Patent GB-412305-A (GB)
Title: Improvements in processes for the manufacture of high molecular sulphides of the aliphatic series
IPC: C07C319/14
Filed: 1933-01-16
Abstract: The high molecular aliphatic sulphides, prepared by interaction of aliphatic mercaptans with aliphatic halogen compounds of which at least one component contains a minimum of eight carbon atoms, are stated to possess emulsifying properties.  Typical examples are (1) sodium dodecyl-thioglycollate, prepared for instance from dodecyl mercaptan and sodium monochloracetate; (2) a -ethylmercapto-stearic acid, prepared from a -bromostearic acid and ethyl mercaptan; (3) 2 - hydroxyl - 3 - dodecylmercapto - propanol - 1 - sulphonic acid, prepared from dodecyl mercaptan and 1 : 2 : 3 - chloropropanol sulphonic acid, and (4) 2-dodecyl-mercapto-ethyl alcohol, prepared from dodecyl mercaptan and glycol chlorhydrin.  The sample furnished comprises an oil which is prepared by dissolving a mixture of octyl, decyl, dodecyl and tetradecyl mercaptans in alcoholic caustic soda and heating with allyl bromide.  The Specification as open to inspection under Sect. 91 describes also the use of components containing groups of any kind, mentioning ether groups in addition to those appearing in the products of the above examples.  The introduction of the sulphonic acid group into the sulphides, either by direct sulphonation or by exchange reactions, is referred to.  In addition, the preparation of the following samples is described --(1) dodecylmercaptoacetone from monochloracetone and dodecyl mercaptan; (2) a brown oil which crystallizes on standing from 2-mercaptobenzothiazole and 1-chlordodecane, and (3) a yellowish brown crystalline product from p-nitrochlorbenzene and dodecyl mercaptan.  This subject-matter does not appear in the Specification as accepted.  Reference has been directed by the Comptroller to Specification 403,882.ALSO:High-molecular aliphatic sulphides are prepared by interaction of aliphatic mercaptans with aliphatic halogen compounds, at least one component containing a minimum of eight carbon atoms.  The use of 1 : 2-propylene oxides substituted in the methyl group by halogen is excluded.  The components may contain carboxylic, sulphonic or hydroxy groups, or double bonds.  Thus, aliphatic mono- or poly-halogen compounds may be reacted with mercapto-fatty acids, and aliphatic mercaptans or polymercaptans with halogen fatty acids.  The products, some of which possess saponaceous and emulsifying properties, may be used in the rubber and pharmaceutical industries.  According to the examples (1) sodium dodecyl-S-thioglycollate is prepared from dodecyl mercaptan and ethyl chloracetate in the presence of sodium methanolate, followed by saponification; the same compound is obtained from dodecyl mercaptan and monochloracetic acid, or a -chlor-n-dodecane and mercapto-acetic acid, in the presence of caustic soda dissolved in ethyl alcohol; (2) a -ethylmercapto-stearic acid is similarly prepared from a -bromostearic acid and ethyl mercaptan, 2 - hydroxyl - 3- dodecylmercapto - propanol - sulphonic acid-1 from dodecyl mercaptan and 1 : 2 : 3 - chloropropanol sulphonic acid, 2 - dodecylmercapto-ethyl alcohol from dodecyl mercaptan and glycol chlorhydrin, and dodecyl-b .  g -dihydroxypropyl-sulphide from dodecyl mercaptan and a -monochlorhydrin; (3) a mixture of the corresponding alkyl-b -hydroxypropyl-sulphides results from the interaction of glycol chlorhydrin with a mixture of higher aliphatic mercaptans such as octyl, decyl, dodecyl, tetradecyl and hexadecyl mercaptans; by using a -monochlorhydrin, the corresponding alkyl - b .g  - dihydroxypropyl - sulphides are formed.  Other aliphatic halogen compounds mentioned are ethyl chloride, octyl chloride and chlorobutyric acid, whilst mercapto-butyric acid and hexyl mercaptan are other mercapto compounds referred to.  The sample furnished comprises an oil which is prepared by dissolving a mixture of octyl, decyl, dodecyl and tetradecyl mercaptans in alcoholic caustic soda and heating with allyl bromide.  The Specification as open to inspection under Sect. 91 describes also the use of components containing groups of any kind, mentioning ether groups in addition to those specified above.  The introduction of the sulphonic acid group into the sulphides either by direct sulphonation or by exchange reactions is referred to. In addition, the preparation of the following samples is described:--(1) dodecylmercapto-acetone from monochloracetone and dodecyl mercaptan; (2) a brown oil which crystallises on standing from 2-mercaptobenzothiazole and 1-chlordodecane; and (3) a yellowish brown crystalline product from p-nitrochlorbenzene and dodecyl mercaptan.  This subject-matter does not appear in the Specification as accepted.  Reference has been directed by the Comptroller to Specification 403,882.