80-63-7

Basic information

• Product Name: Methyl 2-chloro-2-propenoate
• Synonyms: Acrylicacid, 2-chloro-, methyl ester (6CI,7CI,8CI); 2-Chloroacrylic acid methyl ester;Methyl 2-chloro-2-propenoate; Methyl 2-chloroacrylate; Methyl2-chloropropenoate; Methyl a-chloroacrylate; NSC 32608
• CAS NO: 80-63-7
• Molecular Formula: C₄H₅ClO₂
• Molecular Weight: 120.54
• EINECS: 201-298-7
• Mol File: 80-63-7.mol
• Article Data: 12

Chemical Properties

• Boiling Point: 52 °C (50 mmHg)
• Flash Point: 33 °C
• Appearance: /
• Density: 1.189
• Vapor Pressure: 12.6mmHg at 25°C
• Refractive Index: 1.426
• CAS DataBase Reference: Methyl 2-chloro-2-propenoate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl 2-chloro-2-propenoate(80-63-7)
• EPA Substance Registry System: Methyl 2-chloro-2-propenoate(80-63-7)

Safety Data

• Hazardous Substances Data: 80-63-7(Hazardous Substances Data)

Usage

General Description

Methyl 2-chloro-2-propenoate, also known as methyl acryloyl chloride, is a chemical compound with the formula C4H5ClO2. It is an organic compound that is used in the production of pharmaceuticals, agrochemicals, and other fine chemicals. It is a clear, colorless liquid with a sharp, pungent odor, and is highly reactive due to the presence of the acryloyl chloride group. It is classified as a hazardous substance and can cause irritation to the skin, eyes, and respiratory system upon exposure. Methyl 2-chloro-2-propenoate is commonly handled and stored under strict safety protocols to prevent accidents and exposure.

InChI:InChI=1/C4H5ClO2/c1-3(5)4(6)7-2/h1H2,2H3

Synthetic route

endo-5-Carbomethoxy-6-chloro-1,6-diazabicyclo<3.1.0>hexane (89019-24-9, 108392-47-8, 108392-49-0, 113085-27-1, 113158-29-5) → methyl 2-chloroacrylate (80-63-7) + ethene (74-85-1)

Conditions	Yield
In chloroform-d1 at 80℃; for 10h; Product distribution;	A 95% B n/a

exo-6-chloro-5-methoxycarbonyl-1,6-diazabicyclo<3.1.0>hexane (89019-24-9, 108392-47-8, 108392-49-0, 113085-27-1, 113158-29-5) → methyl 2-chloroacrylate (80-63-7) + ethene (74-85-1) + N2

Conditions	Yield
In dichloromethane at 80℃; for 10h;	A 95% B n/a C n/a

methyl 2,3-dichloropropionate (3674-09-7, 132854-28-5) → methyl 2-chloroacrylate (80-63-7)

Conditions	Yield
In water; dimethyl sulfoxide at 120℃; for 6h;	91%
With 10H-phenothiazine; tetrabutylammomium bromide; sodium hydrogencarbonate In dichloromethane; water for 1.5h; Dehydrochlorination; Heating;	66%
beim Erhitzen mit protonierten Kationenaustauschern;

2,3,3-trichloropropene-1-ol → methyl 2-chloroacrylate (80-63-7)

Conditions	Yield
With sulfuric acid In methanol	74%

formaldehyd (50-00-0) + methyl chloroacetate (96-34-4) → methyl 2-chloroacrylate (80-63-7)

Conditions	Yield
Stage #1: methyl chloroacetate With Dimethyl oxalate; sodium methylate In dimethyl sulfoxide at 15 - 25℃; for 1h; Inert atmosphere; Stage #2: formaldehyd With 2,6-di-tert-butyl-4-methyl-phenol In dimethyl sulfoxide at 20 - 25℃; for 1h; Inert atmosphere;	58.1%

methyl-α-bromo-α-chloro-propanoate (166666-36-0) → methyl 2-chloroacrylate (80-63-7)

