3724-55-8

Basic information

• Product Name: METHYL 3-BUTENOATE
• Synonyms: 3-butenoicacid,methylester;CH2=CHCH2C(O)OCH3;METHYL VINYLACETATE;METHYL 3-BUTENOATE;but-3-enoic acid methyl ester;methyl but-3-enoate;Methyl 3-butenoate 95%
• CAS NO: 3724-55-8
• Molecular Formula: C₅H₈O₂
• Molecular Weight: 100.12
• EINECS: 223-076-9
• Mol File: 3724-55-8.mol
• Article Data: 36

Chemical Properties

• Melting Point: -78.42°C (estimate)
• Boiling Point: 112 °C(lit.)
• Flash Point: 60 °F
• Appearance: /
• Density: 0.939 g/mL at 25 °C(lit.)
• Vapor Pressure: 57.3mmHg at 25°C
• Refractive Index: n20/D 1.409(lit.)
• BRN: 1741732
• CAS DataBase Reference: METHYL 3-BUTENOATE(CAS DataBase Reference)
• NIST Chemistry Reference: METHYL 3-BUTENOATE(3724-55-8)
• EPA Substance Registry System: METHYL 3-BUTENOATE(3724-55-8)

Safety Data

• Hazard Codes: F
• Statements: 11
• Safety Statements: 16
• RIDADR: UN 3272 3/PG 2
• WGK Germany: 3
• HazardClass: 3.1
• PackingGroup: II
• Hazardous Substances Data: 3724-55-8(Hazardous Substances Data)

Usage

Uses

Methyl 3-butenoate may be employed for the synthesis of dipeptide olefin isosteres using intermolecular olefin cross-metathesis.

Synthesis Reference(s)

Journal of the American Chemical Society, 99, p. 5184, 1977 DOI: 10.1021/ja00457a052Tetrahedron Letters, 14, p. 2433, 1973 DOI: 10.1016/S0040-4039(01)96239-2

General Description

Methyl 3-butenoate is an olefin ester. It is reported to undergo Iron carbonyl-promoted isomerization to afford α, β-unsaturated esters. It is one of the reaction products formed during flash vacuum thermolysis of (?)-cocaine. The H2 and CH4 chemical ionization mass spectra of methyl 3-butenoate has been reported.

InChI:InChI=1/C5H8O2/c1-3-4-5(6)7-2/h3H,1,4H2,2H3

Upstream product

• 186581-53-3 diazomethane 
• 625-38-7 but-3-enoic acid 
• 67-56-1 methanol 
• 1470-91-3 but-3-enoyl chloride 
• 625-35-4 trans-chrotonyl chloride 
• 201230-82-2 carbon monoxide 
• 18355-71-0 σ-allylmercuryacetate 
• 108-55-4 glutaric anhydride, 
• 623-43-8 crotonic acid methyl ester 
• 817-76-5 2-chloropropyl methyl ester 
• 1117-71-1 methyl-4-bromo-2-butenoate 
• 4897-84-1 Methyl 4-bromobutyrate 
• 1501-27-5 Pentanedioic acid, monomethyl ester 
• 109-75-1 but-3-enenitrile 

Downstream Products

• 53432-87-4 ethyl 2-cyclopropyl acetate 
• 139592-86-2 methyl 2-benzylbut-3-enoate 
• 10202-75-2 4-hydroxy-4-(2-propenyl)-hepta-1,6-diene 
• 623-43-8 crotonic acid methyl ester 
• 170229-12-6 [3-(4-Cyano-phenyl)-4,5-dihydro-isoxazol-5-yl]-acetic acid methyl ester 
• 170726-05-3 4-[4-(5-Methoxycarbonylmethyl-4,5-dihydro-isoxazol-3-yl)-phenoxymethyl]-piperidine-1-carboxylic acid tert-butyl ester 
• 170725-96-9 4-{2-[4-(5-Methoxycarbonylmethyl-4,5-dihydro-isoxazol-3-yl)-phenoxy]-ethyl}-piperidine-1-carboxylic acid tert-butyl ester 
• 70354-00-6 (Z)-3-hexenedioic acid dimethyl ester 
• 1142-21-8 (Z)-1,4-diphenylbut-2-ene 
• 201471-80-9 4-(3,4-Dimethoxy-2-methyl-phenyl)-butyric acid methyl ester 
• 201471-82-1 4-(2,3-Dimethoxy-4-methyl-phenyl)-butyric acid methyl ester 
• 826-34-6 dimethyl cis-cyclopropane-1,2-dicarboxylate 
• 56949-94-1 2-(α-hydroxy-benzyl)-but-3-enoic acid methyl ester 
• 95-20-5 2-methyl-1H-indole 

Relevant articles and documents

Correlation of Alkyl and Polar Groups in the Gas-Phase Pyrolysis Kinetics of α-Substituted Ethyl Chlorides

