34040-62-5

Basic information

• Product Name: Methyl 2-chloromethylbenzoate
• Synonyms: METHYL (2-CHLOROMETHYL)BENZOATE;METHYL O-(CHLOROMETHYL)BENZOATE;2-(CHLOROMETHYL)-BENZOIC ACID METHYL ESTER;o-(Chloromethyl)benzoic acid methyl ester;Benzoic acid,2-(chloroMethyl)-, Methyl ester
• CAS NO: 34040-62-5
• Molecular Formula: C₉H₉ClO₂
• Molecular Weight: 184.62
• EINECS: 251-805-0
• Product Categories: Aromatic Esters
• Mol File: 34040-62-5.mol
• Article Data: 11

Chemical Properties

• Boiling Point: 282 °C at 760 mmHg
• Flash Point: 139.2 °C
• Appearance: COA
• Density: 1.19 g/cm³
• Vapor Pressure: 0.00344mmHg at 25°C
• Refractive Index: 1.5410 to 1.5450
• Storage Temp.: Inert atmosphere,Room Temperature
• CAS DataBase Reference: Methyl 2-chloromethylbenzoate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl 2-chloromethylbenzoate(34040-62-5)
• EPA Substance Registry System: Methyl 2-chloromethylbenzoate(34040-62-5)

Safety Data

• RIDADR: UN 3265 8/PG III
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 34040-62-5(Hazardous Substances Data)

Usage

General Description

Methyl 2-chloromethylbenzoate is a chemical compound with the molecular formula C9H9ClO2. It is a member of the esters class of chemicals and is often used in various industrial and laboratory settings. It is a clear colorless to pale yellow liquid with a slightly fruity odor and is soluble in organic solvents. Methyl 2-chloromethylbenzoate is primarily used in the synthesis of pharmaceuticals, agrochemicals, and other fine chemicals. It is also used as an intermediate in the production of fragrances, flavors, and other specialty chemicals. Additionally, it is important to handle this chemical with caution as it can be irritating to the skin, eyes, and respiratory system and should only be used in a well-ventilated area and with appropriate personal protective equipment.

InChI:InChI=1/C9H9ClO2/c1-12-9(11)8-5-3-2-4-7(8)6-10/h2-5H,6H2,1H3

Synthetic route

methanol (67-56-1) + 2-benzofuran-1(3H)-one (87-41-2) → o-(chloromethyl)benzoic acid methyl ester (34040-62-5)

Conditions	Yield
Stage #1: 2-benzofuran-1(3H)-one With boron trifluoride diethyl etherate; N-benzyl-N,N,N-triethylammonium chloride In xylene at 100℃; Stage #2: With thionyl chloride In xylene at 100 - 132℃; for 3h; Stage #3: methanol at 50 - 60℃; for 2h;	100%
Stage #1: 2-benzofuran-1(3H)-one With dichlorotriphenyl-λ4-phosphane at 180℃; for 2h; Stage #2: methanol With pyridine for 1h;
With pyridine; dichlorotriphenylphosphorane at 180℃;

methanol (67-56-1) + 2-(chloromethyl)benzoic acid (85888-81-9) → o-(chloromethyl)benzoic acid methyl ester (34040-62-5)

Conditions	Yield
With sulfuric acid at 80℃; for 6h; Temperature;	96.5%

2-Chloromethylbenzoyl chloride (42908-86-1) → o-(chloromethyl)benzoic acid methyl ester (34040-62-5)

Conditions	Yield
In methanol	94%
With triethylamine In methanol; dichloromethane	89%

2-Methyl-benzoic acid methyl ester (89-71-4) → o-(chloromethyl)benzoic acid methyl ester (34040-62-5)

Conditions	Yield
With N-hydroxyphthalimide; carbon tetrabromide; trichloroisocyanuric acid; copper(II) acetate monohydrate In dichloromethane at 25℃; for 24h;	61%
With N-hydroxyphthalimide; carbon tetrabromide; trichloroisocyanuric acid; copper(II) acetate monohydrate In dichloromethane at 25℃; for 20h;	49%

methyl 3-<2-(methoxycarbonyl)benzyloxy>phenylacetate (93273-66-6) → o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 3-hydroxy-benzeneacetic acid, methyl ester (42058-59-3) + methyl 3-hydroxy-4-<2-(methoxycarbonyl)benzyl>phenylacetate (93273-67-7)

