Studies on Aggregation of Reactive Carboanions

关于碳负离子的聚集，获得了以下有趣的结果。在β-羟基亚砜的二价阴离子中，含氧阴离子的金属抗衡阳离子与亚磺酰基配位，碳阴离子的抗衡阳离子不受亚磺酰基控制。因此，碳负离子的相互转化很容易发生。顺-和反-β-烷基环丙基苯砜与碱反应分别得到相应的碳负离子。这些负碳离子经过快速的相互转化，形成化学稳定的同分异构体负碳离子，质子或醛攻击负碳离子，得到产物。另一方面，烷基化试剂可以从阴离子的另一侧进攻。在烷氧基或2-吡啶基的存在下，反应受这些基团的影响。产物的同分异构比与关于碳负离子、金属抗衡阳离子和THF溶剂的中间聚集的MM计算一致。

The following interesting results were obtained concerning the aggregation of carbanions.1. In dianions of beta-hydroxysulfoxides the metal counter cation of an oxyanion coordinates to the sulfinyl group, and the counter cation of a carbanion is not controlled by the sulfinyl group. Therefore, the interconversion of that carbanion readily takes place.2. The treatment of cis- and trans- beta-alkylcyclopropy1 pheny1 sulfones with a base gives the corresponding carbaions, respectively. These carbanions undergoes the rapid interconvertion to the thermodynamically stable isomeric carbanions, and a proton or an aldehyde attacks to the carbanion to give the products. On the other hand, an alkylating reagent may attack from the other side of the anion. In the presence of an alkoxy or a 2-pyrildyl group the reaction is affected by these groups.3. The isomeric ration of products is obtained in agreement with the MM calculation concerning the intermediary aggregation of a carbanion, a metal counter cation and THF solvent.