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CAS No. : | 31181-79-0 | MDL No. : | MFCD09025826 |
Formula : | C6H6FNO | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | FKTCIWBKNWUDAX-UHFFFAOYSA-N |
M.W : | 127.12 | Pubchem ID : | 19703803 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-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 |
---|---|---|
80% | With thionyl chloride; In dichloromethane; at 0℃; for 1h; | Preparation 60; 2-Chloromethyl-3-fluoro-pyridine EPO <DP n="167"/>Dissolve <strong>[31181-79-0](3-fluoro-pyridin-2-yl)-methanol</strong> (215 mg, 1.69 mmol) in dichloromethane (10 mL) and cool to 0 0C. Add thionyl chloride (160 muL, 2.20 mmol) and stir the reaction for one hour. Add dichloromethane (50 mL) and stir the reaction with saturated aqueous sodium bicarbonate (2 x 40 mL) and brine (2 x 40 mL). Separate and dry the organic portion over magnesium sulfate, filter, and concentrate under reduced pressure to provide 198 mg (80%) of product, which is used without further purification. MS: m/z 146, 148 [C6H5ClFN + I]+; 1H NMR (300 MHz, CDCl3): delta 8.41-8.44 (m, IH), 7.41-7.47 (m, IH), 7.28-7.34 (m, IH), 4.75 (d, J = 2.0 Hz, 2H); 19F NMR (282 MHz, CDCl3): delta -123.8. |
66.5% | With thionyl chloride; In dichloromethane; at 0 - 20℃; for 2h; | To a solution of <strong>[31181-79-0](3-fluoropyridin-2-yl)methanol</strong> (1.8 g, 13.8 mmol, 1 equiv) in DCM( 20 mL) was added SOCh ( 2.5 mL, 35 mmol, 2.5 equiv) dropwise at 0C. The resulting mixture was stirred at room temperature for 2 hours. The reaction mixture was quenched with saturated aqueous NaHCCb solution and extracted with DCM (3 * 20 mL). The combined organic layers were dried over anhydrous Na2S04 and concentrated in vacuo. The residue was purified by column chromatography (eluted with PE/EtOAc = 5/1) to afford the title compound 2-(chloromethyl)-3-fluoropyridine (1.33 g, 66.5% yield). LC-MS: m/z 146.0, 148.0 (M+H) + |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With hydrogen;palladium over charcoal; In methanol; for 20h; | Preparation 59; (3-Fluoro-pyridin-2-yl)-methanolDissolve (6-bromo-3-fluoro-pyridin-2-yl)-methanol (850 mg, 4.13 mmol) in methanol (40 mL) then purge the solution with nitrogen. Add palladium on carbon (200 mg of 5percent wet) and stir the mixture under a hydrogen atmosphere (2 balloons) for 20 h. Filter the mixture through Celite.(R). and wash the filter cake with methanol. Concentrate the filtrate under reduced pressure and dissolve the resulting residue in chloroform (150 mL). Wash the organics with saturated aqueous sodium bicarbonate (75 mL), dry over magnesium sulfate, filter, and concentrate to give 433 mg (82percent) of the title compound which is used without further purification. 1H NMR (300 MHz, CDCl3): delta 8.40 (m, IH), 7.42-7.36 (m, IH), 7.29-7.23 (m, IH), 4.84 (s, 2H), 3.97 (br s, IH); MS (APCI): m/z 110 [C6H6FNO - H2O + H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
3.78 g (93%) | With sodium borohydrid; In ethanol; ethyl acetate; | 2-Hydroxymethyl-3-fluoropyridine A solution of 2-formyl-3-fluoropyridine (4.0 g, 32 mmol) and sodium borohydride (309 mg, 8 mmol) in absolute ethanol (40 mL) was stirred at 0° C. for 15 minutes and at room temperature for 1 hour. The reaction was quenched with saturated aqueous ammonium chloride (5 mL) and filtered through diatomaceous earth to remove solids. The filtrate was evaporated and the resultant white solid was dissolved in ethyl acetate and water. The aqueous layer was extracted with ethyl acetate (5*30 mL) and the combined extracts