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Watanidipine hydrochloride, Vatanidipine hydrochloride, GJ-0956, AE0047, Calbren

3,5-吡啶二羧酸,1,4-二氢-2,6-二甲基-4-(3-硝基苯基)-,3-[2-[4-[4-(二苯甲基)-1-哌拉嗪基]苯基]乙基] 5-甲基酯,盐酸盐(1:2)Chemical Name: (?-2,6-Dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid 2-[4-[4-(diphenylmethyl)piperazin-1-yl]phenyl]ethyl methyl diester dihydrochloride
CAS No. 133743-71-2, 134028-06-1 ((R)-isomer free base), 134028-07-2 ((R)-isomer monoHCl salt), 134028-04-9 ((S)-isomer free base), 134028-05-0 ((S)-isomer monoHCl salt), 116308-55-5 (free base), 131644-83-2 (HCl), 116308-56-6 (monoHCl), 134054-36-7 (racemic free
项目整合开发状态: Pre-Registered
项目研究机构: Mitsubishi Pharma (Originator), Han All (Licensee)
合成路线:Reaction of 2-(4-aminophenyl)ethanol (I) with bis(2-chloroethyl)amine hydrochloride (II) in butanol gives 2-[4-(1-piperazinyl)phenyl]ethanol (III),which is alkylated with diphenylbromomethane (IV) and potassium carbonate in dimethyl formamide to afford 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethanol (V).Treatment of (V) with diketene (VI) in the presence of 4-dimethylaminopyridine in tetrahydrofuran yields 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethyl acetoacetate (VII),which is finally condensed with 3-nitrobenzaldehyde (VIII) and methyl 3-aminocrotonate (IX) in isopropanol (1-5).This last condensation can be performed in two steps by reaction of compound (VII) with compound (VIII) in the presence of piperidine and acetic acid in benzene to give 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethyl 2-(3-nitrobenzylidene)acetoacetate (X),which is finally treated with (IX) in isopropanol.An alternative procedure involves condensation of 3-nitrobenzaldehyde (VIII),diketene (VI),methyl 3-aminocrotonate (IX) and 3-hydroxypropionitrile (XI) in isopropanol to give 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid 2-cyanoethyl ethyl diester (XII),which is hydrolyzed with sodium hydroxide to 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid monomethyl ester (XIII).Compound (XIII) is finally esterified with compound (V) in a mixture of dimethylformamide and chloroform.
📌 参考资料/链接:
参考文献标题:Use of dihydropyridines in cardiotonic pharmaceutical compsns
文献作者:(Welfide Corporation)
参考来源:EP 0109039; US 4543354

📄 详细内容


合成路线:Reaction of 2-(4-aminophenyl)ethanol (I) with bis(2-chloroethyl)amine hydrochloride (II) in butanol gives 2-[4-(1-piperazinyl)phenyl]ethanol (III),which is alkylated with diphenylbromomethane (IV) and potassium carbonate in dimethyl formamide to afford 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethanol (V).Treatment of (V) with diketene (VI) in the presence of 4-dimethylaminopyridine in tetrahydrofuran yields 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethyl acetoacetate (VII),which is finally condensed with 3-nitrobenzaldehyde (VIII) and methyl 3-aminocrotonate (IX) in isopropanol (1-5).This last condensation can be performed in two steps by reaction of compound (VII) with compound (VIII) in the presence of piperidine and acetic acid in benzene to give 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethyl 2-(3-nitrobenzylidene)acetoacetate (X),which is finally treated with (IX) in isopropanol.An alternative procedure involves condensation of 3-nitrobenzaldehyde (VIII),diketene (VI),methyl 3-aminocrotonate (IX) and 3-hydroxypropionitrile (XI) in isopropanol to give 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid 2-cyanoethyl ethyl diester (XII),which is hydrolyzed with sodium hydroxide to 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid monomethyl ester (XIII).Compound (XIII) is finally esterified with compound (V) in a mixture of dimethylformamide and chloroform.

参考文献标题:Dihydropyridine derivs.and pharmaceutical compsns.Thereof
文献作者:Ashimori,A.; Ono,T.; Inoue,Y.; Fukaya,C.(Welfide Corporation)
参考来源:EP 0257616; JP 1988099042; JP 1988225356; US 4886819


合成路线:Reaction of 2-(4-aminophenyl)ethanol (I) with bis(2-chloroethyl)amine hydrochloride (II) in butanol gives 2-[4-(1-piperazinyl)phenyl]ethanol (III),which is alkylated with diphenylbromomethane (IV) and potassium carbonate in dimethyl formamide to afford 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethanol (V).Treatment of (V) with diketene (VI) in the presence of 4-dimethylaminopyridine in tetrahydrofuran yields 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethyl acetoacetate (VII),which is finally condensed with 3-nitrobenzaldehyde (VIII) and methyl 3-aminocrotonate (IX) in isopropanol (1-5).This last condensation can be performed in two steps by reaction of compound (VII) with compound (VIII) in the presence of piperidine and acetic acid in benzene to give 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethyl 2-(3-nitrobenzylidene)acetoacetate (X),which is finally treated with (IX) in isopropanol.An alternative procedure involves condensation of 3-nitrobenzaldehyde (VIII),diketene (VI),methyl 3-aminocrotonate (IX) and 3-hydroxypropionitrile (XI) in isopropanol to give 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid 2-cyanoethyl ethyl diester (XII),which is hydrolyzed with sodium hydroxide to 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid monomethyl ester (XIII).Compound (XIII) is finally esterified with compound (V) in a mixture of dimethylformamide and chloroform.

