Methanesulfonyl chloride → HCID 89924352, compound

5-Bromo-1-methyl-1H-pyrazol-3-amine (500 mg, 2.84 mmol) and DIPEA (2.47 mL, 14.2 mmol) were stirred in anhydrous 1,2-dichloroethane (8 mL) at room temperature, then mesyl chloride (550 μL, 7.1 mmol) in 1,2-dichloroethane (1.5 mL) was added dropwise. The mixture was stirred at room temperature for 3 h, then partitioned between DCM and water. The organic phases were separated and washed with brine, then dried over sodium sulfate and concentrated. To the resulting orange/brown solid was added 1M tetrabutylammonium fluoride in THF (10.5 mL) and the mixture was heated at reflux for 4 h. The reaction mixture was concentrated and diluted with DCM (40 mL), then washed with water (4×25 mL), followed by brine (25 mL). The organic layers were dried over sodium sulfate and concentrated under vacuum. The residue was purified by FCC, eluting with 35-50% EtOAc in heptane followed by 5-10% MeOH in DCM, to afford the title compound (388 mg, 54%) as a white solid. δH (250 MHz, CDCl3) 6.33 (s, 1H), 3.85 (s, 3H), 3.02 (s, 3H).

1. custompartitioned between DCM and water
2. customThe organic phases were separated
3. washwashed with brine
4. dry with materialdried over sodium sulfate
5. concentrationconcentrated
6. additionTo the resulting orange/brown solid was added 1M tetrabutylammonium fluoride in THF (10.5 mL)
7. temperaturethe mixture was heated
8. temperatureat reflux for 4 h
9. concentrationThe reaction mixture was concentrated
10. additiondiluted with DCM (40 mL)
11. washwashed with water (4×25 mL)
12. dry with materialThe organic layers were dried over sodium sulfate
13. concentrationconcentrated under vacuum
14. customThe residue was purified by FCC
15. washeluting with 35-50% EtOAc in heptane

ORD record

ord-37a5d6ad66024564b3471cde55a8f2ee

Source dataset

uspto-grants-2016_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09309243B2