Bicyclo[2.2.2]octan-2-yl- and exo-bicyclo[3.2.1]octan-2-yl-amines have been deaminated in acetic acid by nitrous acid and via their N-phenyltriazenes; their ethyl N-nitrosocarbamates have also been solvolysed in ethanol. Product distributions by a given method from the structurally Isomeric starting materials are similar to each other and to the common product distribution obtained from bicyclo[2.2.2]-octane-2-yl and exo-bicyclo[3.2.1]octan-2-yl toluene-p-sulphonates. Each amine gives, however, a small but unmistakable excess of the structurally unrearranged product compared (in the case substitution) with the distribution obtained from the solvolysis of the corresponding bicyclo-octyl toluene-p-sulphonates. Each amine gives, however, a small but unmistakable excess of the structurally unrearranged product compared (in the case of substitution)with the distribution obtained from the solovolysis of the corresponding bicyclo-octyl toluene -p-sulphonates. endo-Bicyclo[3.2.1]octan-2-ylamine has also been deaminated in acetic acid by nitrous acid and via its ethyl N-nitrosocarbamate in ethanol. The product ratios of these reactions are characteristically different from those of the isomeric amines but, as far as substitution is concerned, are similar to what is obtained from endo-bicyclo[3.2.1]octan-2-yl toluene-p-sulphonate. A common mechanism describe all the deaminative reactions. We propose that classicalcarbonium ions are the initial products of fragmentation of diazo-intermediates. These are intercepted to only a small extent to give products structurally and sterochemically characteristic of the original amines; to an even smaller extent they rearrange to isomeric classical carbonium ions is rearrangement to non-classical isomers. From both classic carbonium ion is produced as has been implicated in the solvolysis of the corresponding toluene-p-sulphonates. endo-Bicyclo[3.2.1]octan-2-ylamine deamination gives rise to an isomeric symmetrical non-classical carbonium ion, the same one that intervenes in the solvolysis of endo-bicyclo[3.2.1]octan-2-yl toluene-p-sulphonate. Symmetrical and unsymmetrical non-classical carbonium ions once formed give product ratio largely independent of their origins or modes of formation although the symmetrical one appears to undergo a small extent of isomerization to the (more stable) unsymmetrical species. These result are contrasted with those obtained from simple carbocyclic system (without branching at the β-carbon)in which deamination and toluene-p-sulphonate solovolysis give characteristically different and unrelated product distributions.

中文翻译：

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双环[2.2.2]辛-2-基-胺和双环[3.2.1]辛-2-基-胺的脱氨基。非经典碳离子经典前体的证据

双环[2.2.2]辛-2-基-和外-双环[3.2.1]辛-2-基胺已在由亚硝酸和乙酸被脱氨基经由其Ñ -phenyltriazenes; 它们的N-亚硝基氨基甲酸乙酯也已溶剂化在乙醇中。通过给定方法从结构异构的原料中得到的产物分布彼此相似，并且与从双环[2.2.2]-辛烷-2-基和外-双环[3.2.1] octan-2-获得的常见产物分布相似。基甲苯p-磺酸化。然而，与从相应的双环辛基甲苯-对-磺酸盐的溶剂化获得的分布相比，每种胺给出的结构未重排的产物有少量但明显的过量（在取代的情况下）。然而，与从相应的双环辛基甲苯-对-磺酸盐的溶剂分解获得的分布相比，每种胺给出的结构未重整产物的少量但无误的过量。内-双环[3.2.1]辛烷-2-基胺也已在乙酸中被亚硝酸和通过其乙基N脱氨基乙醇中的亚硝基氨基甲酸酯。这些反应的产物比率在特征上不同于异构胺的比率，但就取代而言，类似于从内-双环[3.2.1]辛烷-2-基甲苯-p获得的产物比率。-磺酸化。通用机制描述了所有脱氨基反应。我们提出经典的碳离子是重氮中间体裂解的初始产物。这些仅在很小的程度上被截获，从而提供了原始胺的结构和立体化学特征的产物。它们甚至在较小程度上重排为异构的经典碳鎓离子，也重排为非经典的异构体。由这两种经典的碳酸根离子产生，这与相应的甲苯-对-磺酸盐的溶剂分解有关。内-双环[3.2.1]辛-2-基胺的脱氨基反应生成异构体对称的非经典碳鎓离子，与内-双环[3.2.1]辛-2-基甲苯-的溶剂化作用相同。对-磺酸盐。对称和不对称的非经典碳原子离子一旦形成，其产物比率就基本上不受其起源或形成方式的影响，尽管对称的一个似乎经历了较小程度的异构化为（更稳定的）不对称物质。这些结果与从简单的碳环系统（在β-碳上无支链）获得的结果相反，在该系统中，脱氨基和甲苯-对-磺酸盐溶剂分解产生了特征上不同且无关的产物分布。