68432-92-8

Basic information

• Product Name: 3-CYANOMETHYLBENZOIC ACID METHYL ESTER
• Synonyms: 3-CYANOMETHYLBENZOIC ACID METHYL ESTER;METHYL 3-(CYANOMETHYL) BENZOATE;Methyl m-(cyanomethyl)benzoate
• CAS NO: 68432-92-8
• Molecular Formula: C₁₀H₉NO₂
• Molecular Weight: 175.18
• Product Categories: Aromatic Esters
• Mol File: 68432-92-8.mol
• Article Data: 44

Chemical Properties

• Boiling Point: 314.059 °C at 760 mmHg
• Flash Point: 146.515 °C
• Appearance: /
• Density: 1.141 g/cm³
• Vapor Pressure: 0mmHg at 25°C
• Refractive Index: 1.531
• Storage Temp.: Sealed in dry,Room Temperature
• CAS DataBase Reference: 3-CYANOMETHYLBENZOIC ACID METHYL ESTER(CAS DataBase Reference)
• NIST Chemistry Reference: 3-CYANOMETHYLBENZOIC ACID METHYL ESTER(68432-92-8)
• EPA Substance Registry System: 3-CYANOMETHYLBENZOIC ACID METHYL ESTER(68432-92-8)

Safety Data

• HazardClass: IRRITANT
• Hazardous Substances Data: 68432-92-8(Hazardous Substances Data)

Usage

General Description

3-Cyanomethylbenzoic acid methyl ester is a chemical compound with the molecular formula C10H9NO2. It is a methyl ester derivative of 3-cyanomethylbenzoic acid and is often used as an intermediate in the production of pharmaceuticals and agrochemicals. 3-CYANOMETHYLBENZOIC ACID METHYL ESTER is a white to off-white solid that is sparingly soluble in water but soluble in organic solvents. It is known to be a potential irritant to the skin, eyes, and respiratory system and should be handled with care. Additionally, it is important to note that this chemical should be stored in a cool, dry place away from sources of ignition and incompatible materials.

InChI:InChI=1/C10H9NO2/c1-13-10(12)9-4-2-3-8(7-9)5-6-11/h2-4,7H,5H2,1H3

Synthetic route

trimethylsilyl cyanide (7677-24-9) + 3-methoxycarbonylbenzyl bromide (1129-28-8) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
With potassium carbonate In acetonitrile at 60℃; for 15h;	98%
With tetrabutyl ammonium fluoride In acetonitrile for 20h; Heating / reflux;	43%

potassium cyanide (151-50-8) + 3-methoxycarbonylbenzyl bromide (1129-28-8) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
With 18-crown-6 ether In acetonitrile for 24h; Heating / reflux;	96%
With 18-crown-6 ether In acetonitrile for 24h; Ambient temperature;	92%
With 18-crown-6 ether In acetonitrile at 20℃; for 40h;	91%
In ethanol at 60℃;	68%

3-methoxycarbonylbenzyl bromide (1129-28-8) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
In acetonitrile	91%
In dimethyl sulfoxide
In N,N-dimethyl-formamide

potassium cyanide + 3-methoxycarbonylbenzyl bromide (1129-28-8) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
With 18-crown-6 ether In acetonitrile at 20℃; for 72h;	91%
With 18-crown-6 ether In acetonitrile at 20℃; for 72h;	91%
In methanol; water for 5h; Reflux; Inert atmosphere;	1 g

sodium cyanide (773837-37-9) + 3-methoxycarbonylbenzyl bromide (1129-28-8) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
In N,N-dimethyl-formamide at 20℃;	89%
In N,N-dimethyl-formamide at 20℃;	89%
In water; N,N-dimethyl-formamide at 75℃; for 5h; Inert atmosphere;	85%

sodium cyanide (143-33-9) + 3-methoxycarbonylbenzyl bromide (1129-28-8) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
In water; N,N-dimethyl-formamide at 75℃; for 5h;	70%
In water; N,N-dimethyl-formamide at 75℃; for 5h;	70%
Stage #1: sodium cyanide; 3-methoxycarbonylbenzyl bromide In water; N,N-dimethyl-formamide at 75℃; for 5h; Stage #2: With water In N,N-dimethyl-formamide	70%

