The Chemistry of the Aminochromes: Part Vi. The Reaction of Adrenochrome With Glutathione

Abstract

The reaction between adrenochrome and glutathione has been studied. 'The main products result from the 1,4-addition of glutathione to the Cg unsaturated carbonyl systetns in adrenochrome involving the c6-C~ and the c4-c~~ double bonds, and are probably 7-S-glutathionyl-5,6-dihydroxy-N-methylindole and 9-S-glutathionyl-2,3,6,9-tetrahydro-3,5-dihydroxy-6-0~0-N-methylindole respectively. 5,6-Dihydroxy-N-methylindole is also formed during the interaction of glutathione and adrenochrome. The lnechanisrns by which these compounds are formed are discussed.

Chemistry of the aminochromes. Part X. Some further observations on the reactions of aminochromes with thiols

“…Solutions of adrenochrome (1) are readily decolorized by a wide variety of thiols (1)(2)(3)(4)(5)(6)(7)(8)(9). The nature of the products obtained from aminochromes in reactions of this type and the mechanisms by which they were formed have been the subjects of several recent investigations (6)(7)(8)(9)(10)(11)(12)(13).…”

“…The nature of the products obtained from aminochromes in reactions of this type and the mechanisms by which they were formed have been the subjects of several recent investigations (6)(7)(8)(9)(10)(11)(12)(13). As a result of these studies it was concluded that (6-9) aminochromes react with thiols to form three different types of product: (A) 5,6-dihydroxyindoles; (B) thio-substituted 5,6-dihydroxyindoles; and ( C ) addition products of the aminochrome with the thiol which appear to be structurally similar to the adrenochromesodium bisulfite addition product (cf.…”

“…4) may play a different signifi- (isomeric with adrenochrome) and the thiol groups in the rnyosin molecules (13). Mattok and Heacock had previously suggested that the formation of adrenochrome-thiol adducts (such as 4) offered the possibility that suitable thiols could act as "carriers" for the highly reactive aminochromes in physiological systems (6,7). The structures of the thio-substituted 5,6-dihydroxyindole derivatives (cf.…”

“…3 or 8) were proposed on the basis of chromatographic and spectroscopic evidence (cf. 6-12) and on mechanistic considerations (6)(7)(8). Whilst structures of the type 3 or 8 were not incompatible with the evidence available, the question of the precise position of the thiol residue was not satisfactorily resolved.…”