Studies in the chemistry of enol phosphates and related compounds
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
The reactions of the trichloroacetamide derivatives, Cl₃CCONHY where Y = CONH₂, CONMe₂ , COCH₂Cl, CSNH₂ and CSNHEt with triethyl phosphite have been studied. The major products of the reactions were the corresponding dichloroacetamide derivatives and these were shown to result from an ionic mechanism involving initial attack by phosphite on halogen. The reactions of other α-halogeno-carbonyl compounds with triethyl phosphite were studied in protic solvents and the relevance of the results obtained, to the mechanism of the Perkow reaction, is discussed. In dilute solution some of the trichloroacetamide derivatives gave unexpected products which were identified as vinyl phosphonates, [equation here]. A mechanism is suggested for their formation. Similar dichloroacetamides Cl₂CHCONRY, were found to give vinyl phosphonates for R = H and enol phosphates when R = alkyl. Monochloroacetamides were not observed as products in any of these reactions.