合成路线:It can be prepared in two different ways:1) The cyclization of 3-nitrobenzaldehyde (I),methyl propiolate (II) and ammonium acetate (III) in refluxing acetic acid gives dimethyl 1,4-dihydro-4-(3-nitrophenyl)pyridine-3,5-dicarbocylate (IV),which is aromatized by hot nitric acid affording dimethyl 4-(3-nitrophenyl)pyridine-3,5-dicarbocylate (V).The hydrolysis of (V) with KOH in refluxing ethanol gives the corresponding diacid (VI),which is decarboxylated by treatment with Cu2O in refluxing Dowterm A yielding 4-(3-nitrophenyl)pyridine (VII) (1).The reduction of (VII) with Fe in ethanol-water-acetic acid affords 4-(3-aminophenyl)pyridine (VIII),which is condensed with diethyl ethoxymethylenemalonate (IX) by heating a 135 C,giving diethyl 3-(4-pyridyl)anilinomethylmalonate (X).The thernal cyclization of (X) in refluxing Dowtherm A yields ethyl 1,4-dihydro-4-oxo-7-(4-pyridyl)quinoline-3-carboxylate (XI),which is finally alkylated and saponified by treatment with NaH and ethyl iodide in DMF (1-3).
参考文献标题:
文献作者:
参考来源:CA 999002; GB 1396681; JP 7461176; US 3922278
合成路线:It can be prepared in two different ways:1) The cyclization of 3-nitrobenzaldehyde (I),methyl propiolate (II) and ammonium acetate (III) in refluxing acetic acid gives dimethyl 1,4-dihydro-4-(3-nitrophenyl)pyridine-3,5-dicarbocylate (IV),which is aromatized by hot nitric acid affording dimethyl 4-(3-nitrophenyl)pyridine-3,5-dicarbocylate (V).The hydrolysis of (V) with KOH in refluxing ethanol gives the corresponding diacid (VI),which is decarboxylated by treatment with Cu2O in refluxing Dowterm A yielding 4-(3-nitrophenyl)pyridine (VII) (1).The reduction of (VII) with Fe in ethanol-water-acetic acid affords 4-(3-aminophenyl)pyridine (VIII),which is condensed with diethyl ethoxymethylenemalonate (IX) by heating a 135 C,giving diethyl 3-(4-pyridyl)anilinomethylmalonate (X).The thernal cyclization of (X) in refluxing Dowtherm A yields ethyl 1,4-dihydro-4-oxo-7-(4-pyridyl)quinoline-3-carboxylate (XI),which is finally alkylated and saponified by treatment with NaH and ethyl iodide in DMF (1-3).
参考文献标题:
文献作者:Lesher,G.Y.; Carabateas,P.M.
参考来源:BE 783562; CA 996117; CH 565789; CH 570398; CH 570995; DE 2224090; FR 2138003; GB 1346724; NL 206697; US 3753993
合成路线:2) The thermal cyclization of ethyl 2-[3-(4-pyridyl)anilinomethylene]acetoacetate (XII) gives 1,4-dihydro-4-oxo-7-(4-pyridyl)-3-acetylquinoline (XIII),which is alkylated by treatment with ethyl tosylate (XIV) and K2CO3 in dMF at 100 C yielding 1-ethyl-1,4-dihydro-4-oxo-7-(4-pyridyl)-3-acetylquinoline (XV).Finally the acetyl group of (XV) is oxidized to the corresponding carboxyl residue by treatment with Br2 and NaOH in water.
参考文献标题:
文献作者:
参考来源:JP 7611777; US 4107167
合成路线:It can be prepared in two different ways:1) The cyclization of 3-nitrobenzaldehyde (I),methyl propiolate (II) and ammonium acetate (III) in refluxing acetic acid gives dimethyl 1,4-dihydro-4-(3-nitrophenyl)pyridine-3,5-dicarbocylate (IV),which is aromatized by hot nitric acid affording dimethyl 4-(3-nitrophenyl)pyridine-3,5-dicarbocylate (V).The hydrolysis of (V) with KOH in refluxing ethanol gives the corresponding diacid (VI),which is decarboxylated by treatment with Cu2O in refluxing Dowterm A yielding 4-(3-nitrophenyl)pyridine (VII) (1).The reduction of (VII) with Fe in ethanol-water-acetic acid affords 4-(3-aminophenyl)pyridine (VIII),which is condensed with diethyl ethoxymethylenemalonate (IX) by heating a 135 C,giving diethyl 3-(4-pyridyl)anilinomethylmalonate (X).The thernal cyclization of (X) in refluxing Dowtherm A yields ethyl 1,4-dihydro-4-oxo-7-(4-pyridyl)quinoline-3-carboxylate (XI),which is finally alkylated and saponified by treatment with NaH and ethyl iodide in DMF (1-3).
合成路线:2) The thermal cyclization of ethyl 2-[3-(4-pyridyl)anilinomethylene]acetoacetate (XII) gives 1,4-dihydro-4-oxo-7-(4-pyridyl)-3-acetylquinoline (XIII),which is alkylated by treatment with ethyl tosylate (XIV) and K2CO3 in dMF at 100 C yielding 1-ethyl-1,4-dihydro-4-oxo-7-(4-pyridyl)-3-acetylquinoline (XV).Finally the acetyl group of (XV) is oxidized to the corresponding carboxyl residue by treatment with Br2 and NaOH in water.
参考文献标题:Rosoxacin
文献作者:Blancafort,P.; Serradell,M.N.; Castar,J.; Neuman,M.
参考来源:Drugs Fut 1980,5(4),199
产品链接: CAS No. 40034-42-2››