SYNTHESIS AND REACTIONS OF N-SULFONYLAMINES
SYNTHESIS AND REACTIONS OF N-SULFONYLAMINES
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DOI：
10.1021/ja00772a035
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发表时间：
1972-01-01
影响因子：
15
通讯作者：
BURGESS, EM
中科院分区：
文献类型：
--
作者：
ATKINS, GM;BURGESS, EM
用三乙胺与氨磺酰氯作用，合成了一种新的杂枯烯体系--间磺酰胺。在溶液中合成了N-磺酰基乙胺和IV-磺酰基苯甲酰胺，在不利于开环的条件下，与胺反应生成磺酰胺或与亲核烯烃反应生成1，2-硫氮杂环丁烷1，1-二氧化物。在几种情况下，发生开环，导致β-取代的乙烯基磺酰胺或其他无环产物。N-磺酰基乙胺和N-磺酰基苯甲酰胺都不能从溶液中分离出来，因为前者在室温下在不存在捕集剂的情况下进行放热聚合，而后者在升温至室温时重新形成异氰酸苯酯。以乙氧羰基氨磺酰氯为原料，分别与胺、醇及1-乙烯基-2-吡咯烷酮反应，合成了乙基（羧基氨磺酰基）三乙基氢氧化铵内盐。内盐在60 ℃与四甲基丙二烯反应，得到2-乙氧羰基-3，3-二甲基-4-异亚丙基-1，2-硫氮杂环丁烷1，1-二氧化物和2，3-二氢-2，2-二甲基-3-异亚丙基-6-乙氧-1，4，5-氧杂噻嗪4，4-二氧化物，在另一反应中得到与六甲基双环[2.2.1]的1：1加合物。0]己-2，5-二烯，其结构已牢固确立。用N，N-二甲基苯胺与N-磺酰基乙胺和乙基（羧基氨磺酰基）三乙基氢氧化铵内盐反应，合成了磺胺类化合物。从1848年异氰酸酯开始，对杂累积多烯化学的研究已经进行了世纪，对有机合成的学术和工业发展作出了巨大贡献。如果考虑杂累积烯键的矛盾性质（下文），其中（a）亲核、（B）亲电和（c）电环加成反应是可能的，则可以认识到这类化合物的化学重要性。（X、Y或Z可以是
M-Sulfonylamines, a new heterocumulene system, have been synthesized by the action of triethylamine on sulfamoyl chlorides. 7V-Sulfonylethylamine and IV-sulfonylbenzamidehave been prepared in solution and intercepted with amines to give sulfamides or with nucleophilic olefinsto give 1, 2-thiazetidine 1, 1-dioxides when the reactions were carried out under conditions which did not favor ring opening. In several cases, ring openings occurred leading to^-substituted vinylsulfonamides or other acyclic products. Neither/V-sulfonylethylamine nor/V-sulfonylbenzamide could be isolated from solution as the former underwent exothermic polymerization at room temperature in the absence of a trapping agent, while the latter rearrangedto phenyl isocyanate upon warming to room temperature. Ethyl (carboxysulfamoyl) triethylammonium hydroxide, inner salt, was synthesized from carbethoxysulfamoyl chloride and treated with amines and alcohols as well as with 1-viny 1-2-pyrrolidinone. The inner salt reacted at 60 with tetramethylallene to give 2-carbethoxy-3, 3-dimethyl-4-isopropylidene-l, 2-thiazetidine 1, 1-dioxide and 2, 3-dihydro-2, 2-dimethyl-3-isopropylidene-6-ethoxy-l, 4, 5-oxathiazine 4, 4-dioxide and in another reaction gave a 1: 1 adduct with hexamethylbicyclo [2.2. 0] hexa-2, 5-diene, the structure of which was firmly es-tablished. IV-Sulfonylethylamine and ethyl (carboxysulfamoyl) triethylammonium hydroxide inner salt reacted with N, lV-dimethylamline giving sulfanilamides in fair yields.Investigations of the chemistry of heterocumulenes spanning more than a century (beginning with isocyanates in 1848) have greatly contributed to the area of academic and industrial synthetic organic chemistry. The chemical importance of this class of compounds may be recognized if one considers the ambivalent nature (below) of the heterocumulene linkage where (a) nucleophilic,(b) electrophilic, and (c) electrocyclo-addition reactions are possible.(X, Y or Z may be