Ethyl 2-methyl propenoate

Propenoic acid amide, see Acrylamide 2-Propenoic acid, ethyl ester, see Ethyl acrylate Propenoic acid, methyl ester, see Methyl acrylate 2-Propenoic acid, methyl ester, see Methyl acrylate 2-Propenoic acid, 2-methyl methyl ester, see Methyl methacrylate... 

The Pechmann and Knoevenagel reactions have been widely used to synthesise coumarins and developments in both have been reported. Activated phenols react rapidly with ethyl acetoacetate, propenoic acid and propynoic acid under microwave irradiation using cation-exchange resins as catalyst <99SL608>. Similarly, salicylaldehydes are converted into coumarin-3-carboxylic acids when the reaction with malonic acid is catalysed by the montmorillonite KSF <99JOC1033>. In both cases the use of a solid catalyst has environmentally friendly benefits. Methyl 3-(3-coumarinyl)propenoate 44, prepared from dimethyl glutaconate and salicylaldehyde, is a stable electron deficient diene which reacts with enamines to form benzo[c]coumarins. An inverse electron demand Diels-Alder reaction is followed by elimination of a secondary amine and aromatisation (Scheme 26) <99SL477>. 

A further example of the use of 2//-thiopyrans as surrogates for m-substituted dienes involves the use of the protected 3,4-dihydio-3-(3-oxobutyl)A//-thiopyranA-onc, 3-[2-(2-methyl-l,3-dioxolan-2-yl)ethyl]-4-[tris(l-methy-lethyl)silyl)oxy-2//-thiopyran 328 as an equivalent of l-ethenyl-2-methylcyclohexene in Diels-Alder reactions. The thiopyran reacted with various maleimides to yield the endo cycloadducts and with methyl propenoate to give the exo adduct under either thermal or Lewis-acid-catalyzed conditions. In the latter case concomitant release of the protected ketone functions occurs, acid-catalyzed cyclization of which generates a fused cyclohexenone ring (Scheme 67). Desulfurization, preferably before the aldol cyclization, leads to derivatives of 2,3,4,4a,5,6,7,8-octahy-dro-4a-methylnaphthalenes < 1997CJC681 >. 

Huang, X.-H., He, P.-Y. and Shi, G.-Q., Highly stereoselective addition-elimination reaction of nucleophiles with ethyl 3,3-difluoro-2-[(trimethylsilyl)methyl]propenoate, J. Org. Chem., 65, 627, 2000. 

Synonyms Acrylic/acrylate copolymer Acrylic copolymer 2-Propenoic acid, 2-methyl-, polymer with ethyl 2-propenoate and methyl 2-me-thyl-2-propenoate... 

Methyl propenoate Methyl 2-propenoate. See Methyl acrylate 2-Methylpropenoic acid 2-Methyl-2-propenoic acid. See Methacrylic acid 2-Methyl-2-propenoic acid anhydride. See Methacrylic anhydride 2-Methyl-2-propenoic acid, ethyl ester. See Ethyl methacrylate 2-Methyl-2-propenoic acid, 2-ethylhexyl ester. See2-Ethylhexyl methacrylate... 

Propenoic acid, 2-methyl-, 2-phenoxyethyl ester. See 2-Phenoxyethyl methacrylate 2-Propenoic acid, 2-methyl-, polymer with 1-ethenyl-2-pyrrolidinone and ethyl 2-methyl-2-propenoate. See Acrylates/PVP copolymer 2-Propenoic acid, 2-methyl-, polymer with ethyl 2-propenoate and methyl 2-methyl-2-propenoate. See Acrylates copolymer 2-Propenoic acid, 2-methyl-, polymer with 2-propenoic acid and N-octyl-2-propenamide. 

Two structural isomers are formed when 2-methyl-1,3-butadiene reacts with ethyl acrylate (ethyl 2-propenoate). Draw structures for these isomers. 

Historically, the development of the acrylates proceeded slowly they first received serious attention from Otto Rohm. AcryUc acid (propenoic acid) was first prepared by the air oxidation of acrolein in 1843 (1,2). Methyl and ethyl acrylate were prepared in 1873, but were not observed to polymerize at that time (3). In 1880 poly(methyl acrylate) was reported by G. W. A. Kahlbaum, who noted that on dry distillation up to 320°C the polymer did not depolymerize (4). Rohm observed the remarkable properties of acryUc polymers while preparing for his doctoral dissertation in 1901 however, a quarter of a century elapsed before he was able to translate his observations into commercial reaUty. He obtained a U.S. patent on the sulfur vulcanization of acrylates in 1912 (5). Based on the continuing work in Rohm s laboratory, the first limited production of acrylates began in 1927 by the Rohm and Haas Company in Darmstadt, Germany (6). Use of this class of compounds has grown from that time to a total U.S. consumption in 1989 of approximately 400,000 metric tons. Total worldwide consumption is probably twice that. 

