Ethyl 3,3-dimethylacrylate

Dimethylglutaric acid has been prepared by heating di-methylpropanetricarboxylic acid above its melting point 3 by hydrolysis of the condensation product of ethyl cyanoacetate and ethyl /3,/3-dimethylacrylate 7 by the action of sulfuric acid on diethyl /3,/3-dimethyl-a,a -dicyanoglutarate 8 by hydrolysis of the nitrile obtained by the action of calcium cyanide on /3,/3-di-methylbutyrolactone 4 by the action of sulfuric acid on /3,/3-di-methyl-a,c/-dicyanoglutarimide 9 and by the action of sodium hypobromite on methone.5 The present procedure is essentially that of Walker and Wood.6... 

F.45) 2-Butenoic acid, 3-methyl-, ethyl ester, ethyl 3-methylbut-2-enoate, ethyl 3-methylcrotonate, ethyl 3,3-dimethylacrylate, ethyl isobutenoate, ethyl senecioate [638-10-81... 

Their synthesis began with conversion of ethyl 3,3-dimethylacrylate to (2 , AE)-6-f-butoxycarbonylamino-3-methyl-hexadienal 1233 in six steps (Scheme 1.313). This unsaturated aldehyde was relatively labile and was immediately converted to 960 in four additional steps. The starting oxazole 957 was prepared in one step from ethyl a-formyldiazoacetate and bromoacetonitrile. Coupling 960 with 957 in the presence of activated zinc afforded the target E, )-oxazole-diene fragment 961 after Swem oxidation. ... 

Ethyl dimethylacrylate Ethyl 3,3-dimethylacrylate Ethyl p,p-dimethylacrylate. See Ethyl senecioate... 

CAS 638-10-8 EINECS/ELINCS 211-319-1 Synonyms 2-Butenoic acid, 3-methyl-, ethyl ester Crotonic acid, 3-methyl-, ethyl ester Ethyl dimethylacrylate Ethyl 3,3-dimethylacrylate Ethyl p,p-dimethylacrylate Ethyl isobutenoate Ethyl isopropylideneacetate Ethyl 3-methyl-2-butenoate Ethyl 3-methylcrotonate Ethyl p-methylcrotonate... 

The organometallic reagent (1) reacts with ethyl tetrolate in the sequence above to give ethyl / ,/ -dimethylacrylate (7). 

Nitrostyrene 8 was prepared by heating aldehyde and nitromethane together with NH4OAC in HOAc the product crystallized out of the reaction in 87% yield (eq 3). The ketoester was prepared in a three-step sequence from ethyl dimethylacrylate (eq 4). First, conjugate addition of n-PrMgCl was catalyzed by... 

Einally, the pyrrolidine was crystallized as the tartrate salt. In contrast to the crystallization of racemic pyrrolidine, this crystallization proceeded with good recovery (77%) of >97% ee material. In addition to raising the optical purity, the crystallization provided the first purification from ethyl dimethylacrylate, and the last until the final salt. 

Thus, the synthesis of ABT-546 was accomplished in 11 linear steps from ethyl dimethylacrylate, in 39% overall yield. This represented an 8-fold yield increase from the first generation synthesis. 

Into a 500 nil. round-bottomed flask, provided with a double surface condenser, place 50 g. (63 ml.) of pure, dry acetone, 50 g. (47 ml.) of ethyl cyanoacetate (Section 111,131) and 0 -5 g. of piperidine. Allow to stand for 60 hours and heat on a water bath for 2 hours. Treat the cold reaction mixture with 100 ml. of ether, wash with dilute hydrochloric acid, then with water, and dry over anhydrous sodium or magnesium sulphate. Distil under diminished pressure and collect the ethyl fsopropylidene cyanoacetate (ethyl a-cyano-pp-dimethylacrylate) at 114-116°/14mm.(l). The yield is 39 g. 

The above is an example of the Guareschi reaction. It is applicable to most dialkyl ketones and to alicyclic ketones (e.g., cyclohexanone, cyc/opentanone, etc.). The condensation product (I) is probably formed by a simple Knoe-venagel reaction of the ketone and ethyl cyanoacetate to yield ethyl a-cyano-pp dimethylacrylate (CH3)2C=C(CN)COOCjHj, followed by a Michael ad tion of a second molecule of ethyl cyanoacetate finally, the carbethoxyl groups are converted to the cyclic imide structure by the action of ammonia. 

Ethyl diazoacetate, 228-230,325 Ethyl diethoxyacetate, 230 Ethyldiisopropylamine, 230,368 Ethyl (3,0-dimethylacrylate, 249 l-Ethyl-3-(3 -dunethylaminopropyl)carbo-diimide hydrochloride, 26 Ethyl l,3-dithiane-2-carboxylate, 230-231 Ethylene, 11 Ethylene carbonate, 41 Ethylenediamine, 231,488 Ethylenediaminetetraacetic acid, 204 Ethylenediaminetetraacetic add disodium salt, 321... 

The reader is referred to the synthesis of trimethylacetic acid,74 2-naphthoic acid,75 3,3-dimethylacrylic acid,76 3,3-dimethylglutaric acid,77 3(3-acetoxy-5-androstene-17(3-carboxylic acid,78 ethyl pyrrole-2-carboxylate,79 and bicyclo[ 1,1.1 ]pentane-1,3-dicarboxylic acid80 published in Organic Syntheses. 

Ethyl, j5-dimethylacrylate and acetyl chloride in GSg added dropwise to a gently refluxing suspension of AIGI3 in GSg with initial warming to start the reaction, then refluxed 2 hrs. with continued stirring ethyl (5-oxo- -methyl- ,/ -hexenate. Y 72%. I. Alkonyi, B. 98, 3099 (1965). 

NaAMB Series. 3-Acrylamido 3-methylbutanoic acid (AMBA) was synthesized via a Ritter reaction involving acrylonitrile and 3,3-dimethylacrylic acid in the presence of water and an excess of sulfuric acid. The synthesis basically followed the procedure set forth by Hoke and Robins. The crude product was twice recrystallized from a mixture of methyl ethyl ketone and petroleum ether prior to use (m.p. 89-91 C). The product was analyzed by elemental analysis and FTIR. Acrylamide was twice recrystallized from acetone prior to use. 

In an extension of previous work, it has been found that Pd(0)-catalysed intramolecular cyclization of allylic acetates (21) can be used to prepare the chrysanthemic acid analogues (22). The potentially useful cw-cyclopropane (23) can be simply obtained by base-induced addition of cyanoacetate to ethyl 2-bromo-3,3-dimethylacrylate followed by decarboxylation oddly, a similar reaction using malonate fails to give a cyclopropane. Optically pure dichloro cw-chrysanthemic acid (26) has been obtained by a Favorskii rearrangement of the chiral cyclobutanone (25) prepared from the keten (24) by sequential [2 + 2]cycloaddition, cine-rearrangement, and resolution (Scheme 3). ... 

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