Pyrimidine compounds as jak kinase inhibitors
A compound, methoxypyrimidine technology, applied in the field of pyrimidine compounds, can solve problems such as adverse systemic immunosuppressive effects
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[0249] The following synthetic and biological examples are provided to illustrate the invention and are not to be construed as limiting the scope of the invention in any way. In the examples below, the following abbreviations have the following meanings unless otherwise indicated. Abbreviations not defined below have their generally accepted meanings.
[0250] ACN = acetonitrile
[0251] CPME = cyclopentyl methyl ether
[0252] d = days
[0253] DIPEA=N,N-Diisopropylethylamine
[0254] DMF=N,N-Dimethylformamide
[0255] DMSO = dimethyl sulfoxide
[0256] EtOAc = ethyl acetate
[0257] EtOH = ethanol
[0258] h = hour
[0259] HATU = N,N,N',N'-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate
[0260] IPA = isopropyl alcohol
[0261] MeOH = Methanol
[0262] min=minute
[0263] NMP = N-methylpyrrolidone
[0264] RT = room temperature
[0265] TEA = Triethylamine
[0266] THF = Tetrahydrofuran
[0267] TFA = trifluoroacetic acid
[0268] Xantphos...
example 1
[0346] Example 1: 1-(((1R,3s,5S)-3-((4-((5-(hydroxymethyl)-1H-pyrazol-3-yl)amino)-6-methoxypyrimidine- 2-yl)(methyl)amino)-8-azabicyclo[3.2.1]oct-8-yl)sulfonyl)azetidine-3-carbonitrile
[0347]
[0348]To (3-((2-((1R,3s,5S)-8-azabicyclo[3.2.1]oct-3-yl(methyl)amino)-6-methoxypyrimidin-4-yl )amino)-1H-pyrazol-5-yl)methanol (15mg, 0.042mmol) in DMF (4.0mL) were added successively DIPEA (0.022ml, 0.125mmol) and 3-cyano-1-aza Cyclobutanesulfonyl chloride (7.54 mg, 0.042 mmol). The reaction mixture was stirred overnight at room temperature. The solvent was removed in vacuo and the crude residue was purified by reverse phase HPLC to afford the TFA salt of the title compound (3.2 mg). C 21 h 29 N 9 o 4 S(m / z):[M+H] + The calculated value is 504.21 and the experimental value is 504.1.
example 2
[0349] Example 2: 1-(((1R,3s,5S)-3-((4-((5-(hydroxymethyl)-1H-pyrazol-3-yl)amino)-6-methoxypyrimidine- 2-yl)(methyl)amino)-9-azabicyclo[3.3.1]non-9-yl)sulfonyl)azetidine-3-carbonitrile
[0350]
[0351] (3-((2-(((1R,3s,5S)-9-azabicyclo[3.3.1]non-3-yl)(methyl)amino)-6-methoxy To a solution of pyrimidin-4-yl)amino)-1H-pyrazol-5-yl)methanol HCl (150 mg, 0.402 mmol) and DIPEA (0.351 mL, 2.008 mmol) in DMF (3 mL) was added 3-cyano - 1-azetidinesulfonyl chloride (72.5 mg, 0.402 mmol) and the reaction mixture was stirred at 0°C for 10 min and then at room temperature for 15 h. The reaction mixture was concentrated in vacuo to give a red liquid, which was purified by preparative HPLC to afford the TFA salt of the title compound (72.4 mg, 0.115 mmol, 28.5% yield) as a white solid. C 22 h 31 N 9 o 4 S(m / z):[M+H] + The calculated value is 518.22 and the experimental value is 518.
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