Chemical Designations - Synonyms Ethyl 2-methacrylate Ethyl Methacrylate-inhibited Ethyl Alphamethylmethacrylate Ethyl 2-methyl-2-propenoate Methacrylic Acid, Ethyl Ester Chemical Formula CH = C(CH3)COOQH5... 

The Diels-Alder cycloadclition reaction occurs most rapidly if the alkene component, or dienophile ("diene lover"), has an electron-withdrawing substituent group. Thus, ethylene itself reacts sluggishly, but propenal, ethyl propenoate, maleic anhydride, benzoquinone, propenenitrile, and similar compounds are highly reactive. Note also that alkynes, such as methyl propynoate, can act as Diels-Alder dienophiles. 

Reaction of isoprene (2-methyl-l,3-butadiene) with ethyl propenoate gives a mixture of two Diels-Alder adducts. Show the structure of each, and explain whv a mixture is formed. 

Conjugate Addition. To a solution of 1.5 mmol of lithium dialkylcuprate at — 25 CC is added 1 mmol of methyl ( )-3-[(25,45,55)-3-benzyloxycarbonyl-4-methyl-5-phenyl-2-oxazolidinyl]-propenoate dissolved in 1 mL of dry diethyl ether. After 30 ntin at — 25 C, the mixture is treated with an aq NH3/NH4C1 pH 8 buffer solution and then stirred at r.t. for 15 min. After diethyl ether extraction, the organic layers are dried over Na,S()4 and filtered and the solvent is evaporated under reduced pressure. The crude products are checked by H- and l3C-NMR analyses in order to determine the diastereomer ratios (g 95 5) and then purified by flash chromatography (hexane/ethyl acetate 80 20) yield 70-72%. 

The next three procedures provide useful synthetic intermediates. A stereospecific synthesis of ETHYL (Z)-3-BROMO-2-PROPENOATE affords an alternative vinyl bromide partner for the coupling chemistry in the preceding procedure. A very simple but elegant illustration of the flash vacuum pyrolysis technique is used to prepare BENZOCYCLOBUTENONE from o-toluoyl chloride. Another member of the functionalized indole family of synthetic intermediates is presented in a four-step procedure for 5-METHOXYINDOLE-2-ACETIC ACID METHYL ESTER. 

In addition, phenylsufonylallene (110), a,(3-unsaturated phosphonates (111), and alkenes with perfluorinated substituents (112) are all useful dipolarophiles. The yields observed with methyl 2-propenoate are significantly lower than those with the corresponding acrylate (entries 7 and 9), because of the additional substituent. On the other hand, the dipolar cycloadditions with either ethyl vinyl ether, 1-hexene, cyclohexene, or a trisubstituted dipolarophile provide the corresponding isoxazolidines in either low yields or not at all (18). 

Michael addition of methyl 3-mercaptopropanoate to methyl 3-methylbut-2-enoate and Dieckmann cyclization of the resulting diester yields 2,2-dimethyltetrahydrothiopyran-4-one 539 (Scheme 220) <2005HCA1922>. Similarly, diethyl thiodipropanoate, accessible from ethyl propenoate by treatment with NaSH in methanol, cyclizes to ethyl 4-oxotetrahydrothiopyran-3-carboxylate under basic conditions. The carbon skeleton has also been provided by 1,4-pentadienones <1995JOC1665> and H2S in ethanol has been used as an alternative source of the heteroatom (Scheme 221) <1999SL735>. 

Propenoic acid, 2-(bromomethyl)-, ethyl ester (17435-72-2), 66, 224 2-Propenoic acid, 2-(hydroxymethyl)-, ethyl ester (10029-04-6), 66, 224 2-Propenoic acid, 3-phenyl-, methyl ester (103-26-4), 68,155 2-PROPENOIC ACID, 3-(PHENYLSULFONYL)-, METHYL ESTER, (Z) (91077-67-7), 69, 169... 

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