DIARYLIODONIUM SALTS .4. ION-PAIRS AND COPPER CATALYSIS IN THE REACTIONS OF DIPHENYLIODONIUM IONS WITH HALIDE IONS AND HYDROXYLIC SOLVENTS
DIARYLIODONIUM SALTS .4. ION-PAIRS AND COPPER CATALYSIS IN THE REACTIONS OF DIPHENYLIODONIUM IONS WITH HALIDE IONS AND HYDROXYLIC SOLVENTS
复制标题
DOI：
10.1021/j150536a002
复制
发表时间：
1956-01-01
影响因子：
--
通讯作者：
MAUSNER, M
中科院分区：
文献类型：
--
作者：
BERINGER, FM;GEERING, EJ;MAUSNER, M
二苯基氯鎓在二甲基甲酰胺中以一级动力学快速分解为氯苯和碘苯，在二甘醇中较慢，在水中以二级动力学非常慢。在二甘醇中，氯化钾抑制了竞争性溶剂溶解，氯化亚铜催化量消除了竞争性溶剂溶解，大大加速了氯苯的形成（e从31 kcal./mol下降到19 kcal./mol）。在没有催化剂的情况下，氯苯的形成被认为是通过可逆形成和不可逆分解的二苯基氯离子对进行的，而溶剂溶解被认为是通过自由的二苯基氯离子进行的。催化反应可通过二苯硫鎓阳离子和铜(I)种（如重氯乙酸(I)阴离子）之间的络合物进行。
Diphenyliodonium chloride decomposed to chlorobenzene and iodobenzene by first-order kinetics rapidly in dimethyl-formamide and more slowly in diethylene glycol and by second-order kinetics very slowly in water. In diethylene glycol the competitive solvolysis was repressed by potassium chloride and removed by catalytic amounts of cuprous chloride, which greatly accelerated the formation of chlorobenzene (E. dropped from 31 to 19 kcal./mole). The formation of chlorobenzene in the absence of catalyst is viewed as proceeding through the reversible formation and irreversible decomposition of di-phenyliodonium chloride ion-pairs, while the solvolysis is viewed as proceeding through free diphenyliodonium cations. The catalyzed reaction may proceed through a complex between the diphenyliodonium cation and a copper (I) species, such as the dfichlorocuprate (I) anion.