Sodium hydride → HCID 673691, compound

HRID 546023Notes

Reaction equation

HRID 546023 reaction equation
[N+:1]([C:4]1[CH:8]=[CH:7][NH:6][N:5]=1)([O-:3])=[O:2].[H-].[Na+].[Cl:11][C:12]1[CH:19]=[CH:18][C:15]([CH2:16]Br)=[CH:14][CH:13]=1>CN(C)C=O>[Cl:11][C:12]1[CH:19]=[CH:18][C:15]([CH2:16][N:6]2[CH:7]=[CH:8][C:4]([N+:1]([O-:3])=[O:2])=[N:5]2)=[CH:14][CH:13]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 693291-(Bromomethyl)-4-chlorobenzeneHCID 178526745HCID 178526745, compound

Product 1

HCID 673691HCID 673691, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 3-nitro-1H-pyrazole (prepared in example 3, 200 mg, 1.77 mmol) in anhydrous N,N-dimethylformamide (2 mL), a 60% dispersion of sodium hydride in mineral oil (92 mg, 2.30 mmol) was added while stirring under nitrogen. After the effervescence ceased and the mixture was stirred for additional 30 min, 4-chlorobenzylbromide (473 mg, 2.30 mmol) was added. The mixture was continued to stir under nitrogen for an additional 2 h. The solvent was removed in vacuo and purification by ISCO flash column chromatography (Teledyne Isco RediSep Flash Column 40 g; 2% methanol/methylene chloride to 5% methanol/methylene chloride) afforded 1-(4-chloro-benzyl)-3-nitro-1H-pyrazole (344 mg, 82%) as a white solid: H1-NMR (400 MHz, CDCl3) δ: 5.33 (2H, s), 6.90 (1H, d, J=2.3 Hz), 7.22 (2H, d, J=8.4 Hz), 7.34 (2H, d J=8.6 Hz), 7.40 (1H, d, J=2.6 Hz).

Workup

  1. stirringthe mixture was stirred for additional 30 min
  2. stirringto stir under nitrogen for an additional 2 h
  3. customThe solvent was removed in vacuo and purification by ISCO flash column chromatography (Teledyne Isco RediSep Flash Column 40 g; 2% methanol/methylene chloride to 5% methanol/methylene chloride)

Sources & evidence

ORD record
ord-88c7d428dff14b8daff0b3579f86c465
Source dataset
uspto-grants-2011_05
Patent number
US07935699B2

Reaction notes

Loading…