Sodium Hydroxide → 1-(2,2-Dimethylpropyl)-5-nitro-1H-1,2,3-benzotriazole

HRID 872268Notes

Reaction equation

HRID 872268 reaction equation
F[C:2]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[CH:5][C:3]=1[NH2:4].[CH2:12]([NH2:17])[C:13]([CH3:16])([CH3:15])[CH3:14].[N:18]([O-])=O.[Na+].[OH-].[Na+]>CS(C)=O.O.C(O)(=O)C>[CH3:14][C:13]([CH3:16])([CH3:15])[CH2:12][N:17]1[C:2]2[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[CH:5][C:3]=2[N:4]=[N:18]1

Participants

8

Reactant 4

HCID 14798Sodium HydroxideHCID 677852-Fluoro-5-nitroanilineHCID 79882NeopentylamineHCID 23668193Sodium Nitrite

Product 1

HCID 686564421-(2,2-Dimethylpropyl)-5-nitro-1H-1,2,3-benzotriazole

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent

Conditions

Temperature
120 °C

Procedure

2-Fluoro-5-nitroaniline (2-1) (10.22 g, 65.5 mmol, 1.0 equiv.) was dissolved in anhydrous DMSO (100 ml), and treated with neopentylamine (2-2) (7.71 ml, 65.5 mmol, 1.0 equiv.). The reaction mixture was heated at 120° C. for 2 days when LCMS showed mostly product with trace of starting material. The reaction mixture was cooled to room temperature and treated with acetic acid (25 ml), followed by addition of 2.0 M aqueous solution of sodium nitrite (121 ml, 79 mmol, 1.2 equiv.). LCMS showed product after the reaction mixture was stirred at ambient temperature for 20 minutes. The mixture was then neutralized to pH=7 with NaOH (1N) and diluted with water which caused a precipitation. The solid was collected on top of filter and washed twice with water. The crude solid was purified with silica gel chromatography (EtOAc/hexanes gradient from 0 to 100%) to yield 1-(2,2-dimethylpropyl)-5-nitro-1H-1,2,3-benzotriazole (2-3). 1H NMR (CDCl3) δ 9.02 (d, 1H, J=2.0 Hz), 8.40 (dd, 1H, J=9.1, 2.0 Hz), 7.62 (d, 1H, J=9.1 Hz), 4.47 (s, 2H), 1.07 (s, 9H) ppm. LRMS m/z (M+H) 235.1 found, 235.3 required.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. customa precipitation
  3. customThe solid was collected on top
  4. filtrationof filter
  5. washwashed twice with water
  6. customThe crude solid was purified with silica gel chromatography (EtOAc/hexanes gradient from 0 to 100%)

Sources & evidence

ORD record
ord-328689bb037a4950896f3b9908806e91
Source dataset
uspto-grants-2015_03
Patent number
US08975286B2

Reaction notes

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