参考文献标题:Dihydropyridine derivs.for the treatment of angiospasm
文献作者:Kido,H.; Uchida,T.; Fukaya,C.; Yokoyama,K.; Uchida,Y.(Welfide Corporation)
参考来源:EP 0379737; JP 1990180826


合成路线:Reaction of 2-(4-aminophenyl)ethanol (I) with bis(2-chloroethyl)amine hydrochloride (II) in butanol gives 2-[4-(1-piperazinyl)phenyl]ethanol (III),which is alkylated with diphenylbromomethane (IV) and potassium carbonate in dimethyl formamide to afford 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethanol (V).Treatment of (V) with diketene (VI) in the presence of 4-dimethylaminopyridine in tetrahydrofuran yields 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethyl acetoacetate (VII),which is finally condensed with 3-nitrobenzaldehyde (VIII) and methyl 3-aminocrotonate (IX) in isopropanol (1-5).This last condensation can be performed in two steps by reaction of compound (VII) with compound (VIII) in the presence of piperidine and acetic acid in benzene to give 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethyl 2-(3-nitrobenzylidene)acetoacetate (X),which is finally treated with (IX) in isopropanol.An alternative procedure involves condensation of 3-nitrobenzaldehyde (VIII),diketene (VI),methyl 3-aminocrotonate (IX) and 3-hydroxypropionitrile (XI) in isopropanol to give 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid 2-cyanoethyl ethyl diester (XII),which is hydrolyzed with sodium hydroxide to 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid monomethyl ester (XIII).Compound (XIII) is finally esterified with compound (V) in a mixture of dimethylformamide and chloroform.

参考文献标题:Synthesis and pharmacological effects of optically active 2-[4-(4-benzhydryl-1-piperazinyl)phenyl]ethyl methyl 1,4-dihydro-2,6-dimethyl-4-(3-nitrophenyl)-3,5-pyridinedicrboxylate hydrochloride
文献作者:Ohe,K.; Tanaka,M.; Yokoyama,K.; Uchida,T.; Fukaya,C.; Watanabe,M.; Ohtaki,Y.; Ashimori,A.; Kagitani,M.
参考来源:Chem Pharm Bull 1991,39(1),108-11


合成路线:Reaction of 2-(4-aminophenyl)ethanol (I) with bis(2-chloroethyl)amine hydrochloride (II) in butanol gives 2-[4-(1-piperazinyl)phenyl]ethanol (III),which is alkylated with diphenylbromomethane (IV) and potassium carbonate in dimethyl formamide to afford 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethanol (V).Treatment of (V) with diketene (VI) in the presence of 4-dimethylaminopyridine in tetrahydrofuran yields 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethyl acetoacetate (VII),which is finally condensed with 3-nitrobenzaldehyde (VIII) and methyl 3-aminocrotonate (IX) in isopropanol (1-5).This last condensation can be performed in two steps by reaction of compound (VII) with compound (VIII) in the presence of piperidine and acetic acid in benzene to give 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethyl 2-(3-nitrobenzylidene)acetoacetate (X),which is finally treated with (IX) in isopropanol.An alternative procedure involves condensation of 3-nitrobenzaldehyde (VIII),diketene (VI),methyl 3-aminocrotonate (IX) and 3-hydroxypropionitrile (XI) in isopropanol to give 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid 2-cyanoethyl ethyl diester (XII),which is hydrolyzed with sodium hydroxide to 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid monomethyl ester (XIII).Compound (XIII) is finally esterified with compound (V) in a mixture of dimethylformamide and chloroform.

参考文献标题:Novel 1,4-dihydropyridine calcium antagonists.II.Synthesis and antihypertensive activity of 3-[4-(substituted amino)phenylalkyl]ester derivatives
文献作者:Ono,T.; Ashimori,A.; Inoue,Y.
参考来源:Chem Pharm Bull 1991,39(1),91-9


合成路线:Reaction of 2-(4-aminophenyl)ethanol (I) with bis(2-chloroethyl)amine hydrochloride (II) in butanol gives 2-[4-(1-piperazinyl)phenyl]ethanol (III),which is alkylated with diphenylbromomethane (IV) and potassium carbonate in dimethyl formamide to afford 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethanol (V).Treatment of (V) with diketene (VI) in the presence of 4-dimethylaminopyridine in tetrahydrofuran yields 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethyl acetoacetate (VII),which is finally condensed with 3-nitrobenzaldehyde (VIII) and methyl 3-aminocrotonate (IX) in isopropanol (1-5).This last condensation can be performed in two steps by reaction of compound (VII) with compound (VIII) in the presence of piperidine and acetic acid in benzene to give 2-[4-[4-(diphenylmethyl)-1-piperazinyl]phenyl]ethyl 2-(3-nitrobenzylidene)acetoacetate (X),which is finally treated with (IX) in isopropanol.An alternative procedure involves condensation of 3-nitrobenzaldehyde (VIII),diketene (VI),methyl 3-aminocrotonate (IX) and 3-hydroxypropionitrile (XI) in isopropanol to give 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid 2-cyanoethyl ethyl diester (XII),which is hydrolyzed with sodium hydroxide to 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid monomethyl ester (XIII).Compound (XIII) is finally esterified with compound (V) in a mixture of dimethylformamide and chloroform.
参考文献标题:AE0047
文献作者:Casta馿r,J.; Mealy,N.; Prous,J.
参考来源:Drugs Fut 1994,19(7),627


产品链接: CAS No. 133743-71-2››