Patent GB-878828-A (GB)
Title: Arylmercaptan substituted aliphatic halides and derivatives thereof
IPC: C07B45/00
Filed: 1958-02-21
Abstract: Rubber latex contains as preservative compound of the formula: <FORM:0878828/IV (a)/1> in which each of R and R1 is a hydrogen atom or a hydrocarbon free from aliphatic unsaturation containing 1-6 carbon atoms at least one of R and R1 being a hydrogen atom, X is a nitrile group or a group of the general formula -COY in which Y is a hydrogen atom, an amino group or a hydrocarbon group free from aliphatic unsaturation containing 1-6 carbon atoms, Hal is a halogen having an atomic number of at least 17 and Ar is an aromatic group containing 6-12 carbon atoms and which may include nuclear halogen, alkyl or haloalkyl substituents or a compound of the formula: <FORM:0878828/IV (a)/2> in which R is a hydrocarbon group free from aliphatic unsaturation and containing 1-6 carbon atoms, Hal is halogen having an atomic number of at least 17 and Ar is a halogenated aromatic group containing carbon atoms (see Group IV(b)). Specification 785,133 is referred to.ALSO:The invention comprises aryl mercapto compounds having the general formulae: <FORM:0878828/IV (b)/1> in which R is a hydrogen atom or a hydrocarbon group free from aliphatic unsaturation and containing 1-6 carbon atoms, R1 is a hydrogen atom or hydrocarbon group free from aliphatic unsaturation and containing 1-6 carbon atoms, at least one of R and R1 being a hydrogen atom, X is a nitrile group or a group of the general formula -COY in which Y is a hydrogen atom, an amino group or a hydrocarbon group free from aliphatic unsaturation and containing 1-6 carbon atoms.  Hal is a halogen having an atomic number of at least 17 and Ar is an aromatic group containing 6-12 carbon atoms which may include halogen, alkyl or haloalkyl substituents; <FORM:0878828/IV (b)/2> in which R is a hydrocarbon group free from aliphatic unsaturation and containing 1-6 carbon atoms, Hal is a halogen having an atomic number of at least 17 and Ar is a halogenated aromatic group containing 6-12 carbon atoms and <FORM:0878828/IV (b)/3> in which R is a hydrocarbon group free from aliphatic unsaturation and containing 1-6 carbon atoms, Hal is a halogen having an atomic number of at least 17 and Ar is a halogenated aromatic group containing 6-12 carbon atoms.  Processes for producing sulphur-containing organic compounds comprise (A) treating an olefinic compound having the general formula CHR=CR1X in which R is a hydrogen atom or a hydrocarbon group free from aliphatic unsaturation and containing 1-6 carbon atoms, at least one of R and R1 being a hydrogen atom, and X is a nitrile group or a group of the general formula -COY in which Y is a hydrogen atom, an amino group or a hydrocarbon group free from aliphatic unsaturation and containing 1-6 carbon atoms, with an aromatic sulphenyl halide containing from 6-12 carbon atoms which may contain nuclear halogen, alkyl or haloalkyl substituents; (B) treating a compound of the general formula CH2-CHZ in which Z is a group having one of the general formulae -OR and -O.CO.R in which R is a hydrocarbon group free from aliphatic unsaturation and containing 1-6 carbon atoms with a halogenated aromatic sulphenyl halide containing 6-12 carbon atoms; (C) treating an a -halo-olefinic compound of the general formula CHR=C(Hal)X in which R and X are as defined in (A) and Hal is a halogen atom with a thiophenol containing 6-12 carbon atoms and which may also contain nuclear halogen, alkyl or haloalkyl substituents; (D) treating a trisubstituted ethane of the general formula CH2(Hal).CH(Hal)X in which X is as defined in (A) and each Hal is a halogen atom with an aqueous solution of an alkali metal salt of a thiophenol containing 6-12 carbon atoms and which may contain nuclear halogen or alkyl or haloalkyl substituents; and (E) introducing a hydrogen halide into a solution in an inert solvent of an aryl-mercapto compound having the general formula CH2=C(SAr)X in which Ar is an aryl group containing from 6-12 carbon atoms and which may contain nuclear halogen, alkyl or haloalkyl substituents and X is as defined in (A).  Many starting materials are listed comprising acrylonitrile and acrylamide and the substitution derivatives thereof, acrolein and substitution derivatives thereof, vinyl ketones and esters, 2,3-dihalopropionitriles and propionamides, aromatic sulphenyl halides and substitution derivatives thereof, e.g. containing chlorine bromine, iodine or fluorine, e.g. benzene sulphenyl chloride or bromide and the corresponding thiophenols and substitution derivatives thereof and alkali metal salts thereof. In examples compounds of the general formula given above are prepared by reacting acrylonitrile with benzene sulphenyl chloride (1), p-toluene sulphenyl chloride (2), o-toluene sulphenyl chloride (3), a mixture of isomeric toluene sulphenyl chlorides (4), a mixture of isomeric xylene sulphenyl chlorides (5), p-chloro-benzene sulphenyl chloride (8), (9), pentachloro-, trichloro- and chloromethyl benzene sulphenyl chloride (12), cinnamonitrile with p-toluene sulphenyl chloride (6) and p-chlorosulphenyl chloride (13), methacrylonitrile with p-toluene sulphenyl chloride (7), p-chlorobenzene sulphenyl chloride (14), acrylamide or methacrylamide with p-chlorobenzene sulphenyl chloride (15), vinyl methyl ketone with p-chlorosulphenyl chloride and p-toluene sulphenyl chlorides (18, 19) methyl, ethyl and n-propyl vinyl ethers with p-chlorosulphenyl chloride (20-22), a -chloroacrylonitrile in the presence of aqueous chlorine (23) and with p-chlorophenyl in the presence of sodium methoxide (25), a -chloroacrylamide with 4-methyl- and tribromothiophenols in the presence of trimethyl ammonium hydroxide and a -bromo-acrylamide with chlorobenzenethiol (26), 2,3-dichloro-propionate with sodium thiophenate (27) and with sodium p-chlorophenate (28), 2(phenyl mercapto) acrylonitrile with hydrogen chloride (29) and 2-(p-chlorophenyl mercapto) acrylonitrile (30).  The products have bactericidal, fungical and herbicidal properties and may be incorporated in soap (see Group III) and other disinfecting, herbicidal and sterilising compositions (see Group VI) to preserve rubber latex (see Group IV(a)) and may be used to rotproof cellulosic materials, paper and pulp (see Group VIII), leather, fur, textiles, rope, plastics, paints and wood.  Specification 785,133 is referred to.ALSO:Bactericidal and fungicidal soaps contain a compound of the formula <FORM:0878828/III/1> in which each of R and R1 is a hydrogen atom or a hydrocarbon group free from aliphatic unsaturation containing 1-6 carbon atoms at least one of R and R1 being a hydrogen atom, X is a nitrile group or a group of the general formula -COY in which Y is a hydrogen atom, an amino group or a hydrocarbon group free from aliphatic unsaturation containing 1-6 carbon atoms, Hal is a halogen having an atomic number of at least 17 and Ar is an aromatic group containing 6-12 carbon atoms and which may include nuclear halogen, alkyl or haloalkyl substituents or a compound of either of the formulae <FORM:0878828/III/2> in which R is a hydrocarbon group free from aliphatic unsaturation and containing 1-6 carbon atoms, Hal is a halogen having an atomic number of at least 17 and Ar is a halogenated aromatic group containing 6-12 carbon atoms (see Group IV(b)).  An acetone solution of the acrylonitrile-p-chlorobenzenesulphenyl chloride is added to stock soap solutions in a test of fungicidal and bactericidal activity. Specification 785,133 is referred to.ALSO:In order to protect seeds against attack by microorganisms they are dressed with a composition comprising a halogenated arylmercapto compound (see Group IV(b)) and an inert powder such as talc, bentonite or kieselguhr.  Specification 785,133 is referred to.ALSO:A bactericide, fungicide, herbicide or soil sterilant, which prevents rotting of leather, fur, wood, rope and textiles, comprises a compound of the general formula <FORM:0878828/VI/1> in which each of R and R1 is either a hydrogen atom or a hydrocarbon group free from aliphatic unsaturation containing 1-6 carbon atoms, at least one of R and R1 being a hydrogen atom, X is a nitrile group or a group of the general formula -COY in which Y is a hydrogen atom, an amino group or a hydrocarbon group free from aliphatic unsaturation and containing 1-6 carbon atoms, Hal is a halogen having an atomic number of at least 17 and Ar is an aromatic group containing 6-12 carbon atoms and which may include nuclear halogen, alkyl or haloalkyl substituents or a compound of either of the formulae <FORM:0878828/VI/2> or <FORM:0878828/VI/3> in which R is a hydrocarbon group free from aliphatic unsaturation and containing 1-6 carbon atoms, Hal is a halogen having an atomic number of at least 17 and Ar is a halogenated aromatic group containing 6-12 carbon atoms (see Group IV (b)) with a finely divided solid or liquid carrier.  Many compounds of the kind defined above are described, those preferred being the products obtained by reacting acrylonitrile with benzene-toluene- or xylene sulphenyl halides or benzene sulphenyl halides containing 1-3 nuclear chlorine substituents.  Solid carriers specified include talc, bentonite, kieselguhr and diatomaceous earth.  Liquid carriers specified include water and organic solvents e.g. acetone and kerosene and the products may be employed as aqueous emulsions.  The products may be incorporated in disinfectant soaps and antiseptic creams.  A mixture of an acrylonitrile-p-chlorobenzene-sulphenyl chloride reaction product and soil, an acetone solution of an acrylonitrile-p-chlorobenzene sulphenyl chloride reaction product, an emulsion of an acrylonitrile-p-toluenesulphenyl chloride reaction product or a p-chlorobenzene sulphenyl chloride reaction product containing water, acetone and wetting agent and an aqueous solution of a pentachlorobenzene sulphenyl chloride-acrylonitrile reaction product are described.  Specification 785,133