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1H-CIDNP effects in the reaction of N-hydroxyureas with tert-butylsulfinyl chloride in the presence of a tertiary amine

✍ Scribed by Ido P. Bleeker; Jan B. F. N. Engberts

Publisher
Elsevier Science
Year
2010
Tongue
English
Weight
475 KB
Volume
98
Category
Article
ISSN
0165-0513

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✦ Synopsis

Abstract

tert‐Butylsulfinyl chloride (1) reacts smoothly with N′‐(di)methyl‐ and N′‐(di)phenyl‐N‐hydroxyurea (2) in acetone at room temperature, in the presence of two equivalents of pyridine. An intermediate O‐tert‐butylsulfinyl‐N‐hydroxyurea (3) is postulated, which rearranges via a radical cage mechanism to give the corresponding N‐tert‐butylsulfonylurea as the recombination product. Several escape products are also isolated. This thermally induced rearrangement involves homolytic cleavage of the N‐O bond in 3. The process is accompanied by pronounced ^1^H‐CIDNP effects, which may be interpreted using Kaptein's rule. The fate of the N′‐(di)substituted carbamoylaminyl radicals, formed initially within the radical pair, is discussed. N′,N′‐diphenyl‐N‐hydroxyurea shows deviant behaviour and the major reaction product is in this case diphenylamine.

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