Patent GB-792595-A (GB)
Title: New organic compounds containing nitrogen and phosphorus and their manufacture
IPC: C07F9/40
Filed: 1955-03-04
Abstract: The invention comprises compounds of the general formula: <FORM:0792595/IV (b)/1> in which R, R2, R3 and R4 each represent hydrogen or an organic radical, at least one of R2 and R3 being an organic radical, R1 is the residue of an alcohol, R5 is the residue of an alcohol different from that of R1, and -N(R3)(R2) may also represent the ring structure of morpholine or piperidine, and salts and quaternary ammonium salts of the compounds.  The compounds may be obtained by reacting an asymmetrical phosphite ester of the formula (R1O)(R5O)P(O).H with (a) an aldehyde or ketone of the formula (R)(R4)CO and an amine of the formula (R3)(R2)NH, or (b) an a -alkylolamine of the formula: <FORM:0792595/IV (b)/2> or (c) an alkylidene diamine of the formula: <FORM:0792595/IV (b)/3> or (d) an N-disubstituted aminomethyl ether of the formula (R2)(R3)N.CH2.O.CH3 or (e) an aldimine or ketimine of the formula (R)(R4)C = N.R2, methods (c) and (d) being applicable only to the production of compounds in which R4 and R are hydrogen, and method (e) being applicable only to the production of compounds in which R3 is hydrogen. If desired, the resulting product is converted into a salt or, when it contains a tertiary amino group, is quaternated.  The residue R1 may be aliphatic or cycloaliphatic, e.g. methyl, ethyl or propyl, and the residue R5 may be aliphatic, cycloaliphatic, araliphatic or heterocyclic, examples of the residue R5 being ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylbutyl, actyl, 2-butyloctyl, dodecyl, octadecenyl, octadecyl, allyl, 2-chlorethyl, benzyl, cyclohexyl and tetrahydrofurfuryl groups.  R5 may also be a radical containing thiocyano, cyano or ether groups or halogen atoms. The preferred dialkyl phosphite starting materials are those in which R1 is the residue of a C1-C4 aliphatic alcohol and R5 is the residue of a C8-C30 aliphatic alcohol.  Specified aldehydes or ketones of the formula (R)(R4)CO are formaldehyde, acetaldehyde, propionaldehyde, acetone, methyl ethyl ketone, benzaldehyde, substituted benzaldehydes, acetophenone and furfural.  Specified amines of the formula (R2)(R3)NH are dimethyl, diethyl, diisopropyl, dibutyl and dicyclohexyl amines, methylamine, ethylamine, butylamine, aniline, p-anisidine, N-ethylaniline, b -phenyl ethylamine, morpholine and piperidine.  The compounds used in methods (b) to (e) may be derived from the above mentioned aldehydes or ketones and amines.  Reactions (a) and (b) may be carried out without solvents and are preferably effected at 40-100 DEG  C.  Specified agents which may be used to quaternate the products when they contain a tertiary amino group are methyl iodide, ethyl bromide, isopropyl chloride, secondary butyl bromide, dodecyl bromide, epichlorhydrin, dimethylsulphate, benzyl halides and benzyl halides substituted by halogen atoms or by alkyl or alkoxy groups, e.g. benzyl chloride and p-chlorobenzyl chloride, mennaphthyl chloride, toluene sulphonic acid esters, e.g. the methyl ester, halogen alkyl or halogenaralkylsulphonic acids, e.g. bromethane sulphonic acid and benzyl chloride disulphonic acid.  When salts of tertiary amines are used alkylene oxides such as ethylene oxide, propylene oxide or glycide may be used to effect quaternation. The quaternation may be carried out by heating the components at raised temperature, e.g. 50-200 DEG  C., if desired, under pressure and an inert solvent may be present.  In examples: (1) the compound of the formula (C12H25O)(C2H5O) P.(O)CH2.N(CH3)2 is obtained by reacting formaldehyde with dodecyl ethyl phosphite and an alcoholic solution of dimethylamine at 50-60 DEG  C.; (2) the product of (1) is quaternated by treatment with dimethyl sulphate in solution in ether. Benzyl chloride may be used instead of dimethylsulphate to effect the quaternation.  The products are stated to be useful as pest control agents, as assistants in the textile, leather or paper industries, e.g. as washing, wetting or foaming agents, and as additives to paints or lubricants.  They can also be used as emulsifying or dispersing agents.