Reactions of alkylmercuric halides with sodium borohydride in the presence of molecular oxygen

Abstract

Reaction of alkylmercuric halides with sodium borohydride in dimethylformamide saturated with molecular oxygen produces alcohols and borate esters in good yields. The products obtained following reaction of neophylmercuric bromide (1), l,7,7-trimethylbicyclo[2.2.1]heptyl-2-mercuric bromide (9), and endo-and exo-norbornyl-2-mercuric bromides (13 and 14) with borohydride in the presence of oxygen are compatible with a reaction mechanism involving free, noncaged, alkyl radicals as intermediates. This mechanism finds further support in the observations that reaction of 1 with borohydride and oxygen in solutions containing 2,2,6,6-tetramethylpiperidoxyI radical leads to good yields of the product of coupling of neophyl radical with the nitroxyl. Reaction of a-alkoxyl alkylmercuric halides with borohydride and oxygen generates -alkoxyl alcohols in good yields; similar reaction of Friedel-Crafts Chemistry. VIII.

Properties of carbon dioxide absorption and reduction by sodium borohydride under atmospheric pressure

“…The report on the reaction between S-nitro glutathione and NaBH 4 indicated that this reaction was a NO release process [34], implying indirectly that there was no obvious reaction between NaBH 4 and NO. For the impact of O 2 , Hill [35] reported that O 2 molecule was chemically inert to NaBH 4 if there were no external constrained conditions, being similar to the interpretation of Jeong et al [36].…”

Oxidation products of 5-ethenyl-4-methyl-3-pyridinecarbonitrile and 2- and 4-methylpyridines

“…Besides the desired secondary alcohol, small amounts of glycol were obtained. The replacement of the HgX group by an OH group, required for glycol formation, was reported previously and is attributed to the formation of peroxy compounds in the hydride reduction step (17,18). The oxymercuration step is considered to proceed by an ionic mechanism but the reduction step by a radical mechanism.…”

Absorption of carbon dioxide by hydrogen donor under atmospheric pressure

“…According to the relevant work [30], O 2 only participated in the conversions of B 2 O x and B 2 O 3 , and didn't affect the hydrogen release of NaBH 4 under alkali conditions. Additionally, NaBH 4 was chemically inert in ambient air [37]. Consequently, O 2 had no evidently effect on CO 2 absorption of this reaction system.…”