REACTION OF CARBETHOXYNITRENE WITH ALLENES
REACTION OF CARBETHOXYNITRENE WITH ALLENES
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DOI：
10.1021/jo00890a016
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发表时间：
1975-01-01
影响因子：
3.6
通讯作者：
GILBERT, JC
中科院分区：
文献类型：
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作者：
BINGHAM, EM;GILBERT, JC
N-(对硝基苯磺酰氧基)氨基甲酸酯(9)在碱催化下消除，生成的碳乙氧基氮烯与异分子和1, 1-二甲基丙二烯反应生成1, 2-环加成产物。四甲基丙二烯不能与氮宾产生加合物。结果似乎与环加成机制最一致，其中初始步骤是三线态氮烯与丙二烯部分的末端碳原子的反应。描述了 2-异亚丙基-N-乙酯基氮丙啶 (14) 热异构化为 2-乙氧基-5, 5-二甲基-4-亚甲基-2-恶唑啉 (5b)。各种类型的卡宾或类卡宾与异类化合物的反应已被研究，并以一种不寻常的方式进行，无论如何，都会产生亚甲基环丙烷 二价碳物种是否处于单线态或三线态自旋状态。 2· 5 鉴于最近人们对氮烯（卡宾的 5 种等电子类似物）化学的兴趣，令人惊讶的是该物质与外来物质的相应反应仅得到了粗略的研究。因此，唯一报道的此类反应的研究是 Bleiholder 和 Shechter 的研究，他们研究了叠氮甲酸乙酯 (1) 与四甲基丙二烯 (2) 的热诱导反应以及 1 与 1, 1-二甲基丙二烯 (3) 的光化学引发反应。 6 热处理得到三唑啉 4 (38%) 和异丙叉恶唑啉 5a (29%) 作为加成产物；
Carbethoxynitrene, from base-catalyzed a elimination of N-(p-nitrobenzenesulfonoxy) urethane (9), reacts with aliene and 1, 1-dimethylallene to produce 1, 2-cycloaddition products. Tetramethylallene fails to produce an adduct with the nitrene. The results appearto be most consistent with a cycloaddition mechanism in which the initial step is reaction of triplet nitrene with a terminal carbon atom of the allenic moiety. The thermal isomeriza-tion of 2-isopropylidene-/V-carbethoxyaziridine (14) to 2-ethoxy-5, 5-dimethyl-4-methylene-2-oxazoline (5b) is described.The reaction of various types of carbenes or carbenoids with alienes has been investigated and proceeds in an unex-ceptional fashion to yield methylenecyclopropanes regard-less of whetherthe divalent carbon species is in a singlet or triplet spin state. 2· 5 In view of the recent interest in the chemistry of nitrenes, 5 isoelectronic analogs of carbenes, it is somewhat surprising that the corresponding reaction of this species with alienes has received only cursory examination. Thus, the sole reported investigation of this type of reaction is that of Bleiholder and Shechter in which they studied the thermally induced reaction of ethyl azidoformate (1) with tetramethylallene (2) and the photochemi-cally initiated reaction of 1 with 1, 1-dimethylallene (3). 6 The thermal process afforded the triazoline 4 (38%) and the isopropylideneoxazoline 5a (29%) as addition products;