Reaction of 3-aminopropyltriethoxysilane with triphenylphosphate

Abstract

Interaction of 3-aminopropyltriethoxysilane RNH 2 [R = (EtO) IntroductionMolecules of triethoxysilylpropylamidophosphates (EtO) 3 SiCH 2 CH 2 CH 2 NRP(O)X 2 (R = H, All; X = OR, NR 2 ) contain the easily hydrolyzed group (EtO) 3 Si and the amidophosphate fragment NRP(O)X 2 , which can form coordination compounds with d-and f-elements. Ability of sol-gel polymerization and forming coordination compounds offers a way to obtain metal-containing gels, films [1], transparent glasses [2] on their basis. Target syntheses of such compounds are based on the reaction of 3-aminoprolyltriethoxysilane (EtO) 3 SiCH 2 CH 2 CH 2 NН 2 (APTES) with the derivatives of phosphorous oxychloride ClP(O)X 2 (X = OPh, NR 2 ). Organic bases (triethylamine, pyridine) are used as acceptors of the evolving hydrogen chloride. Voluminous precipitates of triethylamine or pyridine hydrochlorides, produced in this reaction, badly thicken the reaction mixtures and demand great amounts of solvents, which need to be carefully dewatered, as the initial compounds and the products are hydrolytically unstable. In this context finding a more convenient method of obtaining alkoxysilyl derivatives of amidophosphates seems an urgent problem. The alternative way of synthesis involves the reaction of two industrial products: APTES and triorganophosphates (RO) 3 P=O, which can lead to substitution of RO groups at the phosphorus atom and production of alcohol. Nevertheless, in recently performed study [3] it has been shown that interaction of APTES with trimethylphosphate (МеО) 3 Р=О (TMP) leads to release of ethyl (not methyl) alcohol in the first stage and production of organophosphosilicates. Replacement of methyl groups in triorganophosphate by phenyl ones has led to cardinal change of the process direction, so that release of phenol and production of silicon-containing amidophosphate oligomers has been observed. In the present paper the results in investigating APTES interaction with triphenylphosphate (PhО) 3 Р=О (TPP) are described, the comparison of the related reactions is carried out, and the explanation of possible causes for different behavior of two structurally similar compounds (PhO) 3 P=O and (МеO) 3 P=O is suggested.

Hybrid Organic-Inorganic Compounds, Obtained by the Sol-Gel Method from Organoalcoxysilanes and Metal Complexes

“…Целевые синтезы такого рода соединений основываются на реакции АПТЭС с производными хлорокиси фосфора ClP(O)X 2 (X = OPh, NR 2 ). Альтернативный способ синтеза [85] заключается в проведении реакции двух промышленных продуктов -АПТЭС и триорганофосфатов (RO) 3 P=O, которая может приводить к замещению RO групп у атома фосфора и выделению спирта. Однако в работе [86] было показано, что взаимодействие АПТЭС с триметилфосфатом (МеО) 3 Р=О приводит к выделению на первой стадии не метилового, а этилового спирта и образованию органофосфосиликатов.…”