4-isoxazoleboronic acid pinacol ester (928664-98-6) + methyl 3-bromobenzoate (618-89-3) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
With potassium fluoride; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 In dimethyl sulfoxide at 130℃; for 18h; Suzuki Coupling; Inert atmosphere; Sealed tube;	69%

3-azido-2-methylbut-3-en-2-ol (1624363-23-0) + 3-(methoxycarbonyl)benzenediazonium tetrafluoroborate → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
With 2,6-dimethylpyridine In acetonitrile at 20℃; for 4h;	65%

3-bromomethylbenzoyl chloride (54267-06-0) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 91 percent / 18-crown-6 / acetonitrile / 40 h / 20 °C View Scheme

3-Methylbenzoyl chloride (1711-06-4) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: Br2 / 0.5 h / 180 °C 2: 91 percent / 18-crown-6 / acetonitrile / 40 h / 20 °C View Scheme

1-methoxycarbonyl-3-methylbenzene (99-36-5) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: NBS / CCl4 2: dimethylsulfoxide View Scheme
Multi-step reaction with 2 steps 1: N-Bromosuccinimide; dibenzoyl peroxide / tetrachloromethane / 3 h / Inert atmosphere; Reflux; Irradiation 2: methanol; water / 5 h / Inert atmosphere; Reflux View Scheme
Multi-step reaction with 2 steps 1: dibenzoyl peroxide; N-Bromosuccinimide / tetrachloromethane / 4 h / 70 °C 2: dimethyl sulfoxide / 3.25 h / 0 - 10 °C View Scheme
Multi-step reaction with 2 steps 1: N-Bromosuccinimide; dibenzoyl peroxide / tetrachloromethane / Inert atmosphere; Reflux 2: tetra-(n-butyl)ammonium iodide / acetonitrile / Inert atmosphere; Reflux View Scheme

Methyl-3-bromomethylenebenzoate → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
In methanol; dichloromethane; water; acetonitrile

methyl 3-bromobenzoate (618-89-3) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions

Yield

Multi-step reaction with 4 steps 1.1: magnesium; iodine / tetrahydrofuran / 2 h / 70 °C / Inert atmosphere 1.2: 6 h / 0 - 20 °C / Inert atmosphere 2.1: 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium bromide; sodium hypochlorite; sodium hydrogencarbonate / acetonitrile / 2 h / 0.5 °C / pH 9-10 3.1: ammonia; thionyl chloride / 70 °C 4.1: thionyl chloride / chloroform / 8 h / Reflux View Scheme

methyl 3-(2-amino-2-oxoethyl)benzoate (929301-93-9) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
With thionyl chloride In chloroform for 8h; Reflux;	32 g

m-bromobenzoic acid (585-76-2) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: thionyl chloride / 5 h / 70 °C 1.2: 4 h / 20 °C / Cooling with ice 2.1: magnesium; iodine / tetrahydrofuran / 2 h / 70 °C / Inert atmosphere 2.2: 6 h / 0 - 20 °C / Inert atmosphere 3.1: 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium bromide; sodium hypochlorite; sodium hydrogencarbonate / acetonitrile / 2 h / 0.5 °C / pH 9-10 4.1: ammonia; thionyl chloride / 70 °C 5.1: thionyl chloride / chloroform / 8 h / Reflux View Scheme

methyl 3-(2-hydroxylethyl)benzoate (153599-45-2) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium bromide; sodium hypochlorite; sodium hydrogencarbonate / acetonitrile / 2 h / 0.5 °C / pH 9-10 2: ammonia; thionyl chloride / 70 °C 3: thionyl chloride / chloroform / 8 h / Reflux View Scheme

m-Toluic acid (99-04-7) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: thionyl chloride / 4 h / Reflux 1.2: 100 °C 2.1: 40 °C 3.1: methanol / 2 h / 40 - 80 °C View Scheme

sodium cyanide (773837-37-9) + 1-methoxycarbonyl-3-methylbenzene (99-36-5) → methyl 3-cyanomethylbenzoate (68432-92-8)

Conditions	Yield
In methanol at 40 - 80℃; for 2h;

methyl 3-cyanomethylbenzoate (68432-92-8) → methyl 3-(2-amino-2-thioxoethyl)benzoate

