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首页> 外文期刊>Chemistry: A European journal >1-Phenyl-1,2-cyclohexadiene: Generation, Interception by Activated Olefins, Dimerisation and Trimerisation
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1-Phenyl-1,2-cyclohexadiene: Generation, Interception by Activated Olefins, Dimerisation and Trimerisation

机译：1-苯基-1,2-环己二烯：生成，被活化烯烃截留，二聚和三聚

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摘要

Four possible precursors of 1-phenyl-1,2-cyclohexadiene (2) were examined, namely, 6,6-dibromo-1- phenylbicycloACHTUNGTRENUNG[3.1.0]hexane, (1a,5a,6a)- 6-bromo-6-fluoro-1-phenylbicyclo- ACHTUNGTRENUNG[3.1.0]hexane, 1-bromo-2-phenylcyclohexene and 1-bromo-6-phenylcyclohexene. All four compounds could be converted into 2, as demonstrated by the products of the interception of 2 with activated olefins. Styrene, 1,1-diphenyl- ACHTUNGTRENUNGethene, indene, furan and 2,5-dimeth- ACHTUNGTRENUNGylfuran were employed as such. Whereas the first three gave [2+2] cycloadducts of 2, the last two provided one [4+2] cycloadduct each. To create the [2+2] cycloadducts, the p bond of 2 that is more remote from the phenyl group reacted, whereas the p bond of 2 conjugated with the phenyl group exclusively produced the [4+2] cycloadducts. The generation of 2 in the absence of a trapping reagent brought about relatively good yields of a dimer or a trimer of 2 depending on the mode of the liberation of 2. Being derivatives of triphenylene, the dimer as well as the trimer have unusual structures, thereby indicating that a phenyl group is participating in the formation of these compounds. The most surprising structure of the trimer was elucidated by X-ray crystal diffraction. As to the mechanisms, diradical intermediates are proposed both for the cycloadditions and for the dimerisation. The initial steps of the latter seem to proceed also in the trimerisation.
机译：研究了1-苯基-1,2-环己二烯（2）的四种可能的前体，即6,6-二溴-1-苯基双环ACHTUNGTRENUNG [3.1.0]己烷，（1a，5a，6a）-6-溴6 -氟-1-苯基双环-乙酰丙酮[3.1.0]己烷，1-溴-2-苯基环己烯和1-溴-6-苯基环己烯。如通过活化烯烃拦截2的产物所证明的，所有四种化合物都可以转化为2。照原样使用苯乙烯，1，1-二苯基-乙酰丙酮，茚，呋喃和2，5-二甲基-乙酰戊基呋喃。前三个给出[2 + 2]个环加合物，而后两个给出一个[4 + 2]个环加合物。为了产生[2 + 2]环加合物，更远离苯基的2的p键反应，而与苯基共轭的2的p键专门产生[4 + 2]环加合物。在不存在捕集剂的情况下生成2会导致2的二聚体或三聚体的相对较高的产率，具体取决于2的释放方式。作为三亚苯基的衍生物，二聚体和三聚体均具有不同寻常的结构，从而表明苯基正在参与这些化合物的形成。通过X射线晶体衍射阐明了三聚体的最令人惊讶的结构。关于机理，提出了用于自由基加成和二聚的双自由基中间体。后者的初始步骤似乎也在三聚反应中进行。

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