Patent GB-454320-A (GB)
Title: Manufacture of oxyalkylated nitrogen bases
IPC: C07C215/14
Filed: 1935-01-24
Abstract: Oxyalkylated nitrogenous bases, containing in the oxyalkyl radicle at least one exchangeable inorganic or organo-inorganic acid ester group, are obtained by reaction of an alkylene oxide containing at least one such acid ester group with a salt of ammonia or a salt of a basic organic or inorganic substitution product of ammonia, more than 1 mol. of the alkylene oxide being employed when the salt used is a hydrohalide of an aliphatic monoamine having hydrogen attached to the nitrogen atom.  The amine salt used may be an internal salt, e.g. glycocoll or taurine and the reaction may be effected in presence of water and/or of an organic solvent, e.g. chloroform, acetone, ethyl acetate, dioxane or alcohol.  A quaternary salt is formed when a salt of a tertiary amine is used and, in any case, the reaction may proceed up to the formation of a quaternary salt.  In using a salt of a tertiary amine containing an unsaturated aliphatic residue which is easily split off by alkali, more than one of the substituted oxyalkyl residues may be introduced.  When the alkylene oxide used is sparingly soluble in water, it is preferably used in conjunction with an emulsifying agent such as an aliphatic alcohol-polyglycol condensation product, sodium sulphopalmitate, sodium isobutylnaphthalenesulphonate, the hydrochloride of the diethylaminoethylamide of oleic acid and/or a protective colloid such as oxyethylcellulose or gum arabic and, to facilitate the dispersion, the alkylene oxide may be diluted with an organic solvent such as benzene or methylal.  Specified anions of the amine salts are those of the following acids, viz. acetic, lactic, tartaric, oleic, nitric, hydrohalic, alkylsulphonic of high molecular weight, alkylnaphthalenesulphonic, tetrahydronaphthalenesulphonic and toluenethiosulphonic acids. The derivatives of ammonia may be simple primary, secondary and tertiary amines, polyamines, aminoalcohols, aminoaldehydes, aminocarboxylic acids and aminosulphonic acids, e.g. dodecylamine, dodecyltriethylenetriamine, b -aminoethyloleylamide, amine derivatives of chlorinated paraffins of high molecular weight, guanidine, ethers of isourea and isothiourea, hydroxylamine and its alkyl derivatives and aromatic amines.  The following examples are specified: (1) piperidine (1 mol.) neutralized with hydrochloric acid (0.9 mol.) is shaken at 40 DEG  C. with epichlorhydrin (1 mol.); the product is a mixture of chlorohydroxypropylpiperidine hydrochloride, piperidine hydrochloride and di-(g -chloro-b -hydroxypropyl)piperidinium chloride; (2) ethylenediamine dihydrochloride (1 mol.) is shaken in aqueous solution with epichlorhydrin (4 or 6 mols.) for 16 hours at room temperature; (3) dodecylamine hydrochloride (1 mol.) in aqueous solution is mixed with epichlorhydrin (2 or 3 mols.) at 50 DEG  C. and the product is separated by addition of potassium carbonate and extracted with ether; (4) piperidine acetate in aqueous solution is shaken with epichlorhydrin until the odour of the latter disappears; (5) an aqueous solution of tetraoxyethylethylenediamine dihydrochloride (1 mol.) is shaken with epichlorhydrin (2 mols.) overnight at room temperature; the solution then contains mainly the diquaternary salt and any tertiary constituents may be converted into quaternary compound by reaction with dimethyl sulphate or into amine oxides by reaction with hydrogen peroxide; (6) an aqueous solution of triethylenetetramine hydrochloride (1 mol.) is shaken with epichlorhydrin (10 mols.) for 16 hours at 25--30 DEG  C.; (7) an aqueous solution of glycocoll or taurine (1 mol.) is shaken with epichlorhydrin (3 mols.) for several days; (8) ammonium chloride (1 mol.) in solution is shaken with epichlorhydrin (4 mols.) at room temperature for several days; (9) butylamine hydrochloride (1 mol.) is heated at 40 DEG  C. with an aqueous solution of the sulphuric acid ester of a -oxyb  : g  - oxido propane (3 mols.); the aminosulphonic acid derivative obtained may be esterified with higher fatty acids to produce a textile assistant; (10) piperidine hydrochloride (\ba1/2\be mol.) is heated for 12 hours at 40 DEG  C. with an aqueous solution of the sodium salt of methylb  : g -oxidopropylphosphoric acid (1 mol.); the product may be converted as in (9) into a textile assistant.  Specification 267,169, [Class 2 (iii)], is referred to.  The sulphuric acid ester of a -oxy-b  : g -oxido propane is obtained in aqueous solution by adding the calculated quantity of caustic soda to a solution, carefully neutralized, after addition of ice, with sodium bicarbonate, of epichlorhydrin in concentrated sulphuric acid.  The sodium salt of methyl-b  : g -oxidopropylphosphoric acid is obtained by reaction at 60 DEG  C. of the disodium salt of methylphosphoric acid (1 mol.) with epichlorhydrin (1 mol.) in aqueous dispersion.