Importance of repulsion of lone electron pairs in the enhanced reactivity of 1,8-naphthyridine and the large α-effect of hydrazine in the aminolyses of p-toluenesulfonyl chloride

The rates of aminolyses of p-toluenesulfonyl chloride with primary and tertiary amines have been determined both in acetonitrile and in ethanol. The Brönsted plots of log k rel again pK a′ values of amines (except hydrazine and 1,8-naphthyridine in acetonitrile) gave a good correlation when the amin...

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Bibliographic Details
Published in:Canadian journal of chemistry 1986-06, Vol.64 (6), p.1184-1188
Main Authors: Oae, Shigeru, Kadoma, Yoshihito
Format: Article
Language:English
Subjects:
Chemical reactivity
Chemistry
Exact sciences and technology
Organic chemistry
Reactivity and mechanisms
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Summary:The rates of aminolyses of p-toluenesulfonyl chloride with primary and tertiary amines have been determined both in acetonitrile and in ethanol. The Brönsted plots of log k rel again pK a′ values of amines (except hydrazine and 1,8-naphthyridine in acetonitrile) gave a good correlation when the aminolyses were carried out in acetonitrile. In ethanol, however, although Brönsted plots with all tertiary amines show a good correlation, less basic hydrazine shows a higher reactivity than n-butylamine. The abnormal rate enhancement found with hydrazine is undoubtedly due to the α-effect, while that with 1,8-naphthyridine in acetonitrile is considered to be due to the repulsion of two lone electron pairs on the two nitrogen atoms in 1,8-naphthyridine
ISSN:0008-4042
1480-3291
DOI:10.1139/v86-196