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Cisapride hydrate, R-51619(anhydrous), Arcasin, Alimix, Propulsin, Propulsid, Acenalin, Risamol, Prepulsid

西沙必利Chemical Name: cis-4-Amino-5-chloro-N-[1-[3-(4-fluorophenoxy)propyl]-3-methoxypiperidin-4-yl]-2-methoxybenzamide monohydrate; cis-4-Amino-5-chloro-N-[1-[3-(4-fluorophenoxy)propyl]-3-methoxypiperidin-4-yl]-o-anisamide monohydrate
CAS No. 81098-60-4 (anhydrous)
项目整合开发状态: Launched-1988
项目研究机构: Janssen (Originator), Janssen-Cilag (Originator), Esteve (Licensee), Mitsubishi Pharma (Licensee)
合成路线:By condensation of cis-4-amino-5-chloro-2-methoxy-N-(3-methoxy-4-piperidyl)benzamide (I) with 1-(3-chloropropoxy)-4-fluorobenzene (II) by means of KI and triethylamine in hot DMF.

合成路线:By condensation of 4-amino-5-chloro-2-methoxybenzoyl chloride (III) with 4-amino-1-[3-(fluorophenoxy)propyl]-3-methoxypiperidine (IV) by means of triethylamine in CHCl3.

合成路线:The bromination of 4-oxopiperidine-1-carboxylic acid ethyl ester (I) with Br2 in chloroform gives 3-bromo-4-oxopiperidine-1-carboxylic acid ethyl ester (II),which is treated with NaOMe in methanol to yield 3-hydroxy-4,4-dimethoxypiperidine-1-carboxylic acid ethyl ester (III).The methylation of (III) with NaH and MeI in DMF affords 3,4,4-trimethoxypiperidine-1-carboxylic acid ethyl ester (IV),which is hydrolyzed with refluxing 1% aq.H2SO4 to provide 3-methoxy-4-oxopiperidine-1-carboxylic acid ethyl ester (V).The reductocondensation of (V) with benzylamine and H2 over Pd/C in methanol in the presence of thiophene gives cis-4-amino-3-methoxypiperidine-1-carboxylic acid ethyl ester (VI),which is condensed with 4-amino-5-chloro-2-methoxybenzoic acid (VII) by means of ethyl chloroformate and TEA in chloroform to yield the benzamide (VIII).The hydrolysis of the carbamate group of (VIII) with KOH in refluxing isopropanol affords the free piperidine derivative (IX),which is finally condensed with 3-(4-fluorophenoxy)propyl chloride (X) by means of TEA and KI in hot DMF to provide the target,cisapride.
📌 参考资料/链接:
参考文献标题:Novel N-(3-hydroxy-4-piperidinyl)benzamide derivs.
文献作者:Van Daele,G.(Janssen Pharmaceutica NV)
参考来源:US 4962115

📄 详细内容


合成路线:The reaction of 4-amino-5-chloro-2-methoxybenzoic acid (I) with benzyl chloride (II) and NaHCO3 in refluxing water gives the N-benzyl protected compound (III),which is condensed with cis-4-amino-3-methoxypiperidine-1-carboxylic acid ethyl ester (IV) by means of methyl chloroformate and TEA in dichloromethane to yield the benzamide (V).The deprotection of (V) with KOH in refluxing isopropanol affords compound (VI) with a free piperidinic NH group that is acylated with 3-(4-fluorophenoxy)propyl chloride (VII) by means of Na2CO3 in refluxing methylisobutylketone to provide the protected adduct (VIII).Finally,this compound is debenzylated by hydrogenation with H2 over Pd/C in hot methanol to give the target compound.Alternatively,the piperidine derivative (VI) is treated with p-toluenesulfonic acid in refluxing toluene and then debenzylated and simultaneously reductocondensed with 3-(4-fluorophenoxy)propionaldehyde (IX) by means of H2 over Pd/C in methanol to give the target compound.

