ChemicalBook CAS DataBase List Methyl 4-bromo-2-fluorobenzoate

Methyl 4-bromo-2-fluorobenzoate synthesis

5synthesis methods

Product Name:Methyl 4-bromo-2-fluorobenzoate
CAS Number:179232-29-2
Molecular formula:C8H6BrFO2
Molecular Weight:233.03

67-56-1

112704-79-7

179232-29-2

Step 1: To a stirred solution of 4-bromo-2-fluorobenzoic acid (15.0 g, 68.49 mmol, 1 eq.) in methanol (150 mL) was slowly added thionyl chloride (23.09 mL, 136.9 mmol, 2 eq.) at 0 °C. The reaction mixture was kept at 0 °C for 15 minutes before being brought to room temperature and stirring was continued for 12 hours. After completion of the reaction, methanol was removed by evaporation under reduced pressure and the residue was diluted with ethyl acetate (250 mL). The organic layer was washed sequentially with saturated aqueous sodium bicarbonate solution, brine (150 mL) and deionized water (150 mL). The ethyl acetate layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give methyl 4-bromo-2-fluorobenzoate (15 g, 93% yield) as an off-white solid (LC-MS purity 99%; TLC conditions: ethyl acetate/petroleum ether (3:7), Rf value 0.8).

112704-79-7 Synthesis

112704-79-7
545 suppliers
$15.00/5 g

18107-18-1
209 suppliers
$33.00/5g

179232-29-2
249 suppliers
$9.00/5g

Yield:179232-29-2 100%

Reaction Conditions:

in tetrahydrofuran;methanol;hexanes at 0 - 20; for 1 h;

Steps:

45.1
STEP 1 : To a solution of 4-bromo-2-fluorobenzoic acid (2.0 g, 9.1 mmol) in THF (24 mL) and methanol (6 mL) at 0 °C was added a solution of (trimethylsilyl)diazomethane in hexanes (2.0 M, 5.46 mL, 10.9 mmol). The yellow solution was allowed to gradually warm to room temperature over 1 h. The volatile materials were removed and the residue was treated with aqueous hydrochloric acid (1 M). The aqueous mixture was extracted with ethyl acetate. The organic extract was dried over magnesium sulfate, filtered, and concentrated to provide crude methyl 4- bromo-2-fluorobenzoate (2.7 g, quantitative yield). This material was used in the subsequent step without further purification. ¹H NMR (400 MHz, CDCl₃): 7.85-7.81 (m, IH), 7.38-7.33 (m, 2H), 3.93 (s, 3H); MS (EI) for C₈H₆BrFO₂: 232, 234 (MH⁺).

References:

EXELIXIS, INC. WO2009/55077, 2009, A1 Location in patent:Page/Page column 447

FullText

67-56-1 Synthesis

67-56-1
804 suppliers
$7.29/5ml-f

112704-79-7 Synthesis

112704-79-7
545 suppliers
$15.00/5 g

179232-29-2
249 suppliers
$9.00/5g

References

112704-79-7 Synthesis

112704-79-7
545 suppliers
$15.00/5 g