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CAS No. : | 38186-84-4 | MDL No. : | MFCD04972725 |
Formula : | C6H5ClFN | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | FMPYGEFGXUAAKG-UHFFFAOYSA-N |
M.W : | 145.56 | Pubchem ID : | 12852014 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-H332-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 |
---|---|---|
With sodium hydrogencarbonate;palladium diacetate; 1,3-bis-(diphenylphosphino)propane; In methanol; at 20 - 130℃; for 20h; | A. 7-(5 -Fluoro-3 -methylpyridin-2-yl)-N-(5 -(trifluoromethyl)pyrimidin-2-yl)- 1 , 8 -naphthyridin-4- amine (compound 1)1. 2-Acetyl-5-fluoro-3-methylpyridine Dissolve 2-chloro-5 -fluoro-3 -methylpyridine (1.45 g, 0.01 moles) in MeOH (30 mL) at room temperature. Add butylvinylether (3.0 mL) and NaHCO3 (3.0 g) to the reaction mixture and degas with nitrogen for 5 minutes. Add catalyst Pd(OAc)2 (120 mg) and 1,3- bis(diphenylphosphino)propane (360 mg) to the mixture and then heat at 13O0C in a pressure vessel with stirring for 20 hours. Cool the reaction mixture to room temperature and remove the insoluble EPO <DP n="50"/>material by filtration. Wash the solid with MeOH (25 mL) and then add 5.0 mL of 6.0 N aqueous HCl to the filtrate. Stir the mixture at room temperature for 20 hours. Concentrate the reaction mixture under vacuum, dilute it with EtOAc (100 mL), wash the organic layer with aq. Na2CO3 (2 x 50 mL) and dry (MgSO4). Filter the dried extract and concentrate under vacuum to afford crude product as pink oil. Purify the crude product by column chromatography to afford pure product as colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55.2% | To a solution of <strong>[38186-84-4]2-chloro-5-fluoro-3-methylpyridine</strong> D38 (0.50 g, 2.82 mmol) in dry toluene (12.5 ml) were added sodium t-butoxyde (0.462 g, 4.81 mmol), Pd2(dba)3 (0.315 g, 0.344 mmol), BINAP (0.642 g, 1.031 mmol) and benzophenone imine (0.692 ml, 4.12 mmol). The resulting mixture was degassed (3.x.pump/N2) and then heated to 80° C. After 1 h stirring, the mixture was cooled down to room temperature, diluted with Et2O (400 ml) and filtered through a celite pad. Volatiles were evaporated, the resulting oil was dissolved in THF (34 ml) and HCl (1.408 ml of a 2 M aqueous solution, 2.82 mmol) was added. The mixture was stirred at room temperature for 1.5 h, then neutralized with a saturated NaHCO3 aqueous solution and diluted with DCM (200 ml). The inorganic layer was back-extracted with DCM (2.x.50 ml). The collected organic layers were dried (Na2SO4), filtered and evaporated. The residue was purified by flash chromatography on silica gel (Biotage SP4 12M, Cy/EtOAc 60/40). Collected fractions gave the title compound D39 (0.20 g, 1.554 mmol, 55.2percent yield from D38, two steps), as an orange solid. MS: (ES/+) m/z: 127 (M+1). C6H7FN2 requires 126.1H NMR (400 MHz, DMSO-d6) delta(ppm): 7.73 (d, 1H), 7.23 (dd, 1H), 5.60 (bs, 2H), 2.04 (s, 3H). | |
5-Fluoro-3-methyl-2-pyridinamine (DIl): To a solution of <strong>[38186-84-4]2-chloro-5-fluoro-3-methylpyridine</strong> DlO (0.50 g) in dry toluene (12.5 ml) were added sodium t-butoxyde (0.462 g, 4.81 mmol), Pd2(dba)3 (0.315 g, 0.344 mmol), BINAP (0.642 g, 1.031 mmol) and benzophenone imine (0.692 ml, 4.12 mmol). The resulting mixture was degassed (3 x pump/N2) and then heated to 80 0C. After 1 hour stirring, the mixture was cooled down to room temperature, diluted with Et2O (400 ml) and filtered through a celite pad. Volatiles were evaporated, the resulting oil was dissolved in THF (34 ml) and HCl (1.408 ml of a 2 M aqueous solution, 2.82 mmol) was added. The mixture was stirred at room temperature for 1.5 hours, then neutralized with a saturated NaHCO3 aqueous solution and diluted with DCM (200 ml). The inorganic layer was back- extracted with DCM (2 x 50 ml). The collected organic layers were dried (Na2SO4), filtered and evaporated. The residue was purified by flash chromatography on silica gel (Biotage SP4 12M column, Cy/EtOAc 60/40). Collected fractions gave the title compound DIl (0.20 g) as an orange solid. MS: (ES/+) m/z: 127 (M+l). C6H7FN2 requires 126. 1H NMR (400 MHz, DMSO-J6) delta ppm: 7.73 (d, 1 H), 7.23 (dd, 1 H), 5.60 (bs, 2 H), 2.04 (s, 3 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
