Patent GB-437590-A (GB)
Title: Improvements in the manufacture and production of valuable condensation products
IPC: C07B45/06
Filed: 1934-02-26
Abstract: Products having wetting, foaming, washing, and dispersing properties are obtained by treating organic substances containing a mercapto group not directly attached to a carbonyl group or to a heterocyclic nucleus, or an alkali-metal salt of such a mercapto compound, with (a) an oxide derivable from a polyhydric alcohol by intramolecular loss of water, or (b) a polyether derivable from a polyhydric alcohol by condensation of several molecules with loss of water, or (c) a hydrohalide ester of a polyhydric alcohol or of a polyether derived therefrom, the amount or the constitution of the reagent (a), (b) or (c) being such that at least one radicle containing at least four carbon atoms and at least one oxygen-ether linkage is introduced into the substance containing the mercapto group.  The mercapto compounds may be aliphatic, cycloaliphatic, aromatic or aliphatic-aromatic mercaptans which may be substituted by halogen atoms or nitro, sulphonic, carboxylic, ether or ester groups; specified compounds are ethyl, butyl, amyl, heptyl, octyl, decyl, dodecyl, cetyl, octodecyl and oleyl mercaptans, octodecane-7: 18 - dimercaptan, cyclohexyl mercaptan, methylcyclohexyl mercaptans, thiophenols, thionaphthols, thiosalicylic acid, p-nitrothiophenol, and benzyl mercaptan. Specified reagents of types (a),(b) or (c) are ethylene oxide, propylene oxide, glycide compounds, polyglycol ethers, polyglycerols, halogen compounds of polyglycols or polyglycerols, epichlorhydrin, and ethylene chlorhydrin.  The reaction may be effected at atmospheric or raised temperature and pressure in the presence or absence of water or an organic solvent or diluent and preferably in the presence of an alkaline substance, surface-active substance or neutral salt as a catalyst; specified catalysts are caustic soda or potash, sodium carbonate, sodium phosphate, ammonia, sodium methylate, sodium or potassium ethylate, sodium chloride or sulphate, or bleaching earth.  More than one reagent of type (a), (b) or (c) may be caused to react successively on the mercaptan; thus, one molecule of mercaptan may be treated with several molecules of epichlorhydrin and then with a halogen compound of a polyglycerol, or first with several molecules of ethylene chlorhydrin and then with one or more molecules of ethylene oxide or propylene oxide.  Such of the products as contain hydroxyl groups may be further reacted; in particular, they may be (a) treated with organic or inorganic acids such as acetic, butyric, lauric, stearic, oleic, sulphopalmitic, naphthenic, naphthoic, sulphuric, chlorsulphonic, nitric and phosphoric acids, or (b) condensed with halogenated paraffins, chlorocarbonic esters, chlorethane sulphonic acid, or monochloracetic acid, or (c) treated to replace the hydroxyl group by halogen and then condensed with ammonia or amines or hydroxl compounds or alcoholates.  The products obtained by any of the processes described may be applied in the textile, leather, lacquer, paper, rubber, cosmetic, foodstuff and pharmaceutical industries; in particular they may be used (a) as assistants in dyeing, printing, dressing, washing, fulling and other textile-treating processes, or (b) as stabilizers for caoutchouc emulsions or as vulcanization accelerators, or (c) as additions to the spinning solutions or precipitating baths in the manufacture of artificial silk, or (d) as emulsifying agents or protective colloids in the cosmetic, pharmaceutical or foodstuff industries. The products may be used alone or associated with other appropriate substances, and compositions comprising the products and appropriate additional substances may be prepared; specified additional substances are soaps; saponin; sulphuric esters or sulphonic acids, such as turkey red oil, sulphite cellulose lye, and sulphuric esters of higher alcohols; reaction products of fatty acids or their derivatives or chlorocarbonic esters with taurine, hydroxyethane sulphonic acid, or polypeptides; polymerization products of ethylene oxide; condensation products of ethylene oxide with organic substances containing hydroxyl, carboxylic or amino groups; glue; rubber-like substances; dextrin; cellulose ethers; inorganic or organic salts such as ethanolamine tartrate and other salts of mono-, di- or tri-ethanolamine, common salt, Glauber's salt, waterglass, phosphates, or sodium acetate; organic solvents; and bleaching agents such as perborates or alkali peroxides.  