Dimeric cations from alkanesulphenyl chlorides. The elusive nature of sulphenylium ions
Dimeric cations from alkanesulphenyl chlorides. The elusive nature of sulphenylium ions
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来自烷磺基氯的二聚阳离子。
DOI：
10.1039/p29750000361
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发表时间：
1975
期刊：
影响因子：
--
通讯作者：
F. Rivetti
中科院分区：
文献类型：
--
作者：
G. Capozzi;V. Lucchini;G. Modena;F. Rivetti
电导测定和 1H nmr.据报道，甲烷和乙磺苯氯在液体二氧化硫中与路易斯酸（SbF5、BCl3、SbCl3、BF3）反应形成烷基（烷硫基）（氯）锍离子[R[图形省略](Cl)SR]。当存在 BCl3 或 BF3 时，核磁共振中的动态行为观察到导致两个烷基等价的光谱。这是通过氯离子对锍盐的攻击以及它们解离成磺基氯来解释的。核磁共振磺基氯的电导行为表明，即使在不添加路易斯酸的情况下，也可能发生部分电离成烷基（烷硫基）（氯）锍离子。 98%硫酸和氟硫酸中也会形成锍离子。在任何条件下均未发现硫苯基离子 (RS+) 存在的迹象。
Conductimetric and 1H n.m.r. evidence on the formation of alkyl(alkylthio)(chloro)sulphonium ions [R[graphic omitted](Cl)SR] by reaction of methane and ethanesulphenyl chlorides in liquid sulphur dioxide with Lewis acids (SbF5, BCl3, SbCl3,BF3) is reported. In the presence of BCl3 or BF3 dynamic behaviour in the n.m.r. spectra leading to the equivalence of the two alkyl groups is observed. This is explained by attack of chloride ion on the sulphonium salts and their dissociation into sulphenyl chlorides. The n.m.r. and conductimetric behaviour of the sulphenyl chlorides suggests that partial ionization into alkyl(alkylthio)(chloro)sulphonium ions may occur even in the absence of added Lewis acids. Sulphonium ions are also formed in 98% sulphuric acid and fluorosulphuric acid. Under no conditions was an indication of the presence of sulphenylium ions (RS+) found.