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Electrocatalytic eco-efficient functionalization of white phosphorus

“…Combining the advantages of usual homogeneous chemistry in solution and electrochemistry, when the reagents (both nucleophiles and electrophiles) are generated on electrodes directly in the reactions system, we succeeded in gaining high conversion of white phosphorus to target products and choosing conditions of high selectivity of the process [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22].…”

“…The joint action of alkoxy anion and halide on the white phosphorus molecules results in various derivatives of phosphorus acids (phosphates, pyrophosphates, phosphites), depending on electrolysis conditions (Scheme 1) [8][9][10][11][12][13][14][15][16][17].…”

“…The yield of trialkyl phosphates did not exceed 70% in all cases. On the basis of these data it is possible to suggest the general next processes (Scheme 2) [8][9][10][13][14][15][16][17].…”

“…2RO À þ H 2 " Anode : 2I À À 2e À ! ðIÞ 2 It is feasible to obtain a single ultimate product for certain limits of the molar ratio of water and alcohol [11,29]. A comprehensive study of the reaction mechanism allowed to make a conclusion about the influence of hydroxide ions, arising during electrochemical process on the course of this interaction.…”

“…Electrochemical processes in the synthesis of the phosphorus acids derivatives from P 4 . electrolysis carrying out in water-alcohol solutions under optimal conditions and reagents ratio allows to obtain trialkyl phosphates practically with a quantitative yields both in the base of the phosphorus and electric current (see Table 2) [11,29]. As a result of successive reactions dialkylphosphite is formed, which is unstable under electrolysis conditions and may be transformed to trialkylphosphate with an excess of alcohol.…”