Patent GB-484906-A (GB)
Title: Manufacture of carbocyclic basic products
IPC: C07D295/088
Filed: 1936-10-07
Abstract: Carbocyclic compounds containing nitrogen are manufactured by causing an aliphatic halogen ether of an aromatic or hydroaromatic hydroxy compound which is substituted by one or more saturated aliphatic hydrocarbon radicles having more than three carbon atoms or by one or more carbocyclic hydrocarbon radicles having more than three carbon atoms and in which the aliphatic halogen ether radicle, which may be interrupted once or several times by oxygen bound in an ether-like manner, contains at least two carbon atoms, the a -carbon atom being free from halogen, to react with ammonia or an organic compound containing primary, secondary or tertiary nitrogen, e.g. aliphatic primary, secondary or tertiary amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, ethanolamine, diethanolamine, triethanolamine, dodecylamine, dodecylmethylamine, dodecyldimethylamine or dodecyldi - (hydroxyethyl) - amine, aromatic amines such as aniline, methylaniline, ethylaniline, N-dodecylaniline, N-mono-or di - (hydroxyethyl) - aniline, a - or b -naphthylamine, sulphanilic or metanilic acid, also cyclohexylamine, pyridine and its homologues, quinoline, piperidine, morpholine, sarcosine, taurine, methyltaurine, butyltaurine or ethanolamine sulphuric ester.  The reaction may be accelerated by the addition of a catalyst containing copper.  The products may be further reacted as follows: (a) those containing an aromatic ring or a hydroxy group may be treated with sulphonating agents; (b) those which contain one or more free hydrogen atoms attached to nitrogen or in a hydroxy group may be reacted with organic compounds containing carboxylic or sulphonic acid groups or functional derivatives thereof, e.g. with carboxylic acids or esters or sulphonic acids, to form salts, esters or amides, with dicarboxylic acids or their anhydrides to form amidocarboxylic acids, with phosgene to form urea chlorides, or with an alkylating agent; (c) those which are not quaternary ammonium salts may be alkylated or aralkylated by treatment with an alkylating or aralkylating agent, e.g. an alkyl halide, an alkylene oxide, a halogen carboxylic acid or an alkyl sulphate, or may be converted into peralkylated compounds.  The products or their derivatives may be used in the pharmaceutical industry and as insectides or fungicides in solution or dispersion in water or dissolved in an organic liquid, whilst those which are water-soluble have foaming, dispersive, wetting and cleansing action.  The halogen ethers employed as starting materials are obtainable by treating the appropriate aromatic or hydroaromatic hydroxy compounds with an alkylene oxide or chlorhydrin, e.g. ethylene, propylene or a  : b -butylene oxide, glycide, epichlorhydrin, ethylene or propylene chlorhydrin, or glycerol a -chlorhydrin or a  : g -dichlorhydrin, and reacting the resulting hydroxyalkyl, polyhydroxyalkyl or polyglycol ethers with a hydrogen halide, with thionyl chloride, advantageously in the presence of an agent binding hydrochloric acid, or with formaldehyde and hydrochloric acid.  In examples: (1) isododecylphenyl decaethylene glycol ether chloride, the chlorine atom of which has been introduced in place of the last hydroxyl of the side chain, e.g. by treatment with thionyl chloride and pyridine, is heated with methylamine in the presence of methanol; the product may be reacted with diglycollic anhydride; (2) isooctylphenyl triethylene glycol ether chloride (obtainable by reacting the corresponding glycol ether with thionyl chloride and pyridine) is heated with trimethylamine in the presence of methanol; (3) iso-dodecylphenyl diethylene glycol ether chloride (obtainable by reacting isododecylphenol with 2 mols. of ethylene oxide and treating the product with thionyl chloride and pyridine) is heated with an alcoholic solution of dimethylamine in the presence of copper powder; the product may be reacted with chloracetic ester, benzyl chloride or dimethyl sulphate; (4) the chloride obtained from iso-octylcyclohexyl monoglycol ether (obtainable by hydrogenating iso-octylphenyl monoglycol ether in the presence of a nickel catalyst) is heated with an alcoholic methylamine solution in the presence of copper powder; the product may be reacted with a halogen carboxylic acid, a dicarboxylic anhydride or phosgene; (5) iso-octylphenyl triethylene glycol o -chloromethyl ether (obtainable by treating the corresponding glycol with formaldehyde and hydrochloric acid gas) is added gradually with stirring to a methanol solution of methylamine; (6) a dibutylated b -chloro-g -hydroxypropyl b -naphthyl ether (obtainable by reacting dibutylated b -naphthol with glycerol a -chlorhydrin and treating the product with thionyl chloride) is heated with methylaniline; the product may be alkylated or aralkylated, e.g. by treatment with methyl chloride, dimethyl sulphate or benzyl chloride, or may be treated with sulphuric acid monohydrate; (7) p-octadecylphenoxyethyl chloromethyl ether (obtainable by treating p-octadecylphenyl monoglycol ether with paraformaldehyde and hydrochloric acid) is reacted with pyridine in benzine solution; (8) p-hydroxydiphenyl chlorethyl ether (obtainable by treating the hydroxyethyl ether with thionyl chloride and pyridine) is heated in an autoclave with ammonia and alcohol; (9) iso-octylphenyl chlorethyl ether is dissolved in alcohol and heated in an autoclave with an aqueous solution of sodium methylaminoethane sulphonate; (10) perhydro - p - hydroxydiphenyl b  - chlorethyl ether is heated in an autoclave with ammonia and alcohol; (11) iso-tetradecylphenylhydroxyethyl chlormethyl ether (obtainable by reacting iso-tetradecylphenyl monoglycol ether with paraformaldehyde and hydrochloric acid) is dissolved in methylene chloride, and triethylamine is added gradually with stirring; (12) iso-octylphenyl triethylene glycol ether chloride is heated in an autoclave with ammonia and methanol.  Specification 380,431 is referred to.