Methyl chlorodifluoroacetate → 1-Tert-butyl-2-methoxy-5-(trifluoromethyl)-4-nitrobenzene

Participants

Role	Name	HCID	Charge
Reactant	Methyl chlorodifluoroacetate	HCID 73935	—
Reactant	Potassium Bromide	HCID 253877	—
Reactant	Potassium Fluoride	HCID 522689	—
Reactant	1-Bromo-5-(tert-butyl)-4-methoxy-2-nitrobenzene	HCID 57470245	—
Catalyst	Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)	HCID 24350	—
Solvent	Water	HCID 962	—
Solvent	Dimethylformamide	HCID 6228	—
Product	1-Tert-butyl-2-methoxy-5-(trifluoromethyl)-4-nitrobenzene	HCID 57470246	61.6%

Reaction Conditions

Temperature	125 °C

Reaction Steps

A mixture of 1-tert-butyl-2-methoxy-5-bromo-4-nitrobenzene (867 mg, 3.0 mmol), KF (348 mg, 6 mmol), KBr (714 mg, 6 mmol), CuI (684 mg, 3.6 mmol), methyl chlorodifluoroacetate (2.2 mL, 21.0 mmol) in DMF (5 mL) was stirred at 125° C. in a sealed tube overnight, cooled to room temperature, diluted with water and extracted three times with EtOAc. The combined organic layers were washed with brine and dried over anhydrous MgSO4. After removal of the solvent, the residue was purified by column chromatography (0-5% EtOAc-Hexane) to yield 1-tert-butyl-2-methoxy-5-(trifluoromethyl)-4-nitrobenzene (512 mg, 61%). 1H NMR (400 MHz, CDCl3) δ 7.60 (s, 1H), 7.29 (s, 1H), 3.90 (s, 3H), 1.33 (s, 9H).

Provenance & Evidence

DOI	10.6084/m9.figshare.5104873.v1
Patent number	US08354427B2
Source dataset	uspto-grants-2013_01
ORD ID	ord-97a7620c1b734c669f89965c7abf7f61
Source note	uspto-grants-2013_01