Patent GB-624101-A (GB)
Title: Manufacture of amines and quaternary ammonium salts
IPC: C07D317/28
Filed: 1946-09-24
Abstract: Amino compounds of acetal-like cyclic ethers or of their corresponding polyhydric alcohols are obtained by treating an acetal-like ether of a halogen-alcohol containing at least two hydroxyl groups and a carbonyl compound containing no reactive halogen atoms with ammonia, a primary amine or a secondary amine containing at least five carbon atoms at elevated temperatures and at least 110 DEG  C., e.g. 130-140 DEG  C., when a chlorinated acetal is used, and, if desired, splitting off the carbonyl-compound bound in the manner of an acetal by treatment with an acid to form the salt of a polyoxyamine.  The acetal-like products when of a tertiary amine nature may be converted to their quaternary ammonium salts by treatment with alkylating or aralkylating agents, e.g. dimethyl sulphate, methyl iodide and benzyl chloride. Halogen alcohols instanced are the chlor-, brom-and iodo-glycerine-a -monohalogenhydrin, glycerine-b -monochlorhydrin, chlorobutylene glycol, 4-chloro-butane-triol-(1 : 2 : 3), pentaerythritol monochlorhydrin, mannitan bromhydrin and dulcitan chlorhydrin; carbonyl compounds instanced are form-, acet-, butyr-and benz-aldehyde and acetone, methyl ethyl ketone or diethyl ketone; acetal-like cyclic ethers instanced are (g -chloropropylene)-methylene, -ethylidene, -benzylidene, -isobutylidene and -isopropylidene dioxide; primary amines instanced are methyl-, ethyl-, amyl- and dodecyl-amine and secondary amines instanced are diamyl- and didodecyl-amine and piperidine.  From ammonia a mixture of primary and secondary amino products is obtained and from primary amines a mixture of secondary and tertiary amino products results.  In examples (g -chloropropylene)-isopropylidene dioxide is treated with (1) liquid ammonia under pressure, (2) piperidine under pressure, (3) (g -aminopropylene)-isopropylidene dioxide and (9) under pressure with alcoholic ammonia and sodium carbonate to yield (1) and (9) a mixture of (g -aminopropylene)-isopropylidene dioxide and both of which yield acetone and give the hydrochloride of the corresponding polyhydroxyamine when boiled with hydrochloric acid, (2) the corresponding tertiary base, and (8) iminodi - (g  - propylene - isopropylidene dioxide), (g -chloropropylene)-methylene dioxide is treated under pressure with (3) liquid ammonia and (4) piperidine to give (3) (g -aminopropylene)-methylene dioxide and imino-di-(g -propylene-methylene-dioxide) and (4) (piperidino-N-g -propylene) - methylene dioxide, (g  - chloropropylene)-ethylidene dioxide is treated under pressure with (5) liquid ammonia and (6) piperidine to give (5) (g -aminopropylene)-ethylidene dioxide and imino-di-(g -propylene-ethylidene dioxide and (6) g -piperidino-propylene-ethylidene dioxide, in (7) (g -chloropropylene)-isobutylidene dioxide and piperidine under pressure give g -piperidino-propylene-isobutylidene dioxide, in (10) (g -aminopropylene)-isopropylidene dioxide is treated with hydrochloric acid to yield acetone and 3-aminopropanediol-(1:2), in (11) imino-di-(g -propylene-isopropylidene-dioxide) is treated with sulphuric acid to yield acetone and the corresponding secondary aminoalcohol, and in (12) methyl- and (13) dodecyl - imino - di - (g - propylene - methylene-dioxide) is converted to a quaternary ammonium salt on treatment with methyl iodide and dimethyl sulphate respectively.  (g -Chloropropylene) - isobutylidene dioxide used as starting material in (7) is prepared from glycerine - a  - chlorhydrin and methyl - ethyl ketone.