Metacyclophanes and related compounds. 12. Reaction of 8,16-dimethyl[2.2]metacyclophane with iodine monochloride
Metacyclophanes and related compounds. 12. Reaction of 8,16-dimethyl[2.2]metacyclophane with iodine monochloride
复制标题
间环芬及相关化合物。
DOI：
10.1021/jo00192a026
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发表时间：
1984
期刊：
影响因子：
--
通讯作者：
K. Kobayashi
中科院分区：
文献类型：
--
作者：
M. Tashiro;T. Yamato;K. Kobayashi
在HI04和H_2SO_4存在下，8，16-二甲基[2.2]偏环番(1)与碘反应生成5-碘-8，16-二甲基-(2a)和5，13-二碘-8，16-二甲基(2b)，产率分别为10%和67%。然而，用一氯碘处理1，5，8-二氯和5，8-二氯[2.2]偏环番衍生物，这是一种著名的强碘试剂。实验还发现，1与大量的IC1反应生成了L，5，13-三氯-8，16-二甲基[2.2]偏环烷，产率为90%；1与-丁二烯反应生成了5，13-二氯-8，16-二甲基-L-烯。据报道，8，16-二甲基-5，13-二叔丁基[2.2]偏环番(MCP)与过量的一氯碘反应生成了相应的六氯四氢吡喃。2最近，佐藤等人提出。报道说，[2.2]MCP本身与氯碘或与碘和高氯酸银反应生成四氢芘。3.
Reaction of 8, 16-dimethyI [2.2] metacyclophane (1) with iodine in the presence of HI04 and H2S04 afforded 5-iodo-8, 16-dimethyl-(2a) and 5, 13-diiodo-8, 16-dimethyl [2.2] metacyclophane (2b) in 10% and 67% yields, respectively. However, treatmentof 1 with iodine monochloride, which is a well-known powerful iodinating reagent, gave mainly 5-monochloro-and 5, 8-dichloro [2.2] metacyclophane derivatives. It was also found that reaction of 1 with a large excess of IC1 afforded l, 5, 13-trichloro-8, 16-dimethyl [2.2] metacyclophane in 90% yield, and 1 gave 5, 13-dichloro-8, 16-dimethyl [2.2] metacyclophan-l-ene by treatment with--Bu in t-BuOH.It has been reported that reaction of 8, 16-dimethyl-5, 13-di-tert-butyl [2.2] metacyclophane (MCP) with excess iodine monochloride afforded the corresponding hexa-chlorotetrahydropyrene. 2 Recently, Sato et al. reported that reaction of [2.2] MCP itself with iodinemonochloride or with iodine and silver perchlorate afforded tetra-hydropyrene. 3