Patent GB-791526-A (GB)
Title: Improvements in or relating to new dimethyl-(phenyl)-phosphates for use as fuel additives
IPC: C07F9/12
Filed: 1955-07-25
Abstract: The invention comprises dimethyl-(phenyl)-phosphates of formula <FORM:0791526/IV (b)/1> wherein X is chlorine or bromine, R, R1 and R11 are alkyl or haloalkyl radicals having 1 or 2 chlorine or bromine atoms, a, b, x, y and z are 0 or 1, at least one being 1, and the total number of carbon atoms in the R groups is not more than 6. The compounds may be prepared by reacting dimethyl phosphoryl chloride with the appropriate sodium phenoxide formed in aqueous solution. The dimethyl phosphoryl chloride may be obtained by reacting dimethyl hydrogen phosphite with chlorine gas.  In examples: (1) dimethyl phosphoryl chloride prepared as described above was added to an aqueous solution of m-cresol in sodium hydroxide to give dimethyl-(m-tolyl)-phosphate; (2) the following compounds were prepared as in (1) using the appropriate substituted phenol:-dimethyl - (p - tolyl) - or - (3 : 5 - dimethylphenyl)- or -(p-ethylphenyl)- or -(m-sec.-butylphenyl)- or -(3 : 5-diethylphenyl)- or -(2 : 4 : 5-trimethylphenyl)- or -(2 : 4-di-n-propyl-phenyl)-or -(2 - methyl - 4 - isopropyl - 5 - ethylphenyl)-or -(o- or m- or p-chlorophenyl)- or -(o-bromophenyl)- or -(monochlorotolyl)- or -(4-chloro-3-methylphenyl)- or -(p-chloromethylphenyl)-phosphates. Further substituted phenol starting materials are specified and an extensive list of the compounds of the invention is given.ALSO:Dimethyl-(phenyl)-phosphates of formula <FORM:0791526/III/1> wherein X is chlorine or bromine, R, R1 and R11 are alkyl or haloalkyl radicals having 1 or 2 chlorine or bromine atoms, a, b, x, y and z are 0 or 1, at least one being 1, and the total number of carbon atoms in the R groups is not more than 6 (see Group IV (b)) are used as additives in liquid fuel compositions and lubricating oils.  Specified fuels are gasoline stocks such as straight run or cracked fuels, or other fuels obtained by reforming, catalytic reforming or alkylation.  When used in fuel compositions the compounds reduce deposit-induced autoignition.  The compounds may be used in fuel compositions together with organolead antiknock agents such as tetramethyl-, tetraethyl-or tetrapropyl-lead, dimethyldiethyl-lead, trimethylethyl-lead, tetraphenyl-lead and triethyl-lead bromide. The fuel compositions may also contain organic halide scavengers such as trichlorobenzene and dibromotoluenes.  The specified additives may be combined as composite additives together with a blending agent such as kerosene, dyes, antioxidants, rust-inhibitors, anti-icing agents, &c.  The compounds may be used as additives to lubricating oils, in particular those have a viscosity from about 30 SUS. at 100 DEG  F. to about 250 SUS. at 210 DEG  F. In examples the following compounds of the invention were added to various gasoline fuel stocks: dimethyl- (o- or m-tolyl)- or -(p-ethylphenyl)- or -(p-chloro- or -bromophenyl)- or -(monochloro-tolyl)- or (3-chloro-2-methyl-phenyl)-phosphate. Other additives specified in the examples are tetraethyl-lead, ethylene dibromide, ethylene dichloride and kerosene.ALSO:Vinyl polymers, e.g. polyvinyl chloride, are plasticized with dimethyl-(phenyl-phosphates of formula: <FORM:0791526/IV (a)/1> wherein X is chlorine or bromine, R, R1 and R11 are alkyl or haloalkyl radicals having 1 or 2 chlorine or bromine atoms, a, b, x, y and z are 0 or 1, at least one being 1, and the total number of carbon atoms in the R groups is not more than 6 (see Group IV (b)).  Many compounds of the above formula such as dimethyl-(m or p-tolyl) - or (3:5 - dimethylphenyl) - or (p-ethylphenyl) - or (m - sec. butyl - phenyl) - or (3:5 - diethylphenyl) - or (2 : 4 : 5 - trimethylphenyl) - or (2 : 4 - di - n - propyl - phenyl) - or (2 - methyl - 4 - isopropyl - 5 - ethylphenyl) - or (o -, m - or p - chlorophenyl) - or (o - bromophenyl) - or (monochlorotolyl) - or (4 - chloro-3 - methylphenyl) - or (p - chloromethylphenyl)-phosphates are specified.