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

HRID 1618924Notes

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

Conditions

Temperature: 120 °C

Procedure

2-Fluoro-5-nitroaniline (10.22 g, 65.5 mmol, 1.0 equiv.) was dissolved in anhydrous dimethylsulfoxide (100 ml) and treated with neopentylamine (7.71 ml, 65.5 mmol, 1.0 equiv.). The mixture was heated at 120° C. for 2 days, cooled to ambient temperature and treated with acetic acid (25 ml), followed by addition of 0.65 M aqueous solution of sodium nitrite (121 ml, 79 mmol, 1.2 equiv.). After 20 minutes at ambient temperature, the mixture was neutralized to pH 7 with NaOH (1N aqueous) and diluted with water. The mixture was filtered and the solid was collected on top of filter and washed twice with water. The residue was purified via silica gel chromatography (EtOAc/Hexane gradient from 0 to 100%) to provide the titled compound: 1H NMR (500 MHz, CDCl3) 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

temperaturecooled to ambient temperature
filtrationThe mixture was filtered
customthe solid was collected on top
filtrationof filter
washwashed twice with water
customThe residue was purified via silica gel chromatography (EtOAc/Hexane gradient from 0 to 100%)

Sources & evidence

ORD record: ord-fa09cae564d743e298e89d1f1fb349cb
Source dataset: uspto-grants-2014_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08772276B2

Reaction notes

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