Alkylation of Nitrile Anions by Tertiary α-Halo Ketones and Nitriles

Article abstract of DOI:10.1021/jo00122a018

Potassium salts of nitriles bearing carbethoxy, cyano, or phenyl groups at the α carbon <(RR'CCN)K: R' = CO2Et, CN, Ph> react with tertiary α-halo ketones and nitriles (1-5) in DMSO or HMPA to provide the alkylated β-keto- or β-cyano-β,β-dialkyl nitriles 6-10 in useful yields. (PhCHCN)(-) undergoes cyclization with p-XC6H4COCCl(CH3)2 to produce 2(5H)-furanone 11.Reaction of (Ph2CCN)(-) with PhCOCCl(CH3)2 affords the hydrolyzed ketone 12a and recovered carbon acid, while the anion undergoes oxidative dimerization to NCCPh2CPh2CN with p-O2NC6H4COCCl(CH3)2 with concomitant formation of the reduced ketone p-O2NC6H4COCH(CH3)2 and the hydrolyzed ketone 12b.The alkylations of (-) and (-) with p-O2NC6H4COCX(CH3)2 take place by the S_RN1 process.