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Imidapril hydrochloride, TA-6366, SH-6366, Novarok, Tanatril

盐酸咪达普利 咪达普利 Chemical Name: (-)-(4S)-3-[2(S)-[N-[1(S)-(Ethoxycarbonyl)-3-phenylpropyl]amino]propionyl]-1-methyl-2-oxoimidazolidine-4-carboxylic acid hydrochloride; (-)-3-[N-[1(S)-(Ethoxycarbonyl)-3-phenylpropyl]-L-alanyl]-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid hydrochloride
CAS No. 89396-94-1, 89371-37-9 (free base)
项目整合开发状态: Launched-1993
项目研究机构: Nihon Schering (Orphan Drug), Tanabe Seiyaku (Orphan Drug), Tanabe Seiyaku (Originator), Ipsen (Not Determined), Hormosan-Kwizda (Marketer), aaiPharma (Licensee), Dong-A (Licensee), Gerot (Licensee), Nihon Schering (Licensee), Trinity Pharmaceuticals (Lic
合成路线:9,10-Difluoro-3-(hydroxymethyl)-7-oxo-2,3-dihydro-7H-pyrido[1,2,3-de]-1,4-benzoxazine-6-carboxylic acid ethyl ester (I),a racemic intermediate in the synthesis of racemic ofloxacin,is esterified with 3,5-dinitrobenzoyl chloride (II) in the usual way to give the racemic ester (III),which is resolved into its optical isomers by HPLC over a SUMIPAX OA-4200 column,using hexane-1,2-dichloroethane-ethanol as carrier solvent.The (-)-optical isomer (IV) is partially hydrolyzed with ethanolic aqueous NaHCO3 to afford the (-)-alcohol (V),which is treated with triphenylphosphite methiodide in DMF giving the corresponding (-)-iodomethyl derivative (VI).The reduction and simultaneous hydrolysis of (VI) with tributyltin hydride in ethanol yields (-)-9,10-difluoro-3-methyl-7-oxo-2,3-dihydro-7H-pyrido[1,2,3-de]-1,4-benzoxazine-6-carboxylic acid (VII),which is finally treated with N-methylpiperazine (VIII) to give (-)-ofloxacin.

合成路线:This compound can be obtained by two related ways:1) The condensation of 2-O-(p-toluenesulfonyl)-D-lactoyl chloride (IV) with 1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (VIII) by means of potassium tert-butoxide in THF gives 1-methyl-2-oxo-3-[2(R)-(p-toluenesulfonyloxy)propionyl]imidazolidine-4(S)-carboxylic acid tert-butyl ester (IX),which is then condensed with 2(S)-amino-4-phenylbutyric acid ethyl ester (X) by means of triethylamine in DMSO yielding 3-[N-[1(S)-(ethoxycarbonyl)-3-phenylpropyl]-L-alanyl]-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (XI).Finally,this compound is hydrolyzed with HCl in dioxane - water.The starting compounds (IV) and (VIII) are obtained as follows:a) The condensation of D-lactic acid methyl ester with p-toluenesulfonyl chloride and triethylamine gives the corresponding sulfonate (II),which is hydrolyzed with NaOH to the free acid (III).Finally,this compound is treated with refluxing SOCl2 to give acid chloride (IV).b) The esterification of 3-(benzyloxycarbonyl)-2-oxoimidazolidine-4(S)-carboxylic acid (V) with tert-butanol gives the corresponding ester (VI),which is methylated with methyl iodide and K2CO3 to 3-(benzyloxycarbonyl)-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (VII).This compound is debenzylated by hydrogenation with H2 over Pd/C to afford imidazolidine ester (VIII).2) The condensation of 2(S)-bromo-4-phenylbutyric acid ethyl ester (XII) with L-alanine benzyl ester (XIII) by means of K2CO3 in DMSO gives N-[1(S)-(ethoxycarbonyl)-3-phenylpropyl]-L-alanine benzyl ester (XIV),which is debenzylated by hydrogenation as before yielding the free acid (XV).The esterification of (XV) with N-hydroxysuccinimide gives the corresponding active ester (XVI),which is finally condensed with imidazolidine ester (VIII) by means of potassium tert-butoxide to afford the precursor (XI) already obtained.
📌 参考资料/链接:
参考文献标题:Quinolinecarboxylic acid derivs.and method for their preparation
文献作者:Yoneda,N.; Kato,J.; Hayashi,K.; Ochiani,T.; Kinashi,K.(Tanabe Seiyaku Co.,Ltd.)
参考来源:EP 0095163; ES 8603427; US 4508727

