Pyridine → [5-(1-methyl-cyclopropyl)-2-p-tolyl-2H-pyrazol-3-yl]-carbamic acid 2,2,2-trichloroethyl ester

HRID 1993678Notes

Reaction equation

[CH3:1][C:2]1([C:5]2[CH:6]=[C:7]([NH2:17])[N:8]([C:10]3[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][CH:11]=3)[N:9]=2)[CH2:4][CH2:3]1.N1C=CC=CC=1.Cl[C:25]([O:27][CH2:28][C:29]([Cl:32])([Cl:31])[Cl:30])=[O:26].ClC([O-])=O>C1COCC1.O>[Cl:30][C:29]([Cl:32])([Cl:31])[CH2:28][O:27][C:25](=[O:26])[NH:17][C:7]1[N:8]([C:10]2[CH:11]=[CH:12][C:13]([CH3:16])=[CH:14][CH:15]=2)[N:9]=[C:5]([C:2]2([CH3:1])[CH2:3][CH2:4]2)[CH:6]=1

Participants

Conditions

Temperature: 0 °C

Procedure

Treat a cooled (0° C.) solution of the 5-(1-methyl-cyclopropyl)-2-p-tolyl-2H-pyrazol-3-ylamine (5.68 g, 25 mmol) and pyridine (2.2 mL, 27.5 mmol) in THF (3 mL/mmol) with 2,2,2-trichloroethyl chloroformate (3.7 mL, 27.5 mmol). Maintain the reaction temperature at 0° C., and after 2 hours, add small portions of chloroformate (0.3 mL) and pyridine (0.2 mL). One hour later, dilute the reaction with water (150 mL) and extract with EtOAc (3×100 mL). Wash the combined organic phases with water (100 mL), saturated aq. NaHCO3 (50 mL), and saturated aq. sodium chloride (50 mL). Recrystallize the crude syrup from ethyl acetate/hexanes to provide the title compound as a white solid (8.18 g, 20.3 mmol; 81%). LCMS (ES+): m/z=402.2/404.2 [M+H].

Workup

additionTreat
additionOne hour later, dilute
extractionextract with EtOAc (3×100 mL)
washWash the combined organic phases with water (100 mL), saturated aq. NaHCO3 (50 mL), and saturated aq. sodium chloride (50 mL)
customRecrystallize the crude syrup from ethyl acetate/hexanes

Sources & evidence

ORD record: ord-e6bcf66624c14994875b5d5f0d5f30eb
Source dataset: uspto-grants-2010_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07652015B2

Reaction notes

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