at -20℃; for 12h;

methyl 2-(7-hydroxy-4,8-dimethyl-2-oxo-2H-chromen-3-yl)acetate (433703-81-2) + 1-bromomethyl-2-chlorobenzene (611-17-6) → methyl 2-(7-((2-chlorobenzyl)oxy)-4,8-dimethyl-2-oxo-2H-chromen-3-yl)acetate

Conditions	Yield
With potassium carbonate In acetone Reflux;	97%

4-(3-methyl-5-oxo-4H-pyrazol-1-yl)-N-(pyridine-4-ylmethyl)benzamide + 1-bromomethyl-2-chlorobenzene (611-17-6) → 1-[(2-chlorophenyl)methyl]-4-({[4-(3-methyl-5-oxo-4H-pyrazol-1-yl)phenyl]formamido}methyl)pyridin-1-ium bromide

Conditions	Yield
In N,N-dimethyl-formamide at 40 - 50℃;	96.53%

1-bromomethyl-2-chlorobenzene (611-17-6) + triethyl phosphite (122-52-1) → 2-chlorobenzyl diethylphosphonate (29074-98-4)

Conditions	Yield
at 150℃; Inert atmosphere; neat (no solvent);	96%
In xylene for 20h; Reflux;	91%

4,5-dichloro-2H-pyridazin-3-one (932-22-9) + 1-bromomethyl-2-chlorobenzene (611-17-6) → 4,5-dichloro-2-[2-chlorophenyl]methylpyridazin-3-one

Conditions	Yield
With potassium carbonate; potassium iodide In N,N-dimethyl-formamide at 90℃; for 2h;	96%

4-(4-chlorophenyl)-1-(2-methoxyethyl)-6-methyl-2-oxo-3,4-dihydropyridine-5-carboxylic acid + 1-bromomethyl-2-chlorobenzene (611-17-6) → (2-chlorophenyl)methyl 4-(4-chlorophenyl)-1-(2-methoxyethyl)-6-methyl-2-oxo-3,4-dihydropyridine-5-carboxylate

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 20℃; for 1h;	96%

(Z)-β-bromostyrene (588-73-8) + 1-bromomethyl-2-chlorobenzene (611-17-6) → 1-(2-chlorobenzyl)-4-phenyl-1H-1,2,3-triazole (63778-13-2)

Conditions	Yield
With copper(l) iodide; sodium azide; 1,8-diazabicyclo[5.4.0]undec-7-ene at 100℃; for 0.5h;	96%

phenoxyacetylene (4279-76-9) + 1-bromomethyl-2-chlorobenzene (611-17-6) → C15H12ClN3O

Conditions	Yield
Stage #1: 1-bromomethyl-2-chlorobenzene With sodium azide In methanol at 20℃; Green chemistry; Stage #2: phenoxyacetylene In methanol at 20℃; Green chemistry;	96%

1-bromomethyl-2-chlorobenzene (611-17-6) + phenylpropyolic acid (637-44-5) → 1-(2-chlorobenzyl)-4-phenyl-1H-1,2,3-triazole (63778-13-2)

Conditions	Yield
With copper(l) iodide; sodium azide; potassium carbonate at 60℃; for 0.5h;	96%

1,2,3,4-tetrahydroisoquinoline (91-21-4) + 1-bromomethyl-2-chlorobenzene (611-17-6) → 2-(2-chlorobenzyl)-1,2,3,4-tetrahydroisoquinoline (72809-43-9)

Conditions	Yield
With sodium hydride; N,N-dimethyl-formamide In mineral oil at 50℃;	96%

8-tert-butyl-3,3,5-trimethyl-3H,11H-pyrano[3,2-a]carbazole + 1-bromomethyl-2-chlorobenzene (611-17-6) → 8-(tert-butyl)-11-(2-chlorobenzyl)-3,3,5-trimethyl-3,11-dihydropyrano[3,2-a]carbazole

Conditions	Yield
Stage #1: 8-tert-butyl-3,3,5-trimethyl-3H,11H-pyrano[3,2-a]carbazole With sodium hydride In tetrahydrofuran at 0℃; for 0.5h; Stage #2: 1-bromomethyl-2-chlorobenzene In tetrahydrofuran at 0 - 20℃; for 3h;	96%

