GB981113A - Oxidation of organic thiols - Google Patents
Oxidation of organic thiolsInfo
- Publication number
- GB981113A GB981113A GB2339262A GB2339262A GB981113A GB 981113 A GB981113 A GB 981113A GB 2339262 A GB2339262 A GB 2339262A GB 2339262 A GB2339262 A GB 2339262A GB 981113 A GB981113 A GB 981113A
- Authority
- GB
- United Kingdom
- Prior art keywords
- cuprous
- reaction
- tertiary
- aliphatic
- tertiary amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/14—Polysulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A process for producing aliphatic or aryl disulphides or polydisulphides (see also Division C3) comprises reacting one or more aliphatic or aryl mono- or poly-thiols, respectively, with oxygen in the presence of a catalyst comprising a tertiary amine and a cuprous salt capable of existing in the cupric state and forming with the tertiary amine a complex soluble in the reaction medium. The thiols used may be substituted by a halogen or by -OH, -OR, -COOR, -CHO, -CO, -CONH2, -CONHR, -CONR2, -CN, -SR, -SSR, -SOR, -NO2, -SO2R, -NH2, -NHR or -NR2 groups, where R is an aliphatic or aryl radical. Cuprous salts specified are cuprous chloride, cuprous bromide, cuprous sulphate, cuprous azide, cuprous acetate, cuprous propionate, cuprous palmitate and cuprous benzoate; tertiary amine complexes of cuprous nitrate and cuprous fluoride produced in situ may also be used. Tertiary-amines which may be used include aliphatic, including cycloaliphatic, and arylaliphatic tertiary-amines, ring-nitrogen heterocyclic tertiary-amines, and polyamines having one or more aliphatic or ring-nitrogen tertiary amino-radicals interconnected by one or more aliphatic or cycloaliphatic linkages. Mixtures of such tertiary-amines and/or such cuprous salts may be used. An oxygen-containing gas, e.g. air, may be employed. An exothermic reaction occurs with formation of water as a by-product, and the escape of water should desirably be prevented or controlled so as to retain in the reaction mixture one mole of water per mole of the catalyst; in batchwise operation this may be effected by carrying out the reaction under reflux conditions and/or at superatmospheric pressure and/or with cooling and/or in the presence of a desiccant. In continuous operation this may be effected by carrying out the reaction at subatmospheric pressure, by the use of azeotropic distillation or of heat, or by a controlled sweeping of the reaction mixture with an inert gas, e.g. nitrogen, helium or argon. The reaction temperature should preferably not exceed 100 DEG C. Reaction may be terminated by adding a mineral acid, which reacts with the amine and the cuprous salt, or by precipitating the product or the cuprous salt. During the reaction a different mono-thiol or di-thiol may be added to produce mixed disulphides or polydisulphides. The reaction medium may contain an inert organic solvent. Specific examples describe the preparation of (1) b -naphthyl disulphide, (2) bis-(2,6-dimethylphenyl) disulphide, and (3) bis-(2,4,6-trimethylphenyl)-disulphide, using a cuprous chloride-pyridine catalyst.ALSO:A process for producing polydisulphides (see also Division C2) comprises reacting one or more dithiols or polythiols with oxygen in the presence of a catalyst comprising a tertiary amine and a cuprous salt capable of existing in the cupric state and of forming with the tertiary amine a complex soluble in the reaction medium. When dithiols are used fusible polymers or copolymers are obtained; polythiols having three or more thiol radicals yield cross-linked insoluble polymers. The thiols used may be substituted by a halogen or by -OH, -OR, -COOR, -CHO, -CO, -CONH2, -CONHR, -CONR2, -CN, -SR, -SSR, -SOR, -NO2, -SO2R, -NH2, -NHR or -NR2 groups where R is an aliphatic or aryl radical. Cuprous salts specified are cuprous chloride, cuprous bromide, cuprous sulphate, cuprous azide, cuprous acetate, cuprous propionate, cuprous palmitate and cuprous benzoate; tertiary amine complexes of cuprous nitrate and cuprous fluoride prepared in situ may also be used. Tertiary amines which may be used include aliphatic, including cycloaliphatic, and aryl - aliphatic tertiary amines, ring - nitrogen heterocyclic tertiary amines, and polyamines having one or more aliphatic or ring-nitrogen tertiary aminoradicals interconnected by one or more aliphatic or cycloaliphatic linkages. Mixtures of such tertiary amines and/or such cuprous salts may be employed. An oxygen-containing gas, e.g. air, may be used. An exothermic reaction occurs with formation of water as a by-product, and the escape of water should desirably be prevented or controlled so as to retain in the reaction mixture one mole of water per mole of catalyst; in batch-wise operation this may be effected by carrying out the reaction under reflux conditions and/or at superatmospheric pressure and/or with cooling air and/or in the presence of a desiccant. In continuous operation this