3724-55-8

Usage

Uses

Used in Pharmaceutical Industry:
METHYL 3-BUTENOATE is used as a synthetic compound for the synthesis of dipeptide olefin isosteres using intermolecular olefin cross-metathesis. This application is significant in the development of new drugs and pharmaceutical compounds, as it allows for the creation of novel molecular structures with potential therapeutic benefits.
Used in Chemical Research:
METHYL 3-BUTENOATE is used as a research compound for studying its isomerization properties and understanding its behavior under various reaction conditions. This knowledge can be applied to develop new synthetic routes and improve existing ones, ultimately contributing to the advancement of chemical science and technology.
Used in Analytical Chemistry:
METHYL 3-BUTENOATE is used as a sample in mass spectrometry studies, particularly in the analysis of its H2 and CH4 chemical ionization mass spectra. This application aids in the development of more accurate and efficient analytical methods for identifying and characterizing similar compounds, which can be crucial in various fields, including environmental monitoring, forensic science, and drug discovery.

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

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 
• 74785-89-0 Methyl 4-(phenylseleno)butanoate 

Downstream Products

• 3461-38-9 3-methylenebenzenepropanoic acid methyl ester 
• 24891-74-5 4-phenyl-but-3-enoic acid methyl ester 
• 63158-17-8 methyl (E)-4-phenyl-2-butenoate 
• 53163-24-9 [2-(4-chloro-phenyl)-3-(2-nitro-styryl)-isoxazolidin-5-yl]-acetic acid methyl ester 
• 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 

Relevant academic research and scientific papers

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.

Stereospecific synthesis of EET metabolites via Suzuki-Miyaura coupling

Bioactive, chain-shortened EET metabolites, viz. 8,9-epoxytetradec-5(Z)-enoic acid and 9,10-epoxyoctadec-6(Z),12(Z)-dienoic acid, were prepared via Suzuki-Miyaura cross-couplings of n-alkylboronic acids with chiral vinyl iodides.

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.

(Ferrocenylpyrazolyl)palladium(II) complexes: Syntheses, characterization and rearrangement in solution

Reactions of L1-L6 (3-ferrocenylpyrazolyle (L1), 3-ferrocenyl-5-methylpyrazolyle (L2) 3-ferrocenylpyrazolyl-methylenepyridine (L3) and 3-ferrocenyl-5-methylpyrazolylmethylene-pyridine (L4), 3-ferrocenylpyrazolylethylamine (L5) and 3-ferrocenyl-5-methylpyrazolylethyl-amine (L6)) with [PdCl(Me) (cod)] formed the mononuclear complexes [PdCl(Me) (κ1-L1)2] (1), [PdCl(Me) (κ1-L2)2] (2), [PdCl(Me) (κ2-L3)] (3), [PdCl(Me) (κ2-L4)] (4), [PdCl(Me) (κ2-L5)] (5) and [PdCl(Me) (κ2-L6)] (6). Reactions of 1-6 with the halide abstractor, Na[BAr4], (Ar = 3,5-(CF3)2C6H3), led to the formation of the salts, [PdMe(NCMe) (κ1-L1)2][BAr4] (7), [PdMe(NCMe) (κ1-L2)2][BAr4] (8), [PdMe(NCMe) (κ2-L3)][BAr4] (9), [PdMe(NCMe) (κ2-L4)][BAr4] (10), [PdMe(NCMe) (κ2-L5)][BAr4] (11), [PdMe(NCMe) (κ2-L6)][BAr4] (12) respectively. However, when 3 or 4 was reacted with of Na[BAr4] and a slight excess of methyl acrylate, the products were surprisingly the bis(ligand)palladium complexes [Pd(κ2-L3)2][BAr4]2 (13) and [Pd(κ2-L4)2][BAr4]2 (14) instead of the expected acylpalladium chelate complexes ([(κ2-L)Pd{(CH2)2C(O)OMe}][BAr4]). Complexes 1-6, activated with Na[BAr4], and pre-activated complexes 7-12 at 10 bar of ethylene and 30 bar of carbon monoxide produced polyketones, albeit with low activity (ca. 1.00 g.mmol-1Pd.h-1); with the active catalysts rearranging to mainly bis(pyrazolyl)palladium complexes similar to 13 and 14.

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.

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.

Nickel-Catalyzed Alkyl-Alkyl Cross-Electrophile Coupling Reaction of 1,3-Dimesylates for the Synthesis of Alkylcyclopropanes

Cross-electrophile coupling reactions of two Csp3-X bonds remain challenging. Herein we report an intramolecular nickel-catalyzed cross-electrophile coupling reaction of 1,3-diol derivatives. Notably, this transformation is utilized to synthesize a range of mono- and 1,2-disubstituted alkylcyclopropanes, including those derived from terpenes, steroids, and aldol products. Additionally, enantioenriched cyclopropanes are synthesized from the products of proline-catalyzed and Evans aldol reactions. A procedure for direct transformation of 1,3-diols to cyclopropanes is also described. Calculations and experimental data are consistent with a nickel-catalyzed mechanism that begins with stereoablative oxidative addition at the secondary center.

Synthesis of 2-Fluoroacetoacetic Acid and 4-Fluoro-3-hydroxybutyric Acid

The butyric acid scaffold is the base structure of several human metabolites that serve diverse and prominent biochemical roles including as oxidative sources of cellular energy and as substrates for biosynthesis. Derivatization of metabolites through incorporation of fluorine often alters bioactivity and can facilitate detection and analysis by nuclear magnetic resonance or positron emission tomography depending upon the fluorine isotope employed. We describe the synthesis of two new fluorinated butyric acids (and three related esters) that are derivatives of the metabolites acetoacetic acid and 3-hydroxybutyric acid. 4-Fluoro-3-hydroxybutyric acid is prepared from epoxy ester precursors via ring opening by triethylamine trihydrofluoride. 2-Fluoroacetoacetic acid is prepared by electrophilic fluorination of an acid-labile β-keto ester. The gradual pH-dependent decarboxylation of 2-fluoroacetoacetic acid is investigated by 19 F NMR spectroscopy.

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.

Dimethyl malonate/LHMDS system as a new protocol for generating methyl formate anion (-COOMe) in the condensed-phase Dedicated to Professor Charles H. DePuy (1927-2013)

The treatment of dimethyl malonate with LHMDS in anhydrous THF (condensed-phase) generates, in addition to the expected corresponding lithium enolate, methyl formate anion (or methoxycarbonyl anion, -COOMe) which can react with several electrophiles to give corresponding methoxycarbonyl derivatives by nucleophilic substitution reaction.