Verfahren zur Herstellung von Hydroxymethylphosphinen

摘要

Hydroxymethylphosphines of formula RxR1yP(CH2OH)3-,(x+y) where R and R1 are substituted or unsubstituted C1-20 alkyl, C1-20 alkenyl, cycloalkyl, cycloalkenyl or phenyl groups, and x and y are 0 or 1 are added to gasoline to protect against misfiring and surface ignition. Up to about 10 ml. of phosphine per gallon of gasoline may be used. Reference has been directed by the Comptroller to Specification 871,190.ALSO:Hydroxymethylphosphines of formula RxR1yP(CH2OH)3-(x+y) II and hydroxymethpylphosphonium halides of formula where R and R1 are substituted or unsubstituted C1-20 alkyl, C1-20 alkenyl, cycloalkyl, cycloalkenyl or phenyl groups, R11 is C1-20 alkyl, X is halogen, and x and y are 0 or 1, are prepared by reacting a hydroxymethyl phosphonium salt of formula where A is a mineral acid anion with substantially no greater than a stoichiometric amount of base based on the phosphonium salt being present during the reaction in the presence of water and/or a lower aliphatic alcohol and, if desired, reacting the resulting phosphine (II) with a C1-20 alkyl halide to give III. The temperature may be from -20 to +100 DEG C. The base may be an alkali metal or alkaline earth metal base or a tertiary amine. The invention also comprises as novel compounds those compounds of formula II in which x + y = 1 or 2, and also compounds of formula [RR11P(CH2OH)2]+X-Many compounds of formulae II and III are prepared including compounds contain-hydroxy, alkoxy, halogen or nitrile substituents in "R" groups. The hydroxymethylphosphines are used as gasoline additives (see Group III). Tris (hydroxymethyl) phenylphosphonium chloride, bis (hydroxymethyl) diphenylphosphonium chloride, bis (4-chlorophenyl)-bis (hydroxymethyl) phosphonium bromide, bis (4-butoxyphenyl)-bis (hydroxymethyl) phosphonium iodide and tris(hydroxymethyl)-4-methylphenylphosphonium chloride are prepared from appropriate hydrogen halides, phenyl- or diphenyl-phosphines and formaldehyde. An adduct is prepared from tris(hydroxymethyl)-phosphine and benzoquinone. Reference has been directed by the Comptroller to Specification 871,190.