BICYCLO[1.1.0]BUTANE CHEMISTRY .2. CYCLOADDITION REACTIONS OF 3-METHYLBICYCLO[1.1.0]BUTANECARBONITRILES . FORMATION OF BICYCLO[2.1.1]HEXANES
BICYCLO[1.1.0]BUTANE CHEMISTRY .2. CYCLOADDITION REACTIONS OF 3-METHYLBICYCLO[1.1.0]BUTANECARBONITRILES . FORMATION OF BICYCLO[2.1.1]HEXANES
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DOI：
10.1021/ja00955a021
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发表时间：
1966-01-01
影响因子：
15
通讯作者：
BLANCHAR.EP
中科院分区：
文献类型：
--
作者：
CAIRNCROSS, A;BLANCHAR.EP
3-甲基双环[1. 1.0]丁腈（1）与丁二烯、丙烯腈、马来腈、丁二腈、乙烯、苯乙烯、对甲氧基苯乙烯和1-（N，N-二甲基氨基）环戊烯反应形成1：1加合物。在所有情况下，4-甲基双环[2.1. 1]己腈与其它产物一起形成沿着。提出的证据强烈表明，在环加成反应，以及在从乙烯形成单环产品的双自由基中间体。1在液相中于150 ℃热解产生几种二聚体，其中两种已被部分鉴定为1与其热解产物之间的环加合物。简要尝试观察双环[1.1]衍生物的热活化转化。0]丁烷由于竞争性成分而失败。
3-Methylbicyclo [l. 1.0] butanecarbonitrile (1) reacts with butadiene, acrylonitrile, maleonitrile, fumaronitrile, ethylene, styrene, p-methoxystyrene, and l-(N, N-dimethylamino) cyclopentene to form 1: 1 adducts. In all cases, derivatives of 4-methylbicyclo [2.1. 1] hexanecarbonitrile were formed along with other products. Evidence is presented whichstrongly suggests diradical intermediates in the cycloaddition reaction as well as in the formation of monocyclic products from ethylene. Thermolysis of 1 in the liquid phase at 150 produces several dimers, two of which have been partially identified as cycloadducts between 1 and its pyrolysis products. Brief attempts to observe thermally activated inversion of derivatives of bicyclo [1.1. 0] butane failed because of competitivedecomposition.