Patent GB-494766-A (GB)
Title: Production of ammonia derivatives
IPC: D06M13/46
Filed: 1937-05-04
Abstract: Products useful as emulsifying agents and as dispersing agents for pigments are obtained by treating a compound of the formula ROAO AX or ROAOAOAX, in which R is an aromatic radicle, A is an alkylene radicle of more than one carbon atom, and X is halogen, with ammonia or a primary, secondary or tertiary amine, whereby the halogen is replaced by an amino or a quaternary ammonium group; the treatment of compounds of the formula ROAOAX, in which A is an alkylene radicle containing two carbon atoms, is excluded. The free amine or quaternary ammonium base may then be recovered from its hydrohalide or halide by treatment with alkali, and if the product is not a quaternary ammonium compound it may then be treated with an alkylating or aralkylating agent to convert it into a quaternary ammonium salt, from which the free base may be recovered by treatment with alkali; the free amines or bases may also be converted into salts with other acids, e.g. acetic, formic, lactic, acrylic, propionic, crotonic, phosphoric or sulphuric acid.  The halides used as starting materials are obtainable by condensing equimolecular proportions of a monohydric phenol and a dihalogenated ether of the formula XAOAX or XAOAOAX, where X and A are as above.  Specified monohydric phenols are phenol, o-, m- or p-cresol, thymol, carvacrol, p-tert-butylphenol, p-sec-butylphenol, p-tert-amylphenol, p-n-amylphenol, n-amyl-mcresols, p-sec-octylphenol, p-tert-octylphenol, p-sec-hexylphenol, laurylphenols, o-, m- or p-cyclohexylphenol, o-, m- or p-phenylphenol, o- or p-benzylphenol, a - or b -naphthols tert-butyl-b -naphthols, tert-octyl-BETA-naphthols and 1 : 3 : 5-xylenol.  Specified dihalogenated ethers are b , b 1-dichlorodiisopropyl ether, b , b 1-dichlorodi-n-butyl ether, b , b 1-dichloro di-n-amyl ether, the corresponding dibromo compounds b -chloro-b 1-b 11-chloroethoxy) diethyl ether, and their higher homologues containing up to 18 carbon atoms. Specified amines are mono-, di- and tri-methylamine, mono-, di- and tri-ethylamine, and their homologues, mono- and di-ethanolamine, dibenzylamine, cyclohexylamine, dicyclohexylamine, piperidine, morpholine, and benzyldimethylamine.  Specified alkylating or aralkylating agents are dimethyl sulphate, benzyl chloride, diethyl sulphate, dimethyl oxalate, methallyl chloride (CH2: C(CH3)CH2C1), methyl iodide, ethyl bromide, methyl thiocyanate and benzyl thiocyanate.  The Specification as open to inspection under Sect. 91 describes, and includes examples of, the treatment of compounds of the formula ROAOAX in which R and X are as above, and A is an alkylene group containing two carbon atoms.  This subject-matter does not appear in the Specification as accepted.ALSO:A compound of the formula ROAOAX or, ROAOAOAX, in which R is an aromatic radicle, A is an alkylene radicle of more than one carbon atom, and X is halogen, is treated with ammonia or a primary, secondary or tertiary amine, whereby the halogen is replaced by an amino or a quaternary ammonium group; the treatment of compounds of the formula ROAOAX, in which A is an alkylene radicle containing two carbon atoms, is excluded.  The free amine or quaternary ammonium base may then be recovered from its hydrohalide or halide by treatment with alkali, and if the product is not a quaternary ammonium compound it may then be treated with an alkylating or aralkylating agent to convert it into a quaternary ammonium salt, from which the free base may be recovered by treatment with alkali; the free amines or bases may also be converted into salts with other acids, e.g. acetic, formic, lactic, acrylic, propionic, crotonic, phosphoric or sulphuric acid.  The halides used as starting materials are obtainable by condensing equimolecular proportions of a monohydric phenol and a dihalogenated ether of the formula XAOAX or XAOAOAX, where X and A are as above, in the presence of at least an equimolecular proportion of an alkali hydroxide. Specified monohydric phenols are phenol, o-, m- or p-cresol, thymol, carvacrol, p-tert.-butylphenol, p-sec.-butylphenol, p-tert.-amylphenol, p-n-amylphenol, n-amyl-m-cresols, p-sec.-octylphenol, p-tert.-octylphenol, p-sec.-hexylphenol, laurylphenols, o-, m- or p-cyclohexylphenol, o-, m- or p-phenylphenol, o- or p-benzylphenol, a - or b -naphthol, tert.-butyl-b -naphthols, tert.-octyl-b -naphthols, and 1 : 3 : 5-xylenol.  Specified dihalogenated ethers are b , b 1-dichlorodiisopropyl ether, b , b 1-dichloro-di - n - butyl ether, b , b 1 - dichloro di - n - amyl ether, the corresponding dibromo compounds, b -chloro-b 1-(b 11-chloroethoxy)diethyl ether, and their higher homologues containing up to 18 carbon atoms. Specified amines are mono-, di- and tri-methylamine, mono-, di- and tri-ethylamine, and their homologues, mono- and di-ethanolamine, dibenzylamine, cyclohexylamine, dicyclohexylamine, piperidine, morpholine, and benzyldimethylamine.  