Isonitroso compounds s. a. Oximes

There appears to be little reported work on S-nitrosation reactions of simple thioke-tones. Thiocamphor when treated with /50-amyl nitrite in fact gives the oxime58 (formerly called a isonitroso compounds), presumably via the tautomeric form of the thione, i.e. the enethiol. In this respect the reaction is very similar to the reactions of ketones59 which give oximes or C-nitroso compounds via the enol intermediates60. 

Chlorine passed into a methanolic soln. of isonicotinaldehyde oxime at 5-10 for 15 min., the resulting crude isonicotinohydroxamic chloride hydrochloride collected (Y 83%) and added with vigorous stirring in a very efficient hood to a methanolic soln. of KCN, and warmed 1 hr. at 60 with occasional stirring a-isonitroso-4-pyridineacetonitrile. Y 54%.—Although the isonitrosation of acetonitriles is the most convenient general method for the prepn. of a-iso-nitrosoacetonitriles, certain hetero compounds can be better prepared by the above new method. F. e. s. E. J. Poziomek and A. R. Melvin, J. Org. Chem. 26, 3769 (1961). 

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