Y-Ketocarboxylic acids

The nickel hydroxide electrode resembles in its applications and selectivity the chemical oxidant nickel peroxide. The nickel hydroxide electrode is, however, cheaper, easy to use and in scale-up, and produces no second streams/ waste- and by-products [196], Nickelhydroxide electrode has been applied to the oxidation of primary alcohols to acids or aldehydes, of secondary alcohols to ketones, as well as in the selective oxidation of steroid alcohols, cleavage of vicinal diols, in the oxidation of y-ketocarboxylic acids, of primary amines to nitriles, of 2,6-di-tert-butylphenol to 2,2, 6,6 -tetra-rert-butyldiphenoquinone, of 2-(benzylideneamino)-phenols to 2-phenyloxazols, of 1,1-dialkylhydrazines to tetraalkyltetrazenes. For details the reader is referred to Ref. [195]. 

The use of the y-(trimethylsiloxy)nitrile derivatives (190) as a route to 1,4-bifunctional units is exemplified in a convenient synthesis of jasmonoid compounds. The addition of the Grignard reagent to the cyano group as the homologation step results in the keto alcohol (191) after subsequent hydration. The -y-ketocarboxylic acid (192) obtained from the... 

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

G-Garbalkoxylation y -Ketocarboxylic acid esters from ketones... 

Triphenyl orthothioformate treated at -78° under N2 with n-butyllithium in tetrahydrofuran, then cyclohex-2-enone added product. Y 95%. - By Hg2+-catalyzed alcoholysis and subsequent acid treatment, the product can be converted to a y-ketocarboxylic acid ester. F. e. s. A. B. Manas and R. A. J. Smith, Chem. Commun. 1975, 216. 

E)-a,p-Ethylenecarboxylic acids from a,p-acetyleneacetals (E)-a,p-Ethylene-y-ketocarboxylic acids... 

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