2-(Trifluoromethoxy)bromobenzene

General procedure: In the glove box, add KF (78.4mg, 1.35mmol, 4.5equiv) to cis- in 20mL plastic tube (PE).Dicyclohexano-18-crown-6 (503 mg, 1.35 mmol, 4.5 equiv) and 6 mL ethyl acetate.Then a phenylene precursor (0.3 mmol, 1.0 equiv), 1-bromophenylacetylene (218 mg, 1.2 mmol. 4.0 equiv) or perfluorohexyl bromide (479 mg, 1.2 mmol. 4.0 equiv) or pentafluorophenyl bromide (296 mg, 1.2 mmol. 4.0 equiv) and trifluoromethyl benzoate (171 mg, 0.9 mmol, 3 equiv) were capped and allowed to react at room temperature for 12 hours.After the end of the reaction, the F-spectrum yield was first calculated by 19F NMR.After completion of the reaction, the mixture was filtered, dried, and directly subjected to column chromatography.General procedure: In a glovebox, to an oven-dried 20 mL screw cap vial was added 3- methyl-4-nitro-l- ( trifluoromethoxy) -6- (trifluoromethyl ) -1H- benzo[d] [1, 2, 3] triazol-3-ium trifluoromethanesulfonate (lb) (98.0 mg, 0.200 mmol, 1.00 equiv), arene (2.00 mmol, 10.0 equiv) and Ru (bpy) 3 (PFe) 2, (1.72 mg, 2.00 pmol, 1.00 mol%). Then MeCN (1.00 mL, 0.200 M) and a magnetic stir bar were added. The vial was capped and taken out of the glovebox. The reaction mixture was then stirred and irradiated with 2 of 10 W LED (Xmax = 447 nm) at room temperature. After 16 h, an internal standard PhCF3 (24.6 pL, 0.200 mmol, 1.00 equiv) was added to the reaction vial, 0.200 mL of the resulting mixture was transferred to a 2 mL vial containing 0.500 mL of CDC13. After the yield was determined using 19F NMR, the NMR sample was combined with the rest of the reaction mixture and the solvent was removed in vacuo. The crude material was purified by HPLC under noted conditions. The fractions containing the desired product were combined and extracted with CDC13 (3 x 10.0 mL) , dried with magnesium sulfate, and filtered unless otherwise noted. The filtrate was concentrated in vacuo to furnish the desired product of trifluoromethoxylation . For volatile compounds, after purification by HPLC, the desired product was extracted with 1 mL CDCI3 and then directly characterized. The NMR peaks are referring to CCN residue signal (1H-NMR : d 1.94, 13C-NMR: d 118.26, 1.32).2General procedure: Method A ( Buchwald-Hartwia ) To a mixture of C-1 (1 eq), BB-8 (1.3 eq) and sodium tert-butoxide (2 eq) in toluene (3 to 10 mL/mmol) under N2, was added BINAP (0.2 eq) and Pd2(dba)3 (0.1 eq). The rxn mixture was flushed with N2, heated at a given temperature and stirred for a given time (see Table 25). It was partitioned between water and EtOAc and the org. phase was washed with brine, dried over MgSC>4 and concentrated in vacuo. The crude was purified by CC using Hept/EtOAc. When necessary an additional purification by prep. LC-MS was performed.Step A: A solution of compound 12 (556.08mg, 1.18mmol, 1.00eq), 2-trifluoromethoxybromobenzene(281.98mg, 1.17mmol, 174.06uL, 1.00eq), aqueous potassium hydroxide solution (4M, 1.64mL, 5.60eq) and dichlorobis(triphenylphosphine)palladium (24.64mg, 35.10umol, 0.03eq) in 20mL 2-methyltetrahydrofuran was purged with nitrogenfor three times. The reaction solution was stirred at 80C under nitrogen atmosphere for 24 hours, then dilutedwith 20mL water. The mixture was extracted twice with 50mL ethyl acetate each time. The organic phase was combined, washed once with 100mL saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography to give the compound 15 as a yellow oil (380.00mg), which was directly used in the next step.

Used as pesticide and pharmaceutical intermediate

Molecular Weight:241.00
XLogP3:4.1
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:1
Exact Mass:239.93976
Monoisotopic Mass:239.93976
Topological Polar Surface Area:9.2
Heavy Atom Count:12
Complexity:148
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes