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CAS No. : | 143062-84-4 | MDL No. : | MFCD01861147 |
Formula : | C10H14FNO3S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | XUWZMHVPMZXIRU-LMLSDSMGSA-N |
M.W : | 247.29 | Pubchem ID : | 53350313 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H332-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 |
---|---|---|
With triethylamine; In toluene; at -10 - 20℃; for 1h; | 4-[(3S,4S)-3-tertiary butoxycarbonyl amino-4-fluoromethyl-1-pyrrolidinyl]-2,5-difluoro-3-methylbenzoyl acetate (334 mg, 0.729 mmol) and N,N-dimethylformamide dimethylacetal (0.194 ml, 1.46 mmol) were dissolved in benzene (6 ml), and the mixture was stirred 3 hours by heating in an oil bath at an external temperature of 80°C. The reaction solution was allowed to cool, and concentrated under reduced pressure to dryness. The resulting yellow oily product was dissolved in toluene (10 ml), and to this solution was added paratoluenesulfonate salt of (1R,2S)-2-fluorocyclopropylamine (270 mg, 1.09 mmol). The mixture was stirred at -10°C, and triethylamine (0.158 ml, 1.13 mmol) was added dropwise with stirring. The reaction solution was stirred at room temperature for 1 hour, and water (150 ml) and ethyl acetate (20 x 2 ml) were added to the solution. The solution was washed with saturated aqueous solution of sodium chloride (15 ml), and dried with anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure to dryness. The yellow oily product was dissolved in dimethylformamide (5 ml), and potassium carbonate (202 mg, 1.46 mmol) was added in an ice bath, and the solution was stirred at room temperature for 4 days. To the reaction solution was added 10percent aqueous solution of citric acid (20 ml) in an ice bath, and the precipitated crystals were collected by filtration. The crystals were washed with an excess amount of purified water, and the resulting crude crystals were subjected to silica gel column chromatography to obtain 277 mg (73percent) of the title compound as pale yellow powder from the eluate of a mixed solution of chloroform and methanol (95 : 5). 1H-NMR (400 MHz, CDCl3) delta: 1.20-1.34 (2H, m), 1.41 (3H, t, J = 7.1 Hz), 1.46 (9H, s), 2.57 (3H, s), 2.88 (1H, s), 3.14-3.18 (1H, m), 3.44-3.60 (2H, m), 3.80-3.92 (2H, m), 4.39 (2H, q, J = 7.1 Hz), 4.50-4.56 (1H, m), 4.65-4.70 (1H, m), 4.74-4.82 (1H, m), 4.94-4.90 (1H, m), 7.96 (1H, d, J = 13.2 Hz), 8.53 (1H, d, J = 2.9 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With triethylamine; In toluene; at 25℃; for 0.166667h; | Example 3: Ethyl 3-[(1R,2S)-2-fluoro-1-cyclopropylamino]-2-[4-[7-(S)-tert-butoxycarbonylamino-5-azaspiro[2.4]hept-5-yl]-2,5-difluorobenzoyl-3-methoxy]acrylate; A <strong>[143062-84-4](1R,2S)-2-fluorocyclopropylamine p-toluenesulfonic acid salt</strong> (359 mg, 1.0 eq.) was added to a solution containing ethyl 3-ethoxy-2-[4-[7-(S)-tert-butoxycarbonylamino-5-azaspiro[2.4]hept-5-yl]-2,5-difluorobenzoyl-3-methoxy]acrylate (760 mg, 1.45 mmol), toluene (15.2 mL), and triethylamine (0.22 mL, 1.1 eq.), and the mixture was stirred for 10 minutes at 25°C. The formed organic layer was washed with water (10 mL .x. 2) and saturated saline (10 mL) and dried over sodium sulfate. The solvent was removed under reduced pressure, to thereby yield 790 mg of the title compound as a yellow-orange (99percent).1H-NMR (270 MHz, CDCl3) delta: 0.61-1.31 (6H, m), 1.12 (3H, t, J = 7.0 Hz), 1.39 (9H, s), 3.18-4.13 (6H, m), 3.83 (3H, s), 4.10 (2H, q, J = 7.0 Hz, 10.3 Hz), 4.81 (1H, m), 7.25 (1H, m), 8.13 (1H, d, J = 13.8 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With triethylamine; In toluene; at 25℃; for 0.5h; | Example 6: Ethyl 3-[(1R,2S)-2-fluoro-1-cyclopropylamino]-2-[4-[7-(S)-tert-butoxycarbonylamino-5-azaspiro[2.4]hept-5-yl]-2,5-difluorobenzoyl]acrylate; Ethyl 4-[7-(S)-tert-butoxycarbonylamino-5-azaspiro[2.4]hept-5-yl]-2,5-difluorobenzoylacetate (1.00 g, 2.29 mmol) was dissolved in acetic anhydride (2.16 mL, 10 eq.) and ethyl orthoformate (3.79 mL, 10 eq.), and the mixture was stirred for three hours at 130°C. After the reaction mixture was allowed to cool down, the solvent was removed under reduced pressure. Toluene (10 mL) was added to the residue, and the mixture was subjected to co-boiling twice. After completion of co-boiling, toluene (30 mL), triethylamine (0.38 mL, 1.2 eq.), and a <strong>[143062-84-4](1R,2S)-2-fluorocyclopropylamine p-toluenesulfonic acid salt</strong> (564 mg, 1.0 eq.) was added to the co-boiling residue, and the mixture was stirred for 30 minutes at 25°C. The formed organic layer was washed with water (20 mL) and an aqueous sodium bicarbonate solution (10 mL, NaHCO3, 1.0 g) and dried over sodium sulfate, and the solvent was removed under reduced pressure. The residue was subjected to silica gel column chromatography (eluent: hexane/ethyl acetate = 2/1), and several fractions were combined. The solvent of the combined fraction was removed under reduced pressure, to thereby yield 870 mg of the title compound as a pale yellow solid (73percent).1H-NMR (270 MHz, CDCl3) delta: 0.69-1.50 (6H, m), 1.14 (3H, t, J = 7.0 Hz), 1.39 (9H, s), 3.16-4.00 (6H, m), 4.12 (2H, q, J = 7.0 Hz, 14.0 Hz), 4.82 (1H, m), 6.14 (1H, dd, J = 7.0 Hz, 14.0 Hz), 7.15 (1H, dd, J = 7.0 Hz, 14.0 Hz), 8.10 (1H, d, J = 13.5 Hz) MASS: m/e = 524 (FABMS) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ethyl {4-[(3R)-3-(1-tert-butoxycarbonylaminocyclopropyl)-pyrrolidin-1-yl]-2-fluoro-3-methoxybenzoyl}acetate (0.79 g) was dissolved in acetic anhydride (0.48 mL) and ethyl ortoformate (0.71 mL) at room temperature. The reaction liquid was heated (internal temperature: 120°C), stirred for 3 hours and then concentrated under reduced pressure. The concentrated residue was dissolved in toluene and toluene was distilled away under reduced pressure. The residue was added eith ethyl acetate (8.0 mL) and was dissolved therein, followed by addition of <strong>[143062-84-4](1R,2S)-2-fluorocyclopropylamine tosylate</strong> (0.46 g) and triethylamine (0.36 mL) in a water bath and stirring for two hours. An insoluble matter in the reaction mixture was distilled out, and the filtrate was washed with a saturated brine and water, and dried with anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure to give a crude product (1.11 g) of the title compound which is a mixture of E compound and Z compound as a red oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In ethyl acetate; at 20℃; for 2h; | Example 2: Production of ethyl (E,Z)-2-(2,4-difluoro-3-methoxybenzoyl)-3-[(1R,2S)-fluorocy clopropylamine]acrylate To 22.3 g of ethyl 3-dimethylamino-2-(2,4-difluoro-3-methoxybenzoyl)acrylate was added 110 mL of ethyl acetate. While stirring the mixture at room temperature, 20.4 g of <strong>[143062-84-4](1R,2S)-2-fluorocyclopropylamine tosylate</strong> was added, and then 1.5 g of triethylamine was added dropwise to the mixture. After 2 hours, 30 mL of water was added to the