📄 详细内容


合成路线:This compound can be obtained by two related ways:1) The condensation of 2-O-(p-toluenesulfonyl)-D-lactoyl chloride (IV) with 1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (VIII) by means of potassium tert-butoxide in THF gives 1-methyl-2-oxo-3-[2(R)-(p-toluenesulfonyloxy)propionyl]imidazolidine-4(S)-carboxylic acid tert-butyl ester (IX),which is then condensed with 2(S)-amino-4-phenylbutyric acid ethyl ester (X) by means of triethylamine in DMSO yielding 3-[N-[1(S)-(ethoxycarbonyl)-3-phenylpropyl]-L-alanyl]-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (XI).Finally,this compound is hydrolyzed with HCl in dioxane - water.The starting compounds (IV) and (VIII) are obtained as follows:a) The condensation of D-lactic acid methyl ester with p-toluenesulfonyl chloride and triethylamine gives the corresponding sulfonate (II),which is hydrolyzed with NaOH to the free acid (III).Finally,this compound is treated with refluxing SOCl2 to give acid chloride (IV).b) The esterification of 3-(benzyloxycarbonyl)-2-oxoimidazolidine-4(S)-carboxylic acid (V) with tert-butanol gives the corresponding ester (VI),which is methylated with methyl iodide and K2CO3 to 3-(benzyloxycarbonyl)-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (VII).This compound is debenzylated by hydrogenation with H2 over Pd/C to afford imidazolidine ester (VIII).2) The condensation of 2(S)-bromo-4-phenylbutyric acid ethyl ester (XII) with L-alanine benzyl ester (XIII) by means of K2CO3 in DMSO gives N-[1(S)-(ethoxycarbonyl)-3-phenylpropyl]-L-alanine benzyl ester (XIV),which is debenzylated by hydrogenation as before yielding the free acid (XV).The esterification of (XV) with N-hydroxysuccinimide gives the corresponding active ester (XVI),which is finally condensed with imidazolidine ester (VIII) by means of potassium tert-butoxide to afford the precursor (XI) already obtained.

参考文献标题:Agents for the treatment of hypertension
文献作者:Yoneda,N.; Kato,S.; Hayashi,K.; Ochiai,K.(Tanabe Seiyaku Co.,Ltd.)
参考来源:JP 1985013715


合成路线:This compound can be obtained by two related ways:1) The condensation of 2-O-(p-toluenesulfonyl)-D-lactoyl chloride (IV) with 1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (VIII) by means of potassium tert-butoxide in THF gives 1-methyl-2-oxo-3-[2(R)-(p-toluenesulfonyloxy)propionyl]imidazolidine-4(S)-carboxylic acid tert-butyl ester (IX),which is then condensed with 2(S)-amino-4-phenylbutyric acid ethyl ester (X) by means of triethylamine in DMSO yielding 3-[N-[1(S)-(ethoxycarbonyl)-3-phenylpropyl]-L-alanyl]-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (XI).Finally,this compound is hydrolyzed with HCl in dioxane - water.The starting compounds (IV) and (VIII) are obtained as follows:a) The condensation of D-lactic acid methyl ester with p-toluenesulfonyl chloride and triethylamine gives the corresponding sulfonate (II),which is hydrolyzed with NaOH to the free acid (III).Finally,this compound is treated with refluxing SOCl2 to give acid chloride (IV).b) The esterification of 3-(benzyloxycarbonyl)-2-oxoimidazolidine-4(S)-carboxylic acid (V) with tert-butanol gives the corresponding ester (VI),which is methylated with methyl iodide and K2CO3 to 3-(benzyloxycarbonyl)-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (VII).This compound is debenzylated by hydrogenation with H2 over Pd/C to afford imidazolidine ester (VIII).2) The condensation of 2(S)-bromo-4-phenylbutyric acid ethyl ester (XII) with L-alanine benzyl ester (XIII) by means of K2CO3 in DMSO gives N-[1(S)-(ethoxycarbonyl)-3-phenylpropyl]-L-alanine benzyl ester (XIV),which is debenzylated by hydrogenation as before yielding the free acid (XV).The esterification of (XV) with N-hydroxysuccinimide gives the corresponding active ester (XVI),which is finally condensed with imidazolidine ester (VIII) by means of potassium tert-butoxide to afford the precursor (XI) already obtained.

