Potassium Phosphate, Tribasic → methyl 3-methoxy-4-(1H-pyrazol-4-yl)benzoate

Temperature

100 °C

To a solution of methyl 4-bromo-3-methoxybenzoate (1.32 g, 5.39 mmol) in dioxane (30 mL) and water (5 mL) were added tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate (1.901 g, 6.46 mmol), potassium phosphate (2.86 g, 13.47 mmol) and PdCl2(dppf) (0.197 g, 0.269 mmol) at RT. The reaction was stirred under argon at 100° C. for 3 hrs. The reaction mixture was diluted with EtOAc, washed with H2O. The organic phase was dried over sodium sulfate, filtered and concentrated. The residue was dissolved in DCM (10 mL) and TFA (5 mL) was added. The reaction was stirred at RT for 1.5 hrs. Solvent was removed. The residue was taken into EtOAc, which was washed with NaHCO3 (3×) and brine, dried over Na2SO4, filtered and concentrated. The crude product was purified by normal phase chromatography. Desired product was isolated as white solid (0.86 g, 69% yield). LCMS (ESI) m/z: 233.0 (M+H)+; 1H NMR (400 MHz, CDCl3) δ 8.13 (s, 2H), 7.73-7.66 (m, 1H), 7.66-7.56 (m, 2H), 3.98 (s, 3H), 3.94 (s, 3H).

1. washwashed with H2O
2. dry with materialThe organic phase was dried over sodium sulfate
3. filtrationfiltered
4. concentrationconcentrated
5. dissolutionThe residue was dissolved in DCM (10 mL)
6. additionTFA (5 mL) was added
7. stirringThe reaction was stirred at RT for 1.5 hrs
8. customSolvent was removed
9. washwas washed with NaHCO3 (3×) and brine
10. dry with materialdried over Na2SO4
11. filtrationfiltered
12. concentrationconcentrated
13. customThe crude product was purified by normal phase chromatography

ORD record

ord-533d323ac99a4726a23ec985d652f796

Source dataset

uspto-grants-2015_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09126944B2