Potassium Iodide → 4-bromo-1-(2,2-dimethylpropyl)-5-iodo-1H-benzotriazole

HRID 2281056Notes

Reaction equation

O.C1(C)C=CC(S(O)(=O)=O)=CC=1.[Br:13][C:14]1[C:22]2[N:21]=[N:20][N:19]([CH2:23][C:24]([CH3:27])([CH3:26])[CH3:25])[C:18]=2[CH:17]=[CH:16][C:15]=1N.N([O-])=O.[Na+].[I-:33].[K+].C(=O)(O)[O-].[Na+].[O-]S([O-])(=S)=O.[Na+].[Na+]>C(#N)C.O>[Br:13][C:14]1[C:22]2[N:21]=[N:20][N:19]([CH2:23][C:24]([CH3:27])([CH3:26])[CH3:25])[C:18]=2[CH:17]=[CH:16][C:15]=1[I:33]

Participants

Conditions

Temperature: 12.5 °C

Procedure

To a solution of para-toluenesulfonic acid monohydrate (510 mg, 2.68 mmol) in acetonitrile (3.5 mL), was added 4-bromo-1-(2,2-dimethylpropyl)-1H-1,2,3-benzotriazol-5-amine (253 mg, 0.893 mmol). The resulting suspension was cooled to 10-15° C. and treated with an aqueous solution of sodium nitrite (537 μl, 1.787 mmol) and potassium iodide (536 μl, 2.23 mmol). The mixture was stirred for 10 minutes at 0° C. and then warmed to ambient temperature. The mixture was diluted with water and treated with sodium bicarbonate (1 M, aqueous) until the mixture was adjusted to pH 9-10, which was followed by treatment of a 3 M aqueous solution of Na2S2O3 (6 mL). The solid was collected by filtration and washed with cold diethyl ether and hexane. The residue was purified via silica gel chromatography (ethyl acetate/hexane gradient), providing the titled compound: 1H NMR (500 MHz, CDCl3) 7.86 (d, 1H, J=8.7 Hz), 7.25 (d, 1H, J=9.0 Hz), 4.36 (s, 2H), 1.04 (s, 9H) ppm. LRMS m/z (M+H) 393.8 and 395.8 found, 393.9 and 395.9 required.

Workup

temperaturewarmed to ambient temperature
filtrationThe solid was collected by filtration
washwashed with cold diethyl ether and hexane
customThe residue was purified via silica gel chromatography (ethyl acetate/hexane gradient)

Sources & evidence

ORD record: ord-0847c8e0bb564a70b748ad051897248a
Source dataset: uspto-grants-2015_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09139576B2

Reaction notes

Loading…