Conditions	Yield
With sodium hydrogen sulfide; hydrogen sulfide; acetamidine hydrochloride In water at 70℃; under 3750.38 Torr; for 4h; pH=10; Reagent/catalyst; pH-value; Pressure; Temperature; Autoclave;	98.6%
With sodium hydrogen sulfide; triethylamine hydrochloride In methanol at 70℃; for 7h; Concentration; Reagent/catalyst;	95.8%

methyl 3-cyanomethylbenzoate (68432-92-8) → 2-(3-(hydroxymethyl)phenyl)acetonitrile (177665-49-5)

Conditions	Yield
With sodium tetrahydroborate In tetrahydrofuran; methanol at 0 - 10℃; for 16.25h;	95%
With lithium borohydride In tetrahydrofuran for 4h; Heating / reflux;	41%

methyl 3-cyanomethylbenzoate (68432-92-8) + carbonic acid dimethyl ester (616-38-6) → 2-<3-(carboxymethyl)phenyl>propionitrile (146257-39-8)

Conditions	Yield
With potassium carbonate at 180℃; for 8h; Product distribution; Mechanism; the course of reaction according various periods of time;	91%
With potassium carbonate at 180℃; for 8h;	91%
With potassium carbonate at 180℃; for 8h;	91%

methanol (67-56-1) + methyl 3-cyanomethylbenzoate (68432-92-8) → 3-methoxycarbonylphenylacetic acid methyl ester (52787-20-9)

Conditions	Yield
With hydrogenchloride In methanol at 20℃; for 6h;	87%

methyl 3-cyanomethylbenzoate (68432-92-8) → (3-(2-aminoethyl)phenyl)methanol (743384-09-0)

Conditions	Yield
With aluminum (III) chloride; lithium aluminium tetrahydride In tetrahydrofuran; diethyl ether at 20℃; Inert atmosphere;	83%
Stage #1: methyl 3-cyanomethylbenzoate With aluminum (III) chloride; lithium aluminium tetrahydride In tetrahydrofuran; diethyl ether at 20℃; Inert atmosphere; Stage #2: With sulfuric acid; water In tetrahydrofuran; diethyl ether
Multi-step reaction with 2 steps 1: sodium tetrahydroborate / tetrahydrofuran; methanol / 16.25 h / 0 - 10 °C 2: hydrogen; ammonia / Raney-Ni / methanol / 3 h / 10 °C View Scheme

methyl 3-cyanomethylbenzoate (68432-92-8) → 3-(cyanomethyl)benzoic acid (5689-33-8)

Conditions	Yield
With lithium hydroxide; water In tetrahydrofuran at 20 - 50℃;	79%

methyl 3-cyanomethylbenzoate (68432-92-8) + methyl iodide (74-88-4) → methyl 3-(1-cyano-1-methylethyl)benzoate (872091-85-5)

Conditions	Yield
In dimethyl sulfoxide	79%
Stage #1: methyl 3-cyanomethylbenzoate With sodium hydride In dimethyl sulfoxide; mineral oil at 20 - 25℃; Stage #2: methyl iodide In dimethyl sulfoxide; mineral oil at 20℃; for 16h;	79%
Stage #1: methyl 3-cyanomethylbenzoate With sodium hydride In dimethyl sulfoxide; mineral oil at 20℃; for 0.333333h; Cooling with ice; Stage #2: methyl iodide In dimethyl sulfoxide; mineral oil at 20℃; for 16h;	79%

methyl 3-cyanomethylbenzoate (68432-92-8) → 3-(2-Amino-ethyl)-benzoic acid methyl ester (179003-00-0)

Conditions	Yield
With hydrogenchloride; palladium 10% on activated carbon In methanol; water at 20℃; for 2h; Inert atmosphere;	78%
With sodium tetrahydroborate; trifluoroacetic acid In tetrahydrofuran for 4h; Ambient temperature;
With hydrogen; palladium on activated charcoal

methyl 3-cyanomethylbenzoate (68432-92-8) + ethylene dibromide (106-93-4) → methyl 3-(1-cyanocyclopropyl)benzoate (884000-93-5)

