Patent GB-474671-A (GB)
Title: Improvements in the manufacture and production of nitrogenous condensation products
IPC: D06M13/467
Filed: 1936-04-29
Abstract: Amines or quaternary ammonium compounds are obtained by the action of nitrogenous organic bases on compounds of the formula Halogen--CH2CH2OCH2CH2X, in which X is halogen, --OR,, or --OCOR, R indicating hydrogen or an alkyl, cycloalkyl, aralkyl or aryl group, which may be substituted; if the products contain a secondary or tertiary amino group, they may be after-treated to convert them into the quaternary form.  The reagents must be so selected that the final products contain at least one aliphatic or cycloaliphatic radicle having at least six directly connected carbon atoms, or a polyalkylene polyamine chain containing at least six carbon atoms. Further, at least one mol. of organic base must be used for each halogen atom in the halogenated starting material, and the organic base must not contain an aromatic radicle unless X in the formula above is or contains halogen, in which event at least one molecular proportion of the organic base or bases must be free from aromatic radicles. When X in the formula above is halogen, the process may be effected in any of the following ways: (a) one mol. of b  : p  b <1>-dichlorodiethyl ether is reacted with two mols. of a non-aromatic tertiary amine, e.g. dimethyldodecylamine, dimethyloctadecylamine or a tertiary amine mixture containing the radicles of the alcohols corresponding to palm kernel fatty acids; this process yields diquaternary compounds; (b) one mol. of b  : b <1>-dichlorodiethyl ether is reacted with one mol. of a non-aromatic tertiary amine, e.g. one of those specified above or trimethylamine, triethylamine, triethanolamine, diethylethanolamine, pyridine or methylpiperidine, and the product is treated with one mol. of a primary or secondary amine, which may be aromatic, e.g. octadecylamine, octadecenylamine, dimethylamine, aniline, ethylaniline or naphthylamine; (c) one mol. of b  : b <1>-dichlorodiethyl ether is treated simultaneously with one mol. each of a tertiary amine and a primary or secondary amine, or with two mols. of a non-aromatic primary or secondary amine. Compounds in which X in the formula above is --OR are obtainable by treating b  : b <1>-dichlorodiethyl ether with an equimolecular amount of an alkali phenolate or an alkali compound of an aliphatic, cycloaliphatic or araliphatic alcohol, e.g. methyl, ethyl, butyl, amyl, cetyl, benzyl or phenylethyl alcohol, cyclohexanol, or abietinol or its hydrogenation products containing hydroxyl. Compounds in which X in the formula above is --OCOR are obtainable by esterifying b -chloro-b <1>-hydroxydiethyl ether with saturated or unsaturated aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids such as oleic acid, acids obtained by oxidizing paraffin wax, stearic acid, phenylacetic acid, benzoic acid, phthalic acid, montanic acid, naphthenic acids, and resin acids such as abietic acid or colophony or their hydrogenation products; esterification products of b -chloro-b <1>-hydroxydiethyl ether with halogenated carboxylic acids, such as chloracetic, a -chlorobutyric, a -bromolauric or d -bromopropylmalonic acid, may also be used, and in such cases the halogen in the acid radicle may also be reacted with an amine.  As a modification, b -chloro-b <1>-hydroxydiethyl ether may be treated with an equimolecular proportion of a non-aromatic amine, and the product then etherified or esterified. Any primary or secondary amino groups in any of the products obtained as described above may be converted into quaternary ammonium groups, e.g. by reaction with dimethyl sulphate, methyl bromide or iodide, benzyl chloride or bromide, cetyl iodide, or ethylene oxide, and in all cases the halogenated starting material or the amine(s) or the reagents used for the production of quaternary ammonium groups must be selected in accordance with the conditions set out above.  The products have wetting and foaming properties, and they include products useful (a) as dispersing-agents for mineral oils, (b) as washing-agents, (c) as antiseptics and (d) as dressing-agents for artificial silk.  Products containing no quaternary ammonium group may be used as salts, e.g. with acetic, lactic or hydrochloric acid. In the examples, (1) oleic acid is esterified with b -chloro-b <1>-hydroxydiethyl ether, and the ester is heated with pyridine; a solution of the product has wetting and washing properties, and improves the fastness of substantive dyeings to water; (2) b -chloro-b <1>-hydroxydiethyl ether is heated with octadecylamine, then with chloracetic acid, and finally with pyridine, trimethylamine, dimethyldodecylamine, or methylpiperidine; in place of the tertiary amine, a primary or secondary amine, e.g. methylamine, dimethylamine, dodecylamine or piperidine, may be used, and the product after-treated with dimethyl sulphate, methyl bromide or benzyl bromide; the products may be used as softening agents for artificial