The kinetics of the gas-phase pyrolysis of several secondary chlorides were determined in a static system over the temperature range 369.9-490.1 deg C and the pressure range of 28-298 Torr.The reactions in seasoned vessels, with the free radical suppressor propene and/or toluene always present, are homogeneous and unimolecular and obey a first-order rate law.The observed rate coefficients are represented by the following Arrhenius equations: for 2-chloropropionitrile, log k1 (s-1) = (13.45+/-0.57)-(236.1+/-8.2) kJ mol-1; for methyl 2-chloropropionate, log k1 (s-1) = (12.22+/-0.54) - (217.0+/-7.4) kJ mol-1 (2.303RT)-1; for methyl 3-chlorobutyrate, log k-1 (s-1) = (13.65 +/-0.39)-(214.9+/-5.0) kJ mol-1 (2.303RT)-1.The data of this work together with those reported in the literature confirm previous correlations that α-alkyl substituents of ethyl chloride give a good straight line, when log k/k0 vs. ?* values (ρ* = -3.58 +/- 0.24, correlation coefficient = 0.996, and intercept = -0.0066 at 360 deg C) are plotted, while α-polar substituents give rise to an inflection point at ?*(CH3) = 0.00 into another straight line (ρ* = -0.46+/-0.06, correlation coefficient = 0.972, and intercept = 0.017 at 360 deg C).Several other polar α-substituents have been found to enhance the dehydrochlorination process by means of their electron delocalization or resonance effect.Revising a work reported on the pyrolysis kinetics of pinacolyl chloride, a Wagner-Meerwein rearrangement appears to be a reasonable explanation for the formation of about 12percent of the 2,3-dimethylbutene products.

The flash vacuum thermolysis of (-)-cocaine

(-)-Cocaine is thermally labile and, in a series of remarkable thermal reactions, is cleanly partitioned among benzoic acid, N-methylpyrrole and methyl 3-butenoate.

Deoxygenation of Epoxides with Carbon Monoxide

The use of carbon monoxide as a direct reducing agent for the deoxygenation of terminal and internal epoxides to the respective olefins is presented. This reaction is homogeneously catalyzed by a carbonyl pincer-iridium(I) complex in combination with a Lewis acid co-catalyst to achieve a pre-activation of the epoxide substrate, as well as the elimination of CO2 from a γ-2-iridabutyrolactone intermediate. Especially terminal alkyl epoxides react smoothly and without significant isomerization to the internal olefins under CO atmosphere in benzene or toluene at 80–120 °C. Detailed investigations reveal a substrate-dependent change in the mechanism for the epoxide C?O bond activation between an oxidative addition under retention of the configuration and an SN2 reaction that leads to an inversion of the configuration.

Stereoselective Total Synthesis of the Dimeric Naphthoquinonopyrano-?-lactone (-)-Crisamicin A: Introducing the Dimerization Site by a Late-Stage Hartwig Borylation

The first stereoselective total synthesis of the dimeric naphthoquinonopyrano-?-lactone (-)-crisamicin A was realized (13 steps, 5% overall yield). 1,4,5-Trimethoxynaphthalene, reached in five known steps, was brominated at C-3 to install a but-3-enoic ester by an ensuing Heck coupling. An asymmetric Sharpless dihydroxylation followed and gave a β-hydroxy-?-lactone with >99.9% ee. Its OH substituent and acetaldehyde established the dihydropyran ring in a completely diastereoselective oxa-Pictet-Spengler cyclization. The 2,3-fused anisole moiety allowed the C5-H bond under Hartwig's conditions to be borylated. This set the stage for engaging the resulting C5-B bond in an oxidative dimerization, which led to a binaphthohydroquinon-5-yl. The latter was advanced to synthetic crisamicin A by a double CAN oxidation (→ a binaphthoquinon-5-yl) and a double demethylation.

PROCESS FOR PREPARING MONO AND DICARBOXYLIC ACIDS

The present application relates to a process for preparing a dicarboxylic acid or dicarboxylic ester according to general formula (IV) R1OOC-(CH2)m-CH2CH2-(CH2)y-COOR4 (IV), comprising the steps of subjecting alkenoic acid or alkenoate of formula (II) R1OOC-(CH2)m-CH=CH-(CH2)x-H (II) to a metathesis reaction in the presence of a metathesis catalyst to form a longer-chain alkenoic acid or alkenoate of formula (III) R1OOC-(CH2)m-CH=CH-(CH2)y-H (III) where xa carbonylation reaction in the presence of a carbonylation catalyst and a carbonyl source to form said compound of Formula (IV). Alternative embodiments provide: a process for preparing an alkenoic acid or alkenoate comprising the step of subjecting a lactone to a ring opening reaction; a process for preparing a monocarboxylic acid or monocarboxylic ester according to general formula (XI) R1OOC-(CH2)m-CH2-(CH2)y-CH3 (XI) by subjecting an alkenoic acid or alkenoate to alkene hydrogenation; and a process for preparing an alcohol or ether according to general formula (XII) R1O-CH2-(CH2)m-CH2-(CH2)y-CH3 (XII) by subjecting an alkenoic acid or alkenoate to hydrogenation. The use of the respective mono/dicarboxylic acid, mono/dicarboxylic ester, ethers or alcohols in a variety of applications is also disclosed.