The Synthesis of Organophosphorus Compounds from Phosphine and Alcohols in the Presence of Quinones and Redox Polymers on their Basis

Abstract

<p>This article presents the synthesis of phosphoric acid esters from phosphoric hydrogen РН3 and aliphatic alcohols. The process is based on the oxidation of phosphine by quinones and redox polymers on the basis of mono- and disubstituted quinoid derivatives of monoethanolamine vinyl ether. Molecular iodine is used as a catalyst. Two-, three-, four- and multicomp onent systems are studied in order to determine optimal conditions of the oxidation of phosphine quinones and repoxpolymers on their basis. The rate and selectivity of reaction were monitored by the absorption of РН<sub>3</sub>. As alcohols used aliphatic alcohols: BuOH, PrOH, EtOH, MeOH. Organophosphorus compounds were analyzed by a chromatographic method. It was established that alcohol solutions of individual components of reactionary system (quinones, redox ionites or iodine) are characterized by a low activity in relation to phosphine. Organophosphorus compounds are formed in insignificant quantities. In the mixed alcohol<br /> solution of benzoquinone takes place PH<sub>3</sub> oxidation forming trialkylphosphates. Conversion of phosphine constitutes 80-100%. Increasing the concentration of reagents of catalytic system has a positive effect on the process as a whole. Similar patterns were obtained when redox monomers and polymers on the base of quinones in the presence of iodine were used as oxidants. Esters of phosphoric acid – dialkylphosphites and esters of phosphorous acid – trialkylphosphates were identified as organophosphorus compounds. By selecting a redox agent in a zone of the catalysis it is possible to direct process in the desirable direction. The most activity in the oxidation of phosphine by iodine-alcohol solutions of quinoid monomers and polymers, is exhibited by 2-[N-(2-vinyloxy) ethyl]amino-NQ and polymer on their basis. Results of our experiments and literature data on oxidation-reduction processes with participation of iodine and quinones in organic solutions allowed to propose the separate oxidation-reduction mechanism of formation of organophosphorus compounds. In investigated multicomponent systems, the synergetic effect is manifested which is reached at the expense of distribution of oxidation-reduction functions among iodine, quinones and its derivatives. In this report, for the first time, it is established reactionary ability of quinones and redox ionites on their basis in an oxidizing alkoxylation of phosphine to valuable esters of acids of phosphorus. Reaction can be used for purification of exhaust and technological gases from phosphine and its utilization.</p>