Patent GB-282143-A (GB)
Abstract: 282,143. Imray, O. Y., (I. G. Farbenindustrie Akt.-Ges.). Sept. 11, 1926. 4-Amino-2-styrylquinoline and its nuclear substitution products are prepared from 2-methylquinoline compounds of the formula in which R represents a halogen, alkoxy, hydrazino, carbamino, or carbazido group, by exchanging the group R for the amino group and converting the 2-methyl group acid into a styryl residue. Thus, a 4-halogen- or 4-alkoxy-2-styryl quinoline may be heated with ammonia or with a primary or secondary amine, a 4-hydrazino-2-styrylquinoline may be reduced, the 4-carboxylic acid amide of a 2-styrylquinoline may be treated with a hypohalogenite, the 4-carboxylic acid azide of a 2-styrylquinoline may be treated with water or alcohol and the resulting urea or urethane then hydrolyzed, or a 4-R-2-methylquinoline may be converted by any of the preceding methods into a 4-amino-2-methylquinoline and the latter then condensed with an aromatic aldehyde. The products. possess bactericidal properties. According to the examples, (1) 4-chloro-2-methylquinoline is condensed with benzaldehyde and the resulting 2-styryl-4-chloroquinoline is heated with alcoholic ammonia to give 2-styryl-4-aminoquinoline; in the same way 4-chloro-6-ethoxy-2-methylquinoline is connected into 4-amino-6-ethoxy-2-styrylquinoline; (2) 2-styryl-4-chloro-6-ethoxyquinoline is treated with sodium alcoholate and the 4 :6-bisethoxy-2-styrylquinoline produced is heated with alcoholic ammonia to yield 4-amino-6-ethoxy-2- styrylquinoline; (3) 2-styryl-4-phenylhydrazinoquinoline is first prepared by treating 2-styryl-4- chloroquinoline with phenylhydrazine, and then reduced with zinc dust and acetic acid to 2- styryl-4-aminoquinoline; in the same way 2- styryl-4-chloro-6-ethoxyquinoline is transformed into 2-styryl-4-amino-6-ethoxyquinoline; (4) 2- methyl-4-chloro-#-naphthoquinoline, obtained by treating the oxy compound with phosphorus oxychloride, is condensed with benzaldehyde and the resulting 2-styryl compound heated with alcoholic ammonia, whereby 2-styryl-4-amino-#- naphthoquinoline is obtained; (5) 4-chloro-6- ethoxy-2-methylquinoline is heated with alcoholic ammonia and the 4-amino product condensed with m-nitrobenzaldehyde to give 2-m-nitrostyryl-4-amino-6-ethoxyquinoline, which is reduced with iron and hydrochloric acid to 2-maminostyryl-4-amino-6-ethoxyquinoline ; (6) 2- methylquinoline-4-carboxylic acid is condensed with benzaldehyde, the resulting 2-styrylquinoline-4-carboxylic acid esterified, the ester heated with methyl-alcoholic ammonia to give the acid amide, and the latter then treated with a hypobromite solution and caustic potash, whereby 2- styryl-4-aminoquinoline is obtained; the same product results when the afore-mentioned ester is heated with alcoholic hydrazine, the resulting 2-styrylquinoline-4-carboxylic acid hydrazine converted into the azide by treatment in cold acetic acid solution with sodium nitrite, the azide transformed into the urethane by heating with alcohol, and the urethane finally saponified with concentrated hydrochloric acid; (7) 2-maminostyryl-4-amino-6-ethoxyquinoline is prepared from 4-chloro-6-ethoxy-2-methylquinoline by condensation with m-nitrobenzaldehyde, followed by heat treatment with alcoholic ammonia, and finally by reduction;, (8) 2-styryl- 4-chloro-6ethoxyquinoline is heated with an alcoholic solution of ethylamine or diethylamine and forms 2-styryl-4-ethyl- or diethyl-amino-6- ethoxyquinoline ; the 4-diethylamino body may also be prepared by heating 4-chloro-6-ethoxyquinaldine with alcoholic diethylamine and converting the product into the styryl compound by condensation with benzaldehyde.