1-BROMO-3-(1,1,2,2-TETRAFLUOROETHOXY)BENZENE synthesis

Yield:957211-38-0 67%

Reaction Conditions:

Stage #1: 1-bromo-3-(1,1,2,2-tetrafluoro-ethoxy)-benzene;hexamethyldistannanewith triphenylphosphine in toluene; for 0.25 h;
Stage #2: tetrakis(triphenylphosphine) palladium⁽⁰⁾ in toluene at 80; for 2 h;

Steps:

1.A

A mixture of 1-bromo-3-(1,1,2,2-tetrafluoro-ethoxy)-benzene (3.87 g, 14.1 mmol), hexamethylditin (5.11 g, 15.6 mmol), PPh₃ (110 mg, 0.423 mmol) in toluene (70 mL) under a N₂ atmosphere was degassed by bubbling N₂ through the solution for 15 min. Pd(PPh₃)₄ (814 mg, 0.7 mmol) was added and the reaction mixture was heated at 80° C. for 2 h. After cooling to room temperature, the reaction mixture was poured into EtOAc (500 mL). The solution was then washed with H₂O and brine, dried (MgSO₄), concentrated and purified by column chromatography (2% EtOAc/Hex) to afford 3.76 g (67%) A4 as an oil: ¹H NMR (300 MHz, CDCl₃) δ 7.37-7.29 (m, 3 H), 7.16-7.13 (m, 1 H), 5.91 (tt, J=53.2, 2.9 Hz, 1 H), 0.31 (s, 9 H).

References:

US2007/265304,2007,A1 Location in patent:Page/Page column 25; 28