GB1527007A - Preparation of organo-phosphine compounds - Google Patents

Abstract

1527007 Preparing substituted organo-phosphines MONSANTO CO 26 Nov 1976 [28 Nov 1975] 49422/76 Heading C2P A substituted organo phosphine is obtained by reacting a monoolefinic compound containing an electro-negative substituent attached to a carbon atom of the double bond with a metal phosphide, using at least one mole of the olefinic compound per mole of the metal phosphide, the metal phosphide being lithium phosphide, sodium phosphide, potassium phosphide, beryllium phosphide, magnesium phosphide, calcium phosphide, strontium phosphide, barium phosphide, boron phosphide, aluminum phosphide, gallium phosphide, or zinc phosphide at a temperature of from - 10‹ C. to 100‹ C. in the presence of an inert gas atmosphere, the reaction being conducted in the presence of a strongly alkaline catalyst, the said catalyst being present in an amount of from 0À01% to 25% by weight based upon the weight of the olefinic compound, and with at least one mole of water being present per mole of the said metal phosphide. Specified olefinic compounds are acrylonitrile, methacrylonitrile, CH 3 -CH = CHCN, 2-cyanobutene-1, vinyl isobutyl ketone, vinyl phenyl ketone, mesityl oxide, diethyl maleate, methyl ethylenesulphonate, nitro ethylene, maleic anhydride dichloromaleic ethyl ester acrylic acid and its sodium salt acrylic esters in which the ester radical is a C 1 -C 10 alkyl group or an aryl or alkaryl group having up to ten carbon atoms. The basic catalyst may be an alkali metal or an oxide, hydroxide, alcoholate or fluoroborate thereof, an alkyl substituted nitrogen base, pyridine, piperidine, a strongly-basic non-metallic quaternary ammonium hydroxide or a strongly-basic quaternary ammonium ionexchange resin. Specified inert gases are H 2 , N 2 , CO 2 and argon. The phosphine products may be mono-, bis- or tris-substituted phosphines depending on the relative proportion of reactants used. The reaction may be carried out in an inert solvent, e.g. acetonitrile, benzonitrile, dioxane, benzene, toluene, hexane or octane. Several examples are given and the products are useful as plasticizers in polyacrylonitrile.