Conditions	Yield
With aluminium trichloride In 1,2-dichloro-ethane for 0.666667h; Ambient temperature;	A 30.9% B 55.2% C 28.7%

methanol (67-56-1) + 2-Chloromethylbenzoyl chloride (42908-86-1) → o-(chloromethyl)benzoic acid methyl ester (34040-62-5)

Conditions	Yield
With pyridine for 18h; Yield given;
for 3h; Heating;	1000 mg
Stage #1: methanol; 2-Chloromethylbenzoyl chloride at 50 - 60℃; for 2h; Stage #2: With potassium carbonate In water; toluene for 0.5h;

3-(2-carboxybenzyloxy)phenylacetic acid (55690-19-2) → o-(chloromethyl)benzoic acid methyl ester (34040-62-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: 95.3 percent / conc. H2SO4 / 22 h / Heating 2: 30.9 percent / aluminium chloride / 1,2-dichloro-ethane / 0.67 h / Ambient temperature View Scheme

2-benzofuran-1(3H)-one (87-41-2) → o-(chloromethyl)benzoic acid methyl ester (34040-62-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: thionyl chloride; N-benzyl-N,N,N-triethylammonium chloride 2: methanol View Scheme

ortho-methylbenzoic acid (118-90-1) → o-(chloromethyl)benzoic acid methyl ester (34040-62-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: 2,2'-azobis(isobutyronitrile); thionyl chloride / 1,2-dichloro-ethane / 4 h / 60 °C 2: sulfuric acid / 6 h / 80 °C View Scheme

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 2,3-Dihydro-2-oxo-1H-benzimidazole-1-carboxylic acid 1,1-dimethylethyl ester (161468-45-7) → tert-butyl 3-(2-(methoxycarbonyl)benzyl)-2-oxo-2,3-dihydro-1H-benzo[d]imidazole-1-carboxylate

Conditions	Yield
With caesium carbonate In dimethyl sulfoxide at 80℃; for 5h;	100%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + cyclohexylamine (108-91-8) → 2-cyclohexyl-2,3-dihydro-1H-isoindol-1-one (3823-13-0)

Conditions	Yield
In neat (no solvent) at 140℃; for 2h;	98%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + aniline (62-53-3) → N-phenylphthalimidine (5388-42-1)

Conditions	Yield
In neat (no solvent) at 140℃; for 2h;	98%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + Methyl 4-hydroxyphenylacetate (14199-15-6) → 4-(2-methoxycarbonylbenzyloxy)phenyl acetic acid (1009378-92-0)

Conditions	Yield
With potassium carbonate In ethanol for 24h; Reagent/catalyst; Reflux;	96.9%
With potassium carbonate In ISOPROPYLAMIDE at 90℃; for 8h;
With potassium carbonate In ISOPROPYLAMIDE at 90℃; for 8h;

2-mercapto-4-methylbenzonitrile (613263-26-6) + o-(chloromethyl)benzoic acid methyl ester (34040-62-5) → methyl 2-{[(2-cyano-5-methylphenyl)thio]methyl}benzoate

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

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 4-chloro-2-mercaptobenzonitrile (1339650-77-9) → methyl 2-{[(5-chloro-2-cyanophenyl)thio]methyl}benzoate

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

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 4,6-diphenyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile (58327-74-5) → 3-cyano-2-{[2-(methoxycarbonyl)benzyl]thio}-4,6-diphenylpyridine

Conditions	Yield
With triethylamine In chloroform for 0.5h; Reflux;	86%

methanol (67-56-1) + o-(chloromethyl)benzoic acid methyl ester (34040-62-5) → methyl 2-(methoxymethyl)benzoate (942-57-4)

Conditions	Yield
With sodium hydride for 4h; Heating;	85%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 2-cyanothiophenol (34761-11-0) → methyl 2-{[(2-cyanophenyl)thio]methyl}benzoate

Conditions	Yield
With triethylamine In chloroform for 0.666667h; Reflux;	84%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 6-(4-bromophenyl)-3-cyano-4-phenylpyridine-2(1H)-thione → 6-(4-bromophenyl)-3-cyano-2-{[2-(methoxycarbonyl)benzyl]thio}-4-phenylpyridine

