2,5-Difluorobenzohydrazide → Toluene-4-sulfonic acid 3-tert-butyl-7-(2,5-difluorophenyl)-4-methylpyrazolo[1,5-d][1,2,4]triazin-2-yl ester

HRID 985432Notes

Reaction equation

[C:1]([C:4]1[NH:8][N:7]=[C:6]([O:9][S:10]([C:13]2[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=2)(=[O:12])=[O:11])[C:5]=1[C:20]([CH3:23])([CH3:22])[CH3:21])(=O)[CH3:2].[F:24][C:25]1[CH:34]=[CH:33][C:32]([F:35])=[CH:31][C:26]=1[C:27]([NH:29][NH2:30])=O>C1(C)C(C)=CC=CC=1>[C:20]([C:5]1[C:6]([O:9][S:10]([C:13]2[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=2)(=[O:12])=[O:11])=[N:7][N:8]2[C:4]=1[C:1]([CH3:2])=[N:30][N:29]=[C:27]2[C:26]1[CH:31]=[C:32]([F:35])[CH:33]=[CH:34][C:25]=1[F:24])([CH3:23])([CH3:22])[CH3:21]

Participants

Conditions

Temperature: 180 °C

Procedure

5-Acetyl-4-tert-butyl-3-(4-methylphenyl)sulfonyloxypyrazole (0.4 g, 1.19 mmol) was dissolved in xylene (20 ml) with 2,5-difluorobenzoic hydrazide (0.225 g, 1.31 mmol) and heated under reflux for 14 h. The xylene was removed by evaporation and replaced with Dowtherm A (15 ml) and heated at 180° C. for 4 h. The reaction mixture was allowed to cool to room temperature and poured directly onto a silica column and eluted with dichloromethane then 1-5% ethyl acetate/dichloromethane to give the required product (0.3 g) as a white solid. 1H NMR (360 MHz, CDCl3) δ 1.64 (9H, s), 2.42 (3H, s), 3.11 (3H, s), 7.11-7.83 (8H, m); MS (ES+) m/e 473 [MH]+.

Workup

temperatureheated
temperatureunder reflux for 14 h
customThe xylene was removed by evaporation
temperatureto cool to room temperature
additionpoured directly onto a silica column
washeluted with dichloromethane

Sources & evidence

ORD record: ord-77d026fe82574db490cad0b02f5a2128
Source dataset: uspto-grants-2005_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06872720B2

Reaction notes

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