22115-41-9

Basic information

• Product Name: 2-Cyanobenzyl bromide
• Synonyms: 2-(Bromomethyl)benzonitrile >=97%;ALPHA-BROMO-ORTHO-TOLUNITRILE, 97+%;Alpha-Bromo-O-Tolunitrile98%;Benzonitrile, 2-(bromomethyl)-;à-bromo-o-tolunitrile;α-bromo-o-tolunitrile;2-Cyanobenzyl bromide 98%;2-Cyanobenzylbromide98%
• CAS NO: 22115-41-9
• Molecular Formula: C₈H₆BrN
• Molecular Weight: 196.04
• EINECS: 231-555-8
• Product Categories: cyanide| alkyl bromide
• Mol File: 22115-41-9.mol
• Article Data: 16

Chemical Properties

• Melting Point: 72-74 °C(lit.)
• Boiling Point: 111 °C / 1.5mmHg
• Flash Point: 113.8 °C
• Appearance: White to gray-brown/Crystalline Powder or Chunks
• Density: 1.5466 (rough estimate)
• Vapor Pressure: 0.00961mmHg at 25°C
• Refractive Index: 1.6550 (estimate)
• Storage Temp.: Store below +30°C.
• Water Solubility: Slightly soluble in water
• BRN: 742605
• CAS DataBase Reference: 2-Cyanobenzyl bromide(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Cyanobenzyl bromide(22115-41-9)
• EPA Substance Registry System: 2-Cyanobenzyl bromide(22115-41-9)

Safety Data

• Hazard Codes: C
• Statements: 34
• Safety Statements: 26-36/37/39-45-28A
• RIDADR: UN 3261 8/PG 2
• WGK Germany: 3
• F: 10-19-21
• HazardClass: 8
• PackingGroup: II
• Hazardous Substances Data: 22115-41-9(Hazardous Substances Data)

Usage

Description

2-(Bromomethyl)benzonitrile reacts with 2H-tetrazole in the presence of KOH to yield 4-[(2H-tetra-zol-2-yl)meth-yl]benzonitrile. It undergoes base-promoted condensation reaction with homophthalic anhydride to yield 6,11-dihydro-5H-indeno[1,2-c]isoquinolin-5-one.

Chemical Properties

White to light yellow crystal powder

Uses

2-(Bromomethyl)benzonitrile is an intermediate in the synthesis of Alogliptin, an oral antihyperglycemic agent that is a selective inhibitor of the enzyme dipeptidyl peptidase-4 (DPP-4). Antidiabetic agent. Not a dangerous good if item is equal to or less than 1g/ml and there is less than 100g/ml in the package.

General Description

2-(Bromomethyl)benzonitrile reacts with 2H-tetrazole in the presence of KOH to yield 4-[(2H-tetra-zol-2-yl)meth-yl]benzonitrile. It undergoes base-promoted condensation reaction with homophthalic anhydride to yield 6,11-dihydro-5H-indeno[1,2-c]isoquinolin-5-one.

Purification Methods

Purify the nitrile by steam distillation. Extract the distillate with Et2O, dry the extract (Na2SO4), evaporate and distil the residue. The solidified distillate can be recrystallised from pet ether or cyclohexane. NMR (CDCl3) : 7.8-7.2 (m 4H), 4.62 (s, 2H), IR max 2238 cm1 . [Drory Chem Ber 24 2570 1891, Borsche et al. Chem Ber 74 685 1934, Buckley et al. Aust J Chem 22 594 1969, Beilstein 9 III 2312.] LACHRYMATORY.

