612-13-5

Basic information

• Product Name: 2-(Chloromethyl)benzonitrile
• Synonyms: ORTHO-CYANOBENZYLCHLORIDE;O-CYANOBENZYL CHLORIDE;2-(chloromethyl)-benzonitril;alpha-chloro-o-tolunitril;o-(chloromethyl)benzonitrile;AKOS BBS-00003977;2-(Chloromethyl)tolunitrile;2-(CHLOROMETHYL)BENZONITRILE
• CAS NO: 612-13-5
• Molecular Formula: C₈H₆ClN
• Molecular Weight: 151.59
• EINECS: 210-292-3
• Product Categories: Intermediates of Dyes and Pigments
• Mol File: 612-13-5.mol
• Article Data: 4

Chemical Properties

• Melting Point: 56-61°C
• Boiling Point: 252°C(lit.)
• Flash Point: 106.2 °C
• Appearance: white to light yellow crystal powder
• Density: 1.1976 (rough estimate)
• Vapor Pressure: 0.0198mmHg at 25°C
• Refractive Index: 1.5437 (estimate)
• Storage Temp.: Keep in dark place,Sealed in dry,Room Temperature
• Solubility: soluble in Methanol
• CAS DataBase Reference: 2-(Chloromethyl)benzonitrile(CAS DataBase Reference)
• NIST Chemistry Reference: 2-(Chloromethyl)benzonitrile(612-13-5)
• EPA Substance Registry System: 2-(Chloromethyl)benzonitrile(612-13-5)

Safety Data

• RIDADR: UN 2923 8/6.1/PG II
• HazardClass: 8/6.1
• PackingGroup: II
• Hazardous Substances Data: 612-13-5(Hazardous Substances Data)

Usage

Chemical Properties

white to light yellow crystal powde

InChI:InChI=1/C8H6ClN/c9-5-7-3-1-2-4-8(7)6-10/h1-4H,5H2

Synthetic route

2-Methylbenzonitrile (529-19-1) → 2-cyanobenzyl chloride (612-13-5)

Conditions	Yield
With tert-butylhypochlorite; bis(1,10-phenanthroline)silver(I) triflate In acetonitrile at 20℃; for 48h; Inert atmosphere; regioselective reaction;	42%
Stage #1: 2-Methylbenzonitrile With fluorosulphonic acid; lead dioxide at -75℃; for 5h; Stage #2: With hydrogenchloride	29%
With chlorine

2-cyanobenzylselenocyanate → 2-selanylmethyl-benzonitrile; hydrochloride (92380-62-6) + 2-cyanobenzyl chloride (612-13-5)

Conditions	Yield
With hydrogenchloride at 100℃; im geschlossenen Rohr;

2-Methylbenzonitrile (529-19-1) + chlorine (7782-50-5) → 2-cyanobenzyl chloride (612-13-5)

ortho-methylbenzoic acid (118-90-1) → 2-cyanobenzyl chloride (612-13-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: 50 percent / Pb(SCN)2 / 200 - 230 °C 2: 1.) PbO2, HSO3F, 2.) aq. HCl / multistep reaction; various temperatures, reaction time, reagent ratios View Scheme

para-tert-butylphenol (98-54-4) + 2-cyanobenzyl chloride (612-13-5) → 2-(4-tert-butylphenoxymethyl)benzonitrile

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	99.8%

3-methyl-phenol (108-39-4) + 2-cyanobenzyl chloride (612-13-5) → 2-(3-methylphenoxymethyl)benzonitrile (951906-95-9)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	99.3%

ortho-cresol (95-48-7) + 2-cyanobenzyl chloride (612-13-5) → 2-(2-methylphenoxymethyl)benzonitrile (951906-92-6)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	99.3%

4-nitro-phenol (100-02-7) + 2-cyanobenzyl chloride (612-13-5) → 2-((4-nitrophenoxy)methyl)benzonitrile (1004433-16-2)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	99.2%

4-chloro-phenol (106-48-9) + 2-cyanobenzyl chloride (612-13-5) → 2-(4-chlorophenoxymethyl)benzonitrile (92161-45-0)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	99%

4-morpholinecarboxaldehyde (4394-85-8) + 2-cyanobenzyl chloride (612-13-5) → 2-(morpholin-4-ylmethyl)benzonitrile (37812-33-2)

Conditions	Yield
With potassium hydroxide In water at 50℃; for 3h; Green chemistry;	99%
With NHC-Pd(II)-Im; sodium hydroxide In water at 50℃; for 3h; Inert atmosphere; Schlenk technique;	98%

2-cyanobenzyl chloride (612-13-5) + phenol (108-95-2) → 2-(phenoxymethyl)benzonitrile (168971-54-8)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	98.2%
With ethanol; sodium

