A,3-Ethylenecarboxylic acids

Sodium hydrogen carbonate or ammonia a-Halogeno-a,/ -ethylenecarboxylic acid esters Ring opening... 

Nickel chloride/potassium cyanide sodium tetrahydridoborate NiCyKCN/NalBHJ Carboxylic from a,/ -ethylenecarboxylic acids C C-COOH -> CHCHCOOH... 

A soln. of 5.0 g. ethyl 8/, 8a/ -dimethyl-l-oxo-l,2,3,4,6,7,8,8a-octahydro-2-naph-thoate in hexamethylphosphoramide added at 5° under Ng to a stirred mixture of a 60%-dispersion ofNaHin mineral oil and hexamethylphosphoramide, stirring continued 1 hr. at room temp., cooled to 5°, 1.93 g. chloromethyl methyl ether added, and stirred 2 hrs. at room temp. 5.7 g. crude methoxymethyl enol ether dissolved in ether, added rapidly with Dry Ice-cooling under argon to a stirred dark blue soln. of Li in anhydrous NH3, and stirring continued 12 min. at -33°, the b. p. of liq. NHg 2.85 g. ethyl 8/, 8ai -dimethyl-l,2,3,4,6,7,8,8a-octahydro-2j -naphthoate. Overall Y 60%. - 0-Alkylation of the startg. -keto esters occurs under the above conditions to the complete exclusion of the C-alkylated isomer. The subsequent reduction gives the less stable axial isomer. R. M. Coates and J. E. Shaw, J. Org. Chem. 35, 2597 (1970) f. e. s. ibid. 35, 2601 carboxylic acids, also from a,/ -ethylenecarboxylic acids, cf. ibid. 36, 1151 (1971). 

Alkoxy-a, -ethylenecarboxylic acid esters CO CH COOR from y -ketocarboxylic acid esters... 

Palladium-carbon potassium acetate a,/ -Ethylenecarboxylic acids from halogenolactones... 

Bromine via y -amino-a,) -ethylenecarboxylic acid tbioamides from acylisothiocyanates s. 18, 354 Br... 

X0 compounds 19, 746 / -Amiiio-a,/ -ethylenealdehydes s. i -Diethylaminoacrolein / -Amino-a,/ -ethylenecarboxylic acid thioamides... 

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