Conditions	Yield
With triethylamine In chloroform for 0.5h; Reflux;	84%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) → 2-(Chlorosulfonylmethyl)benzoic acid methyl ester (103342-27-4)

Conditions	Yield
With Sodium thiosulfate pentahydrate; chlorine; acetic acid In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; water	83%
Multi-step reaction with 2 steps 1: sodium thiosulfate / water / 3 h / 70 °C 2: water; chlorine / 1,2-dichloro-benzene / 5 h / 10 - 30 °C View Scheme

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) → o-(2-ethoxycarbonyl)phenylmethanesulfonyl chloride (221631-54-5)

Conditions	Yield
With Sodium thiosulfate pentahydrate	81%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) → methyl 2-(chloromethyl)-5-nitrobenzoate (90537-42-1)

Conditions	Yield
With sulfuric acid; potassium nitrate at 0 - 20℃; for 4h;	80%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 1,2,5,6,7,8-hexahydro-2-thioxoquinoline-3-carbonitrile (112629-69-3) → 3-cyano-2-{[2-(methoxycarbonyl)benzyl]thio}-5,6,7,8-tetrahydroquinoline

Conditions	Yield
With triethylamine In chloroform for 0.5h; Reflux;	78%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 2-Fluorobenzaldehyde (446-52-6) → 3-(2-fluorophenyl)-3,4-dihydroisocoumarin (95217-42-8)

Conditions	Yield
With N1,N1,N12,N12-tetramethyl-7,8-dihydro-6H-dipyrido[1,2-a:2,1'-c][1,4]diazepine-2,12-diamine In N,N-dimethyl-formamide at 20℃; for 16h; Glovebox; Inert atmosphere;	77%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 4-phenyl-6-(thiophen-2-yl)-2-thioxo-1,2-dihydropyridine-3-carbonitrile (82127-11-5) → 3-cyano-2-{[2-(methoxycarbonyl)benzyl]thio}-4-phenyl-6-(2-thienyl)pyridine

Conditions	Yield
With triethylamine In chloroform for 0.5h; Reflux;	76%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 4-fluorobenzaldehyde (459-57-4) → 3,4-dihydro-3-(4'-fluorophenyl)isocoumarine

Conditions	Yield
With N1,N1,N12,N12-tetramethyl-7,8-dihydro-6H-dipyrido[1,2-a:2,1'-c][1,4]diazepine-2,12-diamine In N,N-dimethyl-formamide at 20℃; for 16h; Glovebox; Inert atmosphere;	75%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 4,6-Dimethyl-2-thioxo-1,2-dihydro-pyridine-3-carbonitrile (54585-47-6) → 3-cyano-4,6-dimethyl-2-{[2-(methoxycarbonyl)benzyl]thio}pyridine

Conditions	Yield
With triethylamine In chloroform for 0.5h; Reflux;	74%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 2-thioxo-6-phenyl-4-(trifluoromethyl)-1,2-dihydropyridine-3-carbonitrile (104960-49-8) → 3-cyano-2-{[2-(methoxycarbonyl)benzyl]thio}-6-phenyl-4-(trifluoromethyl)pyridine

Conditions	Yield
With triethylamine In chloroform for 0.5h; Reflux;	74%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 1-cyano-2-hydroxynaphthalene (52805-47-7) → C20H15NO3 (1293961-06-4)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 50 - 55℃; for 0.666667h;	72%

m-bromobenzoic aldehyde (3132-99-8) + o-(chloromethyl)benzoic acid methyl ester (34040-62-5) → (dl)-3-(3'-bromophenyl)-3,4-dihydroisocoumarin

Conditions	Yield
With N1,N1,N12,N12-tetramethyl-7,8-dihydro-6H-dipyrido[1,2-a:2,1'-c][1,4]diazepine-2,12-diamine In N,N-dimethyl-formamide at 20℃; for 16h; Glovebox; Inert atmosphere;	71%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + allyltrimethoxysilane (2551-83-9) → methyl 5-allyl-2-methylbenzoate

Conditions	Yield
Stage #1: o-(chloromethyl)benzoic acid methyl ester; allyltrimethoxysilane With tetrakis(triphenylphosphine) palladium(0); tetrabutyl ammonium fluoride In tetrahydrofuran; dichloromethane at 20℃; for 12h; Hiyama Coupling; Inert atmosphere; Stage #2: With toluene-4-sulfonic acid In tetrahydrofuran; dichloromethane at 20℃; for 0.166667h; Inert atmosphere; regioselective reaction;	70%

