Schrauzer G N, Katz R N
Bioinorg Chem. 1978 Aug;9(2):123-43. doi: 10.1016/s0006-3061(00)80285-9.
Vitamin B12s effects the reductive dechlorination of mirex (dechlorane) in protic solvent systems, under both catalytic and stoichiometric conditions, mainly to yield compounds of composition C10Cl12-nHn, with n = 1-8, in which the basic dihomocubane cage structure is retained; the formation of cage-opened, reductively dehalogenated derivatives of 4,7-methanoindene occurs only to a very minor extent. The corresponding reactions of kepone (chlordecone), in contrast, occur with predominant formation of indene derivatives. Under certain mild conditions, vitamin B12s induces a fragmentation of kepone leading to the destruction of the dihomocubane moiety and the formation of an isolable organocobalamin having a C3Cl3H2 residue attached to the cobalt atom. In strongly alkaline media, the reaction of kepone with vitamin B12s may in addition yield high-molecular-weight condensation products of unknown constitution. Reactions of this type are of interest as prototypes of soil-decontamination processes.
在质子溶剂体系中，在催化和化学计量条件下，维生素B12都会影响灭蚁灵（十氯代八氢亚甲基萘）的还原脱氯反应，主要生成组成为C10Cl12-nHn（n = 1 - 8）的化合物，其中基本的二高立方烷笼状结构得以保留；4,7-亚甲基茚的开笼还原脱卤衍生物的形成仅占很小的比例。相比之下，开蓬（十氯酮）的相应反应主要生成茚衍生物。在某些温和条件下，维生素B12会诱导开蓬发生裂解，导致二高立方烷部分被破坏，并形成一种可分离的有机钴胺素，其钴原子上连接有一个C3Cl3H2残基。在强碱性介质中，开蓬与维生素B12的反应还可能生成组成未知的高分子量缩合产物。这类反应作为土壤去污过程的原型很有意思。
