Patent GB-477981-A (GB)
Title: New nitrogen-containing organic compounds and their application
Filed: 1936-03-30
Abstract: Quaternary ammonium compounds are prepared (a) from a tertiary amine and a halogenated compound or (b) by alkylation, cycloalkylation, arylation or aralkylation of an amine, the components in either case being so selected that the products contain at least one group of more than five carbon atoms. Preferably, one of the components contains also an acidic salt-forming group, e.g. a carboxylic, sulphonic, sulphuric ester, phosphoric acid, phosphoric ester or borate group, and in this case inner anhydrides of the betaine type may be obtained by treating the products with alkali.  Other substituents, e.g. halogen or a hydroxyl, amino, benzoylamino, trifluoromethyl, acetyl or alkoxy group or an ester group may also be present. Specified radicles which the products may contain are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. butyl, amyl, hexyl, heptyl, octyl, decyl, lauryl, tetradecyl, myristyl, cetyl, stearyl, oleyl, ricinoleyl, linoleyl, hydroxyethyl, a , b -dihydroxypropyl, sulphoethyl, a -sulpho-b -hydroxypropyl, b -hydroxypropyl-a -sulphuric ester, or a b -hydroxypropyl group having a quaternary ammonium group in a -position, or a residue of propylene oxide, hexylene, octylene, decylene, dodecylene, tetradecylene, hexadecylene or didecylene.  Specified tertiary amines which may be used are trialkylamines such as trimethylamine, dialkylcyclohexylamines such as dimethylcyclohexylamine, dicyclohexylalkylamines, tertiary amines containing from one to three hydroxyalkyl groups, such as dialkylethanolamines and triethanolamine, alkylpiperidines, hydroxyalkylpiperidines, and, in general, compounds of the pyridine, piperidine, quinoline and acridine series.  In the examples, (1) trimethylamine is treated with a -bromostearic acid, and the product is warmed with alcoholic caustic potash; (2) dimethylcyclohexylamine is treated with a -bromostearic acid, and the product is warmed with alcoholic caustic potash; (3) trimethylamine is treated with octadecylene chlorosulphonate (sic) (from octadecylene and chlorsulphonic acid), and the product is warmed with alcoholic sodium ethylate; (4) dimethyloctadecylamine is treated with sodium chloracetate; (5) triethanolamine is treated with octadecylene chlorosulphonate; (6) dimethyloctadecylamine is treated with sodium bromethanesulphonate; (7) dimethyllorolamine is treated with ethylene chlorhydrin; dimethyloctadecylamine or dimethylstenylamine ("stenyl" meaning the radicle of a higher aliphatic alcohol mixture comprising mainly hexadecyl and octadecyl alcohols) may be similarly treated; the free hydroxy groups in the products may be esterified with sulphuric acid; (8) dimethylstenylamine is treated with glycerol a -monochlorhydrin, glycerol a , g -dichlorhydrin, or epichlorhydrin; the product from glycerol dichlorhydrin contains two quaternary ammonium groups; the free hydroxy groups in the products may be esterified with sulphuric acid; (9) dimethylstenylamine is treated with hexadecyl bromide or stenyl chloride, bromide or iodide; (10) dimethylstenylamine is treated with sodium chloropropanol sulphonate.  Other specified products are the inner anhydrides obtainable by the action of alkalies on the products from (a) dimethylstenylamine and chloracetic acid, (b) dimethyllorolamine and chloracetic acid, (c) dimethylstenylamine and a -chloropropionic acid, (d) methyldistenylamine and chloracetic acid, (e) dimethylstenylamine and the sulphuric ester of g -chloropropanol, (f) dimethyllorol amine and the sulphuric ester of g -chloropropanol, (g) dimethylstenylamine and b -chloropropionic acid, (h) dimethylstenylamine and a  - chloro - b - hydroxypropane - g  - sulphonic acid, and (i) dimethylstenylamine and the g -sulphuric ester of glycerol-a -chlorhydrin.  The products are useful as wetting, washing and emulsifying agents, and may be applied in any of the following textile-treating processes: cleansing animal and vegetable fibres; carbonizing; retting flax; fulling; sizing; desizing; impregnating, e.g. in proofing against water or mildew; bleaching; mordanting; mercerizing; delustring; lustring; degumming; kier-boiling; scouring; stripping; felting; oiling or lubricating; weighting; dyeing in neutral, acid or alkaline baths; reserving cotton in acid baths; dyeing with developed dyes; dyeing cellulose acetate fibres with insoluble dyes; dyeing and printing with aniline black; and dyeing leather.  The products may be used also (a) as components of printing pastes for natural or synthetic fibres, (b) for producing inorganic pigments or azo, basic, acid, vat or sulphur dyes in a finely divided condition, (c) for emulsifying hydrocarbons, higher alcohols, fats, oils, waxes, resins and pitches, (d) in tanning, softening and treating baths for hides and skins, particularly in fat-liquoring, and (e) in flotation processes for concentrating minerals or recovering oils, e.g. fixed oil from oil sands.  