Conditions	Yield
With dimethyl sulfoxide	76%
Stage #1: methyl 3-cyanomethylbenzoate With sodium hydride In dimethyl sulfoxide; mineral oil at 20 - 25℃; Stage #2: ethylene dibromide In dimethyl sulfoxide; mineral oil at 20℃; for 10h;	76%
Stage #1: methyl 3-cyanomethylbenzoate With sodium hydride In dimethyl sulfoxide; mineral oil at 20℃; for 0.333333h; Cooling with ice; Stage #2: ethylene dibromide In dimethyl sulfoxide; mineral oil at 20℃; for 16h;	76%
Stage #1: methyl 3-cyanomethylbenzoate With sodium hydride In dimethyl sulfoxide; mineral oil at 20 - 25℃; for 0.5h; Stage #2: ethylene dibromide In dimethyl sulfoxide; mineral oil at 20℃; for 16h;

methyl 3-cyanomethylbenzoate (68432-92-8) → methyl 3-(2-amino-2-oxoethyl)benzoate (929301-93-9)

Conditions	Yield
Stage #1: methyl 3-cyanomethylbenzoate With hydrogenchloride In tetrahydrofuran; water Stage #2: With sodium hydroxide In tetrahydrofuran; water	70%

1,5-dibromo-pentane (111-24-0) + methyl 3-cyanomethylbenzoate (68432-92-8) → methyl 3-(1-cyanocyclohexyl)benzoate (1005788-17-9)

Conditions	Yield
With dimethyl sulfoxide	68%

methyl 3-cyanomethylbenzoate (68432-92-8) + 1-Bromo-2-chloroethane (107-04-0) → methyl 3-(1-cyanocyclopropyl)benzoate (884000-93-5)

Conditions	Yield
Stage #1: methyl 3-cyanomethylbenzoate With sodium hydride In dimethyl sulfoxide; mineral oil Stage #2: 1-Bromo-2-chloroethane In dimethyl sulfoxide; mineral oil at 0 - 25℃; for 18h;	68%
With sodium hydride In dimethyl sulfoxide; mineral oil at 0 - 25℃; for 18h;	68%

methyl 3-cyanomethylbenzoate (68432-92-8) → 3-carboxymethyl-benzoic acid (2084-13-1)

Conditions	Yield
With sulfuric acid; water at 160℃; for 3h;	68%

methyl 3-cyanomethylbenzoate (68432-92-8) → methyl 3-(1-cyano-1-methylethyl)benzoate (872091-85-5)

Conditions	Yield
With sodium hydride In dimethyl sulfoxide at 0 - 25℃; for 12h;	66%

methyl 3-cyanomethylbenzoate (68432-92-8) → [2-(3-methoxycarbonylphenyl)ethyl]ammonium chloride

Conditions	Yield
With hydrogenchloride; palladium 10% on activated carbon; hydrogen In methanol; water	63%
With hydrogenchloride; hydrogen; palladium 10% on activated carbon In methanol; dichloromethane; water at 20℃; under 2585.81 Torr; for 10h;
With hydrogenchloride; hydrogen; palladium 10% on activated carbon In methanol; dichloromethane; water at 20℃; under 2585.81 Torr; for 10h;

methyl 3-cyanomethylbenzoate (68432-92-8) → 4-bromo-3-(cyanomethyl)benzoic acid methyl ester

Conditions	Yield
With N-Bromosuccinimide; palladium diacetate; copper(II) bis(trifluoromethanesulfonate) In 1,2-dichloro-ethane Inert atmosphere; Sealed tube; regioselective reaction;	52%

1,1'-oxybis(2-bromo-ethane) (5414-19-7) + methyl 3-cyanomethylbenzoate (68432-92-8) → methyl 3-(4-cyanotetrahydro-2H-pyran-4-yl)benzoate (884000-92-4)

Conditions	Yield
With dimethyl sulfoxide	46%

methyl 3-cyanomethylbenzoate (68432-92-8) + 1,3-dibromo-propane (109-64-8) → methyl 3-(1-cyanocyclobutyl)benzoate (884000-91-3)

Conditions	Yield
With dimethyl sulfoxide	42%

methyl 3-cyanomethylbenzoate (68432-92-8) → 2-(3-((2,4-dichlorophenoxy)methyl)phenyl)acetic acid

