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CAS No. : | 17408-14-9 | MDL No. : | MFCD00000378 |
Formula : | C9H7F3O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | FYDUUODXZQITBF-UHFFFAOYSA-N |
M.W : | 188.15 | Pubchem ID : | 87095 |
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: |
* 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 |
---|---|---|
93% | With copper(ll) bromide; In chloroform; ethyl acetate; for 5h;Heating / reflux; | Dissolve 2'- (trifluoromethyl)-acetophenone (5.0 g, 26.6 mmol) in CHCl3 (25 ML) and add this mixture to a warmed slurry of CuBr2 (11.86 g, 53.2 mmol) in EtOAc (75 mL). Heat the resulting mixture near reflux for approx. 5 hours. Cool and filter the mixture and concentrate the resulting filtrate. Chromatograph the resulting residue over silica gel (CH2Cl2) to allow for isolation of 2-Bromo-1- (2-trifluoromethyl-phenyl)- ethanone (6.6 g, 93 %). |
With bromine; In diethyl ether; chloroform; at 20 - 25℃; for 1h; | Reference Example 5 ethyl 2-cyano-4-oxo-4-[(2-trifluoromethyl)phenyl]butanoate; 2'-(Trifluoromethyl)acetophenone (10.0 g) was dissolved in chloroform (30 mL) and diethyl ether (30 mL), a solution of bromine (8.50 g) in chloroform (20 mL) was added dropwise while maintaining the reaction temperature at not higher than 25 C. After the dropwise addition, the mixture was stirred at room temperature for 1 hr, water was added to the reaction mixture and the mixture was extracted with chloroform. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, concentration under reduced pressure to give crude 2-bromo-1-(2-trifluoromethylphenyl)ethanone. Potassium carbonate (13.82 g) was added to ethyl cyanoacetate (44.44 g), and the mixture was stirred at 45 C. for 1 hr. A solution of crude 2-bromo-1-(2-trifluoromethylphenyl)ethanone in acetone (100 mL) was added dropwise. After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hr, and stirred overnight at room temperature. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Water was added to the residue, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Excess ethyl cyanoacetate contained in the obtained oil was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (eluent: hexane-ethyl acetate=9:1→7:1) to give the title compound as an oil (yield 10.43 g, from 2'-(trifluoromethyl)acetophenone, yield 66%). 1H-NMR (CDCl3) δ: 1.36 (3H, t, J=7.2 Hz), 3.34-3.46 (1H, m), 3.59-3.70 (1H, m), 4.08-4.22 (1H, m), 4.32 (2H, q, J=7.2 Hz), 7.57-7.80 (4H, m). | |
With bromine; In diethyl ether; at 0 - 20℃; | To a solution of l-[2-(trifluoromethyl)phenyl]ethanone (1 g) in diethyl ether (10 mL) cooled at 0 C was added bromine (0.288 mL) dropwise. The resulting mixture was allowed to warm to room temperature. After stirring for 2 hours, the reaction was complete. Solvent was removed in vacuo to afford 2-bromo-l-[2-(trifluoromethyl)phenyl]ethanone (1.488 g) as a yellow oil. MS(ES+) m/z 267 (MH+). |
With hydrogen bromide; bromine; acetic acid; In chloroform; for 0.5h; | To a solution of l-(2-(trifluoromethyl)phenyl)ethanone (71.0 g, 377.0 mmol)and HBr (2.0 mL, 45% solution of AcOH) in chloroform (500.0 mL) was added the solution of dibromide (60.3 g, 377.0 mmol) in chloroform (200.0 mL). After addition, the solution was stirred for 30 min, then the solvent was evaporated and the residue was used in the next step directly. MS (ESI) calcd for C9H6BrF30: 265.96. | |
With bromine; In diethyl ether; chloroform; at 10 - 35℃; for 1h; | Reference Example 25 Ethyl 2-cyano-4-oxo-4-[(2-trifluoromethylphenyl)butanoate 2'-(Trifluoromethyl)acetophenone (10.0 g) was dissolved in chloroform (30 mL) and diethyl ether (30 mL), a solution of bromine (8.50 g) in chloroform (20 mL) was added dropwise while maintaining the reaction temperature at not higher than 25C. After the dropwise addition, the mixture was stirred at room temperature for 1 hr, water was added to the reaction mixture and the mixture was extracted with chloroform. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure to give crude 1-bromo-1-(2-trifluoromethylphenyl)ethanone. | |
With bromine; In diethyl ether; at 20℃; for 0.5h; | General procedure: To a stirred solution of 2-methylacetophenone 8b (13.42 g, 100 mmol) in Et2O (100 mL) was added dropwise bromine (16.0 g, 100 mmol), and the mixture was stirred at room temperature for 30 min, poured into ice H2O, extracted with Et2O. The extract was washed with brine, dried over anhydrous MgSO4, filtered and concentrated under reduced pressure to obtain an crude oil of 2-bromo-1-(2-methylphenyl)ethanone. | |
With N-Bromosuccinimide; toluene-4-sulfonic acid; In water; acetonitrile; at 80℃; for 4h;Inert atmosphere; | A 200 mL flask was charged with 2′-trifluoromethylacetophenone (9.41 g, 50 mmol), N-bromosuccinimide (9.79 g, 55 mmol, 1.1 eq.), p-toluenesulfonic acid (10.46 g, 55 mmol, 1.1 eq.) and MeCN (100 mL) under nitrogen stream and the mixture was stirred for 4 hours at 80 C. The mixture was allowed to cool to room temperature and then MeCN was removed by an evaporator. CHCl3 (150 mL) and H2O (50 mL) were added to the residue and the lower layer was separated and then washed with saturated aqueous NaHCO3 (50 mL) twice and brine (50 mL). The solution was dried over anhydrous MgSO4 and filtered and then solvents were removed in an evaporator to obtain the crude product as yellow oil (13.66 g) in >99.9% yield. This product was identified as 2-Bromo-2′-trifluoromethylacetophenone contaminated with some dibromo compound. 1H-NMR (CDCl3), delta (ppm): 4.36 (s, 2H), 7.48-7.50 (m, 1H), 7.60-7.64 (m, 2H), 7.72-7.75 (m, 1H), 19F-NMR (CDCl3), delta in ppm, standard: C6F6=-162.2 ppm: -58.68. | |
