维生素B12s对乳糜和酮的还原脱氯和降解

G.N. Schrauzer, R.Nathan Katz
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引用次数: 32

摘要

在催化和化学计量条件下,维生素B12s在质子溶剂体系中影响mirex (decchlorane)的还原脱氯反应,主要生成组分为C10Cl12-nHn的化合物,n = 1-8,其中保留了基本的二异立方烷笼状结构;4,7-甲烷烯的笼开的还原脱卤衍生物的形成只在很小的程度上发生。相反,酮(十氯酮)的相应反应主要是通过4,7-甲甲醇-8- 1衍生物生成茚衍生物C9Cl8-nH (n = 3-5)。在某些温和的条件下,维生素B12s诱导酮的断裂,导致二异叔巴烷部分的破坏,形成可分离的有机钴胺素,钴原子上附着C3Cl3H2残留物。在强碱性介质中,酮与维生素b12的反应还可能产生高分子量的缩合产物。这种类型的反应作为土壤净化过程的原型而引起人们的兴趣。
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Reductive dechlorination and degradation of mirex and kepone with vitamin B12s

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 C9Cl8-nH (with n = 3–5), presumably via 4,7-methanoinden-8-one 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.

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Chapter III. Complexes containing carbon monoxide: synthesis, reactivity, structure, bonding and therapeutic aspects of carbon monoxide–releasing molecules (CORMs) in human beings and plants Frontmatter Chapter IV Advantageous role of gaseous signalling molecule, H2S: hydrogen sulphide and their respective donors, in ophthalmic diseases and physiological implications in plants Chapter I. Coordination chemistry of chlorophylls/ bacteriochlorophylls and its functional aspects in photosynthesis Index
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