Patent GB-881656-A (GB)
Title: Manufacture of quaternary organic phosphorus compounds
IPC: D06M13/285
Filed: 1958-01-30
Abstract: Quaternary organic phosphorus compounds are obtained by reacting tri-(hydroxymethyl) phosphine with a quaternating agent. The invention also comprises quaternary phosphonium compounds of the general formula: <FORM:0881656/IV (b)/1> wherein R is an unsubstituted, substituted or unsaturated aliphatic radical free from ether groups, which contains at least two carbon atoms and which may carry one negative charge, n is a whole number and m is zero or an integer equal to n or (n-1) and when m is equal to (n-1) or zero the radical R carries one negative charge, and X is a monovalent anion or the electrically equivalent fraction of a polyvalent anion.  The quatenating agent used in the process may be an alkyl, alkylene, alkenyl or aralkyl halide, e.g. methyl chloride or iodide, ethyl bromide, amyl iodide, ethylene bromide or benzyl chloride; tris(chloromethyl) phosphine oxide, benzoic acid methyl ester, p-toluene sulphonic acid methyl or butyl ester, dimethyl sulphate, chloracetamide; an aldehyde in which case the reaction is advantageously carried out in the presence of an acid or water, suitable aldehydes being formaldehyde including its polymeric forms, acetaldehyde, acrolein, crotonaldehyde, glyoxal, chloroacetaldehyde, benzaldehyde, p-chlorobenzaldehyde and furfural; alkylene oxides if desired in the presence of water and/or an organic water-miscible solvent and/or an acid, specified alkylene oxides being ethylene oxide, epichlorohydrin, glycide, propylene oxide, styrene oxide and polyepoxides, e.g. triglycide cyanurate; aliphatic a  : b unsaturated carboxylic acids and their esters or amides, e.g. acrylic acid and its methyl, butyl, dodecyl, phenyl and nitrophenyl esters, acrylamide, acrylic acidanilide and -methylamide, the methyl ether of arylic acid methylolamide, methyl methacrylate, crotonic acid and its amide and tri-acrylamide formal.  Suitable acids in which the reaction may be carried out include hydrochloric and sulphuric acids, acetic acid, benzoic acid, oxalic acid, benzene sulphonic (or sulphuric) acid and cyclohexane phosphonic acid.  The reaction may also be carried out in an inert diluent or solvent, e.g. a C1-C6 alcohol or ketone, dimethyl formamide or acetonitrile.  The quaternary phosphorus compounds obtained by the process probably contain in the phosphonium ion in addition to the original three hydroxymethyl groups the organic residue of the quaternating agent bound directly to phosphorus.  When aldehyde or alkylene oxides are used the products probably contain in the phosphonium ion in addition to the original hydroxymethyl groups the aldehyde or alkylene oxide used in carbon-phosphorus linkage with formation of an OH group in the a  or b  position, respectively, and the anion is an acid residue when the reaction is carried out in the presence of an acid or is an hydroxyl group when the reaction is carried out in the absence of an acid but in the presence of water.  When an aliphatic a  : b unsaturated carboxylic acid or ester or amide thereof is used the phosphonium ion probably contains in addition to the hydroxymethyl groups the vinyl compound used in carbon-phosphorus linkage in the form of a saturated organic residue the anion being an acid group if the reaction is carried out in the presence of an acid or being a hydroxyl group if the reaction is carried out in the absence of an acid but in the presence of water.  When the free a  : b  carboxylic acids are used the products are probably phosphonium betaines.  When epichlorohydrin is used the tris-(hydroxymethyl) phosphine is quaternated with the opening of the oxido ring and on further heating all the chloride is converted to ionic form to yield a bis (quaternary phosphorus) monochloride which on treatment with 20% HCl yields a bis-phosphonium dichloride of the probable structure (HOCH2)3 P(Cl)CH2CH(OH)CH2(Cl)P(CH2OH)3. Paraformaldehyde yields tetra(hydroxymethyl) phosphine in yield form.  Several examples are given and the products are useful as flame-proofing agents for wood or textiles (see Group VIII) and as insecticides.  Specification 871,190 is referred to.