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

HRID 2281053Notes

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 room 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 stirring at ambient temperature for 20 minutes, the mixture was neutralized to pH 7 with NaOH (1 N aqueous) and diluted with water, which caused precipitation. The solid was collected by filtration and washed twice with water. The residue was purified via silica gel chromatography (ethyl acetate/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 room temperature
customprecipitation
filtrationThe solid was collected by filtration
washwashed twice with water
customThe residue was purified via silica gel chromatography (ethyl acetate/hexane gradient from 0 to 100%)

Sources & evidence

ORD record: ord-0cd5fe81d24d4497ae3c12c55ba03e0b
Source dataset: uspto-grants-2015_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09139576B2

Reaction notes

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