To an ice-cooled mixture of the crude mesylate (4.53 g, 18.90 mmol) in THF (180 ml), LAH (18.90 ml of a 1.0 M solution in THF, 18.90 mmol) was added dropwise and the reaction was stirred for 1 h. A 2 M HCl aqueous solution (80 ml) was added, the resulting mixture stirred for 30 min and then DCM (400 ml) was added. The organic layer was separated and evaporated to give the title compound D38 (2.28 g, 12.84 mmol, 67.9percent yield from (2-chloro-5-fluoro-3-pyridinyl)methanol, two steps) as a white solid.HPLC (walk-up): rt=3.56 min.1H NMR (400 MHz, DMSO-d6) delta (ppm): 8.31 (d, 1H), 7.86 (dd, 1H), 2.35 (s, 3H). | ||
With lithium aluminium tetrahydride; In tetrahydrofuran;Cooling; | To a -20 0C cooled solution of (2-chloro-5-fluoro-3-pyridinyl)methanol (3.086 g, 19.10 mmol) and TEA (5.32 ml, 38.20 mmol) in anhydrous DCM (180 ml), MsCl (2.233 ml, 28.70 mmol) was added dropwise and the resulting reaction mixture stirred at 0 0C for 30 minutes. Volatiles were evaporated under reduced pressure to afford the desired mesylate (4.53 g) that was used in the next step without further purification. [Mesylate data: MS: (ES/+) m/z: 240 (M+l) and 242 (M+l). C7H7ClFNO3S requires 239]. To an ice-cooled mixture of the crude mesylate (4.53 g, 18.90 mmol) in THF (180 ml), LAH (18.90 ml of a 1.0 M solution in THF, 18.90 mmol) was added dropwise and the reaction was stirred for 1 hour. A 2 M HCl aqueous solution (80 ml) was added, the resulting mixture stirred for 30 minutes and then DCM (400 ml) was added. The organic layer was separated and evaporated to give the title compound DlO (2.28 g) as a white solid. HPLC (walk-up): rt = 3.56 min. 1H NMR (400 MHz, DMSO-J6) delta ppm: 8.31 (d, 1 H), 7.86 (dd, 1 H), 2.35 (s, 3 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
tetrakis(triphenylphosphine) palladium(0); In N,N-dimethyl-formamide; at 120℃; for 0.5h;microwave irradiation; | Acid-22: 5-Fluoro-3-methyl-pyridine-2-carboxylic acid; a) 5-Fluoro-3-methyl-pyridine-2-carbonitrile; A soln. of <strong>[38186-84-4]2-chloro-5-fluoro-3-methyl-pyridine</strong> (CAS 38186-84-4, 408 mg, 2.750 mmol), Zn(CN)2 (230 mg, 1.923 mmol) and Pd(PPh3)4 (190 mg, 0.165 mmol) in DMF (8 ml) was stirred at 120 C for 0.5 h in a microwave. The reaction mixture was filtered over hyflo, diluted with TBME and H20 and extracted with brine. The aq. phases were reextracted with TBME, the combined org. phases were dried over Na2S04, filtered and concentrated. Flash chromatography on silica gel (hexane-EtOAc 100:0 to 80:20) yielded the title compound. HPLC: 0.72 min; 1 H NMR (400 MHz, CDCI3): delta 8.42 (d, 1 H), 7.42-7.39 (m, 1 H), 2.61 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
12% | With hydrogenchloride; at 150℃; for 15h;Microwave irradiation; | <strong>[38186-84-4]2-chloro-5-fluoro-3-methylpyridine</strong> (lg, 6.870 mmol) is dissolved in hydrochloric acid(37percent, 20 mL) and the reaction is heated under microwave irradiation at 15000 for15h. The mixture is diluted with water and washed with DCM. The aqueous layer isbasified with NaOH and re-extracted with DCM several times. The organic layer isseparated, dried and evaporated to furnish 5-fluoro-3-methyl-pyridin-2-ol (140 mg,content 74percent, 12percent).UPLC-MS (Method 2): R = 0.50 mmMS (ESI pos): mlz = 128 (M+H)+ |
With hydrogenchloride; water; at 150℃; for 15h;Microwave irradiation; | 10365] <strong>[38186-84-4]2-chloro-5-fluoro-3-methylpyridine</strong> (1 g, 6.870 mmol) is dissolved in hydrochloric acid (37percent, 20 mE) and the reaction is heated under microwave irradiation at 150° C. for 15 h. The mixture is diluted with water and washed with DCM. The aqueous layer is basified with NaOH and reextracted with DCM several times. The organic layer is separated, dried and evaporated to thrnish 5-fluoro-3-methyl-py-ridin-2-ol (140 mg, content 74percent, 12percent).10366] UPEC-MS (Method 2): R=0.50 mm10367] MS (ESI pos): mlz=128 (M+H) |
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