参考文献标题:Process for preparing optically active 2-oxoimidazolidine derivs
文献作者:Hayashi,K.; Kubota,H.(Tanabe Seiyaku Co.,Ltd.)
参考来源:EP 0373881


合成路线:This compound can be obtained by two related ways:1) The condensation of 2-O-(p-toluenesulfonyl)-D-lactoyl chloride (IV) with 1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (VIII) by means of potassium tert-butoxide in THF gives 1-methyl-2-oxo-3-[2(R)-(p-toluenesulfonyloxy)propionyl]imidazolidine-4(S)-carboxylic acid tert-butyl ester (IX),which is then condensed with 2(S)-amino-4-phenylbutyric acid ethyl ester (X) by means of triethylamine in DMSO yielding 3-[N-[1(S)-(ethoxycarbonyl)-3-phenylpropyl]-L-alanyl]-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (XI).Finally,this compound is hydrolyzed with HCl in dioxane - water.The starting compounds (IV) and (VIII) are obtained as follows:a) The condensation of D-lactic acid methyl ester with p-toluenesulfonyl chloride and triethylamine gives the corresponding sulfonate (II),which is hydrolyzed with NaOH to the free acid (III).Finally,this compound is treated with refluxing SOCl2 to give acid chloride (IV).b) The esterification of 3-(benzyloxycarbonyl)-2-oxoimidazolidine-4(S)-carboxylic acid (V) with tert-butanol gives the corresponding ester (VI),which is methylated with methyl iodide and K2CO3 to 3-(benzyloxycarbonyl)-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (VII).This compound is debenzylated by hydrogenation with H2 over Pd/C to afford imidazolidine ester (VIII).2) The condensation of 2(S)-bromo-4-phenylbutyric acid ethyl ester (XII) with L-alanine benzyl ester (XIII) by means of K2CO3 in DMSO gives N-[1(S)-(ethoxycarbonyl)-3-phenylpropyl]-L-alanine benzyl ester (XIV),which is debenzylated by hydrogenation as before yielding the free acid (XV).The esterification of (XV) with N-hydroxysuccinimide gives the corresponding active ester (XVI),which is finally condensed with imidazolidine ester (VIII) by means of potassium tert-butoxide to afford the precursor (XI) already obtained.

参考文献标题:Studies on angiotensin converting enzyme inhibitors.4.Synthesis and angiotensin converting enzyme inhibitory activities of 3-acyl-1-alkyl-2-oxoimidazolidine-4-carboxylic acid derivatives
文献作者:Hayashi,K.; Nunami,K.-I.; Kato,J.; Yoneda,N.; Kubo,M.; Ochiai,T.; Ishida,R.
参考来源:J Med Chem 1989,32(2),289


