Substitution of Hydroxyl Groups by Deuterium in the Electrochemical Reduction of Methanesulfonates |
| |
| Authors: | P. Kränke M. Wahren M. Findeisen |
| |
| Affiliation: | 1. Institute of Organic Chemistry, University of Leipzig , Germany;2. Institute of Analytical Chemistry, University of Leipzig , Germany |
| |
| Abstract: | Abstract The electrochemical reduction of dodecyl methanesulfonate (ROMs; R = n-C12H25 ?, Ms = CH3SO2 ?) as model compound was studied in deuterated media. This reaction could be of potential use in syntheses of partially deuterated compounds by conversion of C?OH-groups into C?D-bonds in the presence of other reactive groups. In order to obtain detailed information about the origin of the introduced hydrogen all individual components (solvent, supporting electrolyte, substrate) of the reaction system were deuterium labelled in the model reaction. The experiments indicate, that this reduction does not proceed along a uniform pathway. Dodecyl anions play the dominating role in the reaction mechanism. Deuterium is transferred into the product dodecane-d 1 from all components of the reaction mixture in the order of their relative proton acidities Ms-d 3 > Bu4N+-d 36 > DMF-d 7 > R-1,1-d 2-OMs. In the presence of D2O a hydrogen isotope exchange was found with the methyl group of MsO?, catalyzed by electrogenerated bases. |
| |
| Keywords: | Deuterium dimethylformamide dodecane dodecyl methanesulfonate electrochemical reduction isotope exchange NMR reaction mechanism tetrabutylammonium tosylate |
|
|
