Ammonia → 4-(4-Bromo-2-fluorobenzyl)-3-n-butyl-1-(2-chloro-5-nitrophenyl)-1H-pyrazole-5-carboxamide

HRID 257564Notes

Reaction equation

HRID 257564 reaction equation
[Br:1][C:2]1[CH:30]=[CH:29][C:5]([CH2:6][C:7]2[C:8]([CH2:25][CH2:26][CH2:27][CH3:28])=[N:9][N:10]([C:15]3[CH:20]=[C:19]([N+:21]([O-:23])=[O:22])[CH:18]=[CH:17][C:16]=3[Cl:24])[C:11]=2[C:12](Cl)=[O:13])=[C:4]([F:31])[CH:3]=1.[NH3:32]>C1COCC1>[Br:1][C:2]1[CH:30]=[CH:29][C:5]([CH2:6][C:7]2[C:8]([CH2:25][CH2:26][CH2:27][CH3:28])=[N:9][N:10]([C:15]3[CH:20]=[C:19]([N+:21]([O-:23])=[O:22])[CH:18]=[CH:17][C:16]=3[Cl:24])[C:11]=2[C:12]([NH2:32])=[O:13])=[C:4]([F:31])[CH:3]=1

Participants

4

Reactant 2

HCID 222AmmoniaHCID 197831954-(4-Bromo-2-fluorobenzyl)-3-n-butyl-1-(2-chloro-5-nitrophenyl)-1H-pyrazole-5-carbonyl Chloride

Product 1

HCID 542034724-(4-Bromo-2-fluorobenzyl)-3-n-butyl-1-(2-chloro-5-nitrophenyl)-1H-pyrazole-5-carboxamideYield 93%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 4-(4-bromo-2-fluorobenzyl)-3-n-butyl-1-(2-chloro-5-nitrophenyl)-1H-pyrazole-5-carbonyl chloride (from Step D, theoretically 1.32 mmol) in 10 mL of dry THF was cooled to -50° C. and maintained at that temperature under protection from moisture as ammonia gas was gently bubbled in until saturated. The mixture was allowed to warm slowly to room temperature and stirred overnight. Concentration of the reaction mixture yielded a thick yellow oil, which was purified by flash chromatography on silica gel (elution with 1% and then 3% MeOH in CH2Cl2). Evaporation of the pooled product fractions yielded 625 mg (93%) of the title compound as a slightly yellow solid, mp 145°-147° C.; nearly homogeneous by TLC in 95:5 CH2Cl2 ; mass spectrum (FAB) m/e 509, 511 (M+1)+. 200 MHz 1H NMR (CDCl3) δ0.89 (t, J=7.1 Hz, 3H), 1.35 (m, 2H), 1.59 (m, 2H, partially obscured by H2O peak), 2.58 (t, J=7.7 Hz, 2H), 4.04 (s, 2H), 5.51 (br s, 2H), 6.91 (dd, J≈8, 8 Hz, 1H), 7.25-7.32 (m, 2H), 7.66 (d, J=8.8 Hz, 1H), 8.25 (dd, J=8.8, 2.6 Hz, 1H), 8.41 (d, J=2.6 Hz, 1H).

Workup

  1. customwas gently bubbled in until saturated
  2. customConcentration of the reaction mixture yielded a thick yellow oil, which
  3. customwas purified by flash chromatography on silica gel (
  4. washelution with 1%
  5. customEvaporation of the pooled product fractions

Sources & evidence

ORD record
ord-9c08a468582e44078e339b5c8fa1aa84
Source dataset
uspto-grants-1993_11
Patent number
US05262412

Reaction notes

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