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

HRID 1626993Notes

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 (10.2 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 48 hours, 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.). The mixture was then neutralized to pH 7 with sodium hydroxide (1N aqueous) and diluted with water, which caused precipitation. The solid was collected on top of filter and washed twice with water, which was further purified via silica gel chromatography (100:0 to 0:100; hexanes:ethyl acetate), providing the titled compound: 1H NMR (500 MHz, 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

temperaturecooled to ambient temperature
customprecipitation
customThe solid was collected on top
filtrationof filter
washwashed twice with water, which
customwas further purified via silica gel chromatography (100:0 to 0:100; hexanes:ethyl acetate)

Sources & evidence

ORD record: ord-9c6c7947480f48ba81bdc8c34796daaa
Source dataset: uspto-grants-2014_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08785482B2

Reaction notes

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