CYCLOALLENES .9. 1-PHENYL-1-AZA-3,4-CYCLOHEXADIENE, THE 1ST ISODIHYDROPYRIDINE - GENERATION AND INTERCEPTION
CYCLOALLENES .9. 1-PHENYL-1-AZA-3,4-CYCLOHEXADIENE, THE 1ST ISODIHYDROPYRIDINE - GENERATION AND INTERCEPTION
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DOI：
10.1002/cber.19941270626
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发表时间：
1994-06-01
期刊：
影响因子：
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通讯作者：
WAGNER, W
中科院分区：
文献类型：
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作者：
CHRISTL, M;BRAUN, M;WAGNER, W
据报道，根据 Doering-Moore-Skattebol 方法，由 6,6-二溴-3-苯基-3-氮杂双环[3.1.0]己烷 (10) 与甲基锂生成标题环丙二烯 4。在苯乙烯、1,3-丁二烯、呋喃、1,3-环己二烯和 1,3-环戊二烯存在下，4 在 [2 + 2] 和 [4 + 2] 环加成中被拦截，分别形成六氢环丁[c]吡啶 6 和 11 以及六氢异喹啉 12-15。起始化合物10是通过顺式二取代的1，1-二溴环丙烷8和9由已知的二氧杂环庚烷衍生物7制备的，其合成已得到显着改进。用正丁基锂处理后，二氯苯基氮杂双环己烷3也转化为4。然而，在 4 的竞争中，苯乙烯未能成功对抗正丁基锂，正丁基锂将 4 转化为戊二烯胺 5。
The generation of the title cycloallene 4 from 6,6-dibromo-3-phenyl-3-azabicyclo[3.1.0]hexane (10) with methyllithium according to the Doering-Moore-Skattebol method is reported. In the presence of styrene, 1,3-butadiene, furan, 1,3-cyclohexadiene, and 1,3-cyclopentadiene, 4 is intercepted in [2 + 2] and [4 + 2] cycloadditions with formation of the hexahydrocyclobuta[c]pyridines 6 and 11 and the hexahydroisoquinolines 12-15, respectively. The starting compound 10 is prepared via the cis-disubstituted 1,1-dibromocyclopropanes 8 and 9 from the known dioxepine derivative 7, the synthesis of which has been considerably improved. On treatment with n-butyllithium, the dichlorophenylazabicyclohexane 3 is converted into 4 as well. However, in the competition for 4, styrene is not successful against n-butyllithium, which transforms 4 into the pentadienylamine 5.