Conditions	Yield
With lithium carbonate; lithium bromide In N,N-dimethyl-formamide at 70℃; for 24h;	29%

dichloro-methylsulfanyl-acetic acid methyl ester (77825-46-8) → methyl 2-chloroacrylate (80-63-7)

Conditions	Yield
In tetrachloromethane at 490℃; Yield given;

exo-6-chloro-5-methoxycarbonyl-1,6-diazabicyclo<3.1.0>hexane (89019-24-9, 108392-47-8, 108392-49-0, 113085-27-1, 113158-29-5) → methyl 2-chloroacrylate (80-63-7) + ethene (74-85-1)

Conditions	Yield
In chloroform-d1 at 40℃; Rate constant; Mechanism; τ1/2 (h);

methyl 2,2-dichloropropionate (17640-02-7) + benzaldehyde (100-52-7) → methyl 2-chloroacrylate (80-63-7) + methyl 2-chloro-3-hydroxy-2-methyl-3-phenylpropanoate (80532-67-8)

Conditions	Yield
With boron trifluoride; zinc In tetrahydrofuran at 0℃; for 24h;	A 3 % Chromat. B 76 % Chromat.

benzaldehyde (100-52-7) + methyl-α-bromo-α-chloro-propanoate (166666-36-0) → methyl 2-chloroacrylate (80-63-7) + methyl 2-chloro-3-hydroxy-2-methyl-3-phenylpropanoate (80532-67-8) + dimethyl 2,3-dichloro-2,3-dimethylbutanedioate

Conditions	Yield
With boron trifluoride; zinc In tetrahydrofuran at 0℃; for 3h;	A 1 % Chromat. B 85 % Chromat. C 8 % Chromat.

methyl-<2.3-dichloro propionate> → methyl 2-chloroacrylate (80-63-7)

Conditions	Yield
With water; sodium carbonate; hydroquinone at 150℃; staendiges Abdestillieren des entstandenen Methyl-<2.3-dichlor-acrylats>;
With quinoline
With sodium acetate; isopropyl alcohol

methyl 2-chloroacrylate (80-63-7) + 2-[[N-(1,3-thiazol-2-yl)methylene]amino]-3-(1H-pyrazol-1-yl)propanoic acid tert-butyl ester (885264-31-3) → C18H23ClN4O4S

Conditions	Yield
With triethylamine; lithium bromide In tetrahydrofuran at 20℃; for 17h;	100%

methyl 2-chloroacrylate (80-63-7) + Methyl thioglycolate (2365-48-2) → α-Chlor-β-<(methoxycarbonylmethyl)thio>propansaeure-methylester (90237-73-3)

Conditions	Yield
With sodium In dichloromethane at 25℃; for 0.666667h;	99%

methyl 2-chloroacrylate (80-63-7) + benzenecarbothioamide (2227-79-4) → S-<2-Chlor-2-(methoxycarbonyl)ethyl>thiobenzamid-hydrochlorid (116077-23-7)

Conditions	Yield
With hydrogenchloride In dichloromethane for 72h; Ambient temperature;	98%

methyl 2-chloroacrylate (80-63-7) + 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1-heptanol (335-99-9) → dodecafluoroheptyl 2-chloroacrylate

Conditions	Yield
With 10H-phenothiazine; tetrakis(1H,1H,7H-perfluoroheptyl) titanate; hydroquinone In toluene at 80℃; for 3.5h; Large scale;	97.1%

methyl 2-chloroacrylate (80-63-7) + phenylmethanethiol (100-53-8) → 2-Chlor-3-(benzylthio)propansaeure-methylester (60741-22-2)

Conditions	Yield
With sodium benzylmercaptide In dichloromethane for 4h; Ambient temperature;	95%
With sodium methylate

methyl 2-chloroacrylate (80-63-7) + methylenecyclohexane (1192-37-6) → Methyl α-chloro-1-cyclohexene-1-butanoate (89398-16-3)