silk; (3) b  : b <1>-dichlorodiethyl ether is heated with octadecylamine and pyridine to yield a product useful as a wetting-agent and as a softening agent for artificial silk; (4) b  : b <1>-dichlorodiethyl ether is heated with dimethyldodecylamine; the product has wetting, foaming and disinfecting properties; (5) b -chloro-b <1>-hydroxydiethyl ether is heated with an amine obtained by hydrogenating naphthenic acid nitrile, and the product is heated first with chloracetic acid and then with pyridine; (6) b  : b <1>-dichlorodiethyl ether is heated with ethyl-a -naphthylamine and dimethyldodecylamine; (7) b  - b <1>-dichlorodiethyl ether is heated with dihydroabietinylamine and a mixture of tertiary amines of the formula (CH3)2NR, where R is the radicle of the alcohols obtainable from palm-kernel acids; (8) b -chloro-b <1>-hydroxydiethyl ether is heated with colophony, and the product is heated with pyridine; the final product is a water-soluble resin useful for imparting a non-slip finish to artificial silk or for fixing substantive dyes on viscose artificial silk; (9) b  : b <1>-dichlorodiethyl ether is heated with octadecylamine; (10) b  : b <1>-dichlorodiethyl ether is heated with a polyalkylene polyamine mixture containing more than six carbon atoms, obtained by heating ethylene chloride with ammonia and distilling off ethylenediamine, diethylenetriamine, and triethylenetetramine; the product is then treated with dimethyl sulphate, a final product useful for improving the fastness to water of substantive dyeings being obtained; (11) b -chloro-b <1>-hydroxydiethyl ether is heated with octadecylamine; the salts of the product with hydrochloric, formic or acetic acid may be used as softening agents for artificial silk or as additions to spinning solutions; (12) b  : b <1>-dichlorodiethyl ether is heated with dodecylamine, and the product is treated with ethylene oxide; the final product is useful for dispersing calcium soaps and as a levelling agent in vat dyeings; (13) b  : b <1>-dichlorodiethyl ether is treated with octadecenylamine, and the product is treated with ethylene oxide; the final product is useful as a levelling agent in vat dyeing; (14) b -chloro-b <1>-hydroxydiethyl ether or b  - b <1>-dichlorodiethylether is treated with an amine mixture obtained by hydrogenating the nitriles of the unsaturated acids of train oil; products useful for emulsifying or for softening artificial silk and leather are obtained.  Specification 437,104 is referred to. Reference has been directed by the Comptroller to Specifications 459,746 and 465,200.ALSO:Amines or quaternary ammonium compounds are obtained by the action of nitrogenous organic bases on compounds of the formula <FORM:0474671/III/1> in which X is halogen, --OR, or --OCOR, R indicating hydrogen or an alkyl, cycloalkyl, aralkyl or aryl group, which may be substituted; if the products contain a secondary or tertiary amino group, they may be after-treated to convert them into the quaternary form.  The reagents must be so selected that the final products contain at least one aliphatic or cycloaliphatic radicle having at least six directly connected carbon atoms, or a polyalkylene polyamine chain containing at least six carbon atoms.  Further, at least one mol. of organic base must be used for each halogen atom in the halogenated starting material, and the organic base must not contain an aromatic radicle unless X in the formula above is or contains halogen, in which event at least one molecular proportion of the organic base or bases must be free from aromatic radicles.  When X in the formula above is halogen, the process may be effected in any of the following ways: (a) one mol. of b  : b <1>-dichlorodiethyl ether is reacted with two mols. of a non-aromatic tertiary amine, e.g. dimethyldodecylamine, dimethyloctadecylamine, or a tertiary amine mixture containing the radicles of the alcohols corresponding to palm kernel fatty acids; this process yields diquaternary compounds; (b) one mol. of b  : b <1>-dichlorodiethyl ether is reacted with one mol. of a non-aromatic tertiary amine, e.g. one of those specified above or trimethylamine, triethylamine, triethanolamine, diethylethanolamine, pyridine or methylpiperidine, and the product is treated with one mol. of a primary or secondary amine, which may be aromatic, e.g. octadecylamine, octadecenylamine, dimethylimine, aniline, ethylaniline or naphthylamine; (c) one mol. of b  : b <1>-dichlorodiethyl ether is treated simultaneously with one mol. each of a tertiary amine and a primary or secondary amine, or with two mols. of a non-aromatic primary or secondary amine.  Compounds in which X in the formula above is --OR are obtainable by treating b  - b <1>-dichlorodiethyl ether with an equimolecular amount of an alkali phenolate or an alkali compound of an aliphatic, cycloaliphatic or araliphatic alcohol, e.g. methyl, ethyl, butyl, amyl, cetyl, benzyl or phenylethyl alcohol, cyclohexanol or abietinol or its hydrogenation products containing hydroxyl. C