Treatment of Alcohols with Tosyl Chloride Does Not always Lead to the Formation of Tosylates 英文参考文献.docVIP

Molecules 2011, 16, 5665-5673; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Treatment of Alcohols with Tosyl Chloride Does Not always Lead to the Formation of Tosylates Rui Ding, Yong He, Xiao Wang, Jingli Xu, Yurong Chen, Man Feng and Chuanmin Qi * Key Laboratory of Radiopharmaceuticals, College of Chemistry, Beijing Normal University, Beijing 100875, China; E-Mails: dingrui@ (R.D.); heyong@ (Y.H.); wangxiao@ (X.W.); xujingli@ (J.X.); chenyurong@ (Y.C.); fengman@ (M.F.) * Author to whom correspondence should be addressed; E-Mail: qicmin@; Tel.: +86-136-8138-0097; Fax: +86-010-5880-2075. Received: 5 April 2011 / Accepted: 13 June 2011 / Published: 1 July 2011 Abstract: Treatment of substituted benzyl alcohols with tosyl chloride resulted in the formation of the corresponding chlorides, not the usual tosylates. A series of experiments demonstrated that it was possible to predict whether chlorination or tosylation would occur for substituted benzyl alcohols and pyridine methanols. Treatment of electron withdrawing group-substituted benzyl alcohols with tosyl chloride gave the corresponding chlorides in moderate yields under mild conditions, which provided a simple way to directly prepare chlorides from alcohols. Keywords: tosyl chloride; chlorination; tosylation; benzyl alcohols; pyridine methanols 1. Introduction Alkyl tosylates are versatile substrates for substitution reactions. They contain an excellent leaving group and can be readily prepared from tosyl chloride and an alcohol, allow replacement of the hydroxy group by many good nucleophiles. Furthermore they are often crystalline solids that can be isolated and purified before further reaction. Tosylate is often a better leaving group than halide, as its preparation from an alcohol avoids stereochemical uncertainties and skeletal rearrangements. The tosylates can then be used in reactions with a