Conditions	Yield
With ethylaluminum dichloride In hexane; benzene at 25℃; for 20h;	95%
With ethylaluminum dichloride In hexane; benzene at 25℃; for 24h;	95%
With 1-menthyloxyaluminium dichloride In benzene Product distribution; Et2AlCl catalyzed ene reactions of α-substituted acrylate esters with trans 1,2-di and trisubstituted alkenes; regio- and stereoselectivity; reactivity of alkenes and acrylate esters; asymmetric induction;	22%
With 1-menthyloxyaluminium dichloride	22%

methyl 2-chloroacrylate (80-63-7) + cesium 2-((1-methylcyclohexyl)oxy)-2-oxoacetate → methyl 2-chloro-3-(1-methylcyclohexyl)propanoate

Conditions	Yield
With Ir[dF(CF3)ppy]2(dtbbpy)PF6 In 1,2-dimethoxyethane; water; N,N-dimethyl-formamide at 40℃; for 24h; Irradiation; Inert atmosphere;	94%

methyl 2-chloroacrylate (80-63-7) + methyl 2-nitroacetate (2483-57-0) → C7H10ClNO6

Conditions	Yield
With DBN In N,N-dimethyl-formamide at 60 - 65℃; for 4h; Solvent; Temperature;	92.7%

methyl 2-chloroacrylate (80-63-7) + thiophenol (108-98-5) → α-Chlor-β-(phenylthio)propansaeure-methylester (42801-75-2)

Conditions	Yield
With sodium thiophenolate In dichloromethane at 25℃; for 5h;	91%
With sodium thiophenolate In dichloromethane for 4h; Ambient temperature;	91%

methyl 2-chloroacrylate (80-63-7) + dimethyl phenylphosphonate (2240-41-7) + phenol (108-95-2) → Methyl 3-(phenyl-methoxyphosphinyl)-2-chloropropionate

Conditions	Yield
	90.1%

methyl 2-chloroacrylate (80-63-7) + thioacetamide (62-55-5) → S-<2-Chlor-2-(methoxycarbonyl)ethyl>thioacetamid-hydrochlorid (116077-24-8)

Conditions	Yield
With hydrogenchloride In dichloromethane for 18h; Ambient temperature;	88%

methyl 2-chloroacrylate (80-63-7) + methylhydrazine (60-34-4) → 1-methyl-1,2-dihydro-3H-pyrazol-3-one (52867-35-3)

Conditions	Yield
In tetrahydrofuran at 0 - 25℃; for 10h;	88%
In tetrahydrofuran at 20℃; for 16.08h;	84%
In tetrahydrofuran at 20 - 50℃; for 17h;	77%

methyl 2-chloroacrylate (80-63-7) + nitromethane (75-52-5) + orthoformic acid triethyl ester (122-51-0) → 5-nitro-2-hydroxypyridine (5418-51-9)

Conditions	Yield
Stage #1: methyl 2-chloroacrylate; nitromethane With 1,8-diazabicyclo[5.4.0]undec-7-ene at 50 - 55℃; for 5h; Stage #2: orthoformic acid triethyl ester With zinc(II) chloride at 95 - 100℃; for 4h; Stage #3: With ammonium hydroxide; ammonium chloride In methanol at 50 - 55℃; for 6h;	87.8%

methyl 2-chloroacrylate (80-63-7) + methylthiol (74-93-1) → 2-Chlor-3-(methylthio)propansaeure-methylester (20444-25-1)

Conditions	Yield
With sodium thiomethoxide In dichloromethane for 4h; Ambient temperature;	87%
With sodium methylate; benzene

methyl 2-chloroacrylate (80-63-7) + ethyl 3-amino-4,4,4-trifluoro-2-butenoate (372-29-2, 141860-78-8) → 6-hydroxy-2-(trifluoromethyl)nicotinic acid

Conditions	Yield
Stage #1: methyl 2-chloroacrylate; ethyl 3-amino-4,4,4-trifluoro-2-butenoate With sodium ethanolate In ethanol at 22 - 23℃; for 2.5h; Inert atmosphere; Stage #2: With water; sodium hydroxide In ethanol at 70 - 75℃;	87%

methanol (67-56-1) + methyl 2-chloroacrylate (80-63-7) → α-Chlor-β-methoxypropansaeure-methylester (36997-03-2)

