Preparation and chemical behaviour of exo-methylene compounds: isoelectronic compounds of 5-methylenecyclohexa-1,3-diene
Preparation and chemical behaviour of exo-methylene compounds: isoelectronic compounds of 5-methylenecyclohexa-1,3-diene
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外型亚甲基化合物的制备和化学行为：5-亚甲基环己-1,3-二烯的等电子化合物
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发表时间：
1988
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影响因子：
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通讯作者：
S. Yoneda
中科院分区：
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作者：
A. Sugimoto;J. Yamano;M. Yasueda;S. Yoneda
用光解法制备了9-亚甲基-9，10-二氢菲(2)等亚甲基化合物，并研究了它们的化学行为。(2)与酸(CF3CO2H)或碱(-OBut)反应生成9-甲基菲，与溴反应生成9-溴甲基菲。与二甲基乙酰二甲酸二甲酯反应不生成Diels-Alder加合物，而生成烯加合物。用乙烯四碳腈处理也得到了烯加合物。与卡宾或卡宾反应生成9，10-dihydrophenanthrene-9-spirocyclopropanes.考察了其他亚甲基化合物1-亚甲基-1，2-二氢萘和2-亚甲基-2，3-二氢苯并[b]噻吩与四碳腈的反应。除了与卡宾的反应外，芳构化可能对这些外亚甲基化合物的反应起作用。
Some exo-methylene compounds such as 9-methylene-9,10-dihydrophenanthrene (2) were photolytically prepared and their chemical behaviour was investigated. Treatment of (2) with acid (CF3CO2H) or base (–OBut) led to the formation of 9-methylphenanthrene, with bromine to 9-bromomethylphenanthrene. Reaction with dimethyl acetylenedicarboxylate did not give Diels–Alder adduct but gave an ene adduct. Treatment with ethenetetracarbonitrile also gave an ene adduct. Reaction with carbene or carbenoids gave 9,10-dihydrophenanthrene-9-spirocyclopropanes. Reaction with ethenetetracarbonitrile was examined for other exo-methylene compounds, 1-methylene-1,2-dihydronaphthalene and 2-methylene-2,3-dihydrobenzo[b]thiophene. The aromatisation may be responsible for the reactions of these exo-methylene compounds except for the reaction with carbenes.