2634-48-2Relevant academic research and scientific papers
Photoreduction des methanesulfonates d'alkyle dans l'hexamethylphosphortriamide (HMPT)
Pete, Jean-Pierre,Portella, Charles
, p. 195 - 197 (2007/10/02)
Alkyl methanesulfonates are unreactive when irradiated in solvents such as hydrocarbons, benzene, acetone.Irradiation of these esters in HMPT yields the corresponding alkene and alcohol (15percent and 65percent respectively).As shown with carboxylic esters, the reaction consist in an electron transfer from excited HMPT to the sulfonate.Addition of NaBH4, however, increases the efficiency of the reaction.In contrast to the essential role of water in carboxylate photoreduction, the lack of effect is explained here by the neutral character of the radical anion.These photochemical reductions are very similar (nature and distribution of products) to those observed by chemical methods.In a comparative discussion a competition between SO2-O and C-O bond cleavage at the radical anion stage is proposed and the participation of a two-electron mechanism as suggested elsewhere is ruled out.
Action des metaux sur les esters carboxyliques en presence d'hexamethylphosphortriamide: une methode simple et efficace de reduction des alcools en alcanes
Deshayes, Henri,Pete, Jean-Pierre
, p. 2063 - 2072 (2007/10/02)
Carboxylic acids, alcohols (R'OH), and alkanes (R'H) are the main products of the reduction of carboxylic esters (RCO2R') by sodium in hexamethylphosphoric triamide (HMPA).Alkanes are preferentially formed from the carboxylic esters of hindered alcohols.The alkane content, however, is lowered when there is less steric hindrance on the carboxylic group, and increased when tert-butanol is introduced into the reaction mixture.The reduction of esters in HMPA has been compared to the reduction in alkylamines.The alkane is produced mainly by the decomposition of a radical anion intermediate which can be solvated by HMPA.The alcohol is the result of several possible bimolecular nucleophilic reactions; however, unimolecular and bimolecular processes are involved in the production of the carboxylic acid.