Conditions	Yield
With sodium 0 degC, 1 h then r.t., 2 h;	86%

methyl 2-chloroacrylate (80-63-7) + 3-Methyl-cis-2-penten (922-62-3) → (2S,4R)-2-Chloro-4-methyl-5-methylene-heptanoic acid methyl ester (74964-45-7)

Conditions	Yield
With ethylaluminum dichloride In benzene at 25℃; for 19.2h;	86%

methyl 2-chloroacrylate (80-63-7) + mercaptoacetic acid (68-11-1) → 3-(Carboxymethylthio)-2-chlorpropansaeure-methylester (116077-17-9)

Conditions	Yield
With sodium hydroxide In water at 10℃; for 24h;	86%

2-(2-aminophenyl)-3-cyclohexyl-1H-indole-6-carboxylic acid methyl ester (863578-19-2) + methyl 2-chloroacrylate (80-63-7) → dimethyl 13-cyclohexyl-6,7-dihydro-5H-indolo[1,2-d][1,4]benzodiazepine-6,10-dicarboxylate (956580-06-6)

Conditions	Yield
With tetrabutylammomium bromide; potassium carbonate In acetonitrile at 60℃;	84%
With N-benzyl-N,N,N-triethylammonium chloride; potassium carbonate In acetonitrile at 60℃;	75%

methyl 2-chloroacrylate (80-63-7) + (E)-3-methyl-2-pentene (616-12-6) → (Z)-(2S,4R)-2-Chloro-4,5-dimethyl-hept-5-enoic acid methyl ester (74964-46-8, 80865-34-5, 80865-37-8) + (E)-(2S,4R)-2-Chloro-4,5-dimethyl-hept-5-enoic acid methyl ester (74964-46-8)

Conditions	Yield
With ethylaluminum dichloride In benzene at 25℃; for 14.4h; Yields of byproduct given;	A n/a B 82%
With ethylaluminum dichloride In benzene at 25℃; for 14.4h; Product distribution; Mechanism; regiospecificity; further alkenes;

methyl 2-chloroacrylate (80-63-7) + methyl chloroacetate (96-34-4) → cis-1,2-Di(methoxycarbonyl)-1-chlorcyclopropan (39822-01-0, 39822-02-1)

Conditions	Yield
With potassium hydride In N,N-dimethyl-formamide at 25℃; for 6h;	80%

n-butyl magnesium bromide (693-03-8) + methyl 2-chloroacrylate (80-63-7) → 1-chloro-2-pentyl-cyclopropane-1,2-dicarboxylic acid dimethyl ester

Conditions	Yield
With copper(l) chloride In diethyl ether at -78℃; Michael addition;	80%

methyl 2-chloroacrylate (80-63-7) + ethylmagnesium bromide (925-90-6) → 1-chloro-2-propyl-cyclopropane-1,2-dicarboxylic acid dimethyl ester

Conditions	Yield
With copper(l) chloride In diethyl ether at -78℃; Michael addition;	78%

methyl 2-chloroacrylate (80-63-7) + isopropylmagnesium chloride (1068-55-9) → 1-chloro-2-isobutyl-cyclopropane-1,2-dicarboxylic acid dimethyl ester

Conditions	Yield
With copper(l) chloride In diethyl ether at -78℃; Michael addition;	76%

methyl 2-chloroacrylate (80-63-7) + 1,3-dithiapropane (6725-64-0) → 3,3'-bis(2-chlorpropansaeure-methylester) (116077-16-8)

Conditions	Yield
With triethylamine In diethyl ether at 0℃; for 0.166667h;	75%

2-methyl-but-2-ene (513-35-9) + methyl 2-chloroacrylate (80-63-7) → (2R,4S)-2-Chloro-4,5-dimethyl-hex-5-enoic acid methyl ester (74964-44-6)

