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氯溴卡宾与系列取代苯甲醛作用均产生CO(即羰基脱氧产物),取代基的电子效应直接影响CO的产率.捕获反应证实,该反应经历0°,0°型羰基叶立德中间体阶段.氟氯(溴)卡宾与四苯基环戊二烯酮(TPCP)反应除得到高产率的CO外,还生成偕氟卤环戊二烯(8)、双键加成物(9)及其重排产物(10).该类反应以脱CO途径为主,这可能是由于中间体羰基叶立德内部存在着“推-拉”稳定效应和不利于分子内电环化和分子间1,3-偶极加成的0°,90°型构象.本文讨论了这两类反应的微观作用机制.
Chloro-bromocabine and the series of substituted benzaldehyde both produce CO (ie carbonyl deoxygenation products), and the electronic effect of substituents directly affects the yield of CO. The capture reaction confirms that the reaction undergoes the 0 °, 0 ° type carbonyl ylide intermediate stage. The reaction of chlorofluorocarbon (bromine) carbenes with tetraphenylcyclopentadienone (TPCP) leads to the addition of cyclooctylfluorocyclopentadienes (8), double bond adducts (9) and their Rearrange the product (10). This type of reaction is dominated by the CO removal pathway, probably due to the “push-pull” stabilizing effect inside the intermediate carbonyl ylide and the 0 ° ° detrimental to intramolecular cyclization and intermolecular 1,3-dipolar addition , 90 ° conformation. This article discusses the microscopic mechanism of action of these two types of reactions.