2,4-Xylenol (105-67-9) + 2-cyanobenzyl chloride (612-13-5) → 2-(2,4-dimethylphenoxymethyl)benzonitrile (951905-98-9)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	96.5%

methanol (67-56-1) + 2-cyanobenzyl chloride (612-13-5) → 2-Chloromethyl-benzimidic acid methyl ester; hydrochloride

Conditions	Yield
With hydrogenchloride In diethyl ether at 0 - 5℃; for 6h;	96%

phenylacetylene (536-74-3) + 2-cyanobenzyl chloride (612-13-5) → 1-(2-cyanobenzyl)-4-phenyl-1H-1,2,3-triazole

Conditions	Yield
With sodium azide; sodium L-ascorbate In water at 60℃; for 3.5h;	96%

(±)-1-(4-chlorophenyl)-2-(1H-pyrrol-1-yl)ethanol (97210-23-6) + 2-cyanobenzyl chloride (612-13-5) → 2-[1-(4-Chloro-phenyl)-2-pyrrol-1-yl-ethoxymethyl]-benzonitrile; hydrochloride

Conditions	Yield
With sodium hydride In N,N,N,N,N,N-hexamethylphosphoric triamide 25 deg C, 1 h; 50 deg C, 1 h;	95%

2-methoxy-phenol (90-05-1) + 2-cyanobenzyl chloride (612-13-5) → 2-(2-methoxyphenoxymethyl)benzonitrile (951907-13-4)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	95%

β-naphthol (135-19-3) + 2-cyanobenzyl chloride (612-13-5) → 2-[(naphthalen-2-yloxy)methyl]benzonitrile

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	94.6%

7-hydroxy-4-methyl-chromen-2-one (90-33-5, 79566-13-5) + 2-cyanobenzyl chloride (612-13-5) → 2-{[(4-methyl-2-coumarin-7-yl)oxy]methyl}benzonitrile (787562-31-6)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	94.3%

1-cyano-2-hydroxynaphthalene (52805-47-7) + 2-cyanobenzyl chloride (612-13-5) → C19H12N2O (1293961-08-6)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 50 - 55℃; for 0.666667h;	93%

4,6-Dimethyl-2-thioxo-1,2-dihydro-pyridine-3-carbonitrile (54585-47-6) + 2-cyanobenzyl chloride (612-13-5) → 3-cyano-2-(2-cyanobenzylthio)-4,6-dimethylpyridine

Conditions	Yield
With triethylamine In chloroform for 0.666667h; Reflux;	93%

2-cyanobenzyl chloride (612-13-5) → 2-(methoxymethyl)benzonitrile (57991-54-5)

Conditions	Yield
With sodium methylate In methanol at 25℃; for 4h;	93%

2-cyano-4-methylphenol (51282-90-7) + 2-cyanobenzyl chloride (612-13-5) → C16H12N2O (1293960-99-2)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 50 - 55℃; for 0.666667h;	92%

2-mercapto-4-methylbenzonitrile (613263-26-6) + 2-cyanobenzyl chloride (612-13-5) → 2-[(2-cyanobenzyl)thio]-5-methylbenzonitrile

Conditions	Yield
With triethylamine In chloroform for 0.666667h; Reflux;	92%

1,2,5,6,7,8-hexahydro-2-thioxoquinoline-3-carbonitrile (112629-69-3) + 2-cyanobenzyl chloride (612-13-5) → 3-cyano-2-(2-cyanobenzylthio)-5,6,7,8-tetrahydroquinoline

Conditions	Yield
With triethylamine In chloroform for 0.666667h; Reflux;	92%

4-(2,4-difluorophenyl)-phenol (59089-68-8) + 2-cyanobenzyl chloride (612-13-5) → 2-[4-(2,4-difluorophenyl)phenoxymethyl]benzonitrile (1417422-68-4)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	91.5%

(1-((diphenylmethylene)amino)-2-morpholino-2-oxoethyl)zinc pivalate + 2-cyanobenzyl chloride (612-13-5) → 2-(2-((diphenylmethylene)amino)-3-morpholino-3-oxopropyl)benzonitrile

Conditions	Yield
With bis(dibenzylideneacetone)-palladium(0); DavePhos In tetrahydrofuran at 25℃; for 4h; Negishi Coupling; Inert atmosphere;	91%

α-naphthol (90-15-3) + 2-cyanobenzyl chloride (612-13-5) → 2-(1-naphthoxymethyl)benzonitrile (1004489-90-0)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	90.4%

2-cyanobenzyl chloride (612-13-5) + phenylboronic acid (98-80-6) → 2-benzyl-benzonitrile (56153-61-8)

