2,4-Bis(trifluoromethyl)bromobenzene → HCID 59520444, compound

HRID 1162518Notes

Reaction equation

[C:1]([O:5][C:6](=[O:11])[NH:7][CH2:8][CH2:9][OH:10])([CH3:4])([CH3:3])[CH3:2].Br[C:13]1[CH:18]=[CH:17][C:16]([C:19]([F:22])([F:21])[F:20])=[CH:15][C:14]=1[C:23]([F:26])([F:25])[F:24]>CC(N(C)C)=O.O>[C:1]([O:5][C:6](=[O:11])[NH:7][CH2:8][CH2:9][O:10][C:17]1[CH:18]=[CH:13][C:14]([C:23]([F:26])([F:24])[F:25])=[CH:15][C:16]=1[C:19]([F:20])([F:21])[F:22])([CH3:4])([CH3:2])[CH3:3]

Participants

Conditions

Temperature: 60 °C

Procedure

(2-Hydroxy-ethyl)-carbamic acid tert-butyl ester (0.2 mL, 1.29 mmol) is dissolved in 3 mL dry dimethyl-acetamide. 2-Potassium-1,1,1,3,3,3-hexamethyl-disilazane (0.52 g, 2.6 mmol, 2 equiv.) is added, followed by 1-bromo-2,4-bis-trifluoromethyl-benzene 31 (0.26 mL, 1.5 mmol, 1.2 equiv.). The mixture is stirred at 60° C. under nitrogen for 18 hours. The mixture is cooled, diluted with 50 mL water and extracted with dichloromethane (3×50 mL). The combined organic extracts are washed with water and 10% aqueous citric acid, dried over Na2SO4 and concentration. Silica gel chromatography (5% to 25% ethyl acetate in hexanes) yielded [2-(2,4-Bis-trifluoromethyl-phenoxy)-ethyl]-carbamic acid tert-butyl ester 32 as a colorless, mobile oil: 1H-NMR (400 MHz, CDCl3) δ=7.61 (s, 1H), 7.00 (d, J=8 Hz, 1H), 6.76 (d, J=8 Hz, 1H), 5.10 (s, 1H), 4.26 (t, J=4 Hz, 2H), 3.65 (m, 2H), 1.45 (s, 9H). 19F-NMR (376 MHz, CDCl3) δ=−61.5, −62.0. No molecular ion could be obtained; a loss of tert-butyl group is observed: MS calculated for C11H10F6NO3 (M+H+—C4H8) 318.1, found 318.3.

Workup

temperatureThe mixture is cooled
extractionextracted with dichloromethane (3×50 mL)
washThe combined organic extracts are washed with water and 10% aqueous citric acid
dry with materialdried over Na2SO4 and concentration

Sources & evidence

ORD record: ord-c58337729ed94531823e583f3c669af7
Source dataset: uspto-grants-2010_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07820705B2

Reaction notes

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