Methyl prop-2-enoate

The fused tetrahydropyran-2-one (566) is obtained from 2-methylcyclohexanone by Michael addition to methyl prop-2-enoate and reduction of the resulting keto ester (565 Scheme 216) (63JOC34). When the enamine derived from the cyclohexanone reacts with the unsaturated ester, a mixture of keto esters (565) and (567) is formed. The pyranone (568) is formed by reduction of the latter. 

The addition of diazoalkanes to a, -unsaturated esters provided some of the earliest examples of the 4,5-dihydro-3//-pyrazole route to cyclopropanes. For example, the addition of diazomethane to methyl 2-methyl-prop-2-enoate followed by thermal deazetization gave methyl 1-methylcyclopropane-l-carboxylate (5) in 63% overall yield (Houben-Weyl, Vol. 4/3, p47). This reaction is particularly favorable since the double bond is activated to diazoalkane addition... 

Dimethyiethyl)aminolethyl 2-methyl-2-prop-enoate. 4-04-00-01509 (Beilstein Handbook Reference) Ageflex FM-4 AI3-61480 BRN 1761825 2-(tert-Butylamino)ethyl methacrylate N-tert-Butylaminoethyl methacrylate 2-((1,1-Dimethyiethyl)amino )ethyl 2-methyl-2-propenoate EINECS 223-228-4 Ethanol, 2-(tert-butylamino)-, methacrylate (ester) HSDB 6111 Methacrylic acid, 2-(tert-butylamino)ethyl ester Methacrylic acid, 2- tert-butylamino)ethyl ester 2-Methyl-2-propenoic acid, 2-((1,1-dimethylethyl)-amino)ethyl ester 2-Propenoic acid, 2-methyl-, 2-((1,1-dimelhylethyl)amino)ethyl ester. Used in automotive dip tanks, coatings, industrial/consumer adhesives and coatings, dye and lube oil additives, intermediate for water treatment chemicals, oil-water separations. Liquid dJ5 = 0,914. Rit-Chem. 

METHYL (Z)-3-(BENZENESULFONYL)PROP-2-ENOATE (2-Propenoic acid, 3-(phenylsulfonyl)-, methyl ester, (Z)-)... 

A two-phase mixture of methyl propiolate (5.0 g, 59.5 mmol), boric acid (5.5 g, 89 mmol), sodium benzenesulfinate (9.75 g, 59.5 mmol), and tetra-n-butylammonium hydrogen sulfate (3.0 g, 8.75 mmol) (Note 1) in tetrahydrofuran water (200 mL, 1 1) is stirred vigorously at room temperature for 48 hr (Note 2). The solution is acidified to pH 4 (2 N hydrochloric acid) and extracted into diethyl ether (4 x 50 mL) (Note 3). The organic layer is dried (MgSCU) and concentrated under reduced pressure to afford 13.75 g of yellow oil (Note 4) which is subjected to flash column chromatography (1.5 1 hexanes-diethyl ether) to afford initially methyl (E)-3-(benzenesulfonyl)prop-2-enoate (400 mg, 2.9%) and then the desired Z-isomer (10.89 g, 81%) as a pale yellow solid, pure by spectral study (Note 5). 

This procedure describes the short, one-pot, high-yield preparation of methyl (Z)-3-(benzenesulfonyl)prop-2-enoate. This route is shorter than a previously reported preparation.2 We have been able to apply this technique to the preparation of a highly functionalized suifonyi acrylate, although the generality of this reaction has not been studied (eq. 1 ).3... 

When dimethyl hex-2-en-4-yne-l,6-dioate 62, a dimerized product of methyl propiolate, was reacted with 2-aminopyridine in refluxing methanol for 44 hours (E)-3-(2-oxo-2//-pyrido[ 1,2-a]pyrimidin-4-yl)prop-2-enoate 63 was obtained, but the product could not be purified either by chromatography or by recrystallization [82JCS(P1)1905]. 

Trifluoroethyl 2-(trifluoromethyI)prop-2-enoate reacts with various dienes to provide cycloadducts in high yields. A typical example is the reaction with ( )-l-methoxy-2-methyl-3-(trimethylsiloxy)buta-l,3-diene leading to the trifluoromethyl-substituted cyclohexenone 13 which was used as a precursor of 16,16,16-trifluororetinal." The reaction has also been performed with a chiral dienophile."... 

Methyl 3-(Trifluoromethylsulfanyl)prop-2-enoate (15) General Procedure " ... 

With palladium catalysts, such as bis(dibenzylideneacetone)palladium/triisopropylphosphane (1 1) or tris(acetylacetonato)palladium/triisopropylphosphane/ethoxydiethylaluminum (1 1 2), 3,3-dimethylcyclopropene can be reacted in methyl acrylate as solvent to yield small amounts (about 10%) of cotrimers constisting of two molecules of the cyclopropene and one molecule of methyl acrylate, namely, a 1 1 mixture of methyl 3-[2,2-dimethyl-3-(2,2-dimethyl-cyclopropyl)cyclopropyl]prop-2-enoate isomers 40 and methyl 3,3,8,8-tetramethyltri-cyclo[5.1.0.0 ]octane-5-carboxylate (41). These compounds can be obtained in far better yield using trialkylphosphane-modified nickel(O) catalysts (see above). Major products of the palladium-catalyzed reaction are the homo-cyclodimer, 3,3,6,6-tetramethyl-exo-tricy-clo[3.1.0.0 ]hexane (55%), and the homo-cyclotrimer, 3,3,6,6,9,9-hexamethyl-crtt/o,e.TO-tetra-cyclo[6.1.0.0 - .0 ]nonane (33.5%). 

Methyl ( )-3-(l-Cyano-2,2-difluorocyclopropyI)prop-2-enoate (5j) Typical Procedure for Thermolysis ... 

A solution of methyl ( )-3-(2-azido-3,3-difluorocyclobut-l-enyl)prop-2-enoate (19 g, 88.4 mmol) in anhyd benzene (50 mL) was added dropwise, with stirring, to benzene (200 mL) heated at reflux. When the addition... 

Methyl ( )-penta-2,4-dienoate, under analogous conditions, is converted into the cycloadduct methyl ( )-3-(3-methylenecyclopentyl)prop-2-enoate (5) in 25% yield. A cotrimer 6 containing two molecules of MCP is additionally formed. Remarkably, only the product resulting from cycloaddition involving the terminal double bond is formed. When the substrate is changed... 

Employing the chiral acrylate derivatives methyl (E)- and (Z)-3-[(5 )-2,2-dimethyl-l,3-di-oxolan-4-yl]prop-2-enoate (5) yields [3 + 2] cycloadducts in both nickel(O)- and palladium(O)-catalyzed reactions with (l-methylethylidene)cyclopropane (1). ... 

For a consecutive electroeyelic ring closure Claisen rearrangement-intramolecular ami-nation process see refs 206 and 207. For studies on the sequential Claisen rearrangement of methyl-3-aryloxy-2-(aryloxymethyl)prop-2-enoates see ref 208 and for the base-catalyzed aromatic Claisen rearrangement of 3-hydroxyphenyl allyl ethers, cf. ref 209. 

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