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Zafirlukast, ICI-204219, Olmoran, Zafirst, Respix, Accoleit, Accolate

扎鲁司特Chemical Name: 4-(5-Cyclopentyloxycarbonylamino-1-methylindol-3-ylmethyl)-3-methoxy-N-o-tolylsulfonylbenzamide; N-[4-[5-(Cyclopentyloxycarbonylamino)-1-methylindol-3-ylmethyl]-3-methoxybenzoyl]-2-methylbenzenesulfonamide
CAS No. 107753-78-6
项目整合开发状态: Launched-1996
项目研究机构: AstraZeneca (Originator), Chiesi (Licensee), Novartis (Licensee), Recordati (Licensee)
合成路线:Bromination of methyl 3-methoxy-4-methylbenzoate (I) with N-bromosuccinimide in the presence of catalytic amounts of 2,2'-azabisisobutyronitrile in chlorobenzene yields benzylic bromide (II).This compound is coupled with 5-nitroindole via treatment with Ag2CO3 in toluene to afford methyl 4-(5-nitroindol-3-ylmethyl)-3-methoxybenzoate (III).N-Methylation of ester (III),using NaH and MeI in DMF,followed by hydrolysis with NaOH in aqueous THF,affords 4-(5-nitro-1-methylindol-3-ylmethyl)-3-methoxybenzoic acid (IV).Conversion of acid (IV) to the sulfonimide derivative (V) is achieved by sequentially treating (IV) with: (i) SOCl2 plus a catalytic amount of DMF in dichloromethane and (ii) o-tolylsulfonamide and 4-(N,N-dimethylamino)pyridine (DMAP).This intermediate sulfonimide is isolated as the DMAP salt (V),which is converted to ICI 204219 via treatment with H2 over Pd/C in alkaline aqueous methoxyethanol,followed by acylation with cyclopentylchloroformate.
📌 参考资料/链接:
参考文献标题:Heterocyclic amide derivs
文献作者:Brown,F.J.; Bernstein,P.R.; Yee,Y.K.; Matassa,V.G.(AstraZeneca LP)
参考来源:AU 8656164; EP 0199543; EP 0220066; ES 8801787; ES 8802220; ES 8802493; ES 8802494; JP 1987093274; JP 1987099359; US 4859692; US 4918094; US 5030643; US 5049576; US 5179112

📄 详细内容


合成路线:Bromination of methyl 3-methoxy-4-methylbenzoate (I) with N-bromosuccinimide in the presence of catalytic amounts of 2,2'-azabisisobutyronitrile in chlorobenzene yields benzylic bromide (II).This compound is coupled with 5-nitroindole via treatment with Ag2CO3 in toluene to afford methyl 4-(5-nitroindol-3-ylmethyl)-3-methoxybenzoate (III).N-Methylation of ester (III),using NaH and MeI in DMF,followed by hydrolysis with NaOH in aqueous THF,affords 4-(5-nitro-1-methylindol-3-ylmethyl)-3-methoxybenzoic acid (IV).Conversion of acid (IV) to the sulfonimide derivative (V) is achieved by sequentially treating (IV) with: (i) SOCl2 plus a catalytic amount of DMF in dichloromethane and (ii) o-tolylsulfonamide and 4-(N,N-dimethylamino)pyridine (DMAP).This intermediate sulfonimide is isolated as the DMAP salt (V),which is converted to ICI 204219 via treatment with H2 over Pd/C in alkaline aqueous methoxyethanol,followed by acylation with cyclopentylchloroformate.

参考文献标题:A physical form of N-[4-[5-(cyclopentyloxycarbonylamino)-1-methyl-indol-3-ylmethyl]-3-methoxybenzoyl]-2-methylbenzenesulfonamide,a process for its preparation and pharmaceutical compsns.containing it
文献作者:Edwards,M.P.; Sherwood,J.D.(AstraZeneca plc)
参考来源:EP 0490649; US 5294636


合成路线:Bromination of methyl 3-methoxy-4-methylbenzoate (I) with N-bromosuccinimide in the presence of catalytic amounts of 2,2'-azabisisobutyronitrile in chlorobenzene yields benzylic bromide (II).This compound is coupled with 5-nitroindole via treatment with Ag2CO3 in toluene to afford methyl 4-(5-nitroindol-3-ylmethyl)-3-methoxybenzoate (III).N-Methylation of ester (III),using NaH and MeI in DMF,followed by hydrolysis with NaOH in aqueous THF,affords 4-(5-nitro-1-methylindol-3-ylmethyl)-3-methoxybenzoic acid (IV).Conversion of acid (IV) to the sulfonimide derivative (V) is achieved by sequentially treating (IV) with: (i) SOCl2 plus a catalytic amount of DMF in dichloromethane and (ii) o-tolylsulfonamide and 4-(N,N-dimethylamino)pyridine (DMAP).This intermediate sulfonimide is isolated as the DMAP salt (V),which is converted to ICI 204219 via treatment with H2 over Pd/C in alkaline aqueous methoxyethanol,followed by acylation with cyclopentylchloroformate.

参考文献标题:Evolution of a series of peptidoleukotriene antagonists: Synthesis and structure/activity relationships of 1,3,5-substituted indoles and indazoles
文献作者:Aharony,D.; Snyder,D.W.; Keith,R.A.; Shapiro,H.S.; Matassa,V.G.; Maduskuie,T.P.Jr.; Hesp,B.; Krell,R.D.
参考来源:J Med Chem 1990,33(6),1781


合成路线:Bromination of methyl 3-methoxy-4-methylbenzoate (I) with N-bromosuccinimide in the presence of catalytic amounts of 2,2'-azabisisobutyronitrile in chlorobenzene yields benzylic bromide (II).This compound is coupled with 5-nitroindole via treatment with Ag2CO3 in toluene to afford methyl 4-(5-nitroindol-3-ylmethyl)-3-methoxybenzoate (III).N-Methylation of ester (III),using NaH and MeI in DMF,followed by hydrolysis with NaOH in aqueous THF,affords 4-(5-nitro-1-methylindol-3-ylmethyl)-3-methoxybenzoic acid (IV).Conversion of acid (IV) to the sulfonimide derivative (V) is achieved by sequentially treating (IV) with: (i) SOCl2 plus a catalytic amount of DMF in dichloromethane and (ii) o-tolylsulfonamide and 4-(N,N-dimethylamino)pyridine (DMAP).This intermediate sulfonimide is isolated as the DMAP salt (V),which is converted to ICI 204219 via treatment with H2 over Pd/C in alkaline aqueous methoxyethanol,followed by acylation with cyclopentylchloroformate.
参考文献标题:Accolate
文献作者:Bernstein,P.R.
参考来源:Drugs Fut 1994,19(3),217


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