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Otenzepad, AF-DX 116, AF-DX 116 BS

11-((2-((二乙氨基)甲基)-1-哌啶基)乙酰基)-5,11-二氢-(6H)-吡啶并[2.3-b][1.4]苯并二氮杂-6-酮 Chemical Name: (?-11-[[2-[[(Diethylamino)methyl]-1-piperidinyl]acetyl]-5,11-dihydro-6H-pyrido[2,3-b][1,4]benzodiazepin-6-one
CAS No. 100158-38-1, 102394-31-0, 100158-40-5 ((E)-2-butenedioate (1:1) salt), 100158-41-6 ((Z)-2-butenedioate (1:1) salt), 100158-43-8 (diHBr salt), 100158-42-7 (diHCl), 100158-39-2 (monomethanesulfonate salt)
项目整合开发状态: Phase III
项目研究机构: Boehringer Ingelheim (Originator)
合成路线:Synthesis of the intermediate 5,11-dihydro-6H-pyrido[2,3-b][1,4]benzodiazepin-6-one (IV) is accomplished by condensation of 3-amino-2-chloropyridine (I) and the anthranilic ester (II) using potassium tert-butoxide as a catalyst.The resulting anthranilic amide (III) is cyclized under the influence of catalytic amounts of sulfuric acid.Treatment of (IV) with chloroacetylchloride in toluene furnishes the corresponding chloroacetamide (V).The diamine part of AF-DX 116 is prepared starting from 2-(hydroxymethyl)piperidine (VI).Reaction with thionylchloride in dichloromethane affords the pipecolylchloride hydrochloride (VII),which is converted with diethylamine to the required 2-[(diethylamino)methyl]piperidine (IX) via nucleophilic ring opening of the intermediate aziridine (VIII).Minor amounts of 3-(diethylamino)hexahydroazepine (X),formed by a side reaction,are separated by thorough fractional distillation of the diamine (IX) and/or recrystallization of its hydrochloride (XI).Coupling of (V) and (XI) in the presence of sodium carbonate yields AF-DX 116 as its free base.
📌 参考资料/链接:
参考文献标题:Condensed diazepinones,process for their preparation and medicines containing them
文献作者:Schmidt,G.; Hammer,R.; Giachetti,A.; Engel,W.; Trummlitz,G.; Eberlein,W.; Mihm,G.(Dr.Karl Thomae GmbH)
参考来源:AU 8539815; EP 0156191; ES 8607282; ES 8702908; JP 1985215683; US 4550107

📄 详细内容


合成路线:Synthesis of the intermediate 5,11-dihydro-6H-pyrido[2,3-b][1,4]benzodiazepin-6-one (IV) is accomplished by condensation of 3-amino-2-chloropyridine (I) and the anthranilic ester (II) using potassium tert-butoxide as a catalyst.The resulting anthranilic amide (III) is cyclized under the influence of catalytic amounts of sulfuric acid.Treatment of (IV) with chloroacetylchloride in toluene furnishes the corresponding chloroacetamide (V).The diamine part of AF-DX 116 is prepared starting from 2-(hydroxymethyl)piperidine (VI).Reaction with thionylchloride in dichloromethane affords the pipecolylchloride hydrochloride (VII),which is converted with diethylamine to the required 2-[(diethylamino)methyl]piperidine (IX) via nucleophilic ring opening of the intermediate aziridine (VIII).Minor amounts of 3-(diethylamino)hexahydroazepine (X),formed by a side reaction,are separated by thorough fractional distillation of the diamine (IX) and/or recrystallization of its hydrochloride (XI).Coupling of (V) and (XI) in the presence of sodium carbonate yields AF-DX 116 as its free base.

合成路线:Alkylation of 2-pyrrolidinone with 4-chloromethylpyridine and base provides the pyridine (I).Catalytic hydrogenation of (I) with platinum oxide yields the piperidine (II).Condensation of 4-chloro-2-trifluoromethylpyrimidine,which is obtained in two steps from trifluoroacetamidine and the sodium salt of ethyl formylacetate,with (II) then affords BMY-21502.

参考文献标题:Cerebral function enhancing diazinylpiperidine derivs
文献作者:Mattson,R.J.; Yevich,J.P.; Eison,M.S.(Bristol-Myers Squibb Co.)
参考来源:AU 8659787; BE 0905061; CH 671579; DE 3622842; FR 2584408; GB 2177692; US 4826843


合成路线:Synthesis of the intermediate 5,11-dihydro-6H-pyrido[2,3-b][1,4]benzodiazepin-6-one (IV) is accomplished by condensation of 3-amino-2-chloropyridine (I) and the anthranilic ester (II) using potassium tert-butoxide as a catalyst.The resulting anthranilic amide (III) is cyclized under the influence of catalytic amounts of sulfuric acid.Treatment of (IV) with chloroacetylchloride in toluene furnishes the corresponding chloroacetamide (V).The diamine part of AF-DX 116 is prepared starting from 2-(hydroxymethyl)piperidine (VI).Reaction with thionylchloride in dichloromethane affords the pipecolylchloride hydrochloride (VII),which is converted with diethylamine to the required 2-[(diethylamino)methyl]piperidine (IX) via nucleophilic ring opening of the intermediate aziridine (VIII).Minor amounts of 3-(diethylamino)hexahydroazepine (X),formed by a side reaction,are separated by thorough fractional distillation of the diamine (IX) and/or recrystallization of its hydrochloride (XI).Coupling of (V) and (XI) in the presence of sodium carbonate yields AF-DX 116 as its free base.

参考文献标题:Tricyclic compounds as selective muscarinic receptor antagonists.3.Structure-selectivity relationships in a series of cardioselective (M2) antimuscarinics
文献作者:Eberlein,W.G.; Trummlitz,G.; Mihm,G.; Engel,W.W.; Hammer,R.
参考来源:J Med Chem 1989,32(8),1718-24


合成路线:Synthesis of the intermediate 5,11-dihydro-6H-pyrido[2,3-b][1,4]benzodiazepin-6-one (IV) is accomplished by condensation of 3-amino-2-chloropyridine (I) and the anthranilic ester (II) using potassium tert-butoxide as a catalyst.The resulting anthranilic amide (III) is cyclized under the influence of catalytic amounts of sulfuric acid.Treatment of (IV) with chloroacetylchloride in toluene furnishes the corresponding chloroacetamide (V).The diamine part of AF-DX 116 is prepared starting from 2-(hydroxymethyl)piperidine (VI).Reaction with thionylchloride in dichloromethane affords the pipecolylchloride hydrochloride (VII),which is converted with diethylamine to the required 2-[(diethylamino)methyl]piperidine (IX) via nucleophilic ring opening of the intermediate aziridine (VIII).Minor amounts of 3-(diethylamino)hexahydroazepine (X),formed by a side reaction,are separated by thorough fractional distillation of the diamine (IX) and/or recrystallization of its hydrochloride (XI).Coupling of (V) and (XI) in the presence of sodium carbonate yields AF-DX 116 as its free base.
参考文献标题:AF-DX 116
文献作者:Engel,W.; Doods,H.; Wetzel,B.
参考来源:Drugs Fut 1990,15(1),9


产品链接: CAS No. 100158-38-1››

产品链接: CAS No.102394-31-0››