Patent GB-941706-A (GB)
Title: Phosphorus-containing esters and production thereof
IPC: C10L1/30
Filed: 1959-12-15
Abstract: A trivalent phosphorus ester of a hydroxymethyl phosphonate (is defined below) is obtained by reacting (a) a halide or an ester halide of a phosphorus, monothiophosphorous, dithiophosphorous, phosphorous, thiophosphorous, N,N-disubstituted phosphoramidous, N,N-disubstituted phosphoramidous or N,N-disubstituted thiophosphoramidous acid or a halide of a disubstituted phosphinous acid with (b) an aldehyde, a non-cyclic ketone in which at least one of the groups attached to the CO group is a C1-C5-alkyl group, a cycloalkanone, or a b -keto-carboxylic ester and with (c) a neutral ester of phosphorous acid.  The term hydroxymethyl phosphonate is defined as a compound containing a carbon atom which is directly linked to the oxygen atom of an hydroxyl group and to the phosphorus atom of a phosphonate ester grouping said carbon atom having attached thereto one or two hydrogen atoms and/or substituents such as hydrocarbon and heterocyclic groups or may itself form a unit of a cyclic structure.  Suitable reactants for the process are (a) an acid halide of the formula X.P(Y).Z in which X is Cl or Br and each of Y and Z is a Cl or Br atom or an alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkoxy, cycloalkoxy, alkoxyalkoxy, alkenoxy, aroxy, aralkoxy, aroxyalkoxy, alkaroxy, alkathiayl, cycloalkathiayl, arathiayl, alkarathiayl, aralkathiayl, or N,N-disubstituted amino group, or Y and Z together represent an oxyalkyleneoxy or oxyaryleneoxy group, which groups Y and Z may contain one or more halogen substituents, (b) an aldehyde, ketoester or ketone of the formula R1.CO.R2 wherein R1 is a hydrogen atom or an alkyl, carbalkoxymethyl, cycloalkyl, aryl, aralkyl or alkaryl group or a heterocyclic group containing oxygen or sulphur as hetero atom, or an alkenyl or cycloalkenyl group free from a , b -unsaturation, which alkyl, cycloalkyl, aryl, aralkyl, alkaryl or heterocyclic groups may be substituted by halogen, alkoxy, alkathiayl, nitro, cyano, aldehyde, methylene dioxy, hydroxy, carbalkoxy, acylamino or dialkylamino groups, and R2 is a hydrogen atom or a C1-C5-alkyl group and is such alkyl group only when R1 is an alkyl group having one or two carbon atoms or a cyclopropyl group or R1 and R2 taken together with the carbon atom to which both are linked represent a cycloalkylidene group, and (c) a neutral ester of phosphorous acid with an alkanol, a haloalkanol, a haloalkenol, a haloaralkanol, a haloalkoxyalkanol, or a haloaroxyalkanol, at least one molecular proportion of aldehyde, b -keto ester or ketone and of neutral ester being supplied for each halogen atom present in the acid halide. The reaction may be considered to take place in stages depending on the number of halogen atoms in the compound PXYZ  When X alone is halogen the following reaction occurs: <FORM:0941706/C2/1> but if either or both Y and Z are halogen atoms further reaction will occur to give respectively:- <FORM:0941706/C2/2> and <FORM:0941706/C2/3> The invention also includes compounds of the formula <FORM:0941706/C2/4> wherein n is 0, 1 or 2, R is an organic group as defined above for Y and Z, R1 and R2 are as defined above and R3 is an alkyl, haloalkyl, haloalkenyl, haloaralkyl, haloalkoxyalkyl or haloaroxyalkyl group provided that when R is an alkoxy group R3 is a haloalkyl group.  The reaction may be effected by mixing the three reactants at ordinary, increased or decreased temperature and allowing the mixture to stand and may be carried out batchwise or continuously. A diluent or solvent, e.g. benzene, toluene, dioxane, methylene chloride or hexane may be present and a catalyst may also be used.  A large number of suitable reactants of each type is specified and suitable reactants of the formula XP(Y)Z include inter alia esters of the formula <FORM:0941706/C2/5> in which R11 is an alkylene or arylene group having 2 to 6 carbon atoms and X is a halogen atom, and phosphoramidous dihalides in which the nitrogen atom forms part of a heterocyclic ring, e.g. aziridinophosphorous dichloride, 2-methylaziridino-, azetidino-, pyrrolidino-, piperidino-, and morpholino dichloride and the corresponding dibromides. Suitable reactants of the formula R1.CO.R2 include alkanals, substituted alkanals, alicyclic carboxaldehydes, aranals, aralkanals, alkaranals, heterocyclic aldehydes, and keto compounds such as acetone, methyl ethyl ketone, 5-hexen-2-one, methyl cyclopropyl ketone, diethyl ketone, acetophenone, cyclopentanone, cyclohexanone, and ethyl acetoacetate. The neutral esters of phosphorous acid used in the reaction may have like or unlike ester radicals. Particularly suitable for use in the process as reactants (a) and (c) are the equimolecular mixtures of bis(haloalkyl)phosphorohalides and tri(haloalkyl)phosphites obtained by the reaction of two mols of a phosphorus trihalide, e.g. PCl3, with five mols of an alkylene oxide, e.g. ethylene oxide.  Several examples are given and the products are useful as pre-ignition additives for hydrocarbon fuels for spark ignition internal combustion engines (see Division C5).ALSO:A hydrocarbon fuel comprises gasoline, an organo-lead antiknock compound and a gasoline-soluble trivalent phosphorus ester of a hydroxymethyl phosphonate obtainable by reacting (a) a halide or an ester halide of a phosphorous, monothiophosphorous, dithiophosphorous, phosphonous, thiophosphonous, N,N-disubstituted phosphoramidous, N,N-disubstituted phosphonamidous or N,N-disubstituted thiophosphoramidous acid or a halide of a disubstituted phosphinous acid with (b) an aldehyde, a noncyclic ketone in which at least one of the groups attached to the -CO group is an alkyl group having not more than five carbon atoms, a cycloalkanone or a b -keto-carboxylic ester, and with (c) a neutral ester of phosphorous acid (see Division C2). The phosphorous esters may contain numerous substituent groups, e.g. various oxyhydrocarbon groups, halogen, amino, nitro, cyano, aldehyde and hydroxy groups, and various other groups containing oxygen or sulphur atoms as hetero atoms or not as hetero atoms.  A halo-hydrocarbon may also be present in the composition, specified halohydrocarbons being ethylene dibromide, ethylene dichloride, acetylene tetrabromide, a mono- or poly-halo-propane, -butane or -pentane, and a polyhaloalkyl benzene. Specified organo-lead compounds are tetra-ethyl-, tetramethyl-, dimethyldiethyl-, and tetraphenyl lead.  Other conventional additives, e.g. rust-inhibitors, stabilizers, anti-oxidants and dyes may also be present.