With bromine; In dichloromethane; for 1.5h; | 2-Amino-4-(2-trifluoromethyl-phenyl)-thiazole-5-carboxylic acid amide (V.17); Step 1; To a solution of 20.00 g (0.11 mole) of 2'-(trifluoromethyl)acetophenone in 200 mL of dichloromethane was added 5.5 mL (0.11 mole) of bromine over 90 minutes. A stream of nitrogen was bubbled through the reaction mixture for 15 minutes. The mixture solvent was removed under reduced pressure. The residue was dissolved with ethanol, and then concentrated under reduced pressure to give 27.25 g of 2-bromo-1-(2-trifluoromethyl-phenyl)-ethanone as a yellow oil, which was used in the next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | General procedure: Under nitrogen atmosphere the copper based catalyst 1 (8 7 mmg0.01 mmol), tBuOK ( 5 6 mmg0.05 mmol) and toluene (3 mL) were placed in a tube equipped with a Teflon coated magnetic stirring bar. T he mixture was stirred at 25 C for 15 min and then polymethylhydrosiloxane (PMHS, 0.0 9 m L, 1.5 mmol mmol) was injected. After 15mins, ketone (0.5 mmol) was introduced and the mixture was stirred at 25 C for therequired reaction time. The mixture was quenched with MeOH (1 mL) and 10%NaOH solution (3 mL), and the mixture was stirred for 4 h. T he mixture was extractedwith ethyl acetate (5 mL × 3) and the combined organic layer was washed with waterand saturated sodium chloride solution, dried over anhydrous Na2SO4. the solvent was removed under vacuum and the residue was purified by flash chromatography (silica gel) to afford the desired product. All the product alcohols were analyzed by 1H NMR, 13C NMR, or GC analysis. | |
91.02% | With methanol; sodium tetrahydridoborate; at 0 - 20℃; for 3h; | To a stirred solution of 1-[2-(trifluoromethyl)phenyl]ethan-1-one (5 g, 26.575 mmol, 1 equiv.) in MeOH (15 mL) was added NaBH4 (2.01 g, 53.128 mmol, 2.00 equiv.) in portions at 0 degrees C. The resulting mixture was stirred for 3 h at room temperature. The reaction was monitored by TLC PE/EA(5:1). The resulting mixture was concentrated under vacuum. The residue was purified by silica gel column chromatography, eluted with PE/EtOAc (50:1 to 5:1) to afford 1-[2- (trifluoromethyl)phenyl]ethan-1-ol (4.6 g, 91.02%) as a light yellow oil. |
86% | With sodium tetrahydridoborate; In methanol; for 0.75h; | General procedure: Racemic secondary alcohols 2a-e were prepared by reducing ketones 1a-e with sodium borohydride in methanol. The ketones (1a, 7.1mmol; 1b, 3.2mmol; 1c, 3.2mmol; 1d, 3.8mmol; 1e, 6.7mmol), NaBH4 (1.1 equivalents of the quantity of ketone) and methanol (10mL) were mixed in a 25mL flask equipped with a magnetic stirrer. The mixtures were stirred for 45min in on ice bath (Scheme 1). The reactions were then quenched by adding water (1mL), the methanol was removed by evaporation under vacuum and the residue extracted with ethyl acetate (3× 20mL). The combined organic phases were dried over anhydrous sodium sulfate (Na2SO4) and then filtered. The organic solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography, using hexane and ethyl acetate as eluents to produce racemic alcohols 2a-e in excellent yields (2a, 93%; 2b, 78%; 2c, 82%; 2d, 97%; 2e, 86%). |
With sodium tetrahydridoborate; In methanol; at 20℃;Schlenk technique; | General procedure: The ketone (1mmol) was dissolved in MeOH (5cm3) in a schlenk tube, then NaBH4 (3mmol) was added slowly and the mixture was stirred at r.t. for o/n. The solvent was removed and the mixture was dissolved in DCM (10 cm3), washed with water (10cm3), filtered and solvent removed. a small amount of the residue was dilluted inEtOAc and then injected on the GC to determine the conversion. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With tert.-butylhydroperoxide; eosin y; In decane; acetonitrile; at 25℃; for 72h;Inert atmosphere; Irradiation; Molecular sieve; Green chemistry; | General procedure: Oven dried round bottom flask was charged with Eosin Y (5 mmol) alcohol (1 mmol) and 3 equiv. of TBHP (5.5 M in decane) in dry ACN. The resulting mixture was degassed for 15 mins, followed by back filling N2, and then irradiated under Blue LED light (12W, 455 nm) at room temperature (25 oC). After reaction completion monitored through TLC, the mixture was diluted with 15 ml of 10% NaHCO3 solution, and extracted with EtOAc (3 × 20 ml). The combined organic extracts were washed with brine (20 ml), dried over Na2SO4, and concentrated on vacuo. Purification of the crude product on silica gel using EtOAc:Hexane as solvent system afforded the desired product. |
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