Patent GB-694563-A (GB)
Title: Compositions of matter
IPC: C21D1/58
Filed: 1949-05-09
Abstract: Organic halogen containing phosphorus compounds of the general formula <FORM:0694563/IV (b)/1> where X is oxygen, sulphur, selenium or tellurium, R1 and R2 are metal atoms or non-aromatic organic radicals, and R4 is a non-aromatic organic radical bonded to the phosphorus atom through one of its carbon atoms and containing at least one halogen atom not more than 4 carbon atoms removed from the phosphorus atom or 3 halogen atoms attached to a terminal carbon atom, are prepared by reacting a polyhalogenated organic compound and a compound of the formula <FORM:0694563/IV (b)/2> or <FORM:0694563/IV (b)/3> or <FORM:0694563/IV (b)/4> where R3 is an organic radical attached to X through one of its carbon atoms, R1 and R2 are non-aromatic organic radicals, and X and M have the meanings given above.  In the general formula of the halogen-containing phosphorus compound, R1 and R2 may be for example, methyl, ethyl, butyl, amyl, octyl, stearyl, allyl, oleyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexylethyl, cyclohexylamyl, cyclohexylbutyl, methylcyclohexyl, ethylcyclohexyl, amylcyclohexyl, cetylcyclohexyl, methylcyclohexylamyl, methylcyclohexyllauryl, stearoylethyl, and lauroxyethyl.  The organic radicals R1, R2 and R3 may be substituted by hydroxyl, mercapto, amino, nitro or sulphonic acid groups or halogen atoms.  The metal M may be one of certain metals of Groups I-VIII, a list of which is given.  Polyhalogenated compounds referred to are carbon tetrachloride, chloroform, methylene chloride, carbon tetrabromide, bromoform, methylene bromide, 1-bromo-3-chloropropane, iodoform, methylene chloroiodide, hexachloroethane, di- and trichloroethane, polyhalogenated fatty acids for example, dichloroacetic, trichloroacetic, a ,a -dichloropropionic, a ,a ,b ,b -tetrachloropropionic, a ,b  - dichloropropionic, a ,a  - dichlorobutyric, a ,b  - dichlorobutyric, a ,a ,b  - trichlorobutyric, a ,b  - dichloroisobutyric, dibromoacetic, tribromoacetic, a ,a  - dichloropentanoic, a ,a -dibromopentanoic, diiodoacetic, triiodoacetic, b ,b  - dibromopropionic, and a ,a -dichlorocaprylic acids; and polyhalogenated aldehydes, ketones and ethers such as chloral, bromal, trichlorobutanone, polychloromethyl isobutyl ketone and dichloroethyl ether.  In an example, triethyl phosphite is refluxed with carbon tetrachoride and distilled under reduced pressure to yield diethyl trichloromethane phosphonate.  Di - n - butyl trichloromethane phosphonate, dibutyl 3-chloropropane-1-phosphonate, dibutyl - (2 - chloroethoxy) - 2 - ethane - 1-phosphonate and a product of formula <FORM:0694563/IV (b)/5> may also be prepared similarly.  Diethyl 1,1,3-trichlorononane phosphonate is also referred to.  The Specification as open to inspection under Sect. 91, refers also to the preparation of phosphorus compounds of formula <FORM:0694563/IV (b)/6> by reacting the polyhalogenated compound with a compound of formula <FORM:0694563/IV (b)/7> or <FORM:0694563/IV (b)/8> or <FORM:0694563/IV (b)/9> , where R1, R2, R3, R4 and X have the meanings given above.  This subject-matter does not appear in the accepted Specification.ALSO:A composition comprises a substantially neutral liquid or solid medium and a minor proportion of an organic halogen containing phosphorus compound of formula: <FORM:0694563/III/1> where X is oxygen, sulphur, selenium or tellurium, R1 and R2 are metal atoms or non-aromatic organic radicals, and R4 is a non-aromatic organic radical bonded to the phosphorus atom through one of its carbon atoms, and containing either at least one halogen atom not more than 4 carbon atoms removed from the phosphorus atom or 3 halogen atoms attached to a terminal carbon atom.  R1 and R2 may be, for example, methyl, ethyl, butyl, amyl, octyl, stearyl, allyl, oleyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexylethyl, cyclohexylamyl, cyclohexylbutyl, methylcyclohexyl, ethylcyclohexyl, amylcyclohexyl, cetylcyclohexyl, methylcyclohexylamyl, methylcyclohexyllauryl, stearoylethyl and lauroxylethyl.  The organic radicals R1, R2 and R3 may be substituted by hydroxyl, mercapto, amino, nitro or sulphonic acid groups or halogen atoms.  The metal M in the formula above may be one of certain metals of Groups I-VIII, a list of which is given.  