Nitrogen → 4-(4-fluoro-3-nitrophenyl)-1-methyl-1H-pyrazole

HRID 64080Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.N#N.[CH3:14][N:15]1[CH:19]=[C:18](B2OC(C)(C)C(C)(C)O2)[CH:17]=[N:16]1.C(=O)([O-])[O-].[Na+].[Na+]>O1CCOCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[F:8][C:5]1[CH:6]=[CH:7][C:2]([C:18]2[CH:17]=[N:16][N:15]([CH3:14])[CH:19]=2)=[CH:3][C:4]=1[N+:9]([O-:11])=[O:10]

Participants

Conditions

Temperature: 90 °C

Procedure

A solution of 4-bromo-1-fluoro-2-nitrobenzene (2 g, 9.095 mmol) in 1,4-dioxane (20 ml) was degassed by N2 bubbling for 5 min. 1-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (2.27 g, 10.91 mmol, 1.2 eq.) and aqueous sodium carbonate (2.89 g, 27.27 mmol, 3.0 eq.) were added and the mixture was degassed for another 15 min. Pd(PPh3)2Cl2 (0.638 g, 0.909 mmol, 0.1 eq.) was added sequentially and the mixture was further degassed for 15 min and then heated at 90° C. for 2 h. The mixture was quenched and extracted as in Intermediate Example 5(c). The solvent was distilled off to afford the crude residue which was purified by column chromatography (60-120 silica gel, 40-50% ethyl acetate in hexane) to yield the product in 79% yield (1.6 g). 1H NMR (300 MHz, DMSO-d6): δ 8.32-8.26 (m, 2H), 8.0-7.97 (m, 2H), 7.62-7.55 (m, 1H).

Workup

customthe mixture was degassed for another 15 min
customthe mixture was further degassed for 15 min
customThe mixture was quenched
extractionextracted as in Intermediate Example 5(c)
distillationThe solvent was distilled off

Sources & evidence

ORD record: ord-ba28ad7ffb784c12addb0aa6e66640f9
Source dataset: uspto-grants-2016_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09447091B2

Reaction notes

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