For the purposes specified, the products may be used as such or in admixture with one another or with soap or other saponaceous substances.ALSO:Quaternary ammonium compounds are prepared (a) from a tertiary amine and a halogenated compound, or (b) by alkylation, cycloalkylation, arylation or aralkylation of an amine, the components in either case being so selected that the products contain at least one group of more than five carbon atoms. Preferably, one of the components contains also an acidic salt-forming group, e.g. a carboxylic, sulphonic, sulphuric ester, phosphoric acid, phosphoric ester or borate group, and in this case inner anhydrides of the betaine type may be obtained by treating the products with alkali. Other substituents, e.g. halogen or a hydroxyl, amino, benzoylamino, trifluoromethyl, acetyl or alkoxy group or an ester group may also be present. Specified radicles which the products may contain are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. butyl, amyl, hexyl, heptyl, octyl, decyl, lauryl, tetradecyl, myristyl, cetyl, stearyl, oleyl, ricinoleyl, linoleyl, hydroxyethyl, a , b -di-di-hydroxypropyl, sulphoethyl, a -sulpho-b -hydroxypropyl, b -hydroxypropyl-a -sulphuric ester, or a b -hydroxypropyl group having a quaternary ammonium group in a -position, or a residue of propylene oxide, hexylene, octylene, decylene, dodecylene, tetradecylene, hexadecylene or didecylene.  Specified tertiary amines which may be used are trialkylamines such as trimethylamine, dialkyl-cyclohexylamines such as dimethylcyclohexylamine, dicyclohexylalkylamines, tertiary amines containing from one to three hydroxyalkyl groups, such as dialkylethanolamines and triethanolamine, alkylpiperidines, hydroxyalkylpiperidines, and in general, compounds of the pyridine, piperidine, quinoline and acridine series.  In the examples: (1) trimethylamine is treated with a -bromostearic acid and the product is warmed with alcoholic caustic potash; (2) dimethylcyclohexylamine is treated with a -bromostearic acid, and the product is warmed with alcoholic caustic potash; (3) trimethylamine is treated with octadecylene chlorosulphonate (sic), and the product is warmed with alcoholic sodium ethylate; (4) dimethyloctadecylamine is treated with sodium chloracetate; (5) triethanolamine is treated with octadecylene chlorosulphonate; (6) dimethyloctadecylamine is treated with sodium bromethanesulphonate; (7) dimethyllorolamine is treated with ethylene chlorhydrin; dimethyloctadecylamine or dimethylstenylamine ("stenyl" meaning the radicle of a higher aliphatic alcohol mixture comprising mainly hexadecyl and octadecyl alcohols) may be similarly treated; the free hydroxy groups in the products may be esterified with sulphuric acid; (8) dimethylstenylamine is treated with glycerol a -monochlorhydrin, glycerol a - g -dichlorhydrin, or epichlorhydrin; the product from glycerol dichlorhydrin contains two quaternary ammonium groups; the free hydroxy groups in the products may be esterified with sulphuric acid; (9) dimethylstenylamine is treated with hexadecyl bromide or stenyl chloride, bromide or iodide; (10) dimethylstenylamine is treated with sodium chloropropanol sulphonate.  Other specified products are the inner anhydrides obtainable by the action of alkalies on the products from (a) dimethylstenylamine and chloracetic acid, (b) dimethyllorolamine and chloracetic acid, (c) dimethylstenylamine and a -chloropropionic acid, (d) methyldistenylamine and chloracetic acid, (e) dimethylstenylamine and the sulphuric ester of g -chloropropanol, (f) dimethyllorolamine and the sulphuric ester of g -chloropanol, (g) dimethylstenylamine and b -chloropropionic acid, (h) dimethylstenylamine and a  - chloro - b  - hydroxypropane - g -sulphonic acid, and (i) dimethylstenylamine and the g -sulphuric ester of glycerol-a -chlorhydrin.  The products may be applied in oiling or lubricating fibres.  They are useful also for emulsifying hydrocarbons, higher alcohols, fats, oils, waxes, resins and pitches, in flotation processes for recovering oils, e.g. fixed oil from oil sands.  For the purposes specified, the products may be used as such or in admixture with one another or with soap or other saponaceous substances.ALSO:Quaternary ammonium compounds are prepared (a) from a tertiary amine and a halogenated compound or (b) by alkylation, cycloalkylation, arylation or aralkylation of an amine, the components in either case being so selected that the products contain at least one group of more than five carbon atoms. Preferably, one of the components contains also an acidic salt-forming group, e.g. a carboxylic sulphonic, sulphuric ester, phosphoric acid, phosphoric ester or borate group, and in this case inner anhydrides of the betaine type may be obtained by treating the products with alkali.  Other substituents, e.g. halogen or a hydroxyl, amino, benzoylamino, trifluoromethyl, acetyl or alkoxy group or an ester group may also be present. Specified radicl