参考文献标题:Process for the preparation of benzamides
文献作者:Gutierrez Fuentes,L.G.
参考来源:ES 2019047


合成路线:The title compound has been obtained by condensation of methanesulfonate (I) with 4-fluorophenol (II) by means of NaNH2 in DMF.

参考文献标题:Process for the preparation of 4-aminopiperidine derivs.
文献作者:Gallardo Carrera,A.(Fordonal SL)
参考来源:ES 8601133


合成路线:The title compound has been obtained by hydrogenation of 4-amino-5-chloro-N-[1-[3-(4-fluorophenoxy)propyl]-3-methoxy-1,2,5,6-tetrahydropyridin-4-yl]-2-methoxybenzamide (I) with H2 over Pt/C or Rh/Al2O3 in methanol.

参考文献标题:Process for obtaining cis-4-amino-5-chloro-2-methoxy-N-[1-[3-(4-fluorophenoxy)propyl]-3-methoxy-4-piperidinyl]benzamide
文献作者:Huguet Clotet,J.; Caldero Ges,J.M.
参考来源:ES 2019235


合成路线:The title compound has been obtained by hydrogenation of 4-(4-amino-5-chloro-2-methoxybenzamido)-1-[3-(4-fluorophenoxy)propyl]-3-methoxypyridinium iodide (I) with H2 over PtO2 in methanol,or with NaBH4 and RhCl3 or NiCl2 in methanol.

参考文献标题:Process for obtaining cis-4-amino-5-chloro-2-methoxy-N-[1-[3-(4-fluorophenoxy)propyl]-3-methoxy-4-piperidinyl]benzamide
文献作者:Caldero Ges,J.M.; Huguet Clotet,J.
参考来源:ES 2019234


合成路线:The title compound has been obtained by hydrogenation of 4-(4-amino-5-chloro-2-methoxybenzamido)-1-[3-(4-fluorophenoxy)propyl]-3-methoxypyridinium iodide (I) with H2 over PtO2 in methanol,or with NaBH4 and RhCl3 or NiCl2 in methanol.

参考文献标题:Process for obtaining cis-4-amino-5-chloro-2-methoxy-N-[1-[3-(4-fluorophenoxy)propyl]-3-methoxy-4-piperidinyl]benzamide
文献作者:Huguet Clotet,J.; Caldero Ges,J.M.
参考来源:ES 2020128


合成路线:The title compound has been obtained by condensation of 4-amino-5-chloro-2-methoxybenzoic acid (I) with cis-1-[3-(4-fluorophenoxy)propyl]-3-methoxypiperidine-4-amine (II) by means of DCC in dichloromethane or PCl3 in benzene.

合成路线:The reductive amination of 4-cyano-4-(4-fluorophenyl)cyclohexanone (I) with (-)-benzyl 3-methyl-4-phenyl-4-piperidinecarboxylate (II) by means of H2 and Pt/C 5% in the presence of thiophene in isopropyl alcohol at normal pressure and at 50 C gives a 9:1 mixture of (-)-benzyl [3S-[1(cis)-3alpha,4beta]]-1-[4-cyano-4-(4-fluorophenyl)cyclohexyl]-3-methyl-4-phenyl-4-piperidinecarboxylate and (-)-benzyl [3S-[1(trans)-3alpha,4beta]]-1-[4-cyano-4-(4-fluorophenyl)cyclohexyl]-3-methyl-4-phenyl-4-piperidine-carboxylate.Chromatographic separation [dry column,silica gel,eluted with organic phase of a mixture of chloroform and methanol (99.0:1.0 by volume) yields the pure (-)-benzyl [3S-[1(cis)-3alpha,methyl-4-phenyl-4-piperidinecarboxylate (III),which is hydrogenolized in tetrahydrofuran at normal pressure and room temperature.The resulting free carboxylic acid is transformed to the monohydrochloric acid in methanol.

参考文献标题:Process for obtaining a 4-amino-5-chloro-2-methoxybenzoic acid deriv.
文献作者:Izquierdo Sanjos? M.; Mart韓 Escudero,U.
参考来源:ES 2002640


产品链接: CAS No. 81098-60-4››