Specified alkylating or aralkylating agents are dimethyl sulphate, benzyl chloride, diethyl sulphate, dimethyl oxalate, methallyl chloride (CH2 : C(CH)3CH2Cl), methyl iodide, ethyl bromide, methyl thiocyanate and benzyl thiocyanate.  The products, particularly those prepared from aromatic hydroxy compounds substituted in the nucleus by an alkyl group of 4-12 carbon atoms, are useful as wetting, emulsifying and cleansing agents and may be applied (a) in dyeing, bleaching, mercerizing and mordanting processes, (b) as spreaders for insecticides, (c) as dispersing-agents for pigments, (d) as pickling inhibitors, and (e) as assistants in leather tanning and finishing processes; the water-soluble quaternary ammonium salts are useful for rendering dyeings with acid, direct or chrome dyes on regenerated-cellulose artificial silk, cotton or cellulose esters or ethers faster to light and washing, and for this purpose the textile is treated with a solution of the quaternary ammonium salt before it is dyed; the quaternary ammonium bases are particularly useful as mercerizing assistants.  In the examples: (1) the condensation product from equimolecular proportions of p-(a , a , g , g -tetramethylbutyl)-phenol and b , b 1-dichlorodiisopropyl ether is treated with dimethylamine, and the amine so produced, after recovery from its hydrochloride, is treated with dimethyl sulphate to yield a quaternary ammonium salt; the latter forms a lake with Congo red, and is useful for improving the fastness to washing of direct dyes; (2) p-(a , a , g , g -tetramethylbutyl)-phenol is condensed with an equimolecular proportion of b -chloro-b 1-(b 11-chloroethoxy) diethyl ether (prepared from triethylene glycol and thionyl chloride); the product is treated with diethanolamine, and the p  amine so produced, after recovery from its hydrochloride, is treated with diethyl sulphate to yield a quaternary ammonium compound; in place of diethanolamine there may be used diethylamine, piperidine, morpholine, dicyclohexylamine, or benzylamine, and the amines so produced may be converted into their phosphates, lactates or acetates.  The Specification as open to inspection under Sect. 91 describes the treatment of compounds of the formula ROAOAX in which R and X are as above, and A is an alkylene group containing two carbon atoms.  The following examples are given: (1A) p-(a , a , g , g -tetramethylbutyl) phenol is condensed with an equimolecular proportion of b , b 1-dichlorodiethyl ether, and the product is treated with diethanolamine; the amine produced is isolated from its hydrochloride, and may then be dissolved in phosphoric acid solution to yield a foaming solution useful for wetting metal surfaces, e.g. in cleaning steel or in rustproofing steel by treatment with solutions of metal phosphates and phosphoric acid; (2) the amine obtained as in example 1A is treated with diethyl sulphate to yield a quaternary ammonium salt, from which the free base may be recovered; (3) the initial condensation product of example 1A is treated with morpholine, and the amine produced is isolated from its hydrochloride; it yields foaming solutions in dilute lactic, phosphoric, oxalic and acetic acids, and may be treated with diethyl sulphate to yield a quaternary ammonium salt, from which the free base may be recovered; (4) the initial condensation product of example 1A is treated with piperidine, and the amine so produced, after recovery from its hydrochloride, is treated with benzyl chloride to yield a quaternary ammonium salt, from which the free base may be recovered; (5) the initial condensation product of example 1A is treated with diethylamine or diamylamine, and the amine so produced, after recovery from its hydrochloride, is treated with dimethyl sulphate to yield a quaternary ammonium salt; (6) the condensation product from equimolecular proportions of p-tert.-butylphenol and b , b 1-dichlorodiethyl ether is treated with diethanolamine; the amine so obtained, after recovery from its hydrochloride, may be converted into its acetate, phosphate or lactate, or into a quaternary ammonium compound by reaction with dimethyl or diethyl sulphate or benzyl chloride; (7) b  - (p-tert. - amylphenoxy) - b 1-chlorodiethyl ether is treated with trimethylamine to yield a quaternary ammonium chloride useful for fixing direct dyes on the fibre; (8) b -(p-tert.-butylphenoxy)-b 1-chlorodiethyl ether is treated with benzyldimethylamine to yield a quaternary ammonium chloride; (9) b  - (p-tert. - amylphenoxy) - b 1-chlorodiethyl ether is treated with diethanolamine; the amine so obtained, after recovery from its hydrochloride, may be converted into its oxalate, phosphate or lactate, or it may be treated with diethyl sulphate to yield a quaternary ammonium salt; (10) the initial condensation product of example 1 is treated with dimethylamine, and the amine so produced, after recovery from its hydrochloride, is treated with diethyl sulphate to yield a quaternary ammonium salt useful for fixing acid dyes on the