Polytertiary Phosphines and Arsines. I. The Synthesis of Polytertiary Phosphines and Arsines by the Base-Catalyzed Addition of Phosphorus-Hydrogen and Arsenic-Hydrogen Bonds to Vinylphosphines

Abstract

Novel polytertiary phosphines and phosphine-arsines can be prepared by the addition of phosphorus-hydrogen and arsenic-hydrogen bonds across the carbon-carbon double bonds of vinylphosphines in the presence of a base catalyst such as phenyllithium or potassium tert-butoxide. Thus the reaction between diphenylphosphine and diphenylvinylphosphine gives (C6H5)2PCH2CH2P(C6H5)2. The tritertiary phosphine [(C6H5)2PCH2CH2]2PC6H5 can be prepared either by the reaction between phenylphosphine and diphenylvinylphosphine or by the reaction between diphenylphosphine and phenyldivinylphosphine. The tripod tetratertiary phosphine [(C6H5)2PCH2CH2]3P can be prepared either by the reaction between phosphine and diphenylvinylphosphine or the reaction between diphenylphosphine and trivinylphosphine. The linear tetratertiary phosphine (C6H5)2PCH2CH2P(C6H5)CH2CH2P-(C6H5)CH2CH2P(C6H5)2 can be prepared by the reaction between 1,2-bis(phenylphosphino)ethane and diphenylvinylphosphine. The hexatertiary phosphine [(C6H5)2PCH2CH2]2PCH2CH2P[CH2CH2P(C6H5)2]2 can be prepared by the reaction between H2PCH2CH2PH2 and diphenylvinylphosphine. The phosphine-arsine (C6H5)2PCH2CH2-As(C6H5)2 can be prepared by the reaction between diphenylarsine and diphenylvinylphosphine. The phosphine-diarsine C6H5P[CH2CH2As(C6H5)2]2 can be prepared by the reaction between diphenylarsine and phenyldivinylphosphine. Similar addition of phosphorus-hydrogen bonds across the carbon-carbon triple bond of ethynylphosphines gives olefinic ditertiary phosphines with the phosphorus atoms in trans positions, as exemplified by the reaction between diphenylphosphine and diphenylethynylphosphine to give the known trans-(C6H5)2PCH= CHP(C6H5)2. The reaction between diphenylarsine and diphenylethynylphosphine gives the olefinic phosphine-arsine trans-(C6H5)2PCH=CHAs(C6H5)2. The infrared, proton, and 31P nmr spectra and the mass spectra of the new polytertiary phosphines and phosphine-arsines are discussed. © 1971, American Chemical Society. All rights reserved.