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Brodimoprim, Ro-10-5970, Unitrim, Hyprim

溴莫普林 2,4-嘧啶二胺,5-[(4-溴-3,5-二甲氧基苯基)甲基]-,盐酸盐 (1:) Chemical Name: 2,4-Diamino-5-(4-bromo-3,5-dimethoxybenzyl)pyrimidine; 5-(4-Bromo-3,5-dimethoxybenzyl)-2,4-pyrimidinediamine
CAS No. 56518-41-3, 56518-40-2 (HCl)
项目整合开发状态: Launched-1993
项目研究机构: Helsinn (Originator), AstraZeneca (Licensee)
合成路线:The reaction of dimethyl 2,6-dimethoxyterphthalate (I) with hydroxylamine by means of polyphosphoric acid at 70 C gives methyl 4-(N-hydroxycarbamoyl)-3,5-dimethoxybenzoate (II),which by further reaction with PPA is converted into methyl 4-amino-3,5-dimethoxybenzoate (III).The reaction of (III) with NaNO2 and HBr affords the corresponding diazonium salt,which without isolation is treated with CuBr yielding methyl-4-bromo-3,5-dimethoxybenzoate (IV).The reduction of (IV) with diisobutylaluminum hydride in THF gives 4-bromo-3,5-dimethoxybenzaldehyde (V),which is condensed with 3-methoxypropionitrile (VI) by means of sodium methoxide in refluxing methanol to yield 4-bromo-3,5-dimethoxy-alpha-(methoxymethyl)cinnamic acid nitrile (VII).Finally,this compound is cyclized with guanidine (A) by means of sodium methoxide in hot methanol DMSO.2) The hydrolysis of (IV) with KOH in ethanol gives 4-bromo-3,5-dimethoxybenzoic acid (VIII),which is treated with SOCl2 in refluxing benzene - DMF to afford 4-bromo-3,5-dimethoxybenzoylchloride (IX).Then the reduction of (IX) with H2 over Pd/BaSO4 in xylene yields (V),already obtained.
📌 参考资料/链接:
参考文献标题:Benzylpyirimidine derivates
文献作者:Kompis,I.(F.Hoffmann-La Roche AG)
参考来源:CA 1017743; DE 2452889; FR 2250533; GB 1449387; JP 50077378; NL 7414528

📄 详细内容


合成路线:The reaction of dimethyl 2,6-dimethoxyterphthalate (I) with hydroxylamine by means of polyphosphoric acid at 70 C gives methyl 4-(N-hydroxycarbamoyl)-3,5-dimethoxybenzoate (II),which by further reaction with PPA is converted into methyl 4-amino-3,5-dimethoxybenzoate (III).The reaction of (III) with NaNO2 and HBr affords the corresponding diazonium salt,which without isolation is treated with CuBr yielding methyl-4-bromo-3,5-dimethoxybenzoate (IV).The reduction of (IV) with diisobutylaluminum hydride in THF gives 4-bromo-3,5-dimethoxybenzaldehyde (V),which is condensed with 3-methoxypropionitrile (VI) by means of sodium methoxide in refluxing methanol to yield 4-bromo-3,5-dimethoxy-alpha-(methoxymethyl)cinnamic acid nitrile (VII).Finally,this compound is cyclized with guanidine (A) by means of sodium methoxide in hot methanol DMSO.2) The hydrolysis of (IV) with KOH in ethanol gives 4-bromo-3,5-dimethoxybenzoic acid (VIII),which is treated with SOCl2 in refluxing benzene - DMF to afford 4-bromo-3,5-dimethoxybenzoylchloride (IX).Then the reduction of (IX) with H2 over Pd/BaSO4 in xylene yields (V),already obtained.

合成路线:The reaction of (V) with 3-morpholinopropionitrile (X) by means of sodium methoxide in methanol - DMSO gives 4-bromo-3,5-dimethoxy-alpha-(morpholinomethyliden)hydrocinnamic acid nitrile (XI),which by reaction with aniline (B) and HCl in refluxing isopropanol is converted into 4-bromo-3,5-dimethoxy-alpha-(anilinomethyliden)hydrocinnamic acid nitrile (XII).Finally,this compound is condensed with guanidine (A) as before.

参考文献标题:Brodimoprim
文献作者:Sweetman,A.J.; Serradell,M.N.; Castar,J.; Blancafort,P.
参考来源:Drugs Fut 1982,7(2),93


合成路线:The reaction of dimethyl 2,6-dimethoxyterphthalate (I) with hydroxylamine by means of polyphosphoric acid at 70 C gives methyl 4-(N-hydroxycarbamoyl)-3,5-dimethoxybenzoate (II),which by further reaction with PPA is converted into methyl 4-amino-3,5-dimethoxybenzoate (III).The reaction of (III) with NaNO2 and HBr affords the corresponding diazonium salt,which without isolation is treated with CuBr yielding methyl-4-bromo-3,5-dimethoxybenzoate (IV).The reduction of (IV) with diisobutylaluminum hydride in THF gives 4-bromo-3,5-dimethoxybenzaldehyde (V),which is condensed with 3-methoxypropionitrile (VI) by means of sodium methoxide in refluxing methanol to yield 4-bromo-3,5-dimethoxy-alpha-(methoxymethyl)cinnamic acid nitrile (VII).Finally,this compound is cyclized with guanidine (A) by means of sodium methoxide in hot methanol DMSO.2) The hydrolysis of (IV) with KOH in ethanol gives 4-bromo-3,5-dimethoxybenzoic acid (VIII),which is treated with SOCl2 in refluxing benzene - DMF to afford 4-bromo-3,5-dimethoxybenzoylchloride (IX).Then the reduction of (IX) with H2 over Pd/BaSO4 in xylene yields (V),already obtained.

合成路线:The reaction of (V) with 3-morpholinopropionitrile (X) by means of sodium methoxide in methanol - DMSO gives 4-bromo-3,5-dimethoxy-alpha-(morpholinomethyliden)hydrocinnamic acid nitrile (XI),which by reaction with aniline (B) and HCl in refluxing isopropanol is converted into 4-bromo-3,5-dimethoxy-alpha-(anilinomethyliden)hydrocinnamic acid nitrile (XII).Finally,this compound is condensed with guanidine (A) as before.
参考文献标题:Synthesis of 4-halo-substituted analogs of trimethropin
文献作者:Kompis,I.; Wick,A.
参考来源:Helv Chim Acta 1977,60(8),3025-34


产品链接: CAS No. 56518-41-3››

产品链接: CAS No.56518-40-2››