合成路线:This compound can be obtained by two related ways:1) The condensation of 2-O-(p-toluenesulfonyl)-D-lactoyl chloride (IV) with 1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (VIII) by means of potassium tert-butoxide in THF gives 1-methyl-2-oxo-3-[2(R)-(p-toluenesulfonyloxy)propionyl]imidazolidine-4(S)-carboxylic acid tert-butyl ester (IX),which is then condensed with 2(S)-amino-4-phenylbutyric acid ethyl ester (X) by means of triethylamine in DMSO yielding 3-[N-[1(S)-(ethoxycarbonyl)-3-phenylpropyl]-L-alanyl]-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (XI).Finally,this compound is hydrolyzed with HCl in dioxane - water.The starting compounds (IV) and (VIII) are obtained as follows:a) The condensation of D-lactic acid methyl ester with p-toluenesulfonyl chloride and triethylamine gives the corresponding sulfonate (II),which is hydrolyzed with NaOH to the free acid (III).Finally,this compound is treated with refluxing SOCl2 to give acid chloride (IV).b) The esterification of 3-(benzyloxycarbonyl)-2-oxoimidazolidine-4(S)-carboxylic acid (V) with tert-butanol gives the corresponding ester (VI),which is methylated with methyl iodide and K2CO3 to 3-(benzyloxycarbonyl)-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (VII).This compound is debenzylated by hydrogenation with H2 over Pd/C to afford imidazolidine ester (VIII).2) The condensation of 2(S)-bromo-4-phenylbutyric acid ethyl ester (XII) with L-alanine benzyl ester (XIII) by means of K2CO3 in DMSO gives N-[1(S)-(ethoxycarbonyl)-3-phenylpropyl]-L-alanine benzyl ester (XIV),which is debenzylated by hydrogenation as before yielding the free acid (XV).The esterification of (XV) with N-hydroxysuccinimide gives the corresponding active ester (XVI),which is finally condensed with imidazolidine ester (VIII) by means of potassium tert-butoxide to afford the precursor (XI) already obtained.

参考文献标题:Imidapril Hydrochloride
文献作者:Prous,J.; Casta馿r,J.
参考来源:Drugs Fut 1992,17(7),551


合成路线:This compound can be obtained by two related ways:1) The condensation of 2-O-(p-toluenesulfonyl)-D-lactoyl chloride (IV) with 1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (VIII) by means of potassium tert-butoxide in THF gives 1-methyl-2-oxo-3-[2(R)-(p-toluenesulfonyloxy)propionyl]imidazolidine-4(S)-carboxylic acid tert-butyl ester (IX),which is then condensed with 2(S)-amino-4-phenylbutyric acid ethyl ester (X) by means of triethylamine in DMSO yielding 3-[N-[1(S)-(ethoxycarbonyl)-3-phenylpropyl]-L-alanyl]-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (XI).Finally,this compound is hydrolyzed with HCl in dioxane - water.The starting compounds (IV) and (VIII) are obtained as follows:a) The condensation of D-lactic acid methyl ester with p-toluenesulfonyl chloride and triethylamine gives the corresponding sulfonate (II),which is hydrolyzed with NaOH to the free acid (III).Finally,this compound is treated with refluxing SOCl2 to give acid chloride (IV).b) The esterification of 3-(benzyloxycarbonyl)-2-oxoimidazolidine-4(S)-carboxylic acid (V) with tert-butanol gives the corresponding ester (VI),which is methylated with methyl iodide and K2CO3 to 3-(benzyloxycarbonyl)-1-methyl-2-oxoimidazolidine-4(S)-carboxylic acid tert-butyl ester (VII).This compound is debenzylated by hydrogenation with H2 over Pd/C to afford imidazolidine ester (VIII).2) The condensation of 2(S)-bromo-4-phenylbutyric acid ethyl ester (XII) with L-alanine benzyl ester (XIII) by means of K2CO3 in DMSO gives N-[1(S)-(ethoxycarbonyl)-3-phenylpropyl]-L-alanine benzyl ester (XIV),which is debenzylated by hydrogenation as before yielding the free acid (XV).The esterification of (XV) with N-hydroxysuccinimide gives the corresponding active ester (XVI),which is finally condensed with imidazolidine ester (VIII) by means of potassium tert-butoxide to afford the precursor (XI) already obtained.
参考文献标题:Studies on angiotensin converting enzyme inhibitors.V.The diastereoselective synthesis of 2-oxoimidazolidine derivatives
文献作者:Hayashi,K.; Kubota,H.; Yamagishi,M.; Nunami,K.-I.; Nishimoto,S.
参考来源:Chem Pharm Bull 1991,39(6),1374


产品链接: CAS No. 89396-94-1››

产品链接: CAS No.89371-37-9››