Patent GB-369614-A (GB)
Title: Improvements in the manufacture and production of organic compounds containing nitrogen
IPC: C07C209/18
Filed: 1930-09-15
Abstract: To effect alkylation of ammonia bases, at least two molecules of the latter are reacted with one molecule of neutral or acid esters of oxygen bearing, preferably polybasic mineral acids with aliphatic alcohols containing more than five carbon atoms.  If salts of the acid esters are employed one molecule or more of the ammonia bases may be used for each molecule of the esters.  The products are stated to be emulsifying agents.  Suitable mineral acid esters are sulphuric esters of aliphatic primary, secondary or tertiary alcohols, such as hexyl alcohol, ethylpropyl carbinol, dimethyl-isobutylcarbinol, decanol, dodecanol, pentadecanol, cetyl alcohol, heptadecanol, octodecyl alcohol, 9 : 10-octodecene-1-ol, octodecandioll, sorbitol, alcohols obtained by the oxidation of paraffin wax or by the reduction of aliphatic carboxylic acids or their esters, such as tallow, olive oil, soya bean oil, train oil, castor oil, or coconut oil or other animal or vegetable fats and oils.  The sulphuric esters obtained from any hydroxy containing aliphatic compound, e.g. hydroxystearic acid, ricinoleic acid, tetradecyldihydroxypropylether or from unsaturated aliphatic compounds, e.g. hexylene, octodecylene, oleic acid or its esters or amides may also be employed.  In place of the sulphuric esters, esters of boric, phosphoric or sulphurous acids may be used.  Suitable ammonia bases, besides ammonia, are methylamine, ethylamine, butylamine, hexylamine, diethylamine, trimethylamine, tributylamine, ethylenediamine or cycloaliphatic amines, aniline, mono- or di-methylaniline, naphthylamine, benzylamine, aminoanthraquinone, piperidine, pyridine, quinoline, and pyrrol.  Amines which contain hydroxyl, halogen, nitro, ester, ether or other groups attached to a carbon atom, e.g. ethanolamines, propanolamines or other mono-, di- or tri-alkylolamines are also suitable.  Unless a very large excess of base is used, more than one aliphatic residue is introduced into the base.  In examples: (1) the sulphuric ester of crude dodecyl alcohol is heated in an autoclave with aqueous ammonia; (2) the sodium or ammonium salt of the sulphuric ester of octodecyl alcohol is heated with aqueous ammonia, methylamine, mono- or tri-ethanolamine or 1 : 3-propanolamine; (3) the alcohols obtained by the catalytic reduction of coco fat are esterified by means of phosphorus oxychloride and then treated with cyclohexylamine; (4) the same mixture of alcohols are sulphonated with chlorsulphonic acid, and the resulting esters, either as such or in the form of their sodium salts are treated with dimethylaniline, crude monoethanolamine, hexamethylenetetramine, di- or tri-methylamine and with tetraethylammoniumchloride; when the latter is used the reaction is effected in the presence of p  aqueous caustic soda; (5) the sodium salt of olein alcohol sulphuric ester is treated with dimethylamine; (6) n-butylamine is alkylated by means of the sodium salt of the disulphuric ester of octodecandiol and of sorbitol sulphuric ester.ALSO:To effect alkylation of ammonia bases, at least two molecules of the latter are reacted with one molecule of neutral or acid esters of oxygen bearing, preferably polybasic mineral acids with aliphatic alcohols containing more than five carbon atoms.  If salts of the acid esters are employed one molecule or more of the ammonia bases may be used for each molecule of the esters.  The products are stated to be wetting, cleansing and emulsifying agents, and also intermediates for dyes and pharmaceutical products.  Suitable mineral acid esters are sulphuric esters of aliphatic primary, secondary, or tertiary alcohols, such as hexyl alcohol, ethylpropyl carbinol, dimethyl-isobutylcarbinol, decanol, dodecanol, pentadecanol, cetyl alcohol, heptadecanol, octodecyl alcohol, 9 : 10-octodecene-1-ol, octodecandiol, sorbitol, alcohols obtained by the oxidation of paraffin wax or by the reduction of aliphatic carboxylic acids or their esters such as tallow, olive oil, soya bean oil, train oil, castor oil, or coco nut oil or other animal or vegetable fats and oils.  The sulphuric esters obtained from any hydroxy containing aliphatic compound, e.g. hydroxystearic acid, ricinoleic acid, tetradecyldihydroxypropylether (obtained from tetradecylalcoholate and glycerol-a -chlorhydrin) or from unsaturated aliphatic compounds, e.g. hexylene, octodecylene, oleic acid or its esters or amides may also be employed.  In place of the sulphuric esters, esters of boric, phosphoric or sulphurous acids may be used.  Suitable ammonia bases, besides ammonia, are methylamine, ethylamine, butylamine, hexylamine, diethylamine, trimethylamine tributylamine, ethylenediamine or cycloaliphatic amines, aniline, mono- or di-methylaniline, naphthylamine, benzylamine, aminoanthraquinone, piperidine, pyridine, quinoline and pyrrol.  Amines which contain hydroxyl, halogen, nitro, ester, ether, or other groups attached to a carbon atom, e.g. ethanolamines, propanolamines or other mono-, di- or tri-alkylolamines, are also suitable.  Diluents, e.g. water, ethyl alcohol, benzene, dibutylether, xylene or nitrobenzene and copper containing catalysts, e.g. copper, copper alloys or salts, may be used for the reaction. Unless a very large excess of base is used, more than one aliphatic residue is introduced into the base. In examples: (1) the sulphuric ester of crude dodecyl alcohol, obtained by means of chlorsulphonic acid, is heated in an autoclave with aqueous ammonia: (2) the sodium or ammonium salt of the sulphuric ester of octodecyl alcohol is heated with aqueous ammonia, methylamine, mono- or triethanolamine or 1 : 3-propanolamine; (3) the alcohols obtained by the catalytic reduction of cocofat are esterified by means of phosphorus oxychloride and then treated with cyclohexylamine; (4) the same alcohols are sulphonated with chlorsulphonic acid, and the resulting esters, either as such or in the form of their sodium salts, are treated with dimethylaniline, crude monoethanolamine, hexamethylenetetramine, di- or tri-methylamine and with tetraethylammoniumchloride; when the latter is used the reaction is effected in the presence of aqueous caustic soda; (5) the sodium salt of olein alcohol sulphuric ester, obtained by sulphonation with chlorsulphonic acid in presence of ether is treated with dimethylamine; (6) butylamine is alkylated by means of the sodium salts of the disulphuric ester of octodecandiol, obtained by treatment with chlorsulphonic acid in the presence of ether, and of sorbitol sulphuric ester, obtained by sulphonation with oleum. Specifications 267,132, 278,982, 306,116, [all in Class 2 (iii), Dyes &c.], and 350,080 are referred to.