AMINOLYSES OF SULFINIC ACID DERIVATIVES

A series of alkane- and arenesulfinamides was prepared from the corresponding sulfinyl chloride. Treatment of the chlorolysis product of dithiodiglycolic acid with morpholine produced 4-morpholinosulfinylacetomorpholide (1). Dimorpholide 1 was a stable, water-soluble, and slightly acidic substance. The infrared spectrum resembled that of the simple alkanesulfinamides in the region of 1500-650 cm-1. However, between 3000 and 2500 cm-1 the spectrum exhibited a series of bands characteristic of amine salts. In addition, there were two strong bands at 1630 and 1610 cm-1 assignable to conjugated C=C stretching and C=O stretching vibrations. The ultraviolet spectrum of 1 exhibited one maximum at 273 mµ (ε 14,000) which did not shift in the presence of base. From a consideration of the spectral data and the saltlike physical properties of compound 1, it appears that its structure is best represented by the betaine resonance hybrid 1a ↔ 1b. Under controlled conditions, oxidation of 3,3ʹ-dithiodipropionic acid by chlorine led to 1,2-oxathiolan-5-one 2-oxide (3), which upon aminolysis with aromatic amines gave sulfonyl dipropionamides 5. The structure of 3 was confirmed by molecular weight determinations (Rast method), saponification equivalent, alkaline permanganate oxidation, and elementary analysis. Mechanisms for the formation of 3 and its aminolysis products are presented. © 1969, American Chemical Society. All rights reserved.