Patent GB-436793-A (GB)
Title: The manufacture of new quaternary ammonium compounds
Filed: 1934-04-13
Abstract: Quaternary ammonium compounds containing attached to nitrogen an unsulphonated aralkyl radicle and a high-molecular aliphatic radicle of at least 8 carbon atoms, which may be interrupted by an oxygen, sulphur or nitrogen atom, are prepared by (1) reacting upon an aralkylamine with a reactive ester, e.g. a halide or benzenesulphonyl ester, of the high-molecular aliphatic alcohol; (2) treating an amine containing the high-molecular substituent with a reactive ester of an aryl alcohol; (3) reacting an appropriate alcohol or amine with an aralkylamine having an aliphatic radicle containing a replaceable substituent, such as chlorine, attached to the nitrogen; (4) treating with a reactive ester of an aliphatic alcohol an aralkylamine having attached to the nitrogen an aliphatic radicle containing an amino, hydroxyl or sulphydryl group; in each case the product is converted, if necessary, into the quaternary form.  The compounds possess bactericidal and fungicidal properties.  According to the examples, (1) diethyl-benzyl-n-octylammonium chloride is prepared by reacting upon diethyl-n-octylamine, obtained from n-octyl bromide and diethylamine, with benzyl chloride; (2) diethyl-benzyl-dodecyl-ammonium chloride results from the interaction of benzyl chloride with diethyl-dodecylamine, obtained from dodecyl bromide and diethylamine; (3) diethyl - benzyl - (g  - dodecyloxy-b -hydroxypropyl)-ammonium chloride is obtained by reacting with benzyl chloride upon g -dodecyloxy-b -hydroxypropyl-diethylamine, the latter being prepared by heating g -dodecyloxy-b -hydroxypropyl chloride with diethylamine; (4) dimethyl-dodecyl-benzyl-ammonium iodide is prepared by treating dodecyl-benzylamine, obtained from dodecylamine and benzyl chloride, with methyl iodide. Methylhydroxyethyl - benzyl - dodecyl - ammonium chloride is similarly prepared.  The samples furnished under Sect. 2 (5) comprise (1) dimethyl-alkyl-benzyl-ammonium chloride from benzyl chloride and the dimethylalkylamine obtained in accordance with example 10 of Specification 369,614; (2) dimethyldodecyl-benzyl-ammonium chloride from dimethyl-dodecylamine and benzyl chloride; (3) dimethyl-dodecyl-benzyl-ammonium bromide from dimethyl - dodecylamine and benzyl bromide; (4) diethyl-benzyl-(g -dodecyloxy-b -hydroxypropyl)-ammonium chloride by treating g  - (ethyl - benzylamino) - b  - hydroxypropyl bromide, obtained by reacting ethyl-benzylamine with epibromhydrin, with sodium dodecylate and heating the product with ethyl chloride; (5) diethyl-benzyl-dodecylthioethylammonium bromide by treating ethyl-benzylamino-thioethanol, obtained by reacting upon ethyl-benzylaminoethyl chloride with sodium hydrosulphide, first with sodium and then with dodecyl bromide, and heating the resulting ethyl - benzyl - dodecylthioethylamine with ethyl bromide.  Specification 394,196 also is referred to.  The Specification as open to inspection under Sect. 91 describes the high-molecular aliphatic radicle as preferably containing 8--18 carbon atoms and states that other substituents, such as alkoxy and amino groups and halogen atoms, may be present therein. It further states that, instead of aralkyl groups such as benzyl and phenylethyl groups, aliphatic radicles containing at least one double bond may be present, e.g. alkenyl groups such as allyl and crotyl groups.  Again the reactive esters of the high-molecular aliphatic alcohols employed in process (1) above may be esters of alcohols derived from the mixtures of fatty acids obtainable by saponification of naturally-occurring fats and resins, such as palm oil, coconut oil and colophony.  The preparation of the following compounds is also described: (1) allyl-dibutyl-dodecyl-ammonium bromide by heating dibutyl-dodecylamine with allyl bromide; (2) ethyl-crotyl-diethylaminoethyl - dodecyl - ammonium bromide by treating triethyl-dodecyl-ethylenediamine, obtained from dodecylethylamine and diethylaminoethyl chloride, with crotyl bromide; (3) diallyl-dodecyl-phenylethyl-ammonium bromide by reacting upon diallyl-dodecylamine, obtained from diallylamine and dodecyl bromide, with phenylethyl bromide; (4) methyl - ethyl - benzyl - dodecyl - ammonium chloride from methyl-benzyl-dodecylamine and ethyl bromide; similarly, methyl-ethyl-crotyl-decyl-ammonium iodide from ethyl-crotyl-decylamine and methyl iodide, and methyl-ethyl-dodecyloxyethyl-benzyl-ammonium iodide from methyl-dodecyloxyethyl-benzylamine and ethyl iodide. Trimethyl-octadecyl-ammonium iodide, diethyl-crotyl-(g -dodecyloxy-a -hydroxypropyl)-ammonium bromide, methyl-allyl-didodecylammonium bromide and ethyl-cyclohexyl-allyldodecyl-ammonium chloride are referred to. Finally, it is stated that the quaternary ammonium products in the form of their hydrohalides may be converted into salts with nitric, sulphuric, alkyl- and phenyl-sulphonic, phosphoric, formic, acetic, lactic, citric, tartaric, benzoic and salicylic acids, or may be treated with caustic alkali to give the free bases.  This subject-matter does not appear in the Specification as accepted.