Patent GB-842593-A (GB)
Title: Substituted organic phosphine derivatives
Inventor: COATES HAROLD
IPC: C07F9/54
Filed: 1955-07-19
Abstract: Polymeric products are obtained by the reaction of compounds containing a reactive hydrogen atom with a substituted phosphine of the formula: P(CH2NR1R11)n-1 R4-n where R, R1 and R11 are alkyl, cycloalkyl aralkyl, aryl or heterocyclic radicals and R11 may additionally be hydrogen, or R1 R11 and N together constitute a heterocyclic radical, and n is 2, 3 or 4.  The amine NHR1R11 is eliminated and products containing carbon-phosphorus linkages are obtained.  In examples, products are obtained by the reaction of tris-diethylamino-methylphosphine with p-cresol, hydroquinone, diphenylolpropane or p-cresol followed by hydroquinone; of tris-di-n-butylaminomethylphosphine with diphenylolpropane; and of tris-morpholinomethylphorphine with hydroquinone.  The product from tris-diethylaminomethylphosphine and diphenylolpropane is treated with hydrogen peroxide to give, presumably, the corresponding phosphine oxide.  Specification 761,985 is referred to.ALSO:The invention comprises phosphine derivatives of formula: P(CH2NR1R11)n-1,R4-n where n is 2, 3 or 4, R1 is an alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical, R1 is an alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical and R11 is an alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical or hydrogen or R1 and R11 form a heterocyclic ring with the nitrogen atom to which they are attached.  They are prepared by reacting a hydroxymethyl phosphonium salt X-.P+(CH2OH)n , R4-n where X is the cation of an acid, and a primary or secondary amine NHR1R11.  Either the amine is used in stoichiometric excess or one mole of amine is replaced by an organic tertiary or inorganic base.  An inert atmosphere and inert solvent may be used.  Preferably a molar ratio of amine to phosphonium salt of 4:1 or more is used.  The products may be used as starting materials in the production of flameproof plastics, surface coatings, flameproof textiles and insecticides. The phosphine products will react with compounds containing a reactive hydrogen atom with the elimination of HNR1R11 to give compounds containing carbon-phosphorus linkages.  Suitable reactive hydrogen compounds include ethyl acetoacetate, dialkyl phosphites, hydroquinone, p-cresol, phenol and diphenylol propane. The products of such reactions may be used in connection with the preparation of insecticides, hydraulic fluids, lubricant additives, plastics (see Group IV(a)) plasticisers and surface-active agents.  The phosphines may also be converted to the corresponding phosphine oxides and sulphides.  The former may be obtained by the direct action of oxygen or by the action of p  hydrogen peroxide on an aqueous suspension of the phosphine and the latter by treatment with sulphur with or without an inert solvent.  Examples describe the preparation of tri-diethylaminomethyl-phosphine (TDEP), tris-di-n-butylaminomethyl-phosphine, tris-morpholinomethylphosphine, trisdiethylaminomethylphosphine oxide (by the action of H2O2 on TDEP), P(CH2CH(COCH3) COOC2H5)3 and ((C2H5)2NCH2) 2 P,CH2CH (COCH3) - COOC2H5, which is converted to the oxide with H2O2, from TDEP and ethyl acetoacetate, ((C2H5)2NCH2)2 PCH2PO (OEt)2 from TDEP and diethyl phosphite and a compound from TDEP and p-cresol. Specification 761,985 is referred to.