Conditions	Yield
Stage #1: methyl 3-cyanomethylbenzoate With sodium tetrahydroborate In tetrahydrofuran at 80℃; Stage #2: With methanol In tetrahydrofuran at 20 - 80℃; for 16.5h;	40%

methyl 3-cyanomethylbenzoate (68432-92-8) → 3-carbamimidoylmethyl-benzoic acid methyl ester hydrochloride

Conditions	Yield
With hydrogenchloride; ethanol; ammonia 1.) CH2Cl2, EtOH, 0 deg C, 6 days, 2.) MeOH, 50 deg C, 18 h; Multistep reaction;
With ammonia In methanol; ethanol; dichloromethane

methyl 3-cyanomethylbenzoate (68432-92-8) + acrylic acid methyl ester (292638-85-8) → C18H21NO6

Conditions	Yield
With N-benzyl-trimethylammonium hydroxide In acetonitrile Michael reaction; Heating;

Upstream product

• 151-50-8 potassium cyanide 
• 1129-28-8 3-methoxycarbonylbenzyl bromide 
• 618-89-3 methyl 3-bromobenzoate 
• 99-04-7 m-Toluic acid 
• 773837-37-9 sodium cyanide 
• 99-36-5 1-methoxycarbonyl-3-methylbenzene 
• 1624363-23-0 3-azido-2-methylbut-3-en-2-ol 
• 153599-45-2 methyl 3-(2-hydroxylethyl)benzoate 
• 585-76-2 m-bromobenzoic acid 
• 929301-93-9 methyl 3-(2-amino-2-oxoethyl)benzoate 
• 928664-98-6 4-isoxazoleboronic acid pinacol ester 
• 7677-24-9 trimethylsilyl cyanide 
• 1711-06-4 3-Methylbenzoyl chloride 
• 54267-06-0 3-bromomethylbenzoyl chloride 

Downstream Products

• 146257-39-8 2-<3-(carboxymethyl)phenyl>propionitrile 
• 179003-00-0 3-(2-Amino-ethyl)-benzoic acid methyl ester 
• 872091-85-5 methyl 3-(1-cyano-1-methylethyl)benzoate 
• 929301-93-9 methyl 3-(2-amino-2-oxoethyl)benzoate 
• 177665-49-5 2-(3-(hydroxymethyl)phenyl)acetonitrile 
• 884000-91-3 methyl 3-(1-cyanocyclobutyl)benzoate 
• 1005788-17-9 methyl 3-(1-cyanocyclohexyl)benzoate 
• 884000-93-5 methyl 3-(1-cyanocyclopropyl)benzoate 
• 884000-92-4 methyl 3-(4-cyanotetrahydro-2H-pyran-4-yl)benzoate 
• 743384-09-0 (3-(2-aminoethyl)phenyl)methanol 
• 1253889-44-9 N⁽¹⁾-(4-butylphenyl)-N⁽²⁾-(3-(hydroxymethyl)phenethyl)phthalamide 
• 872091-00-4 3-(1-cyano-1-methylethyl)benzoic acid 
• 1093938-04-5 methyl 3-(2-(methylamino)ethyl)benzoate 
• 1093938-76-1 methyl 3-(2-(tert-butoxycarbonyl(methyl)amino)ethyl)benzoate 

Relevant articles and documents

Cyano ketoprofen synthesis process

The invention relates to a cyano ketoprofen synthesis process, which comprises the following steps: acylating chlorination, chlorination, esterification, cyaniding, distillation, methylation, hydrolysis, refining, acylation Friedel-Crafts ice precipitation distillation, and refining to finally obtain the cyano ketoprofen finished product. According to the cyano ketoprofen synthesis process, the synthesized product is low in cost, by acylating chlorination, esterification, cyaniding, methylation, Friedel-Crafts acylation and hydrolysis reaction, the product is prepared from m-toluic acid as a starting material, the process and the operation process are simplified, the safety and the reliability are provided, the wastewater and the waste gas generated during the reaction process are recycled, and the residue generated in the kettle is subjected to hazardous waste treatment, such that the environment is protected, the industrial production is promoted, the production efficiency is improved, and the purity of the synthesized finished product achieves 99% or more.

Preparation method of m-cyanomethyl methyl benzoate

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