Conditions	Yield
With ethylaluminum dichloride In benzene at 25℃; for 28.8h;	74%

Upstream product

• 3674-09-7 methyl 2,3-dichloropropionate 
• 79-01-6 Trichloroethylene 
• 292638-85-8 acrylic acid methyl ester 
• 67280-59-5 3-bromo-2-chloro-propionic acid methyl ester 
• 89019-24-9 endo-5-Carbomethoxy-6-chloro-1,6-diazabicyclo<3.1.0>hexane 
• 17640-02-7 methyl 2,2-dichloropropionate 
• 100-52-7 benzaldehyde 
• 166666-36-0 methyl-α-bromo-α-chloro-propanoate 
• 89019-24-9 exo-6-chloro-5-methoxycarbonyl-1,6-diazabicyclo<3.1.0>hexane 
• 50-00-0 formaldehyd 
• 96-34-4 methyl chloroacetate 
• 77825-46-8 dichloro-methylsulfanyl-acetic acid methyl ester 
• 67-56-1 methanol 
• 3266-39-5 2,3,3-trichloro-2-propen-1-ol 

Downstream Products

• 1552-79-0 2,2-Dichlor-3-p-tolyl-propionsaeure-methylester 
• 1552-77-8 methyl α,α-dichloro-β-(4-chlorophenyl)propionate 
• 1552-78-9 2,2-Dichlor-3-<4-methoxy-phenyl>-propionsaeure-methylester 
• 30267-68-6 methyl α,α-dichloro-β-(3-chloro-o-tolyl)propionate 
• 1552-80-3 2,2-Dichlor-3-phenyl-propionsaeure-methylester 
• 1552-76-7 2,2-Dichlor-3-<3-nitro-phenyl>-propionsaeure-methylester 
• 4284-72-4 2-Chloro-3-(toluene-4-sulfonyl)-propionic acid methyl ester 
• 4284-75-7 (E)-3-(3-Nitro-benzenesulfonyl)-acrylic acid methyl ester 
• 4284-70-2 3-(4-Acetylamino-benzenesulfonyl)-2-chloro-propionic acid methyl ester 
• 4284-73-5 (Z)-3-(4-Acetylamino-benzenesulfonyl)-acrylic acid methyl ester 
• 4284-74-6 (E)-3-(4-Methyl-3-nitro-benzenesulfonyl)-acrylic acid methyl ester 
• 4284-71-3 2-Chloro-3-(4-methyl-3-nitro-benzenesulfonyl)-propionic acid methyl ester 
• 5118-06-9 methyl 3-hydroxy-2-thiophenecarboxylate 
• 1865-29-8 2-phenyl-acrylic acid methyl ester 

Relevant articles and documents

Method for the preparation of compounds

The invention provides a preparation method of a compound as described in the formula 1. The method comprises the steps of (1) contacting a compound as described in the formula 2 and a compound as described in the formula 3 in the existence of alkali to obtain a compound as described in the formula 4; and (2) directly contacting a reaction product obtained in the step (1) and paraformaldehyde to obtain the compound as described in the formula 1, wherein weak acid is added in the reaction product before the reaction product obtained in the step (1) is in contact with the paraformaldehyde so that the residual alkali in the reaction product can be neutralized. By using the method, the compound as described in the formula 1 can be effectively prepared.

Synthesis and oxidative fragmentation of catharanthine analogs. Comparison to the fragmentation - Coupling of catharanthine and vindoline

Two new analogs of catharanthine have been synthesized in racemic form. They differ from catharanthine in the fusion of the indole ring to the non- aromatic portion of the iboga skeleton, with the [2,3] fusion present in catharanthine being replaced by [2,1] and [3,2] fusions. The corresponding deethyl analogs were also and methodological improvements were applied to an existing synthesis of deethylcatharanthine and a formal synthesis of racemic catharanthine. The reactivity of the catharanthine analogs toward coupling with vindoline was examined. Coupling was attempted by both the amine oxide fragmentation (Potier) and Fe3+ methods. Under Potier conditions the [2,1] fused analogs give low yields of coupling products in which vindaline is attached to the 3-position of the indole ring. The [3,2] isomers undergo fragmentation of the C16-C21 bond, as observed for catharanthine, but no coupling to vindoline occurs. The reactivity, oxidation potentials and conformation of the analogs are compared with catharanthine, deethylcatharanthine and N-methylcatharanthine.