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Phenoxathiin cation radical perchlorate (IC) reacted with alkylamines to form protonated N-alkylsulfilimine perchlorates (2c) and with dialkylamines to form N,N-dialkylaminosulfonium perchlorates (3c). Analogous reactions were obtained with thianthrene cation radical (Id), giving products 2d and 3d. Reaction of Id with alkylamines also gave in every case some 5,5-dihydro-5-(5-thianthreniumylimino)thianthrene perchlorate (4d). Only in one case, reaction with propylamine, did IC give the analogous 4c. The salts 2c were deprotonated to give the N-alkylsulfilimines (5c and 5d) and these were methylated with methyl iodide giving N-alkyl-N-methylaminosulfonium iodides (6c and 6d). Most of the sulfonium salts (6c and 6d) were converted into the corresponding perchlorates (3c and 3d) which were also obtained directly by reactions of IC and Id with N-alkylmethylamines.

A method of preparing crystalline phenoxathiin cation radical perchlorate (1) by oxidation of phenoxathiin with perchloric acid in benzene-acetic anhydride is reported. Reaction of 1 with ammonia was controlled so as to give either phenoxathiin sulfilimine perchlorate (2) or the dimeric product 5,5-dihydro-5-(5-phenoxathiiniumylimino)phenoxathiin perchlorate (3a). Deprotonation of 2 gave phenoxathiin sulfilimine (4a). Reaction of 4a with p-toluenesulfonyl chloride gave the known tosyl derivative, obtainable also by reaction of phenoxathiin with chloramine-T. Methylation of 4a led to the same product obtainable by direct reaction of 1 with methylamine, i.e., 5,5-dihydro-5(methylimino)phenoxathiin perchlorate (6). Reaction of 4a with 1 led to 3a. Reaction of 4a with thianthrene cation radical perchlorate led, similarly, to 5,5-dihydro-5-(5-thianthreniumylimino)phenoxathiin perchlorate (9).

Aus dem Phenoxathiinkationradikal (I) entsteht mit Aceton (II) das Sulfoniumsalz (III).