4-Trifluoromethylbenzaldehyde (455-19-6) + o-(chloromethyl)benzoic acid methyl ester (34040-62-5) → 3-(4-(trifluoromethyl)phenyl)-3,4-dihydroisocoumarin

Conditions	Yield
With N1,N1,N12,N12-tetramethyl-7,8-dihydro-6H-dipyrido[1,2-a:2,1'-c][1,4]diazepine-2,12-diamine In N,N-dimethyl-formamide at 20℃; for 16h; Glovebox; Inert atmosphere;	68%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 5-chloro-2-hydroxybenzonitrile (13589-72-5) → C16H12ClNO3 (1293960-94-7)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 50 - 55℃; for 0.666667h;	67%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + 2-cyano-4-methylphenol (51282-90-7) → C17H15NO3 (1293960-91-4)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 50 - 55℃; for 0.666667h;	65%

o-(chloromethyl)benzoic acid methyl ester (34040-62-5) + benzaldehyde (100-52-7) → 3-phenyl-isochroman-1-one (2674-44-4, 146518-60-7)

Conditions	Yield
With N1,N1,N12,N12-tetramethyl-7,8-dihydro-6H-dipyrido[1,2-a:2,1'-c][1,4]diazepine-2,12-diamine In N,N-dimethyl-formamide at 20℃; for 16h; Reagent/catalyst; Solvent; Temperature; Glovebox; Inert atmosphere;	64%

salicylonitrile (611-20-1) + o-(chloromethyl)benzoic acid methyl ester (34040-62-5) → methyl 2-[(2-cyanobenzyl)oxy]benzoate (1293960-89-0)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 50 - 55℃; for 0.666667h;	62%

Upstream product

• 67-56-1 methanol 
• 42908-86-1 2-Chloromethylbenzoyl chloride 
• 93273-66-6 methyl 3-<2-(methoxycarbonyl)benzyloxy>phenylacetate 
• 87-41-2 2-benzofuran-1(3H)-one 
• 85888-81-9 2-(chloromethyl)benzoic acid 
• 118-90-1 ortho-methylbenzoic acid 
• 89-71-4 2-Methyl-benzoic acid methyl ester 
• 55690-19-2 3-(2-carboxybenzyloxy)phenylacetic acid 

Downstream Products

• 54759-03-4 2-(4-Phenoxy-phenoxymethyl)-benzoic acid methyl ester 
• 24832-18-6 methyl α-(o-nitrophenoxy)-o-toluate 
• 37489-95-5 Methyl-α-(o-Acetamidophenoxy)-o-toluat 
• 942-57-4 methyl 2-(methoxymethyl)benzoate 
• 64088-81-9 3-[4-(2-Carboxybenzyloxy)-phenyl]-propionsaeure 
• 329781-57-9 methyl 2-(azidomethyl) benzoate 
• 289712-57-8 2-(azidomethyl)benzoic acid 
• 501432-17-3 2-Azidomethyl-benzoic acid (3aR,5S,6R,6aR)-2,2-dimethyl-5-(S)-thiiranyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yl ester 
• 501432-19-5 2-Azidomethyl-benzoic acid (2S,3R,4S,5S,6R)-2,3,5-trihydroxy-6-hydroxymethyl-tetrahydro-thiopyran-4-yl ester 
• 501432-20-8 2-Azidomethyl-benzoic acid (3aS,4aR,8aS,9S,9aR)-2,2,7,7-tetramethyl-hexahydro-[1,3]dioxolo[4',5':5,6]thiopyrano[3,2-d][1,3]dioxin-9-yl ester 
• 501432-18-4 2-Azidomethyl-benzoic acid (3aR,5S,6R,6aR)-5-((R)-2-acetoxy-1-acetylsulfanyl-ethyl)-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yl ester 
• 25652-68-0 11,12-Dihydro-6H-dibenz<1,4>-oxazocin 
• 16882-87-4 12-benzyl-11,12-dihydro-6H-dibenzo[b,f][1,4]oxazocine 
• 37489-70-6 2-(2-Formylamino-phenoxymethyl)-benzoic acid 

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