reaction mixture, and the mixture was extracted with 25 mL of ethyl acetate and dried with anhydrous sodium sulfate. Sodium sulfate was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 20.5 g of the title compound as a dark brown oily product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In dichloromethane; at -10 - 20℃; for 17h; | 3-Cyano-2,4,5-trifluorobenzoylethyl acetate (883 mg, 3.25 mmol) was dissolved in ethyl orthoformate (1.35 mL, 8.13 mmol). Acetic anhydride (1.07 mL, 11.4 mmol) was added thereto, and the resultant mixture was stirred at 100°C for 5 hours. The reaction mixture was concentrated under reduced pressure and co-boiled with toluene (5 mL .x. 3). The residue was dissolved in dichloromethane (20 mL). A <strong>[143062-84-4]2-(S)-fluoro-1-(R)-cyclopropylamine p-toluenesulfonic acid salt</strong> (964 mg, 3.90 mmol) was added thereto, triethylamine (679 muL, 4.88 mmol) was added dropwise to the resultant mixture under stirring at -10°C. After completion of dropwise addition, the reaction mixture was stirred at room temperature for 17 hours. Subsequently, water (150 mL) was added to the reaction mixture, and the resultant mixture was extracted with ethyl acetate (150 mL .x. 2). The organic layers were combined and washed with saturated brine (150 mL), followed by drying with sodium sulfate anhydrate. After filtration, the filtrate was concentrated under reduced pressure. The residue was dissolved in dimethylformamide (8 mL). Potassium carbonate (898 mg, 6.50 mmol) was added thereto under stirring while cooling with ice, and the resultant mixture was stirred at room temperature for 3 hours. The reaction mixture was cooled with ice, and 1N aqueous hydrochloric acid (15 mL) and water (30 mL) were added thereto, followed by stirring at room temperature for 2 hours. The solid matter that precipitated was collected through filtration and washed with water and a small amount of ethanol, to thereby yield the title compound as a pale yellow solid (890 mg, 82percent). 1H-NMR (CDCl3) delta ppm: 1.41(3H, t, J=7.1Hz), 1.74 (1H, d, J=25.4Hz), 1.86-1.97(1H,m), 3.95-4.00(1H,m), 4.41(2H,q,J=7.1Hz), 5.11(1H,d,J=62.3Hz), 8.55 (1H, dd, J=17.3, 8.5Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate; In dichloromethane; | The reaction of the 5-bromo-2-([1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazol-5-yl]carbonyl}amino)isonicotinic acid takes place analogously to the reaction procedure in Example (Ik-127) using:100 mg (196 mumol) of 5-bromo-2-([1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazol-5-yl]carbonyl}amino)isonicotinic acid, 9.0 ml of dichloromethane, 48.3 mg (196 mumol) of (1R,2S)-2-fluorocyclopropanaminium 4-methylbenzenesulphonate, 96.6 mg (254 mumol) of HATU, 0.097 ml (587 mumol) of Huenig's base.The remaining residue is purified by means of column chromatography on silica gel using the eluent mixture cyclohexane:acetone (gradient).This gives 89.4 mg of 5-bromo-N-[(1R,2S)-2-fluorocyclopropyl]-2-([1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazol-5-yl]carbonyl}amino)isonicotinamide (80percent).1H-NMR (600 MHz, d3-acetonitrile): delta=9.65 (br. s, 1H), 8.52 (d, 1H), 8.22 (d, 1H), 4.75 (m, 1H), 3.97 (s, 3H), 2.88 (br. s, 1H), 1.01-1.22 (m, 2H) ppm.13C-NMR (600 MHz, d3-acetonitrile): delta=157.5; 151.8; 150.7; 148.3; 137.1; 114.2; 113.4; 111.2; 70.8; 39.6; 26.4; 12.2 ppm.HPLC-MSa): log P=3.19; mass (m/z)=568, 570 [M+1]+. |
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