SOME ASPECTS OF THE CHEMISTRY OF N-ARYLSULFONOXY AMINE DERIVATIVES: THEIR ELIMINATION AND REARRANGEMENT REACTIONS.

摘要

The reaction of primary and secondary amines with arylsulfonyl peroxides at -78(DEGREES) results in attachment of the arylsulfonate group to nitrogen to generate N-alkyl-O-arylsulfonylhydroxylamines. N-sulfonoxyamine derivatives can be prepared in situ, and in many cases they have been isolated. The base-promoted elimination in these adducts was studied from two viewpoints: (a) as a method for oxidative deamination of amine derivatives, and (b) as a method of preparing azo-compounds from the hydrazine derivatives. Furthermore, the ionization of N-sulfonoxyamines was pursued because it offered an unambiguous entry into electron-deficient nitrogen chemistry.;The oxidation of hydrazine derivatives proceeds, via presumed N-sulfonoxy hydrazine intermediates, to azo-products under mild conditions. Arylhydrazines, N-acylhydrazides, and N,N'-bio-acylhydrazides all gave the corresponding azo-compound and ultimately normal products derived therefrom in good yields (> 60%).;A series of N-alkylated-O-arylsulfonylhydroxylamines were prepared. In the absence of base, these amine derivatives underwent rearrangement involving the migration of various groups from carbon to nitrogen. The migratory tendencies of the groups in rearrangement were found to be in order: Ph > H > alkyl > Me. The migratory ratios Ph/Me (> 72) and n-hexyl/Me (4.2) suggested that rearrangements in N-alkylated-O-arylsulforylhydroxylamines are polar in nature and migration of groups to electron-deficient nitrogen probably is concerted with the loss of leaving group. Furthermore, the migration of groups in these rearrangements was found to be sensitive to the migration origin and stereoelectronic requirements. The rearrangement reaction provides a means to utilize electron-deficient nitrogen species in a variety of synthetic problems.;The yield of oxidative deamination was measured as a function of several reaction parameters: the peroxide, the heterogeneous base employed, and the solvent. It was found that the best yields were obtained with m-trifluoromethylbenzenesulfonyl peroxide and powdered potassium hydroxide in ethyl acetate. Moreover, except for some noted exceptions, the technique was found to be a general method for the oxidative deamination of primary and secondary amines.