Patent GB-913574-A (GB)
Title: Process for the manufacture of organic phosphine derivatives
IPC: C07F9/50
Filed: 1959-05-14
Abstract: Organic phosphine derivatives are obtained by reacting 3 molecular proportions of an aliphatic aldehyde which contains 2 to 8 carbon atoms and is saturated or contains a single olefinic bond or is halogen-substituted, or a mixture of two or more of such aldehydes with 1 molecular proportion of phosphine in the presence of a catalytic proportion of a finely divided or dissolved compound of a metal of Group IB, IIB or VIII of the Periodic Table which compound is capable of reacting with phosphine, and/or of a reaction product of such metal compound with phosphine.  The reaction is advantageously carried out in the presence of water or a water-soluble organic solvent, e.g. ethanol, dioxane or acetonitrile, at temperatures between -10 DEG C. and +40 DEG C. with vigorous stirring and may be carried out under super-atmospheric pressure. The initial pH is generally between 4 and 9 and is about 7 at the end of the reaction.  Specified catalysts include the water-soluble hydroxides of copper, silver, gold, zinc, cadmium, mercury, iron, cobalt, nickel, ruthenium, rhodium, p  palladium, osmium, iridium or platinum, and salts of such metals with organic or inorganic acids, e.g. phosphoric, nitrous, chloric, perchloric, hydrohalic, sulphuric, nitric, formic, acetic, benzoic, salicyclic, alkyl or aryl sulphonic, lactic, and oxalic acids; also complex or double salts of the above metals and acids may be used.  The cadmium and platinum salts are especially suitable, especially the chlorides.  The products are oily, wax-like or solid substances and probably comprise tris(hydroxy alkyl)phosphines.  They can generally be characterized by formation of their mercuric chloride addition products and by oxidation to the corresponding phosphine oxides.  Examples are given for the production of: (1) tris-(a -hydroxyethyl) phosphine from acetaldehyde using isopropanol as solvent and platinum (IV) chloride as catalyst, or by using water as solvent and potassium platinum (II) cyanide, palladium (II) chloride, or cadmium chloride as catalyst, addition of acrolein to the product in aqueous solution yields a phosphonium base of the formula:- <FORM:0913574/IV (b)/1> (2) a resinous phosphorus compound and a compound having the empirical formula C32H50O9P from crotonaldehydes in the presence of water, ethanol, or isopropanol and of platinum (IV) chloride as catalyst; (3) an oily product which solidifies on standing, from chloracetaldehyde in aqueous solution in the presence of platinum (IV) chloride, the product being converted to its mercuric chloride addition product or to a water-insoluble phosphine oxide by reacting with hydrogen peroxide in alcoholic solution; other catalysts which may be used in this reaction include cadmium-sulphate, -hydroxide or -carbonate, a mixture of silver phosphate and platinum (IV) chloride and a preformed reaction product of phosphine and cadmium chloride; (4) tris-(a -hydroxy-butyl)-phosphine from butyraldehyde dissolved in acetonitrile or dioxane and in the presence of platinum (IV) chloride, the product being oxidised to the corresponding oxide by treatment with H2O2 in alcoholic solution; other aldehydes which yield analogous products are 2,2,3-trichlorobutyraldehyde 2-ethyl hexanal, 2-ethyl-hexenal, propionaldehyde and isovaleric aldehyde; (5) a product having the structure P[CHOHCH(OH)2]3 from an aqueous neutralised solution of glyoxal in the presence of platinum (IV) chloride or sodium platinum (IV) chloride.  Other aldehyde starting materials specified include glutaric aldehyde, glycerine aldehyde, oxo-aldehydes, mono-bromo- and mono-iodo-acetaldehyde, chloral, and chloral hydrate.  The products are useful as insecticides, additives to fuels and lubricants, and as intermediates in the manufacture of insecticides or such additives.