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CAS No. : | 117324-58-0 | MDL No. : | MFCD08234902 |
Formula : | C9H8F3NO2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | QGFUDNJZHZNPCS-UHFFFAOYSA-N |
M.W : | 219.16 | Pubchem ID : | 14233808 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H315-H319-H335 | Packing Group: | |
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 |
---|---|---|
75% | With triethylamine; In dichloromethane; at -78 - 20℃; | To a solution of <strong>[117324-58-0]methyl 2-amino-5-(trifluoromethyl)benzoate</strong> (0.25 g, 1.141 mmol) and triethylamine (0.115 g, 0.16 ml, 1.14 mmol) in 3 ml of dry dichloromethane was added trifluoromethane sulfonic anhydride (0.64 g, 2.28 mmol) at -78 C. The mixture was maintained below -40 C. for 3 h and stirred at RT for over night. Water was added and extracted with dichloromethane. The organic layer was dried and concentrated. The product was purified by flash chromatography to give 0.3 g (75%) of methyl 5-(trifluoromethyl)-2-(trifluoromethylsulfonamido)benzoate as white solid. MS found: (M+H)+=352. |
75% | With triethylamine; In dichloromethane; at -78 - 20℃; | Preparation B6, Step 3: To a solution of <strong>[117324-58-0]methyl 2-amino-5-(trifluoromethyl)benzoate</strong> (0.25 g, 1.141 mmol) and triethylamine (0.115 g, 0.16 ml, 1.14 mmol) in 3 ml of dry dichloromethane was added trifluoromethane sulfonic anhydride (0.64 g, 2.28 mmol) at -78 C. The mixture was maintained below -40 C. for 3 h and stirred at RT for over night. Water was added and extracted with dichloromethane. The organic layer was dried and concentrated. The product was purified by flash chromatography to give 0.3 g (75%) of methyl 5-(trifluoromethyl)-2-(trifluoromethylsulfonamido)benzoate as white solid. MS found: (M+H)+=352. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
To a solution of N-(4-(trifluoromethyl)phenyl)pivalamide (1 g, 4.08 mmol) in 20 ml of dry THF under nitrogen was added n-butyllithium (0.65 g, 4.1 ml) at 0 C. The reaction mixture was maintained at 0 C. for 3 h and added onto dry ice and stirred at RT over night. The reaction mixture was concentrated and the solid product obtained was dissolved in 25 ml of dry methanol and purged HCl gas for 30 min at 0 C. The mixture was stirred at RT for 2 h and heated at 55 C. over night. The reaction mixture was concentrated, basified with sodium bicarbonate solution and extracted with ethyl acetate. The organic layer was washed with water, brine and concentrated. The crude product was purified by flash chromatography to give methyl 2-amino-5-(trifluoromethyl)benzoate (0.55 g) as white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With triethylamine;1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; In dimethyl sulfoxide; at 80℃; under 5171.62 Torr; for 14 - 16h; | Example 139 Synthesis of 5- [Acetyl- (3, 5-bis-trifluoromethyl-benzyl)-amino]-7-trifluoromethyl-2, 3,4, 5- tetrahydro-benzo [b] azepine-1-carboxylic acid tert-butyl ester. Step 1. Preparation of Methyl-3-trifluoromethyl-2-aminobenzoate Add palladium (II) acetate (1.89 g, 8.4 mmol), 1,1- bis (diphenylphosphino) ferrocene (6.83 g, 12.3 mmol), and triethyl amine (32 mL, 44.0 mmol) to a solution of 2-bromo-4-trifluoromethylanaline (10.0 g, 42.0 mmol) in dimethylsulfoxide (283 mL) and methanol (187 mL). At 100 psi of carbon monoxide, heat the mixture to 80 C. After heating for 14-16 h cool the reaction to room temperature and filter. Dilute the organics with ethyl acetate (500 mL), wash with water (3x200 mL) and brine (200 mL). Dry the organics over sodium sulfate and filter. Remove solvent under vacuum and chromatograph the crude product using ethyl acetate/hexane (10 %) to elute. This provides the title compound (8.0 g, 88%) as an off white solid: H NMR (CDC13,400 MHz) 8 3.93 (s, 3H), 6.11 (bs, 2H), 6.73 (d, J = 8.4 Hz, 1H), 7.49 (dd, J = 2.0, 8.4 Hz, 1H), 8.17 (d, J = 2.0 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With triethylamine; In dichloromethane; at 20℃; for 72h; | Step 2. Preparation of Methyl-3-trifluoromethyl-2-t-butoxycarbonylaminobenzoate. Add di-t-butyl dicarbonate (2.0 g, 9.1 mmol) to a solution of methyl-3- trifluoromethyl-2-aminobenzoate (2.0 g, 9.1 mmol) in dichloromethane (20 mL). To this mixture, add triethylamine (9.1 mmol) and stir at room temperature under an atmosphere of nitrogen for 72 h. Dilute the reaction with dichloromethane (100 mL) and wash with water (100 mL x 2). Dry the separated organic phase over sodium sulfate, filter, and remove solvent under vacuum. Chromatograph the product on silica gel