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A-319492, ABT-492, WQ-3034

德拉沙星Chemical Name: 1-(6-Amino-3,5-difluoropyridin-2-yl)-8-chloro-6-fluoro-7-(3-hydroxyazetidin-1-yl)-4-oxo-1,4-dihydroquinoline-3-carboxylic acid
CAS No. 189279-58-1
项目整合开发状态: Phase II
项目研究机构: Wakunaga (Originator), Abbott (Licensee)
合成路线:Reaction of 2,3,5,6-tetrafluoropyridine (I) with benzylamine (II) in refluxing acetonitrile gives 2-(benzyl-amino)-3,5,6-trifluoropyridine (III),which is debenzylated with H2 over Pd/C in methanol to yield 3,5,6-trifluoropyridine-2-amine (IV).Reaction of amine (IV) with 4-methoxybenzylamine (V) in N-methylpyrrolidone at 140 C affords 3,5-difluoro-6-(4-methoxybenzylamino)pyridine-2-amine (VI),which is cyclized with 2-(3-chloro-2,4,5-trifluorobenzoyl)-3-ethoxyacrylic acid ethyl ester (VII) ?obtained by condensation of 2-(3-chloro-2,4,5-trifluorobenzoyl)acetic acid ethyl ester (VIII) with triethyl orthoformate (IX) by means of acetic anhydride ?in hot DMF in the presence of K2CO3 to provide the N-protected aminoquinolone derivative (X).Reaction of quinolone (X) with HCl in refluxing acetic acid gives 4-(6-amino-3,5-difluoropyridin-2-yl)-8-chloro-6,7-difluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid (XI),which is finally condensed with 3-hydroxyazetidine (XII) by means of N-methylpyrrolidine in refluxing acetonitrile.
📌 参考资料/链接:
参考文献标题:Novel pyridonecarboxylic acid derivs.or their salts and antibacterial agent comprising the same as the active ingredient
文献作者:Yazaki,A.; Niino,Y.; Ohshita,Y.; Hirao,Y.; Amano,H.; Hayashi,N.; Kuramoto,Y.(Wakunaga Pharmaceutical Co.,Ltd.)
参考来源:EP 0911327; EP 0992501; JP 1999322715; JP 2000136191; US 5998436; US 6133284; WO 9711068

📄 详细内容


合成路线:Reaction of 2,3,5,6-tetrafluoropyridine (I) with ammonia in formamide gives the 2-aminopyridine derivative (IV),which is condensed with tert-butylamine (XIII) in N-methylpyrrolidone to yield 6-(tert-butylamino)-3,5-di- fluoropyridine-2-amine (XIV).Condensation of amine (XIV) with 2-(3-chloro-2,4,5-trifluorobenzoyl)-3-ethoxyacrylic acid ethyl ester (VII) gives the adduct (XV),which is cyclized by means of K2CO3 in DMF to afford the quinolone derivative (XVI).Treatment of quinolone (XVI) with HCl in AcOH produces simultaneous ester hydrolysis and tert-butyl group removal,providing 4-(6-amino-3,5-difluoropyridin-2-yl)-8-chloro-6,7-difluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid (XI).Finally,this compound is condensed with 3-hydroxyazetidine (XII) by means of N-methylpyrrolidine in DMF.

参考文献标题:Structure-activity relationships of fluoroquinolones containing various heteroaromatics at N-1; WQ-3034/ABT-492 and its derivatives
文献作者:Ohshita,Y.; Kuramoto,Y.; Niino,Y.; Yazaki,A.
参考来源:42nd Intersci Conf Antimicrob Agents Chemother (Sept 27 2002,San Diego) 2002,Abst F-544


合成路线:Reaction of 2,3,5,6-tetrafluoropyridine (I) with benzylamine (II) in refluxing acetonitrile gives 2-(benzyl-amino)-3,5,6-trifluoropyridine (III),which is debenzylated with H2 over Pd/C in methanol to yield 3,5,6-trifluoropyridine-2-amine (IV).Reaction of amine (IV) with 4-methoxybenzylamine (V) in N-methylpyrrolidone at 140 C affords 3,5-difluoro-6-(4-methoxybenzylamino)pyridine-2-amine (VI),which is cyclized with 2-(3-chloro-2,4,5-trifluorobenzoyl)-3-ethoxyacrylic acid ethyl ester (VII) ?obtained by condensation of 2-(3-chloro-2,4,5-trifluorobenzoyl)acetic acid ethyl ester (VIII) with triethyl orthoformate (IX) by means of acetic anhydride ?in hot DMF in the presence of K2CO3 to provide the N-protected aminoquinolone derivative (X).Reaction of quinolone (X) with HCl in refluxing acetic acid gives 4-(6-amino-3,5-difluoropyridin-2-yl)-8-chloro-6,7-difluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid (XI),which is finally condensed with 3-hydroxyazetidine (XII) by means of N-methylpyrrolidine in refluxing acetonitrile.

合成路线:Reaction of 2,3,5,6-tetrafluoropyridine (I) with ammonia in formamide gives the 2-aminopyridine derivative (IV),which is condensed with tert-butylamine (XIII) in N-methylpyrrolidone to yield 6-(tert-butylamino)-3,5-di- fluoropyridine-2-amine (XIV).Condensation of amine (XIV) with 2-(3-chloro-2,4,5-trifluorobenzoyl)-3-ethoxyacrylic acid ethyl ester (VII) gives the adduct (XV),which is cyclized by means of K2CO3 in DMF to afford the quinolone derivative (XVI).Treatment of quinolone (XVI) with HCl in AcOH produces simultaneous ester hydrolysis and tert-butyl group removal,providing 4-(6-amino-3,5-difluoropyridin-2-yl)-8-chloro-6,7-difluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid (XI).Finally,this compound is condensed with 3-hydroxyazetidine (XII) by means of N-methylpyrrolidine in DMF.
参考文献标题:ABT-492
文献作者:Mealy,N.E.; Castar,J.
参考来源:Drugs Fut 2002,27(11),1033


产品链接: CAS No. 189279-58-1››