Participation of Anions of Dialkyl Phosphites and Thiophosphites in Aliphatic SRN1 Reactions

Article abstract of DOI:10.1021/jo00347a021

Dialkyl phosphite or thiophosphite anions react with 2-chloro- or 2(p-tolylsulfonyl)-2-nitropropane, p-nitrobenzyl chloride, and α,α-dimethyl-p-nitrobenzyl chloride to form in a free radical chain process the α-nitroalkyl or p-nitrobenzyl phosphonates or thiophosphonates which may be reduced to the amino derivatives. 2,2-Dinitropropane reacts with dialkyl phosphite or dimethyl thiophosphite ions to form dialkyl phosphate or thiophosphate esters of acetone oxime.The relative reactivities of a series of anions toward Me2CNO2, p-O2NPhCH2, and p-O2NPhC(Me)2 are reported.