(2-chlorophenyl)methaneselenenyl cyanide (57239-47-1) + 1-bromomethyl-2-chlorobenzene (611-17-6) → bis-(2-chloro-benzyl)-selenide (56344-09-3)

Conditions	Yield
With sodium tetrahydroborate In benzene for 1h; Ambient temperature;	95%

1-bromomethyl-2-chlorobenzene (611-17-6) → α-deuterio-o-chlorotoluene (138433-41-7)

Conditions	Yield
With lithium aluminium deuteride In tetrahydrofuran	95%
With sodium borodeuteride In dimethylsulfoxide-d6 at 0 - 20℃; for 4h; Inert atmosphere;	72%

1-bromomethyl-2-chlorobenzene (611-17-6) → 2-chlorobenzylazide (63777-70-8)

Conditions	Yield
With sodium azide In N,N-dimethyl-formamide at 20 - 80℃; for 4h;	95%
With sodium azide In dimethyl sulfoxide at 20℃; for 24h;	92%
With sodium azide In water; acetone at 20 - 60℃;

2-aminopyrimidine (109-12-6) + 1-bromomethyl-2-chlorobenzene (611-17-6) → N-(2-chlorobenzyl)-(2-pyrimidyl)amine (23676-58-6)

Conditions	Yield
Stage #1: 2-aminopyrimidine With sodium hydride In tetrahydrofuran for 0.25h; Cooling with ice; Stage #2: 1-bromomethyl-2-chlorobenzene In tetrahydrofuran at 20℃; for 24h; Cooling with ice;	95%

benzyl 2-(benzyloxy)-4-(N-(4-cyclohexylbenzyl)-2-(perfluorophenylsulfonamido)acetamido)benzoate (1455006-14-0) + 1-bromomethyl-2-chlorobenzene (611-17-6) → benzyl 2-(benzyloxy)-4-(2-(N-(2-chlorobenzyl)-2,3,4,5,6-pentafluorophenylsulfonamido)-N-(4-cyclohexylbenzyl)acetamido)benzoate (1455006-27-5)

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 20℃; Inert atmosphere;	95%

Upstream product

• 118-91-2 ortho-chlorobenzoic acid 
• 611-19-8 1-chloro-2-(chloromethyl)benzene 
• 108-90-7 chlorobenzene 
• 74-95-3 1,1-dibromomethane 
• 1058649-12-9 2-chloro-1-(methoxymethoxy)methyl benzene 
• 1058649-16-3 2-chloro-1-[(ethoxymethoxy)methyl]benzene 
• 506-68-3 bromocyane 
• 10175-31-2 1-(2-chlorophenyl)-N,N-dimethylmethanamine 
• 89-98-5 2-chloro-benzaldehyde 
• 95-49-8 2-methylchlorobenzene 
• 17849-38-6 2-Chlorobenzyl alcohol 
• 854392-01-1 (2-chloro-benzyl)-methyl-(2-nitro-benzyl)-amine 
• 876476-07-2 (2-bromo-benzyl)-(2-chloro-benzyl)-methyl-amine 
• 65763-39-5 (2-chloro-benzyl)-methyl-(4-nitro-benzyl)-amine 

Downstream Products

• 109017-79-0 1-(2-chloro-benzyl)-tetrahydro-thiophenium; bromide 
• 10175-31-2 1-(2-chlorophenyl)-N,N-dimethylmethanamine 
• 89-98-5 2-chloro-benzaldehyde 
• 77738-21-7 diethyl 2-(2-chlorobenzyl)malonate 
• 10131-11-0 bis-(2-chloro-benzyl)-malonic acid diethyl ester 
• 876476-08-3 (3-bromo-benzyl)-(2-chloro-benzyl)-methyl-amine 
• 670748-78-4 dimethyl 2-(2-chlorobenzyl)malonate 
• 94-64-4 N-methyl-N-(2-chlorobenzyl)amine 
• 7375-69-1 bis-(2-chloro-benzyl)-methyl-amine 
• 5440-50-6 N-acetyl-3-(2-chlorophenyl)-2-ethoxycarbonyl alanine ethyl ester 
• 25251-55-2 (2-chloro-benzyl)-trimethyl-ammonium; bromide 
• 345-34-6 1-chloro-2-(fluoromethyl)benzene 
• 70450-40-7 2-chlorobenzyl iodide 
• 118-91-2 ortho-chlorobenzoic acid 

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