Patent GB-442525-A (GB)
Title: Improvements in the manufacture and production of organic sulphur compounds
Filed: 1934-08-08
Abstract: Organic sulphur compounds are manufactured by causing a compound containing at least one nitrogen atom bearing at least one reactive hydrogen atom to react with a compound of the general formula R.SO2R1 or R.SO.R1, where R is an alkenyl group, e.g. vinyl or allyl, R1 is an alkyl group containing at least six carbon atoms, e.g. octodecyl or octodecenyl, or a cyclic radicle such as an aryl group, e.g. phenyl, the radicle of a polynuclear isocyclic or heterocylic compound, e.g. naphthyl, an aralkyl group, e.g. benzyl or phenylethyl, or a cycloaliphatic radicle, which groups or radicles may contain substituents, e.g. halogens or alkyl, hydroxyalkyl, nitro, hydroxy or carboxylic groups.  Suitable nitrogen compounds are ammonia, primary and secondary alkylamines and hydroxyalkylamines, e.g. ethylamine, propylamine, butylamine, octodecylamine, octodecenylamine and mono- and di-hydroxyethylamines, primary and secondary aromatic amines, e.g. aniline, phenylenediamine, naphthylamine and aminoanthraquinone, mono-amines or polyamines of other isocyclic and heterocyclic compounds, aralkylamines, e.g. phenylethylamine, cycloaliphatic amines, e.g. cyclohexylamine, and their mono - N - alkyl, hydroxyalkyl, aryl, aralkyl and acyl compounds, and also compounds having at least one NH-group combined in a ring, e.g. piperidine or carbazole.  These compounds may also contain halogen atoms, tertiary combined nitrogen atoms or alkyl, hydroxyalkyl, nitro, hydroxy or carboxylic groups.  The reaction may be performed at elevated temperatures, e.g. 60--200 DEG , preferably 100-160 DEG  C., at ordinary or increased pressure, if desired in the presence of diluents, e.g. alcohols (ethyl, propyl or benzyl alcohol), ketones (acetophenone), ethers (dibenzyl ether), hydrocarbons (toluene or xylene) or halogen hydrocarbons (chlorbenzene), and if desired with the aid of catalysts consisting of substances having a basic character, e.g. alkali or alkaline-earth metal oxides, hydroxides, sulphides, carbonates, acetates, phenolates, alcoholates or mercaptides, zinc or cadmium oxide, zinc or cadmium salts of organic acids, e.g. acetic acid, or organic bases such as pyridine or dimethylaniline.  The products may be used for the preparation of dyestuffs, in some cases as dyestuffs themselves, as assistants for the textile and related industries or for combating animal or vegetable pests.  In examples: (1) vinyl-p-tolyl sulphone is refluxed with aqueous ammonia, producing bis-(b -(p-tolyl) - sulphonethyl) - amine; the ammonia may be replaced with mono- or di-ethanolamine; (2) vinyl-p-tolyl sulphone is refluxed with piperidine; (3) vinyl-p-tolyl sulphone is refluxed with b -naphthylamine in benzyl alcohol; the b -naphthylamine may be replaced by 5-aminoanthrapyrimidine and the sulphone by other alkenyl sulphones; (4) vinyl-p-tolyl sulphone is heated with an aqueous solution of the sodium salt of 1-hydroxy-8-aminonaphthalene-3 : 6-disulphonic acid; other aminohydroxy compounds may be similarly reacted; (5) vinyl-p-tolyl sulphone is heated with monoethylaniline, or with monohydroxyethylaniline, monoethyl - m - toluidine, monohydroxyethylm - toluidine, monoalkyl - b  - naphthylamines, 2 - methoxy - 5 - methyl - N - hydroxyethylaniline (obtainable by the action of ethylene p  chlorhydrin on 2-methoxy-5-methylaniline) or other N-oxyalkyl-derivatives of aniline, phenylenediamines, diphenylamine, cyclohexylamine, monoalkyl-, alkoxyaryl- or aralkyl-cyclohexylamines; the sulphone may be replaced by other alkenyl sulphones; (6) vinyl-p-tolyl sulphone is refluxed with diethylamine, or with other monoalkyl or dialkyl or alkoxyamines, e.g. dibutylamine; the sulphone may be replaced by other alkenyl sulphones; by introducing a nitro group and reducing it to amino, there are obtained compounds suitable for the preparation of dyestuffs; vinyl-p-tolyl sulphone or other vinyl sulphones may similarly be reacted with urea and its derivatives, urethanes, semicarbazides, hydrazines or aminoalkylsulphonic acids; (7) vinyl-p-tolyl sulphone is refluxed with carbazole in cyclohexane in the presence of metallic potassium or of other alkali or alkaline-earth metals or their oxides, hydroxides, sulphides, acetates, phenolates, alcoholates or mercaptides or of tertiary bases such as pyridine or dimethylaniline; (8) allyl-p-tolyl sulphone is refluxed with aqueous ammonia, or with diethylamine; (9) vinyl-octodecyl sulphoxide is heated with an aqueous solution of the sodium salt of methyltaurine; (10) vinyl-p-tolyl sulphone is refluxed with 1-chloro-4-aminoanthraquinone in cyclohexane in the presence of metallic potassium; alternatively, the reacting materials and catalyst are fused together; (11) vinyl - p - tolyl sulphoxide is refluxed with diethylamine in the presence of metallic potassium; (12) vinyl-p-tolyl sulphone is refluxed with N-monoacetyl-p-phenylenediamine in ethanol in the presence of zinc and cadmium oxides; the acetyl group may be removed by saponification; other acylated polyamines and other vinyl sulphones or sulphoxides may be similarly reacted; (13) vinyl-p-tolyl sulphone is refluxed with 4-acetylaminodiphenylamine in xylene in the presence of metallic potassium; (14) p-nitraniline and vinyl-p-tolyl sulphone are similarly reacted; the product may be acetylated or benzoylated; (15) vinyl-octodecyl sulphoxide is heated with an aqueous solution of the sodium salt of taurine with the addition of caustic soda; the sulphoxide may be replaced by vinyl-dodecyl sulphoxide or the corresponding sulphones or the vinyl sulphoxides or sulphones of mixtures, such as those corresponding to the mercaptans obtainable from palm kernel oil, coconut oil or sperm oil; (16) the mixture of vinyl sulphoxides obtainable by reacting the mercaptans corresponding to the palm kernel alcohols with acetylene and oxidizing the product with sodium hypochlorite, or the corresponding sulphones, are heated with an aqueous solution of the sodium salt of methyltaurine. Specification 442,524 is referred to.  According to the Provisional Specification, the group R in the formul  given above may be any alkyl group, ethyl, propyl and butyl groups being additionally specified.