InChI:InChI=1/C8H6BrN/c9-5-7-3-1-2-4-8(7)6-10/h1-4H,5H2

Synthetic route

2-Methylbenzonitrile (529-19-1) → 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
With dihydrogen peroxide; bromine In dichloromethane; water for 4h; Reflux;	98%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane at 90℃; for 2h;	80%
With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane at 80 - 90℃; for 5.08333h; Inert atmosphere;	69%

C14H21NOSi → 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
With phosphorus tribromide In dichloromethane at 40℃; for 8h; Time;	93%

dicyanozinc (557-21-1) + 1-Bromo-2-bromomethyl-benzene (3433-80-5) → 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; 1,2-Ph2-3,4-bis(2,4,6-(t-Bu)3-phenylphophinidene)cyclobutene; zinc In various solvent(s) at 100℃; for 16h;	60%

bicyclo[4.2.0]octa-1(6),2,4-trien-7-one O-(4-(trifluoromethyl)benzoyl) oxime → 2-cyanobenzyl 4-(trifluoromethyl)benzoate + 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
With carbon tetrabromide; N,N,N',N'',N'''-pentamethyldiethylenetriamine; tetrabutylammomium bromide; copper(I) bromide In N,N-dimethyl-formamide at 20℃; for 12h; Schlenk technique; Inert atmosphere;	A 52% B 13%

2-Methylbenzonitrile (529-19-1) → 2-(dibromomethyl)benzonitrile (655-63-0) + 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
at 150 - 200℃; bei der Bromierung im Sonnenlicht;

2-cyanobenzylselenocyanate → 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
With hydrogen bromide at 100℃; im Druckrohr;

2-cyanobenzylselenocyanate → 2-selanylmethyl-benzonitrile; hydrobromide + 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
With hydrogen bromide at 100℃; im geschlossenen Rohr;

2-Methylbenzonitrile (529-19-1) + bromine (7726-95-6) → 2-(bromomethyl)benzonitrile (22115-41-9)

2-cyanobenzylselenocyanate + hydrogen bromide (10035-10-6, 12258-64-9) → 2-(bromomethyl)benzonitrile (22115-41-9) + hydrobromide of pseudoselenophthalimidein/e

Conditions	Yield
at 100℃; im Druckrohr;

2-cyanobenzyl chloride (612-13-5) → 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: alcohol 2: fuming hydrobromic acid / 100 °C / im Druckrohr View Scheme
Multi-step reaction with 2 steps 1: alcohol 2: fuming hydrobromic acid / 100 °C / im geschlossenen Rohr View Scheme

benzyl bromide (100-39-0) + (E)-3-[2-(7-chloro-2-quinolinyl)ethenyl]benzaldehyde (120578-03-2) + N,N-dimethyl-3-mercaptopropionamide (92065-71-9) + thioacetic acid (507-09-5) → 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
In methanol; hexane; ethyl acetate; trifluoroacetic acid; trifluoroacetic anhydride

benzocyclobutenone (3469-06-5) → 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
Multi-step reaction with 3 steps 1: hydroxylamine hydrochloride; sodium acetate / methanol / 12 h / 75 °C / Inert atmosphere 2: triethylamine / dichloromethane / 1 h / 0 °C / Inert atmosphere 3: carbon tetrabromide; copper(I) bromide; tetrabutylammomium bromide; N,N,N',N'',N'''-pentamethyldiethylenetriamine / N,N-dimethyl-formamide / 12 h / 20 °C / Schlenk technique; Inert atmosphere View Scheme

bicyclo[4.2.0]octa-1(6),2,4-trien-7-one oxime → 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: triethylamine / dichloromethane / 1 h / 0 °C / Inert atmosphere 2: carbon tetrabromide; copper(I) bromide; tetrabutylammomium bromide; N,N,N',N'',N'''-pentamethyldiethylenetriamine / N,N-dimethyl-formamide / 12 h / 20 °C / Schlenk technique; Inert atmosphere View Scheme

o-bromobenzyl alcohol (18982-54-2) → 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1H-imidazole / dichloromethane / 20 °C 2: tris-(dibenzylideneacetone)dipalladium(0); zinc / N,N-dimethyl-formamide / 6 h / 100 °C / Inert atmosphere 3: phosphorus tribromide / dichloromethane / 8 h / 40 °C View Scheme