using hexane/ethyl acetate (gradient, 2-10 % ethyl acetate/hexane) to elute. This provides the title compound as a colorless solid (1.43 g, 49%) : H NMR (CDCl3, 400 MHz) 8 1.54 (s, 9H), 3.99 (s, 3H), 7.75 (dd, J = 2.0, 9.2 Hz, 1H), 8.30 (d, J = 1.6 Hz, 1H), 8.64 (d, J = 9.2 Hz), 10.48 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluoroacetic acid; In dichloromethane; | REFERENCE EXAMPLE 28 Methyl 2-Amino-5-trifluoromethylbenzoate To a solution of methyl 2-t-butoxycarbonylamino-5-trifluoromethylbenzoate (3.80 g; prepared in Reference Example 27.) in methylene chloride (30 ml), trifluoroacetic acid (6 ml) was added. The mixture was stirred for 8 hours at room temperature. The solvent was distilled off azeotropically with toluene three times. To the reaction mixture, an aqueous sodium hydrogencarbonate solution was added to neutralize. The mixture was extracted with ethyl acetate, washed, dried, filtered and concentrated under the reduced pressure. The residue was purified on silica gel column chromatography (hexane:AcOEt 5:1) to give the title compound (2.35 g) having the following physical data. TLC: Rf 0.20 (hexane:AcOEt=5:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4.0 g (71%) | In methanol; chloroform; | PREPARATION 39 Methyl 2-Amino-5-trifluoromethylbenzoate A solution of 7.46 g (0.026 mol) of 2-(N-pivaloyl)-5-trifluoromethylbenzoic acid in 300 ml of methanol was cooled to 5 C. and saturated with gaseous hydrochloric acid. The reaction mixture was then heated at reflux for 20 hours, and evaporated to a solid. The crude solid was dissolved in chloroform and washed with saturated aqueous sodium bicarbonate. The organic layer was dried and evaporated to a viscous oil, which was purified by silica gel chromatography (9:1 hexane:ethylacetate). The title compound was isolated as a white solid, m.p. 51-52 C.; yield 4.0 g (71%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine;tetrakis(triphenylphosphine) palladium(0); In N,N-dimethyl-formamide; at 50℃; for 120h; | Step 1 Synthesis of [2-iodo-5-(trifluoromethyl)phenyl]methanol 2-Iodo-4-(trifluoromethyl)aniline (8.0 g, 27.9 mmol), methanol (5 ml) and triethylamine (10 ml) were dissolved in dimethylformamide (50 ml) and, under a carbon monoxide atmosphere, tetrakis(triphenylphosphine)palladium (1.6 g, 1.4 mmol) was added and the mixture was stirred at 50C for 5 days. The solvent was evaporated and work-up according to a conventional method gave a crude product of methyl 2-amino-5-(trifluoromethyl)benzoate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In dichloromethane; at 0 - 20℃; | Step 1 Synthesis of methyl {2-(cyclopropylcarbonyl)amino-5-trifluoromethyl}benzoate Methyl 2-amino-5-(trifluoromethyl)benzoate (0.20 g, 0.91 mmol) obtained as an intermediate for Step 1 of Example 7 was dissolved in methylene chloride (10 ml), triethylamine (0.25 ml, 1.82 mmol) and cyclopropanecarbonyl chloride (0.11 g, 1.1 mmol) were added at 0C, and the mixture was stirred overnight at room temperature. After work-up according to a conventional method, the mixture was purified by silica gel column chromatography (10% to 30% mixed solvent of ethyl acetate/hexane) to give the title compound (0.10 g, 0.35 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
The obtained crude product was dissolved in tetrahydrofuran (20 ml), lithium aluminum hydride (1.0 g, 26.3 mmol) was added under cooling, and the mixture was stirred for 2 hr. Water (1 ml), 30% aqueous sodium hydroxide solution (1 ml) and water (3 ml) were sequentially added, the precipitate was filtered off, and the filtrate was concentrated to give a crude product of [2-amino-5-(trifluoromethyl)phenyl]methanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Preparation B6, Step 2: To a solution of N-(4-(trifluoromethyl)phenyl)pivalamide (1 g, 4.08 mmol) in 20 ml of dry THF under nitrogen was added n-butyllithium (0.65 g, 4.1 ml) at 0° C. The reaction mixture was maintained at 0° C. for 3 h and added onto dry ice and stirred at RT over night. The reaction mixture was concentrated and the solid product obtained was dissolved in 25 ml of dry methanol and purged HCl gas for 30 min at 0° C. The mixture was stirred at RT for 2 h and heated at 55° C. over night. The reaction mixture was concentrated, basified with sodium bicarbonate solution and extracted with ethyl acetate. The organic layer was washed with water, brine and concentrated. The crude product was purified by flash chromatography to give methyl 2-amino-5-(trifluoromethyl)benzoate (0.55 g) as white solid. |
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