Chemistry of the Aliphatic Esters of Thiophosphoric Acids. II. O,O,S-Trialkyl Thionophosphates by the Addition of O,O-Dialkyl Thiolthionophosphoric Acids to Olefins¹

Reactions of O,O-dialkyldithiophosphoric acids with non-activated α-olefins

“…In accordance with the Markovnikov's rule, the reaction of unactivated olefins with dithiophosphoric acids results in the adducts, which were not specifically purified from the phosphorus sulfides impurities [4,6]. The explanation of this phenomenon lies in the fact that the starting olefins, especially those produced by the industry, contain the traces of peroxide compounds, which direct the addition of dithiophosphoric acid on the double bond against the Markovnikov's rule, i. e., in this case there is a radical addition [5]. The role of the phosphorus sulfides impurities, contained in the crude dithiophosphoric acid, is the destruction of the peroxides which favors the Markovnikov's adducts formation in the Ad-processes occurring by an ionic mechanism [5,8].…”

“…The explanation of this phenomenon lies in the fact that the starting olefins, especially those produced by the industry, contain the traces of peroxide compounds, which direct the addition of dithiophosphoric acid on the double bond against the Markovnikov's rule, i. e., in this case there is a radical addition [5]. The role of the phosphorus sulfides impurities, contained in the crude dithiophosphoric acid, is the destruction of the peroxides which favors the Markovnikov's adducts formation in the Ad-processes occurring by an ionic mechanism [5,8]. Oct-1-ene, purified from peroxides, react with O,O-diethyldithiophosphoric acid to give exclusively the Markovnikov's adduct [6].…”

“…Synthetic results of the reactions of four-coordinated phosphorus thioacids with olefins depend significantly on the reogiochemistry of addition of thiophosphoric fragments to the double bonds of asymmetric olefins, i. e., on the possibility of formation of the carbon-carbon double bond adducts in accordance with or opposite to the Markovnikov's rule [1][2][3][4][5][6][7][8][9]. The unsaturated compounds containing electronwithdrawing groups adjacent to the double bond, for example, acrylonitrile, alkenyl acylates, etc., add O,Odialkyldithiophosphoric acid against the Markovnikov's rule [2][3][4].…”

“…The unsaturated compounds containing electronwithdrawing groups adjacent to the double bond, for example, acrylonitrile, alkenyl acylates, etc., add O,Odialkyldithiophosphoric acid against the Markovnikov's rule [2][3][4]. The reactions of O,O-dialkyldithiophosphoric acids with unsaturated compounds containing the electron-donating substituents (vinyl ethers, vinyl acetate) or asymmetric olefins (oct-1-ene, oct-2-ene, cycloalkenes, 2-methylprop-1-ene) result in the Markovnikov's adducts [1, [5][6][7][8][9]. In accordance with the Markovnikov's rule, the reaction of unactivated olefins with dithiophosphoric acids results in the adducts, which were not specifically purified from the phosphorus sulfides impurities [4,6].…”

S-Methylation of O,O-Dialkyl Phosphorodithioic Acids: O,O,S-Trimethyl Phosphorodithioate and Phosphorothiolate as Metabolites of Dimethoate in Mice

“…(MeO)2P(S)SMe was prepared as described by Lin et al(14) and (MeO)2P(O)SMe according to Norman et al(15). (EtO)2P-(S)SMe was synthesized from (EtO)2P(S)SK by reacting with excess MeI in refluxing methanol.…”