【药物名称】BMS-187308
化学结构式(Chemical Structure):
参考文献No.22215
标题:Phenyl sulfonamide and their use as endothelin antagonists
作者:Murugesan, N.; Hunt, J.T. (Bristol-Myers Squibb Co.)
来源:EP 0569193; JP 1994049046; US 5514696
合成路线图解说明:

The intermediate protected sulfonamide (IV) was prepared by condensation of 2-bromobenzenesulfonyl chloride (I) with 5-amino-3,4-dimethylisoxazole (II), followed by protection of the resulting sulfonamide (III) with (2-methoxyethoxy)methyl chloride and NaH.

合成路线图解说明:

Reaction of 1-bromo-4-isobutylbenzene (V) with magnesium generated the corresponding Grignard reagent (VI), which was condensed with trimethyl borate to afford, after acid hydrolysis, arylboronic acid (VII). This was nitrated with acetyl nitrate to produce nitro derivative (VIII). Subsequent reduction of the nitro group of (VIII) by hydrogenation over Pd/C gave 2-amino-4-isobutylphenyl boronic acid (IX). Suzuki coupling of boronic acid (IX) with bromosulfonamide (IV) produced the required biphenyl (X). The methoxyethoxymethyl group was finally deprotected by treatment with HCl to furnish the title compound.

参考文献No.483122
标题:Biphenylsulfonamide endothelin antagonists: Structure-activity relationships of a series of mono- and disubstituted analogues and pharmacology of the orally active endothelin antagonist 2'-amino-N-(3,4-dimethyl-5-isoxazolyl)-4'-(2-methylpropyl)[1,1'-biphe
作者:Murugesan, N.; Gu, Z.; Stein, P.D.; Bisaha, S.; Spergel, S.; Girotra, R.; Lee, V.G.; Lloyd, J.; Misra, R.N.; Schmidt, J.; Mathur, A.; Stratton, L.; Kelly, Y.F.; Bird, E.; Waldron, T.; Liu, E.C.; Zhang, R.; Lee, H.; Serafino, R.; Abboa-Offei, B.; et al.
来源:J Med Chem 1998,41(26),5198
合成路线图解说明:

The intermediate protected sulfonamide (IV) was prepared by condensation of 2-bromobenzenesulfonyl chloride (I) with 5-amino-3,4-dimethylisoxazole (II), followed by protection of the resulting sulfonamide (III) with (2-methoxyethoxy)methyl chloride and NaH.

合成路线图解说明:

In an alternative procedure, Wittig reaction of 3-nitrobenzaldehyde (XI) with isopropyltriphenylphosphonium iodide gave isobutenyl compound (XII). Then, the nitro group of (XII) was selectively reduced to aniline (XIII) by hydrogenation over Pt/C, and this was protected as the pivaloyl amide (XIV) with pivaloyl chloride. Further hydrogenation of (XIV) using Pd/C produced the isobutyl derivative (XV). Lithiation of (XV) with tert-butyllithium generated the intermediate organolithium reagent (XVI), which was subsequently converted to boronic acid (XVII). Further Suzuki coupling of (XVII) with bromosulfonamide (IV) produced biphenyl (XVIII). Reductive removal of the pivaloyl group of (XVIII) using DIBAL-H then gave the precursor (X), which was finally deprotected with HCl to afford the target compound.

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