Patent GB-767018-A (GB)
Title: Improvements in or relating to liquid hydrocarbon fuels and additives therefor
IPC: C07F9/09
Filed: 1953-12-22
Abstract: Neutral chloro-, bromo- or chlorobromoalkyl esters of monomeric acids of pentavalent phosphorus are employed as ingredients of internal combustion engine fuels or of additives therefor (see Group III). The esters may have the general formula: <FORM:0767018/IV(b)/1> wherein Z1, Z2, Z3 and Z4 are chosen from oxygen and sulphur and may be the same or different, and R1, R2, and R3 are chosen from halo-substituted alkyl, halo-substituted cycloaliphatic-substituted alkyl and halo-substituted aralkyl and may be the same or different, the halogen in each case being chosen from chlorine and bromine. R1, R2 and R3 may each have 1-3 halogen substituents.  A list of suitable esters is given.  They may be prepared by reaction btween a phosphorus oxyhalide or thiohalide and an epoxide, cyclic sulphide, halo-alcohol or halomercaptan. Alternatively, an alkylene oxide or cyclic sulphide or mixture thereof may be reacted first with a phosphorus trihalide and then with elemental sulphur.  In the examples, (1) propylene oxide is reacted with thiophosphoryl chloride in the presence of titanium tetrachloride to produce tris-(2-chloropropyl) thionophosphate and (2 and 3) propylene oxide or ethylene oxide is reacted first with phosphorus trichloride and then with elemental sulphur to produce tris-(2-chloropropyl)- or -(2-chloroethyl)-thionophosphate.ALSO:Sparking plug fouling and deposit-induced autoignition is prevented in internal combustion engines of the spark-ignition type by employing a fuel comprising hydrocarbons of the gasoline boiling range to which has been added a composition comprising an organolead antiknock agent and a neutral chloro-, bromo- or chlorobromoalkyl ester of a monomeric acid of pentavalent phosphorus, the proportion of the ester being such as to provide about 0.05 to about 0.50 theories of phosphorus.  A theory of phosphorus is defined as the amount of phosphorous theoretically required to react with the lead to form lead orthophosphate, which quantity is two atoms of phosphorus per three atoms of lead. Organolead anti-knock agents mentioned are tetraphenyl, tetramethyl, tetraethyl, tetrapropyl, tetrabutyl, dimethyl diethyl and methyl triethyl lead.  The phosphorus esters may have the general formula <FORM:0767018/III/1> wherein Z1, Z2, Z3 and Z4 are chosen from oxygen and sulphur and may be the same or different, and R1, R2 and R3 are chosen from halo-substituted alkyl, halo-substituted cycloaliphatic-substituted alkyl and halo-substituted aralkyl and may be the same or different, the halogen in each case being chosen from chlorine and bromine R1, R2 and R3 may each have 1-3 halogen substituents.  A list of suitable esters is given.  The engine fuel may be straight run gasoline or gasoline obtained by thermal or catalytic cracking, reforming or platforming operations. Halogen scavengers (e.g. ethylenedichloride and dibromide), dyes, diluents, antioxidants, metal deactivators and solubilizers may also be added, for example to the composition added to the fuel. In the examples the organolead anti-knock agent is tetraethyl lead, while the phosphorus ester is tris-(2-chloro-ethyl)- or -(2-chloropropyl-, phosphate or thionophosphate.