may be effected by carrying out the reaction at subatmospheric pressure, by the use of azeotropic distillation or of heat, or by a controlled sweeping of the reaction mixture with an inert gas, e.g. nitrogen, helium or argon. The reaction temperature should preferably not exceed 100 DEG C. The reaction medium may contain an inert organic solvent. Polymerization may be controlled by addition of a monothiol, and the reaction may be terminated by adding a mineral acid, which reacts with the amine and the cuprous salt, or by precipitating the product or the cuprous salt. The products may be blended with up to 75% by wt. of polymers of alkenes having 3 to 8 carbon atoms, polybutadiene, polyisoprene, polychloroprene, copolymers of butadiene and styrene or acrylonitrile, polyorganosiloxanes, polyalkylmethacrylates, polystyrene, and chlorosulphonated or chlorinated polyethylenes. One or more fillers may be added, e.g. carbon blacks and various silicas including silica aerogels, zerogels and fumed silicas, which may be treated with a hydrophobic agent such organosilicon halide, Catalpo clay, diatomaceous earth, chromic oxide, titanium dioxide, ferric oxide, calcium carbonate, cadmium sulphide, asbestos, wood flour, cellulose fibres, mineral fibres, glass fibres, alumina, lithopone, talc, and calcium silicate. One or more dyes and/or pigments and one or more plasticizers may also be added. Specific examples describe the preparation of polydisulphides from a ,a 1-dimercapto-p-xylene, toluene 3,4-dithiol, naphthalene 1,5-dithiol, ethylene dithioglycol, 1,9-nonane dithiol, 1,10-decane dithiol and 1,3-propane dithiol.ALSO:Naturally occurring thiols are removed from petroleum by treatment with oxygen in the presence of a catalyst comprising a tertiary amine and a cuprous salt capable of existing in the cupric state and of forming with the tertiary amine a complex soluble in the reaction medium.ALSO:The oxidation of organic thiols is catalysed by a tertiary amine and a cuprous salt capable of existing in the cupric state and forming with the tertiary amine a complex soluble in the reaction medium. Numerous tertiary amines and cuprous salts are specified.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11783661A | 1961-06-19 | 1961-06-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB981113A true GB981113A (en) | 1965-01-20 |
Family
ID=22375098
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB2339262A Expired GB981113A (en) | 1961-06-19 | 1962-06-18 | Oxidation of organic thiols |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB981113A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114736373A (en) * | 2022-04-28 | 2022-07-12 | 武汉纺织大学 | Ladder-shaped polyphenylene sulfide and preparation method and application thereof |
-
1962
- 1962-06-18 GB GB2339262A patent/GB981113A/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114736373A (en) * | 2022-04-28 | 2022-07-12 | 武汉纺织大学 | Ladder-shaped polyphenylene sulfide and preparation method and application thereof |
CN114736373B (en) * | 2022-04-28 | 2023-09-19 | 武汉纺织大学 | Ladder-shaped polyphenylene sulfide and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4695609A (en) | Vulcanizable rubber compositions containing xanthogen polysulfide and xanthate compounds | |
US5254635A (en) | Rubber composition containing dibenzyl thiuram sulfide | |
US3219638A (en) | Polysulfide polymers and process for their preparation | |
JPH0533704B2 (en) | ||
CN106866466A (en) | A kind of method for synthesizing N-acetylsulfanilyl chloride as sulfonating agent with sulfur trioxide | |
GB981113A (en) | Oxidation of organic thiols | |
ES2717151T3 (en) | Silane-mediated potentiation of rubber storage stability | |
US3836524A (en) | Preparation of esters of thiocarbamic acids | |
ES2711618T3 (en) | Preparation procedure for methyl disulfide | |
JPS61115075A (en) | Manufacture of storable benzthiazole sulfenamides | |
GB896497A (en) | Sulfonyl semicarbazides as new blowing agents | |
GB619706A (en) | Manufacture of new cycloaliphatic diamines | |
CN108623623A (en) | A method of reducing mercaptopropyltriethoxysilane in the production of polysulfide silanes coupling agent | |
EP0091091B1 (en) | A process for producing oxocarboxylic acids | |
US2851391A (en) | Processes and products | |
US3251811A (en) | Process for the preparation of polysulfide polymers | |
CA1285946C (en) | Process for the production of thiuram polysulfides | |
US2149858A (en) | Vulcanization accelerator and process of making the same | |
EP0219446B1 (en) | Process for the preparation of n-tetrathiodimorpholine | |
JPH041740B2 (en) | ||
US1873935A (en) | Accelerator for vulcanization processes | |
US2450771A (en) | Plastic sulfur vulcanizing agent, method for its utilization and vulcanizable compositions containing the same | |
JPS6320346A (en) | Rubber composition | |
US2022953A (en) | Vulcanization of rubber | |
JP4461784B2 (en) | Process for producing ω-mercaptoalkylpyridines |