Carbodiimide-sulfoxide reactions. XII. Reactions of sulfonamides
Carbodiimide-sulfoxide reactions. XII. Reactions of sulfonamides
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碳二亚胺-亚砜反应。
DOI：
10.1021/jo00823a006
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发表时间：
1971
期刊：
影响因子：
--
通讯作者：
U. Lerch
中科院分区：
文献类型：
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作者：
J. G. Moffatt;U. Lerch
芳基磺酰胺和烷基磺酰胺在无水磷酸存在下与DMSO和DCC反应，高产率地得到S，S-二甲基-N-磺酰亚胺。N-烷基磺酰胺不能形成硫亚胺，而是与DMSO和DCC缓慢反应形成A7-烷基1-7-（1，3-二环己基1-1-脲基甲基1）磺酰胺。A 7-苄基-对-甲苯磺酰胺与DMSO和五氧化二磷的类似反应得到作为主要产物的A，A 7 ′-亚甲基双（A 7-苄基-对-甲苯磺酰胺）。X-芳基磺酰胺如对甲苯磺酰苯胺与DMSO和DCC反应，从而在未取代的邻位之一或两者上引入甲硫基甲基。在苯胺化的邻位上含有甲基、硝基和氰基取代基的几种磺酰苯胺，其产物中甲硫基甲基被引入到氮原子上或可利用的邻位上。酸性很强的磺酰胺糖精不以类似的方式反应，而是以高产率与DCC生成1：1的加合物。在本系列的前一篇论文中，将上述温和的酸催化的醇、3酚、4烯醇、5和肟6与二甲基亚砜（DMSO）和二环己基碳二亚胺（DCC）的反应推广到羧酸、异羟肟酸和羧酸酰胺。发现羧酸的简单伯酰胺容易转化为N-酰基-S，S-二甲基硫亚胺，而苯甲酰苯胺等化合物完全惰性，各种酰亚胺反应缓慢，生成N-（甲硫基甲基）或N-（1，3-二环己基-1-脲基甲基）衍生物。在本文中，我们将这些研究扩展到几种类型的磺酰胺的反应。
The reactions of aryl-and alkylsulfonamides with DMSO and DCC in the presence of anhydrousorthophosphoric acid has been shownto give S, S-dimethyI-iV-sulfonylsulfilimmes in high yields.. V-Alkylsulfonamides cannot form sulfilimines but rather react slowly with DMSO and DCC to form A7-alky 1-7-(1, 3-dicy clohexy 1-1-ureidomethy 1) sulfonamides. A similar reaction of A7-benzyl-p-toluenesulf onamide with DMSO and phosphorus pentoxide gave A, A7'-methylenebis (A7-benzyl-p-toluenesulfonamide) as the major product. X-Arylsulfonamides such as p-toluenesulfonanilide react with DMSO and DCC so as to introduce methylthiomethyl groups in either or both of the unsubstituted ortho positions. Several sulfonanilides containingmethyl, nitro, andcyano sub-stituents in the ortho positions of the anilinering gave products in which methylthiomethyl groups were intro-duced on nitrogen or at an available ortho position. The very acidic sulfonamide saccharin did not react in a similar way but rather gave a 1: 1 adduct with DCC inhigh yield.In the precedingpaper in this series1 the previously described mild acid-catalyzedreactions of alcohols, 3 phenols, 4 enols, 5 and oximes6 with dimethyl sulfoxide (DMSO) and dicyclohexylcarbodiimide (DCC) were extended to carboxylic acids, hydroxamic acids, and car-boxylic acid amides. Simple primary amides of carbox-ylic acids were found to be readily converted into N-acyl-S, S-dimethylsulfilimines, while compoundssuch as benzanilide were completely inert and imides of various sorts reacted slowly to give either N-(methylthiomethyl) or V-(l, 3-dicy clohexy 1-1-ureidomethyl) deriv-atives. In the present paper we extend these studies to the reactions of several types of sulfonamides.