((2-bromobenzyl)oxy)(tert-butyl)dimethylsilane (94236-20-1) → 2-(bromomethyl)benzonitrile (22115-41-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: tris-(dibenzylideneacetone)dipalladium(0); zinc / N,N-dimethyl-formamide / 6 h / 100 °C / Inert atmosphere 2: phosphorus tribromide / dichloromethane / 8 h / 40 °C View Scheme

piperidine (110-89-4) + 2-(bromomethyl)benzonitrile (22115-41-9) → 2-Piperidinomethyl-benzonitril (135277-08-6)

Conditions	Yield
In diethyl ether for 8h;	100%

2-(bromomethyl)benzonitrile (22115-41-9) → 2-(bromomethyl)benzaldehyde (60633-91-2)

Conditions	Yield
Stage #1: 2-(bromomethyl)benzonitrile With diisobutylaluminium hydride In n-heptane; dichloromethane at 0 - 20℃; for 3h; Inert atmosphere; Stage #2: With hydrogen bromide In n-heptane; dichloromethane at 0℃; for 1h; Inert atmosphere;	100%
With diisobutylaluminium hydride In n-heptane; dichloromethane at 0 - 20℃; for 3h; Reduction;	97%
With diisobutylaluminium hydride In n-heptane; dichloromethane at 20℃; for 3.5h; Inert atmosphere; Cooling with ice;	97%

C21H33NO2 (1088482-37-4) + 2-(bromomethyl)benzonitrile (22115-41-9) → N-(2'-cyanobenzyl)-N,N-dimethyl-N-{(1S)-1-[(-)-8-phenylmenthyloxycarbonylethyl]}ammonium bromide (1088481-89-3)

Conditions	Yield
In acetonitrile at 20℃; for 48h;	100%

N-methylmethane sulphonamide (1184-85-6) + 2-(bromomethyl)benzonitrile (22115-41-9) → N-(2-cyano-benzyl)-N-methyl-methanesulfonamide (1257706-19-6)

Conditions	Yield
With potassium carbonate In acetone at 20℃; for 18h;	100%

1-hydroxy-3,6,7-tris(methoxymethoxy)-9H-xanthen-9-one (1314917-55-9) + 2-(bromomethyl)benzonitrile (22115-41-9) → C27H25NO9 (1314917-91-3)

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

benzyl 2-(benzyloxy)-4-(N-(4-cyclohexylbenzyl)-2-(perfluorophenylsulfonamido)acetamido)benzoate (1455006-14-0) + 2-(bromomethyl)benzonitrile (22115-41-9) → benzyl 2-(benzyloxy)-4-(2-(N-(2-cyanobenzyl)-2,3,4,5,6-pentafluorophenylsulfonamido)-N-(4-cyclohexylbenzyl)acetamido)benzoate (1455006-33-3)

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 20℃; Inert atmosphere;	100%

3-mercapto-5H-1,2,4-triazino[5,6-b]indole (28668-95-3) + 2-(bromomethyl)benzonitrile (22115-41-9) → 3-((2’-cyanobenzyl)thio)-5H-[1,2,4]triazino[5,6-b]indole (292057-70-6)

Conditions	Yield
With triethylamine In methanol at 20℃; for 16h;	100%

(2-cyanophenyl)carbamic acid ethyl ester (41534-70-7) + 2-(bromomethyl)benzonitrile (22115-41-9) → ethyl (2-cyanobenzyl)(2-cyanophenyl)carbamate

Conditions	Yield
Stage #1: (2-cyanophenyl)carbamic acid ethyl ester With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.5h; Inert atmosphere; Stage #2: 2-(bromomethyl)benzonitrile In N,N-dimethyl-formamide; mineral oil at 0℃; for 1h; Inert atmosphere;	100%

2-(bromomethyl)benzonitrile (22115-41-9) + ethanethiol (75-08-1) → 2-Ethylsulfanylmethyl-benzonitrile (176983-04-3)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran for 5h;	99%