were dried over anhydrous sodium sulfate. Solvent removal provided 3.78 g (93percent) of the titled product as a pale yellow oil: IR (CHCl3, cm-1) 3607, 3439, 3019, 1607, 1576, 1451, 1416, 1312, 1257, 1218, 1209, 1167, 1105, 1053, 857, 803; 1 H NMR (300 MHz, CDCl3) delta8.38 (m, 1H), 7.39 (m, 1H), 7.26 (m, 1H), 4.83 (s, 2H), 3.73 (br s, 1H); MS (FD) m/e 127 (M+); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With thionyl chloride; In dichloromethane; | 2-chloromethyl-3- fluoropyridine hydrochloride To a solution of <strong>[31181-79-0]2-hydroxymethyl-3-fluoropyridine</strong> (3.43 g, 27 mmol) in dichloromethane (30 mL) cooled to -10° C. was added neat thionyl chloride (4.4 mL, 60 mmol) dropwise over 5 minutes. The resultant pale green solution was stirred at -10° C. for 3 hours followed by evaporation to dryness to provide 4.66 g (.95percent) of the titled product as an off-white crystalline solid: IR (CHCl3, cm-1) 2984, 1732, 1551, 1470, 1452, 1333, 1286, 1273, 1237, 1219, 1208, 1193, 1094, 905, 863, 806; 1 H NMR (300 MHz, CDCl3) delta8.69 (m, 1H), 8.06 (m, 1H), 7.89 (m, 1H), 5.09 (s, 2H); MS (FD) m/e 145 (M+ free base), 147 (M+2 free base) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With diethylamine; In dichloromethane; at 0℃; | General procedure: Intermediate 18: (3,5-difluoro-2-pyridinyl)methyl methanesulfonate Intermediate 9 (3,5-difluoro-2-pyridinyl)methanol (114 mg, 0.786 mmol) was dissolved in DCM (anh) (6 mL) at 0° C. N,N-diethylethanamine (ALDRICH, 0.131 mL, 0.943 mmol) and methanesulfonyl chloride (ALDRICH, 0.067 mL, 0.864 mmol) were added. Reaction mixture was stirred at 0° C. for 1 h 30 min. Crude of reaction was partitioned between water and DCM, aqueous layer was extracted with DCM (2*10 mL). Organic layers were dried over MgSO4 (anh) and filtered. Solvent was eliminated to yield title compound (3,5-difluoro-2-pyridinyl)methyl methanesulfonate (137 mg, 0.614 mmol, 78percent yield). 1H NMR (400 MHz, DMSO-d6) delta ppm: 1H NMR (300 MHz, DMSO-d6) delta ppm: 8.58 (d, 1H), 8.06-8.11 (m, 1H), 5.36 (d, 2H), 3.27 (s, 3H). [ES+MS] m/z 224 (MH+). Intermediates 19-21 were prepared by methods analogous to that described for Intermediate 18 but replacing the alcohol ((3,5-difluoro-2-pyridinyl)methanol) with that indicated in Table 2. Reaction times varied from 1 h to 4 h. |
With triethylamine; In tetrahydrofuran; at 0℃; for 2h; | To a solution of <strong>[31181-79-0](3-fluoropyridin-2-yl)methanol</strong> (230 mg) and triethylamine (74 mg) in THF (5 mL) was added methanesulfonyl chloride (71 mg) at 0°C, and the reaction mixture was stirred at 0°C for 2 hr. The reaction mixture was concentrated under reduced pressure, a saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, and dried over magnesium sulfate. The solvent was evaporated under reduced pressure to give the title compound. MS (ESI+) : [M+H]+206.2. | |
With triethylamine; In dichloromethane; at 0 - 20℃; | The mesylate of <strong>[31181-79-0](3-fluoropyridin-2-yl)methanol</strong> (100 mg) was prepared by reaction with methanesulfonyl chloride (1 .1 eq) and triethylamine (2 eq) in DCM at 0 °C, with warming to ambient temperature. N-[1 -(Fluoromethyl)cyclopropyl]-3-[(1 -methylpyrazol-4- yl)methyl]-2,4-dioxo-1 1H-quinazoline-6-sulfonamide (100 mg, 0.260 mmol), the crude mesylate (55 mg, 0.286 mmol) and potassium carbonate (43 mg, 0.312 mmol) in DMF was conventionally heated to 70 °C for 4 h. Usual work-up afforded the desired product (15 mg, 0.030 mmol, 1 1 percent) as a white powder. |
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