Patent GB-449172-A (GB)
Title: Process for the manufacture of derivatives of basically substituted enol and thioenol compounds
IPC: H03J1/02
Filed: 1934-12-20
Abstract: Ethers and esters of basically substituted enolic compounds, and ethers of basically substituted thioenolic compounds, are prepared by any of the following processes: (1) a basically substituted acetylenic compound, which may be in the quaternary form, is treated with an alcohol, a phenol, a carboxylic acid, a mercaptan or a thiophenol in the presence of an alkaline condensing agent; (2) a compound containing two reactive halogen atoms in a -b -position, and a basic substituent which may be in the quaternary form, is treated as in method 1; (3) an ether, ester or thioether, containing both a basic substituent and a quaternary ammonium hydroxide group, the latter being linked to a carbon atom adjacent to that bearing the ether, ester or thioether group, is heated, whereby water and tertiary amine are split off while the ether, ester or thioether group is retained; a modification of this method consists in starting from compounds containing a free hydroxyl or mercapto group in place of an ether, ester, or thioether group, whereupon the hydroxyl or mercapto group is alkylated by reaction with a part of the quaternary ammonium compound; (4) an enol or thioenol alkyl ether or an enol ester containing a reactive substituent such as halogen is reacted with ammonia or a primary, secondary or tertiary amine; when a tertiary amine is used, a quaternary ammonium compound is obtained. In the examples: (1) N-trimethyl-N-propinyl-ammonium bromide and methyl alcohol, heated in presence of sodium methylate, yield N-trimethyl-N-(2-methoxy-2 : 3-propenyl)-ammonium bromide; the same product is obtained starting from N-trimethyl-N-(2 : 3-dibromallyl)-ammonium bromide; N-trimethyl-N-(2-ethoxypropenyl)-and N - trimethyl - N - (2 - butyloxypropenyl)-ammonium bromide are similarly obtainable; (2) N - trimethyl - N - propinyl - ammonium bromide, heated with ethylene glycol monomethyl ether containing dissolved sodium, yields N-trimethyl-N-(2-methoxyethoxy-2 : 3-propenyl)-ammonium bromide; N-trimethyl-N - (2 - dimethylaminoethoxy - 2 : 3 - propenyl)-ammonium bromide is similarly obtainable by using dimethylaminoethanol in place of the glycol ether; (3) N - trimethyl - N - propinylammonium bromide, heated with ethyl mercaptan containing its sodium compound, yields N-trimethyl-N-(2-thioethoxy-2 : 3-propenyl)-ammonium bromide; (4) N-trimethyl-N-propinyl-ammonium bromide, heated with acetic acid and zinc oxide, yields N-trimethyl-N-(2-acetoxy-2 : 3-propenyl)-ammonium bromide; (5) (a) 2-methoxy-3-chloropropene-1 : 2, heated with dimethylamine, yields 2-methoxy-3-dimethylaminopropene-1 : 2, which is treated with methyl bromide, without isolation, to yield N-trimethyl-N-(2-methoxy-2 : 3-propenyl)-ammonium bromide; (b) 2-ethoxy-3-chloropropene-1 : 2 and trimethylamine yield N - trimethyl - N - (2 - ethoxy - 2 : 3 - propenyl)-ammonium chloride; (c) 2-ethoxy-2 : 3-cyclohexenyl chloride and trimethylamine yield N-trimethyl-N-(2-ethoxy-2 : 3-cyclohexenyl)-ammonium chloride; (d) 2-ethoxy-3-chloropropene-1 : 2 and N-methylpiperidine yield N-methyl-N-(2-ethoxypropenyl)-piperidinium chloride; (e) 2-ethoxy-5-bromopentene-1 : 2 and trimethylamine yield N-trimethyl-N-(2-ethoxy - 1 : 2 - pentenyl) - ammonium bromide; (6) 2-methoxy-3-chloropropene-1 : 2 and tetramethylethylenediamine yield N : N<1>-tetramethyl-N : N<1> - di(2 - methoxy - 2 : 3 - propenyl)-ethylenediammonium dichloride; (7) 1 : 3-tetramethyldiamino - 2 - propanol dichloromethylate, heated with alcoholic caustic potash, yields N-trimethyl - N - (2-methoxy - 2 : 3-propenyl)-ammonium hydroxide, which is recovered as the picrolonate; (8) the carbonate of 1 : 3-tetramethyldiamino - 2 - propanol dichloromethylate, heated with alcoholic caustic potash, yields the carbonate of N-trimethyl-N-(2-hydroxypropenyl)-ammonium chloride; (9) the dimethylurethane of 1 : 3-tetramethyldiamino-2-propanol dichloromethylate, heated with alcoholic caustic potash, yields the dimethylurethane of N-trimethyl-N-(2-hydroxypropenyl)-ammonium chloride; (10) 2-ethoxy-3-chloropropene-1 : 2 and 6-methoxy-8-aminoquinoline yield 2-ethoxy-3-(6<1>-methoxy-8<1>-quinolylamino)-propene-1 : 2; (11) 2-ethoxy-3-chloropropene-1 : 2 and diethylamine yield 2 - ethoxy - 3 - diethylaminopropene - 1 : 2.  Basically substituted compounds containing more than one enol ester or ether group, and esters and ethers of basically substituted enol compounds containing aromatic substituents, are stated to be obtainable.  Samples have been furnished under Sect. 2(5) of the following products: (1) N-trimethyl-N-(2-phenoxy-2 : 3-propenyl)-ammonium bromide prepared from N-trimethyl-N-propinyl-ammonium bromide and sodium phenolate; (2) the same compound prepared by heating 1 : 3-tetramethyldiamino - 2 - phenoxypropane dichloromethylate with caustic potash; (3) N-trimethyl-N-(2-p-methylthiophenoxy-2 : 3-propenyl)-ammonium bromide prepared from N-trimethyl-N-propinyl-ammonium bromide and p-thiocresol; (4) the same product as sample 3 prepared by heating 1 : 3-tetramethyldiaminopropane - 2 - thiocresyl ether dibromomethylate.  2-Methoxy-3-chloropropene-1 : 2, used in some of the examples, is prepared by heating with quinoline phosphate monochloracetone dimethyl acetal, which is obtained from formimino methyl ether, methanol, and chloracetone.  2-Ethoxy-3-chloropropene-1 : 2, used in some of the examples, is prepared by heating monochloracetone diethylacetal with quinoline phosphate.  2-Ethoxy-2 : 3-cyclohexenyl chloride, used in example 5 (c), is prepared by heating with quinoline phosphate chlorocyclohexanone diethylacetal, which is obtainable from chlorocyclohexanone and ethyl orthoformate. Carbonate of 1 : 3-tetramethyldiamino-2-propanol dichloromethylate, used in example 8, is prepared from 1 : 3-tetramethyldiamino-2-propanol by reaction with phosgene and methyl chloride successively.  Dimethylurethane of 1 : 3-tetramethyldiamino-2-propanol dichloromethylate, used in example 9, is prepared from glycerol a , g -dichlorhydrin by reaction with phosgene, dimethylamine, and methyl chloride successively.