The kinetics and mechanisms of aromatic halogen substitution. Part XXIV. The stereochemistry of addition of chlorine to naphthalene
The kinetics and mechanisms of aromatic halogen substitution. Part XXIV. The stereochemistry of addition of chlorine to naphthalene
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芳香族卤素取代的动力学和机理。
DOI：
10.1039/j29660000827
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发表时间：
1966
期刊：
影响因子：
--
通讯作者：
V. D. Olmo
中科院分区：
文献类型：
--
作者：
P. Mare;M. D. Johnson;J. Lomas;V. D. Olmo
氯与萘在醋酸中反应，生成取代产物(主要是1-氯代萘)、氯加成产物(主要是萘-α-四氯化物，熔点182°)和其他加成产物(主要是乙酰氧基三氯化物)。在添加的氯化锂存在下，四氯化物混合物中含有很大比例的立体异构体δ-异构体，熔点96°。在四氯化碳中光催化加成得到一种异构体混合物，最难溶解的是萘-γ-四氯化物，熔点为134°，其余大部分是一种新的异构体--萘-1-四氯化物，熔点为85-87°。用质子磁共振波谱确定了γ-，δ-、I-四氯化物和三氯乙酸乙酯的构型和构象。结果表明，α-四氯化物不是通过氯离子从环境中捕获碳正离子中间体而形成的。
The reaction of chlorine with naphthalene in acetic acid gives products of substitution (mainly 1-chloronaphthalene); products of addition of chlorine (mainly naphthalene-α-tetrachloride, m. p. 182°); and other products of addition (mainly an acetoxytrichloride). In the presence of added lithium chloride, the mixture of tetrachlorides contains a major proportion of the stereoisomeric δ-isomer, m. p. 96°. Light-catalysed addition in carbon tetrachloride gives a mixture of isomers, the least soluble being naphthalene-γ-tetrachloride, m. p. 134°, and the major part of the remainder being a new isomer, naphthalene-Iµ-tetrachloride, m. p. 85–87°. The configurations and conformations of the γ-, δ-, and Iµ-tetrachlorides and of the acetoxytrichloride have been established by proton magnetic resonance spectroscopy. The results establish that the α-tetrachloride is not formed through capture of a carbonium ionic intermediate by chloride ion from the environment.