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CAS No. : | 57381-62-1 | MDL No. : | MFCD10566822 |
Formula : | C8H6BrClO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | BIFARHLBYAKSSN-UHFFFAOYSA-N |
M.W : | 249.49 | Pubchem ID : | 15110995 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
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* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran; | REFERENCE EXAMPLE 3 Cyclopropylmethylketone (4.0 g) was added to a suspension of sodium hydride (3.2 g, 60percent oil dispersion) in dry tetrahydrofuran (10 ml). When the evolution of hydrogen had subsided, a solution of <strong>[57381-62-1]methyl 2-bromo-4-chlorobenzoate</strong> (10.0 g) in tetrahydrofuran was added dropwise. The resulting mixture was heated at reflux overnight, cooled, evaporated to dryness and poured onto dilute hydrochloric acid. The mixture was extracted (dichloromethane), dried (magnesium sulphate) and evaporated to give, after purification by chromatography, 1-(2-bromo-4-chlorophenyl)-3-cyclopropyl-propan-1,3-dione (3.07 g), m.p. 42°-45° C. as an orange solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With tetrabutyl ammonium fluoride; In toluene; at -70 - 20℃; for 14h; | <strong>[57381-62-1]2-bromo-4-chloro-benzoic acid methyl ester</strong> (12.4 g, 50 mmol) in toluene (200 ml) was cooled to -70 ° C and trifluoroMethyltrimethylsilane (13 ml, 70 mmol). Tetrabutylammonium fluoride (IM, 2.5 ml) was added dropwise and the mixture was allowed to stand for 4 hoursHeated to room temperature, followed by stirring at room temperature for 10 hours. The reaction mixture was concentrated to give crude [l- (2-bromo-4-chloro-phenyl) -2,2,2-trifluoro-1-methoxy-ethoxy] -trimethyl-silane. The crude intermediate was dissolved in methanol (100 ml) and added6N HCl (100 ml). The mixture was maintained at 45-50 & lt; 0 & gt; C for 12 hours. The methanol was removed and the crude product was extracted with dichloromethane (200 ml)Extract. The combined DCM layers were washed with water (50 ml), NaHCO3 (50 ml), brine (50 ml) and dried over sodium sulfate. Removal of dissolvedThe crude product was purified by ISCO column chromatography using 1-2percent ethyl acetate in hexanes as solventTo give 1- (2-bromo-4-chloro-phenyl) -2,2,2-trifluoro-ethanone (10 g, 70percent). |
With tetrabutyl ammonium fluoride; In toluene; at -70 - 20℃; for 14h; | 2-Bromo-4-chloro-benzoic acid methyl ester (12.4 g, 50 mmol) in toluene (200 ml) was cooled to -70° C., and trifluoromethyl trimethyl silane (13 ml, 70 mmol) was added. Tetrabutylammonium fluoride (1M, 2.5 ml) was added dropwise, and the mixture was allowed to warm to room temperature over 4 h, after which it was stirred for 10 h at room temperature. The reaction mixture was concentrated to give the crude [1-(2-bromo-4-chloro-phenyl)-2,2,2-trifluoro-1-methoxy-ethoxy]-trimethyl-silane. | |
In toluene; | 2-Bromo-4-chloro-benzoic acid methyl ester (12.4 g, 50 mmol) in toluene (200 ml) was cooled to -70° C., and trifluoromethyl trimethyl silane (13 ml, 70 mmol) was added. Tetrabutylamonium fluoride (1M, 2.5 ml) was added dropwise, and the mixture was allowed to warm to room temperature over 4 h, after which it was stirred for 10 h at room temperature. The reaction mixture was concentrated to give the crude [1-(2-bromo-4-chloro-phenyl)-2,2,2-trifluoro-1-methoxy-ethoxy]-trimethyl-silane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | Step 1: Synthesis of 1-(2-bromo-4-chloro-phenyl)-2,2,2-trifluoro-ethanone. To a 500 ml 2 necked RB flask containing anhydrous methanol (300 ml) was added thionyl chloride (29.2 ml, 400 mmol) dropwise at 0-5 C. (ice water bath) over 10 min. The ice water bath was removed, and 2-bromo-4-chloro-benzoic acid (25 g, 106 mmol) was added. The mixture was heated to mild reflux for 12 h. Progress of the reaction was monitored by TLC and LCMS. After completion of the reaction, the reaction mixture was concentrated. Crude product was dissolved in dichloromethane (DCM, 250 ml), washed with water (50 ml), sat. aq. NaHCO3 (50 ml), brine (50 ml), dried over sodium sulfate, and concentrated to give the 2-bromo-4-chloro-benzoic acid methyl ester (26 g, 99%), which was directly used in the following step. | |
99% | With thionyl chloride; at 0℃;Reflux; | Thionyl chloride (29.2 ml, 400 mmol) was added dropwise over 10 minutes at 0-5 C (ice-water bath) in a 500 ml 2-necked RB flask containing anhydrous methanol (300 ml).Remove the ice-water bath and add 2-bromo-4-chloro-benzoic acid (25 g, 106 mmol).The mixture was heated to moderate reflux for 12 hours.Reaction progress was monitored by TLC and LCMS. After completion of the reaction, the reaction mixture was concentrated.The crude product was dissolved in dichloromethane (DCM, 250 ml)Washed with water (50 ml), saturated aqueous NaHCO3 (50 ml), brine (50 ml)Dried over sodium sulfate,Concentration gave 2-bromo-4-chloro-benzoic acid methyl ester (26 g, 99%) which was used directly in the next step. |
98% | With sulfuric acid;Cooling with ice; Heating; Reflux; | Concentrated sulfuric acid (5 ml_) was added drop-wise to an ice-cold mixture of 2- bromo-4-chloro-benzoic acid (10.14 g, 0.0431 mol) and methanol (40 ml_). The resulting mixture was heated at reflux for 17 hours. After this time, the reaction mixture was cooled to room temperature, and then poured into ice-cold water (150 ml_), creating a white suspension. The suspension was extracted with ethyl acetate (150 ml_). The organic phase was washed with saturated aqueous NaHCO3 (I OO ml_), followed by saturated aqueous NaCI (100 ml_). The organic layer was dried over Na2SO4, filtered, and concentrated to afford 2-bromo-4-chloro-benzoic acid methyl ester (10.57 g, 98% yield) as a clear oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With thionyl chloride; In methanol; dichloromethane; | Step 1: Synthesis of 1-(2-bromo-4-chloro-phenyl)-2,2,2-trifluoro-ethanone. To a 500 ml 2 necked RB flask containing anhydrous methanol (300 ml) was added thionyl chloride (29.2 ml, 400 mmol) dropwise at 0-5° C. (ice water bath) over 10 min. The ice water bath was removed, and 2-bromo-4-chloro-benzoic acid (25 g, 106 mmol) was added. The mixture was heated to mild reflux for 12 h. Progress of the reaction was monitored by TLC and LCMS. After completion of the reaction, the reaction mixture was concentrated. Crude product was dissolved in dichloromethane (DCM, 250 ml), washed with water (50 ml), sat. aq. NaHCO3 (50 ml), brine (50 ml), dried over sodium sulfate, and concentrated to give the 2-bromo-4-chloro-benzoic acid methyl ester (26 g, 99percent), which was directly used in the following step. |
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