Conditions	Yield
With potassium phosphate tribasic trihydrate In ethanol at 80℃; for 1h; Catalytic behavior; Suzuki-Miyaura Coupling;	90%
With potassium carbonate; sodium chloride; palladium dichloride; cucurbituril In ethanol; water at 90℃; for 1h; Suzuki Coupling; Inert atmosphere;	88%
With potassium carbonate; N,N-dimethyl-formamide; palladium dichloride In water at 90℃; for 1h; Suzuki Coupling;	88%

2.6-dimethylphenol (576-26-1) + 2-cyanobenzyl chloride (612-13-5) → 2-(2,6-dimethylphenoxymethyl)benzonitrile (951905-86-5)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	89.4%

vanillin (121-33-5) + 2-cyanobenzyl chloride (612-13-5) → 2-((4-formyl-2-methoxyphenoxy)methyl)benzonitrile (443289-08-5)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 6h;	88.2%
With potassium carbonate In acetonitrile Reflux;
With potassium carbonate In acetonitrile Reflux;

5-chloro-2-hydroxybenzonitrile (13589-72-5) + 2-cyanobenzyl chloride (612-13-5) → C15H9ClN2O (1293961-01-9)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 50 - 55℃; for 0.666667h;	86%

4-chloro-2-mercaptobenzonitrile (1339650-77-9) + 2-cyanobenzyl chloride (612-13-5) → 5-chloro-2-[(2-cyanobenzyl)thio]benzonitrile

Conditions	Yield
With triethylamine In chloroform for 0.666667h; Reflux;	86%

3-methyl-6-chlorouracil (4318-56-3) + 2-cyanobenzyl chloride (612-13-5) → 2-((6-chloro-3-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)methyl)benzonitrile (865758-96-9)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In dimethyl sulfoxide at 60℃; for 1h;	85.62%
With potassium carbonate; potassium iodide In N,N-dimethyl acetamide at 50 - 100℃;

salicylonitrile (611-20-1) + 2-cyanobenzyl chloride (612-13-5) → 2-[(2-cyanobenzyl)oxy]benzonitril (1002241-42-0)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 50 - 55℃; for 0.666667h;	84%

Upstream product

• 529-19-1 2-Methylbenzonitrile 
• 7782-50-5 chlorine 
• 118-90-1 ortho-methylbenzoic acid 

Downstream Products

• 861796-89-6 (2-cyano-benzylsulfanyl)-acetic acid 
• 550-44-7 N-methylphthalimide 
• 76850-37-8 2-(2-Oxo-4-oxy-2H-pyrazin-1-ylmethyl)-benzonitrile 
• 303222-16-4 2-[3-(quinolin-2-ylmethoxy)-phenoxymethyl]-benzonitrile 
• 97934-35-5 hydrochloride of 2-(o-cyanobenzyl)-1-imino-3H-isoindole 
• 5388-42-1 N-phenylphthalimidine 
• 304-19-8 (N-isobutyl)phthalimide 
• 87-41-2 2-benzofuran-1(3H)-one 
• 13169-51-2 2-(chloromethyl)benzamide 
• 22115-43-1 2,3-bis(2-cyanophenyl)propionitrile 
• 23973-65-1 2-cyano-benzylphosphonic acid diethyl ester 
• 78022-18-1 2-(dimethylphosphonomethyl)benzonitrile 
• 63443-11-8 4-(2-Cyanostyryl)benzaldehyde 
• 78022-14-7 1-(2-Methylstyryl)-4-(2-cyanostyryl)benzene 

Relevant articles and documents

Reaction of PbO2 with Solutions of Methylbenzonitriles

The yield of products formed by low-temperature oxidation of methylbenzonitriles with PbO2 in fluorosulfonic acid solutions was studied in relation to the stabilization factor of the reaction system. The revealed correlation is common for methylbenzonitriles differing in the degree of alkylation and in the oxidation mechanism.

Oxidation of Aromatic Compounds. V. Oxidation of Substituted Benzonitriles and 2,4,6-Triaryl-1,3,5-Triazines in System HSO3F-PbO2

Low-temperature oxidation of substituted benzonitriles by the system HSO3F-PbO2 proceeds with intermediate formation of cation-radicals and leads to substitution of hydrogen atoms of the methyl group or benzene ring. This reaction provides a route for preparation of chloromethylsubstituted benzonitriles, diarylmethanes, diaryls, arylfluorosulfonates and substituted benzamides with cyano groups. In the case of methyl derivatives of 2,4,6-triphenyl-1,3,5-triazine substitution of the first and then the second hydrogen atom of the same methyl group transforms it into hydroxy or chloromethyl group, or into the aldehyde function.