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(+)-N-Desmethylzopiclone, (S)-DMZ, SEP-174559

N-去甲基异佐吡克隆盐酸盐 Chemical Name: (+)-6-(5-Chloro-2-pyridyl)-7(S)-(piperazin-1-ylcarbonyloxy)-6,7-dihydro-5H-pyrrolo[3,4-b]pyrazin-5-one; Piperazine-1-carboxylic acid 6-(5-chloro-2-pyridyl)-7-oxo-6,7-dihydro-5H-pyrrolo[3,4-b]pyrazin-5(S)-yl ester
CAS No. 151776-26-0, 300701-71-7 (monoHCl)
项目整合开发状态: Phase I
项目研究机构: Aventis Pharma (Originator), Sepracor (Licensee)
合成路线:The title compound has been obtained from racemic zopliclone (I) by several related procedures.Demethylation of (I) to afford (II) has been achieved by treatment with diethyl azodicarboxylate (DEAD) in boiling toluene,followed by mild hydrolysis with NH4Cl in refluxing EtOH.In a higher yield demethylation procedure,treatment of (I) with chloroethyl chloroformate produced carbamate (III),which was further hydrolyzed to (II) in boiling MeOH.Resolution of racemic N-demethyl zopiclone (II) has been accomplished via formation of the diastereomeric salts with N-Z-L-phenylalanine or,alternatively,by means of semi-preparative chiral HPLC.In a related strategy,racemic zopiclone (I) was first resolved using D-malic acid to provide the (S)-enantiomer (IV).This was then dealkylated by means of either DEAD or employing the chloroethyl chloroformate method.
📌 参考资料/链接:
参考文献标题:Methods of making and using N-desmethylzopiclone
文献作者:Hong,Y.; Senanayake,C.H.; Jerussi,T.P.; Rubin,P.D.; Bakale,R.A.; Xiang,T.; McConville,F.A.(Sepracor Inc.)
参考来源:US 6339086; WO 0069442

📄 详细内容


合成路线:Eszopiclone can also be obtained by optical resolution of zopiclone by several different methods:i) crystallization of the D-(+)-O,O'-dibenzoyltartaric acid salt in acetonitrile,followed by treatment with NaOH in dichloromethane/water; ii) crystallization of the (+)-malic acid salt in MeOH/acetone followed by treatment with KHCO3 in MeOH water and extraction with dichloromethane/ethyl acetate;iii) chiral chromatography over a Chiralpak AS column; iv) capillary electrophoresis in the presence of octakis-(2,3,6-tri-O-methyl)-g-cyclodextrin.

合成路线:The title compound has been obtained from racemic zopliclone (I) by several related procedures.Demethylation of (I) to afford (II) has been achieved by treatment with diethyl azodicarboxylate (DEAD) in boiling toluene,followed by mild hydrolysis with NH4Cl in refluxing EtOH.In a higher yield demethylation procedure,treatment of (I) with chloroethyl chloroformate produced carbamate (III),which was further hydrolyzed to (II) in boiling MeOH.Resolution of racemic N-demethyl zopiclone (II) has been accomplished via formation of the diastereomeric salts with N-Z-L-phenylalanine or,alternatively,by means of semi-preparative chiral HPLC.In a related strategy,racemic zopiclone (I) was first resolved using D-malic acid to provide the (S)-enantiomer (IV).This was then dealkylated by means of either DEAD or employing the chloroethyl chloroformate method.

参考文献标题:Semi-preparative chiral resolution of zoplicone and N-desmethylzopiclone
文献作者:Mannaert,E.; Daenens,P.
参考来源:J Pharm Biomed Anal 1996,14(8-10),1367


合成路线:The title compound has been obtained from racemic zopliclone (I) by several related procedures.Demethylation of (I) to afford (II) has been achieved by treatment with diethyl azodicarboxylate (DEAD) in boiling toluene,followed by mild hydrolysis with NH4Cl in refluxing EtOH.In a higher yield demethylation procedure,treatment of (I) with chloroethyl chloroformate produced carbamate (III),which was further hydrolyzed to (II) in boiling MeOH.Resolution of racemic N-demethyl zopiclone (II) has been accomplished via formation of the diastereomeric salts with N-Z-L-phenylalanine or,alternatively,by means of semi-preparative chiral HPLC.In a related strategy,racemic zopiclone (I) was first resolved using D-malic acid to provide the (S)-enantiomer (IV).This was then dealkylated by means of either DEAD or employing the chloroethyl chloroformate method.
参考文献标题:Synthesis of enantiomerically pure desmethylzopiclone and determination of its absolute configuration
文献作者:Hong,Y.; et al.
参考来源:Tetrahedron Asymmetry 2000,11(23),4623


产品链接: CAS No. 151776-26-0››

产品链接: CAS No.300701-71-7››