6,7-dimethoxy-1-(2',2'-diphenyl-1'-ethenyl)-3,4-dihydroisoquinoline (537040-39-4) + 2-(bromomethyl)benzonitrile (22115-41-9) → 2-(2-cyanobenzyl)-1-(2',2'-diphenyl-1-ethenyl)-6,7-dimethoxy-3,4-dihydroisoquinolinium bromide

Conditions	Yield
In diethyl ether	99%

2-(bromomethyl)benzonitrile (22115-41-9) + 5,6-dimethyl-2-mercaptobenzimidazole (3287-79-4) → 2-((5,6-dimethylbenzimidazole-2-ylthio)methyl)benzenecarbonitrile

Conditions	Yield
With triethylamine In N-methyl-acetamide; water	99%

4-(4-chlorophenyl)-1-(2-methoxyethyl)-6-methyl-2-oxo-3,4-dihydropyridine-5-carboxylic acid + 2-(bromomethyl)benzonitrile (22115-41-9) → (2-cyanophenyl)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 18h;	99%

dimethyl amine (124-40-3) + 2-(bromomethyl)benzonitrile (22115-41-9) → 2-((dimethylamino)methyl)benzonitrile (53369-76-9)

Conditions	Yield
In diethyl ether; water at 20℃;	98%
In benzene
In diethyl ether
In diethyl ether for 8h;
In N,N-dimethyl-formamide at 20℃; for 10h;

ethyl (RS)-2-(benzylideneamino)propanoate (60930-36-1) + 2-(bromomethyl)benzonitrile (22115-41-9) → ethyl (RS)-2-(benzylideneamino)-3-(2-cyanophenyl)-2-methylpropanoate (1142954-12-8)

Conditions	Yield
With potassium hydroxide; N-benzyl-N,N,N-triethylammonium chloride; potassium carbonate In dichloromethane	98%

Upstream product

• 94236-20-1 ((2-bromobenzyl)oxy)(tert-butyl)dimethylsilane 
• 18982-54-2 o-bromobenzyl alcohol 
• 3469-06-5 benzocyclobutenone 
• 100-39-0 benzyl bromide 
• 120578-03-2 (E)-3-[2-(7-chloro-2-quinolinyl)ethenyl]benzaldehyde 
• 92065-71-9 N,N-dimethyl-3-mercaptopropionamide 
• 507-09-5 tiolacetic acid 
• 612-13-5 2-cyanobenzyl chloride 
• 557-21-1 dicyanozinc 
• 3433-80-5 1-Bromo-2-bromomethyl-benzene 
• 10035-10-6 hydrogen bromide 
• 529-19-1 2-Methylbenzonitrile 
• 7726-95-6 bromine 

Downstream Products

• 135277-07-5 2-(1-Pyrrolidinyl-methyl)benzonitril 
• 115174-11-3 o-Heptamethyleniminomethylbenzonitrile 
• 130569-96-9 1-(2-cyanobenzyl)pyrrole-2-carboxyaldehyde 
• 113918-49-3 2-bromo-1-(2-cyanobenzyl)pyridinium bromide 
• 113918-58-4 6-imino-1-methyl-11-phenyl-6,11-dihydropyrido<1,2-b><2,4>benzodiazepine hydrobromide 
• 135277-09-7 2-(Perhydroazepin-1-yl-methyl)benzonitril 
• 130569-98-1 ethyl 1-(2-cyanobenzyl)pyrrole-2-glyoxylate 
• 87-41-2 2-benzofuran-1(3H)-one 
• 140837-23-6 2-(2,6-Dimethylpiperidinomethyl)benzonitril 
• 140837-22-5 2-(2-Methylpiperidinomethyl)benzonitril 
• 133447-94-6 4-(2-Cyanophenyl)-2,3,3-trimethyl-1-butene 
• 134541-51-8 2-Prop-2-ynyloxymethyl-benzonitrile 
• 34463-66-6 N-(2-(3',4'-Dimethoxyphenyl)-ethyl)-2,3-dihydro-1H-isoindol-1-on 
• 129053-56-1 <<(1-formyl-2-phenyl)oxy>methyl>benzonitrile 

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