S-2474

2,6-二甲丁基-4-[(E)-(2-乙基-1,1-二氧基-1,2-噻唑烷-5-烯醚)甲基苯Chemical Name: (E)-5-(3,5-Di-tert-butyl-4-hydroxybenzylidene)-2-ethylisothiazolidine 1,1-dioxide
CAS No. 158089-95-3, 158089-96-4 ((Z)-isomer)
项目整合开发状态: Phase II
项目研究机构: Shionogi (Originator)
合成路线:The intermediate gamma-sultam (III) was prepared by condensation of 3-chloropropylsulfonyl chloride (I) with ethylamine,followed by cyclization of the resulting chloro sulfonamide (II) under basic conditions.Condensation of 3,5-di-tert-butyl-4-(methoxymethoxy)benzaldehyde (IV) with sultam (III) in the presence of LDA produced the aldol addition compound (V).Then,acid-promoted dehydration and simultaneous methoxymethyl group deprotection gave rise to a mixture of the desired E-benzylidene sultam and the corresponding Z-isomer (VII),which were separated by column chromatography.
📌 参考资料/链接:
参考文献标题:Benzylidene derivs.
文献作者:Matsumoto,S.; Tsuri,T.; Inagaki,M.; Jyoyama,H.(Shionogi & Co.Ltd.)
参考来源:EP 0595546; JP 1994211819; US 5418230

📄 详细内容


合成路线:An improved synthesis has been reported.Acid-catalyzed ketalization of aldehyde (VIII) with trimethyl orthoformate provided the dimethyl acetal (IX) which,upon thermal decomposition in refluxing xylene,gave rise to the alpha-methoxy methylenequinone derivative (X).This was then condensed with the lithio derivative of sultam (III) to form selectively the desired E-adduct.In an analogous procedure,aldehyde (VIII) was converted to the chloromethylene compound (XI) with methanesulfonyl chloride and triethylamine in refluxing CH2Cl2.Condensation of (XI) with the lithiated sultam (III) furnished the desired E-benzylidene sultam.

参考文献标题:Method for producing benzylidene derivs.
文献作者:Haga,N.; Inagaki,M.; Matsumoto,S.; Kamata,S.(Shionogi & Co.Ltd.)
参考来源:EP 0626377


合成路线:The intermediate gamma-sultam (III) was prepared by condensation of 3-chloropropylsulfonyl chloride (I) with ethylamine,followed by cyclization of the resulting chloro sulfonamide (II) under basic conditions.Condensation of 3,5-di-tert-butyl-4-(methoxymethoxy)benzaldehyde (IV) with sultam (III) in the presence of LDA produced the aldol addition compound (V).Then,acid-promoted dehydration and simultaneous methoxymethyl group deprotection gave rise to a mixture of the desired E-benzylidene sultam and the corresponding Z-isomer (VII),which were separated by column chromatography.

参考文献标题:A novel antiarthritic agent S-2474: Synthesis and pharmacological effects
文献作者:Inagaki,M.; Tsuri,T.; Jyoyama,H.; yamada,K.; Ono,T.; Matsumoto,S.
参考来源:17th Symp Med Chem (Nov 19 1997,Tsukuba) 1997,Abst 2-P-25


合成路线:The intermediate gamma-sultam (III) was prepared by condensation of 3-chloropropylsulfonyl chloride (I) with ethylamine,followed by cyclization of the resulting chloro sulfonamide (II) under basic conditions.Condensation of 3,5-di-tert-butyl-4-(methoxymethoxy)benzaldehyde (IV) with sultam (III) in the presence of LDA produced the aldol addition compound (V).Then,acid-promoted dehydration and simultaneous methoxymethyl group deprotection gave rise to a mixture of the desired E-benzylidene sultam and the corresponding Z-isomer (VII),which were separated by column chromatography.

参考文献标题:Novel antiarthritic agents with 1,2-isothiazolidine-1,1-dioxide (gamma-sultam) skeleton: Cytokine suppressive dual inhibitors of cyclooxygenase-2 and 5-lipoxygenase
文献作者:Inagaki,M.; Tsuri,T.; Jyoyama,H.; Ono,T.; Yamada,K.; Kobayashi,M.; Hori,Y.; Arimura,A.; Yasui,K.; Ohno,K.; Kakudo,S.; Koizumi,K.; Suzuki,R.; Kawai,S.; Kato,M.; Matsumoto,S.
参考来源:J Med Chem 2000,43(10),2040


合成路线:An improved synthesis has been reported.Acid-catalyzed ketalization of aldehyde (VIII) with trimethyl orthoformate provided the dimethyl acetal (IX) which,upon thermal decomposition in refluxing xylene,gave rise to the alpha-methoxy methylenequinone derivative (X).This was then condensed with the lithio derivative of sultam (III) to form selectively the desired E-adduct.In an analogous procedure,aldehyde (VIII) was converted to the chloromethylene compound (XI) with methanesulfonyl chloride and triethylamine in refluxing CH2Cl2.Condensation of (XI) with the lithiated sultam (III) furnished the desired E-benzylidene sultam.
参考文献标题:Highly E-selective and effective synthesis of antiarthritic drug candidate S-2474 using quinone methide derivatives
文献作者:Inagaki,M.; Haga,N.; Kobayashi,M.; Ohta,N.; Kamata,S.; Tsuri,T.
参考来源:J Org Chem 2002,67(1),125


产品链接: CAS No. 158089-95-3››