1,2,3-BENZOXATHIAZOLE 2,2-DIOXIDES - SYNTHESIS, MECHANISM OF HYDROLYSIS, AND REACTIONS WITH NUCLEOPHILES
1,2,3-BENZOXATHIAZOLE 2,2-DIOXIDES - SYNTHESIS, MECHANISM OF HYDROLYSIS, AND REACTIONS WITH NUCLEOPHILES
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DOI：
10.1021/jo00023a012
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发表时间：
1991-11-08
影响因子：
3.6
通讯作者：
YOUNG, KM
中科院分区：
文献类型：
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作者：
ANDERSEN, KK;BRAY, DD;YOUNG, KM
一些五元环状氨基磺酸酯 X-3-(对甲苯磺酰基)-1,2,3-苯并恶噻唑 2,2-二氧化物 (1a, X = H; 1b, X = 5-Me; 1c, X = 5-t-Bu; 1d, X = 5-Br; 1e, X = 5-Cl; 1f, X = 5-Ac；1g，X = 5-NO2；8a，X = 6-NO2) 在乙腈水溶液中测量。 水解随着环内 N-SO2 键的断裂而发生。 使用 1a-g 的 sigma-m 值和 8a 的 sigma-p 绘制的哈米特图的 rho = +2.20。 测量了 1a 和 3-甲基-1,2,3-苯并恶噻唑 2,2-二氧化物 (10) 的活化焓和熵。 测定 1g 和 8a 的活化体积。 水解的机理类似于类似的磺内酯和环状硫酸盐的皂化。 1,2,3-苯并恶噻唑2,2-二氧化物(1a-g,8a)的这些第一实施例是通过用磺酰氯和三乙胺处理N-(2-羟基苯基)-对甲苯磺酰胺或通过使用间氯过苯甲酸氧化一氧化物前体来制备的。 用氟化钾处理 1a 得到 1,2,3-苯并恶噻唑 2,2-二氧化物 (9)，将其甲基化得到 10。氨基磺酸酯 1a 用各种亲核试剂处理：苯基锂、甲基锂、氟化钾、甲胺、叔丁胺和甲醇钠。 前三个攻击甲苯磺酰基硫原子并裂解环外 N-SO2 键。 胺攻击环内磺酰基硫原子并裂解环内N-SO2键。 甲醇钠攻击两个磺酰基。
The rates of base-induced hydrolysis of some five-membered cyclic sulfamates, X-3-(p-tolylsulfonyl)-1,2,3-benzoxathiazole 2,2-dioxides (1a, X = H; 1b, X = 5-Me; 1c, X = 5-t-Bu; 1d, X = 5-Br; 1e, X = 5-Cl; 1f, X = 5-Ac; 1g, X = 5-NO2; 8a, X = 6-NO2) were measured in aqueous acetonitrile. The hydrolyses occurred with cleavage of the endocyclic N-SO2 bond. A Hammett plot using sigma-m values for 1a-g and sigma-p for 8a had rho = +2.20. Activation enthalpies and entropies were measured for 1a and for 3-methyl-1,2,3-benzoxathiazole 2,2-dioxide (10). Volumes of activation were determined for 1g and for 8a. The mechanistic profile for hydrolysis resembled that for the saponification of the analogous sultones and cyclic sulfates. These first examples of 1,2,3-benzoxathiazole 2,2-dioxides (1a-g, 8a) were prepared by treating N-(2-hydroxyphenyl)-p-toluenesulfonamides with sulfuryl chloride and triethylamine or by oxidizing the monoxide precursors using m-chloroperbenzoic acid. Treatment of 1a with potassium fluoride gave 1,2,3-benzoxathiazole 2,2-dioxide (9), which was methylated to give 10. Sulfamate 1a was treated with various nucleophilic reagents: phenyllithium, methyllithium, potassium fluoride, methylamine, tert-butylamine, and sodium methoxide. The first three attacked the tosyl sulfur atom and cleaved the exocyclic N-SO2 bond. The amines attacked the endocyclic sulfonyl sulfur atom and cleaved the endocyclic N-SO2 bond. Sodium methoxide attacked both sulfonyl groups.