Patent GB-893303-A (GB)
Title: Preignition additives for motor fuels
Inventor: WAGNER ROSS I
IPC: C07F9/02
Filed: 1960-07-21
Abstract: A motor fuel contains, as a pre-ignition additive, a small amount of at least one phosphine borine or phosphinoborine having an organic substituent linked to phosphorus.  The additive may be of any of the general formulae <FORM:0893303/III/1> (wherein R is hydrogen, C1 to C12-alkyl, phenyl, tolyl, or halo-substituted phenyl, at least one R being a hydrocarbon radical, R1 is fluorine, chlorine, bromine, C1 to C8 alkyl or hydrogen, R11 is hydrogen or C1 to C8-alkyl, R111 is alkylene of 1 to 5 carbon atoms, n is 0 or 1, m is 0 or 1 when n is 1, and 3 when n is 0, a is 3 to 6 and b is 3 or 4; [RR1 PBH2] n[R11 PBH]m wherein the R symbols may be alkyl, phenyl, cycloalkyl, biphenyl, naphthyl, or C1-C8-alkyl-substituted phenyl, and n and m are integers indicating degree of polymerization; or R3P:BX2R1X2B:PR3 wherein X is F, Br, or Cl, R is H or C1-C8-alkyl and R1 is C1 to C5-alkylene.  Many examples of each type are given.  The fuels may also contain tetraethyl lead, tetramethyl lead, iron carbonyl, dicyclopentadienyl iron, xylidine, N-methyl-aniline, ethylene dichloride, dyes, tri-cresyl phosphate, dimethyl xylyl phosphate, diphenyl cresyl phosphate, lower alkyl phosphates and phosphites, other boron compounds, N-N1-di-sec-butyl-p-phenylene diamine. N-n-butyl-p-amino-phenol, 2, 6-di-tert-butyl-4-methyl-phenol, N, N1-disalicylal-1, 2-propane-diamine, polymerized linoleic acid and N, C-disubstituted imidazolines.  Methyl cyclopentadienyl manganese tricarbonyl may replace the lead alkyl compound.ALSO:Phosphine-borines of the general formula H2RP : BX3 where R represents a hydrocarbon group and X is halogen or hydrogen, at least one of the X symbols representing halogen, are prepared by reacting a primary phosphine of the general formula H2RP and a boron trihalide or halogenated boron.  The reaction may take place within the temperature range -110 DEG C. to 50 DEG C.  Phosphine-borines having three alkyl radicals or two alkyl and one aryl radical bonded to phosphorus and at least one alkyl or aryl radical and at least one halogen bonded to boron, such materials having the general formula R3P : BR1YX, where Y is chlorine, bromine or lower alkyl and X is chlorine or bromine, are produced by adding to a halogenated borine of the formula BR1YX an equimolar quantity of a tertiary phosphine. This reaction may take place between -110 DEG C. and 30 DEG C. Preparation of phosphine borines of the general formula R3P : BX3 where R is alkyl or aryl of higher molecular weight is effected by by adding to a boron trihalide an equimolar quantity of a tertiary phosphine, the temperature range being as in the previous case. Compounds having the formula R3P : BR3 wherein the hydrocarbon radicals are of relatively large molecular weight may be prepared by reacting a tertiary borine with a tertiary phosphine. Phosphinoborines having the general formula (HRPBR1R11)n wherein R is hydrogen, alkyl, cycloalkyl or aryl and wherein R1 and R11 are hydrogen, alkyl or aryl, at least one of R, R1 and R11 prepresenting a constituent other than halogen, and wherein n is an integer indicative of the degree of polymerization may be prepared by first preforming a phosphinoborine by the reaction of a primary phosphine of the formula H2RP and a partially halogenated borine or borane of the formula BR1R11X, the resultant phosphinoborine of the formula RH2P : BR1R11X being then reacted with an equimolar quantity of a tertiary amine, which latter reaction may be carried out in a solvent such as diethyl ether at a temperature between 10 DEG C. and 30 DEG C.  Phosphinoborine polymers of the general formula (RR1PBXY)n wherein n is 3 or 4, R and R1 are aliphatic or aromatic radicals and X and Y are chlorine, bromine, iodine, hydrogen or alkyl, at least one of X and Y representing one of the halogens, may be prepared from the corresponding phosphine borines by dehydrohalogenating the corresponding phosphine borine by means of a tertiary amine.  The phosphine borine precursor is prepared by allowing a primary or secondary phosphine to react with a halogenated borine or a borine trihalide at 20 DEG C.-30 DEG C.  Phosphinoborine copolymers of the general formula (RR1PBH2)n(R11PBH)m where n and m are integers indicative of the degree of polymerization and each of the R symbols is either alkyl, phenyl, cycloalkyl, biphenyl, naphthyl or lower alkyl (C1 to C8)-substituted phenyl, and in which the ratio of n to m is no greater than 6 to 1, are prepared by the pyrolysis of a mixture of a primary phosphine borine addition compound such as phosphine borine of the formula R11H2P : BH3, e.g. methyl phosphine borine (CH3)H2P : BH3 and a secondary phosphine borine of the formula RR1HP : BH3, e.g. dimethyl phosphine borine, (CH3)2HP : BH3. Preferred of this class of copolymer are [(CH3)2PBH2]4[CH3PBH] and [(CH3)2PBH2]5[CH3PBH].  The pyrolysis may be carried out under reflux in the absence of a solvent or in a refluxing solvent having a high boiling point such as n-butyl ether.  All the compounds so prepared may be used as additives to motor fuels such as gasoline (see Group III).