In the examples: (1) dodecyl mercaptan (from dodecyl bromide and sodium hydrosulphide) is treated with about five molecular proportions of ethyle oxide to yield a product of the probable formula C12H25SCH2CH2(OCH2CH2)3 OCH2CH2OH; the product is useful as a wetting agent, or as an emulsifying agent for mineral or fatty oils or fats, or for washing wool; its sulphonation product also is useful as a wetting and dispersing agent; (2) oleyl mercaptan (from oleyl bromide and sodium hydrosulphide) is treated with about ten molecular proportions of ethylene oxide to yield a product of the probable formula C18H35SCH2CH2(OCH2 CH2)8OCH2CH2OH; the product is useful for emulsifying olein, as an agent for preventing the precipitation of calcium soaps in hard water, and as an addition to soaps, soap preparations, bath essences and hair preparations; (3) cetyl mercaptan (from cetyl bromide and sodium hydrosulphide) is treated with twenty molecular proportions of ethylene oxide to yield a product of the probable formula C16H33SCH2CH2 (OCH2CH2)18OCH2CH2OH, useful as a levelling agent in dyeing with vat dyes; a similar product is obtained by using glycide instead of ethylene oxide; (4) decyl mercaptan (from decyl bromide and sodium hydrosulphide) is treated with five molecular proportions of ethylene oxide to yield a product suitable, in aqueous solution, for washing wool; (5) decyl or dodecyl mercaptan is treated with a polyglycerol chloride to yield a product suitable, in aqueous solution, for washing wool containing suint; (6) the potassium salt of decyl mercaptan is treated with an equimolecular amount of epichlorhydrin and the product is treated with two molecular proportions of ethylene oxide to yield a compound of the probable formula C10H21SCH2CHOHCH2(OCH2CH2) 2OH useful in preparing creams and ointments; thus, the product may be mixed with specified proportions of cetyl alcohol, wool fat, soft paraffin, petroleum jelly, glycerol and water to form a skin cream; treatment of the product with chlorosulphonic acid yields a sulphuric ester, the alkali or amine salts of which are useful as washing agents. Specification 409,030 is referred to.ALSO:Products having washing and dispersing properties are obtained by treating organic substances containing a mercapto group not directly attached to a carbonyl group or to a heterocyclic nucleus, or an alkali-metal salt of such a mercapto compound, with (a) an oxide derivable from a polyhydric alcohol by intramolecular loss of water, or (b) a polyether derivable from a polyhydric alcohol by condensation of several molecules with loss of water, or (c) a hydrohalide ester of a polyhydric alcohol or of a polyether derived therefrom, the amount or the constitution of the reagent (a), (b) or (c) being such that at least one radicle containing at least four carbon atoms and at least one oxygenether linkage is introduced into the substance containing the mercapto group.  The mercapto compounds may be aliphatic, cycloaliphatic, aromatic or aliphatic-aromatic mercaptans which may be substituted by halogen atoms or nitro, sulphonic, carboxylic, ether or ester groups; specified compounds are ethyl, butyl, amyl, heptyl, octyl, decyl, dodecyl, cetyl, octodecyl and oleyl mercaptans, octodecane7 : 18-dimercaptan, cyclohexyl mercaptan, methylcyclohexyl mercaptans, thiophenols, thionaphthols, thiosalicylic acid, p-nitrothiophenol, and benzyl mercaptan.  Specified reagents of types (a), (b) or (c) are ethylene oxide, propylene oxide, glycide compounds, polyglycol ethers, polyglycerols, halogen compounds of polyglycols or polyglycerols, epichlorhydrin, and ethylene chlorhydrin.  More than one reagent of type (a), (b) or (c) may be caused to react successively on the mercaptan; thus, one molecule of mercaptan may be treated with several molecules of epichlorhydrin and then with a halogen compound of a polyglycerol, or first with several molecules of ethylene chlorhydrin and then with one or more molecules of ethylene oxide or propylene oxide.  Such of the products as contain hydroxyl groups may be further reacted.  In particular, they may be (a) treated with organic or inorganic acids such as acetic, butyric, lauric, stearic, oleic, sulphopalmitic, naphthenic, naphthoic, sulphuric, chlorsulphonic, nitric and phosphoric acids, or (b) condensed with halogenated paraffins, chlorocarbonic esters, chlorethane sulphonic acid, or monochloracetic acid, or (c) treated to replace the hydroxyl group by halogen and then condensed with ammonia or amines or hydroxyl compounds or alcoholates.  The products obtained by any of the processes described may be applied in the textile, leather, lacquer, paper, rubber, cosmetic, foodstuff and pharmaceutical industries; in particular they may be used (a) as stabilizers for caoutchouc emulsions or (b) as emulsifying agents or protective colloids in the cosmetic, pharmaceutical or foodstuff industries, or (c) as assistants in washing processes.  The products may be used alone or associated with other appropriate substances, and compositions comprising the products and appropriate additional substances may be prepared; specified additional substances are soaps; saponin; sulphuric esters or sulphonic acids, such as turkey red oil, sulphite cellulose lye, and sulphuric esters of higher alcohols; reaction products of fatty acids or their derivatives or chlorocarbonic esters with taurine, hydroxyethane sulphonic acid, or polypeptides; polymerization products of ethy