ALKYLATION OF NITRILE ANIONS BY TERTIARY ALPHA-HALO KETONES AND NITRILES

Potassium salts of nitriles bearing carbethoxy, cyano, or phenyl group s at the alpha carbon [(RR'CCN)K:R' = CO(2)Et, CN, Ph] react with tert iary alpha-halo ketones and nitriles (1-5) in DMSO or HMPA to provide the alkylated beta-keto- or beta-cyano-beta,beta-dialkyl nitriles 6-10 in useful yields. (PhCHCN)(-) undergoes cyclization with p-XC(6)H(4)C OCCl(CH3)(2) to produce 2(5H)-furanone 11. Reaction of (Ph(2)CCN)(-) w ith PhCOCCl(CH3)(2) affords the hydrolyzed ketone 12a and recovered ca rbon acid, while the anion undergoes oxidative dimerization to NCCPh(2 )CPh(2)CN with p-O2NC6H4COCCl(CH3)(2) with concomitant formation of th e reduced ketone p-O2NC6H4COCH(CH3)(2) and the hydrolyzed ketone 12b. The alkylations of [NCC(CH3)CO(2)Et](-) and [NCC(CH3)CN](-) with p-O(2 )NC(6)H(4)COCX(CH3)(2) take place by the S(RN)1-process.