65184-58-9Relevant academic research and scientific papers
Reactions of 1,3-dioxolanes with Iodine Monochloride: Formation of Chlorohydrin Esters and Diol Monoesters
Glass, Beverley D.,Goosen, Andre,McCleland, Cedric W.
, p. 2175 - 2182 (2007/10/02)
2-Mono-substituted 1,3-dioxolanes are oxidised by iodine monochloride to the appropriate 2-substituted 1,3-dioxolan-2-ylium ions, whose stability is dependent upon the presence and nature of substituents on C-4 and C-5.Some dioxolanylium ions are labile and under the reaction conditions afford chlorohydrin esters, with inversion of configuration taking place at the ring carbon attacked by chloride.Others are stable under the reaction conditions and may be converted on aqueous workup to diol monoesters with retention of configuration at C-4 and C-5.The effect of substituents and reaction conditions on these competing reactions are described.The stereo- and regio-chemistry of both hydroxy- and chloro-ester formation was confirmed through NMR studies, which necessitated the prior detailed analysis of the 1H and 13C spectra associated with the acyloxy sidechains of the relevant esters.
Reaction of 1,3-dioxolans with Iodine Monochloride: the Scope and Mechanism of Formation of 1,3-dioxolan-2-ylium Dichloroiodates(I)
Goosen, Andre,McCleland, Cedric W.
, p. 977 - 983 (2007/10/02)
Treatment of a series of 2-substituted-4,4,5,5-tetramethyl-1,3-dioxolanes with iodine monochloride afforded the appropriate 2-substituted-4,4,5,5-tetramethyl-1,3-dioxolan-2-ylium dichloroiodate(I) salts in excellent yields.In contrast to the stable 2-aryl-substituted salts, the 2-alkyl and unsubstituted derivatives were relatively labile.While 2-phenyl-1,3-dioxolan and 2-phenyl-1,3-dioxan afforded low yields of unstable salts,crystalline products could not be isolated from 4,5-disubstituted dioxolans.The reaction was inhibited by electron-withdrawing 4- and 5-substituents.From a study of the effects of photolysis and added iodine, the mechanism is proposed to involve a hydride ion transfer.Possible reasons for the formation of dichloroiodate(I) rather then monohalide salts, are outlined.The stability of the 2-aryl-substituted salts is dicussed in terms of charge distribution in the cation and possible aryl-anion interactions.
