Selective N,N-Dibenzylation of primary aliphatic amines with dibenzylcarbonate in the presence of phosphonium salts

In the presence of catalytic amounts of tetraalkylphosphonium salts and under solventless conditions, primary aliphatic amines (RNH2: R ) PhCH2, Ph(CH2)2, n-decyl, and 1-naphthylmethyl) are efficiently N-benzylated to the corresponding RN(CH2Ph)2, using dibenzyl carbonate as the benzylating reagent. Compared to the reaction run without salt, where the competitive formation of the benzyl carbamate is favored, the phosphonium salt promotes high selectivity toward the benzylated amine and an increase of the reaction rate as well. However, in a single case explored for an amino acidic compound, namely 4-(aminomethyl)benzoic acid [4-(NH2CH2)C6H4CO2H], both N,N-dibenzylation and esterification of the acid group were observed. Analysis of the IR vibrational modes of benzylamine in the presence of tetrabutylphosphonium bromide supports the hypothesis that this enhanced selectivity may be due to an acid-base interaction between the salt and the amine, which increases the steric bulk of the amine and favors attack of the nucleophile on the less hindered alkyl terminus of dibenzyl carbonate

Journal of The Electrochemical Society, 162 (9) D435-D443 (2015) D435 0013-4651/2015/162(9)/D435/9/$33.00 © The Electrochemical Society Electrochemical Mechanism of Cr(III) Reduction for Preparing Crystalline Chromium Coatings Based on

The electrochemical mechanism of Cr(III) reduction and chromium nucleation/growth process on a glassy carbon (GC) electrode in 1-ethyl-3-methylimidazolium bisulfate ([EMIM]HSO4) ionic liquid are studied. These results from the cyclic voltammetry (CV