The phosphorus compounds of the invention may be formed by reacting phosphite esters with polyhalogenated compounds such as carbon tetrachloride, chloroform, methylene chloride, carbon tetrabromide, bromoform, methylene bromide, 1-bromo-3-chloropropane, iodoform, methylene chloroiodide, hexachloroethane, di-and tri-chlorethane; polyhalogenated fatty acids for example, dichloroacetic, trichloroacetic, a, a-dichloropropionic, a, a, b , b -tetrachloropropionic, a, b -dichloropropionic, a, a-dichlorobutyric, a, b -dichlorobutyric, a, a, b -trichlorobutyric, a, b -dichloroisobutyric, dibromoacetic, tribromoacetic, a, a-dichloropentanoic, a ,a -dibromopentanoic, diiodacetic, triiodacetic, b , b -dibromopropionic and a, a-dichlorocaprylic acids; and polyhalogenated aldehydes, ketones and ethers such as chloral, bromal, trichlorobutanone, polychloromethyl isobutyl ketone and dichloroethyl ether.  Particular additives referred to are diethyl 1, 1, 3-trichlorononane phosphonate, dibutyl monochloropropane phosphonate, diethyl trichloromethane phosphonate, di-n-butyl trichloromethane phosphonate and dibutyl-(2-chloroethoxy) - 2-ethane - 1 - phosphonate.  The neutral or solid media to which the additives are added are any neutral liquid or solid hydrocarbon or lubricant, for example butanes, pentanes, hexanes, heptanes, octanes, octenes, benzene, toluene, xylene, cumene, indene, hydrindene, alkyl naphthalenes, gasoline, kerosene, fuel oil, gas oil, turbine oil, motor oil, mineral spirits, aromatic solvents, mineral lubricating oils, petrolatum, paraffin waxes and albino bitumen; natural waxes, oils and fats such as carnauba wax, candelilla wax, Japan wax, jojoba oil, sperm oil, tallow, lard oil, olive oil, cottonseed oil, Perilla oil, linseed oil, tung oil, soya bean oil, flaxseed oil and castor oil; synthetic lubricating oils such as polymerized olefins, copolymers of alkylene glycols and alkylene oxides, organic esters, for example, di (2-ethyl-hexyl) sebacate, allyl laurate and polymers thereof, dioctyl phthalate and trioctyl phosphate, polymeric tetrahydro furan and polyalkyl silicon polymers; esters of carboxylic acids such as ethyl, propyl, butyl, amyl, octyl, stearyl, oleyl, phenyl and cresyl laurates, myristates palmitates, stearates, oleates, ricinoleates, phthalates and salicylates; petroleum resins and rosin; and water and water-in-oil and oil-in-water emulsions.  Optional additives referred to and corrosion inhibitors, examples of which include oil-soluble detergents, anti-oxidants are given.  The Specification as open to inspection under Sect. 91 refers also to phosphorus compounds of formula <FORM:0694563/III/2> , where R1, R2, R4 and X have the meanings given above.  This subject-matter does not appear in the accepted Specification.ALSO:A composition comprises albino bitumen and a minor proportion of an organic halogen containing phosphorous compound of formula:- <FORM:0694563/V/1> where X is oxygen, sulphur, selenium or tellurium, R1 and R2 are metal atoms or non-aromatic organic radicals, and R4 is a non-aromatic organic radical bonded to the phosphorus atom through one of its carbon atoms, and containing either at least one halogen atom not more than 4 carbon atoms removed from the phosphorus atom or 3 halogen atoms attached to a terminal carbon atom.  R1 and R2 may be, for example, methyl, ethyl, butyl, amyl, octyl, stearyl, allyl, oleyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexylethyl, cyclohexylamyl, cyclohexylbutyl, methylcyclohexyl, ethylcyclohexyl, amylcyclohexyl, cetylcyclohexyl, methylcyclohexylamyl, methylcyclohexyllauryl, stearoylethyl and lauroxylethyl.  The organic radicals R1, R2 may be substituted by hydroxyl, mercapto, amino, nitro or sulphonic acid groups or halogen atoms.  The metal M in the formula above may be one of certain metals of Groups I-VIII, a list of which is given. Optional additives referred to include oil-soluble detergents, anti-oxidants and corrosion inhibitors, examples of which are given.  The Specification as open to inspection under Sect. 91, refers also to phosphorus compounds of formula <FORM:0694563/V/2> where R1, R2, R4 and X have the meanings given above.  This subject-matter does not appear in the Specification as accepted.