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CAS No. : | 456-24-6 | MDL No. : | MFCD03095059 |
Formula : | C5H3FN2O2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | XOZAJNLUAODXSP-UHFFFAOYSA-N |
M.W : | 142.09 | Pubchem ID : | 95264 |
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 |
---|---|---|
84% | With potassium fluoride; In dimethyl sulfoxide; at 70℃; for 18h;Heating / reflux; | To 100 g of 2-chloro-5-nitropyridine (Aldrich) in 600 mL of dimethyl sulfoxide under an inert atmosphere was added 100 g of anhydrous KF. The reaction was heated at 70° C. for 18 hours before cooling and diluting with 500 mL each of brine, ethyl acetate, and hexanes. This mixture was filtered through a pad of celite, the organic phase was separated, and the aqueous phase was extracted three times with equal volumes of ethyl acetate and hexanes. The pooled organic phases were washed with brine, dried with anhydrous sodium sulfate, and stripped of the solvents. This crude product was passed through a plug of silica gel with a gradient of 10-30percent ethyl acetate/hexanes and stripped to constant weight on a rotary evaporator to give 76 g (84percent) of 2-fluoro-5-nitropyridine as an oil, which was used in the following procedure. To 76 g of 2-fluoro-5-nitropyridine in 500 ml of ethyl acetate under nitrogen was added 100 g of Raney nickel which had been washed three times with ethanol and three times with ethyl acetate. The nitrogen was replaced with hydrogen and the reaction was allowed to proceed for 18 hours at 30 lb/in2. After the hydrogen atmosphere had been replaced by nitrogen, the reaction was filtered through celite and stripped of solvent. The product was purified by passing through a plug of silica gel with chloroform and recrystallized from chloroform to give 42 g (70percent) of 6-fluoro-pyridin-3-ylamine in two crops as white platelets: melting point 90-91° C.; mass spectrum (m/e): M+H 112.7. |
84% | With potassium fluoride; In dimethyl sulfoxide; at 70℃; for 18h; | To 100 g of 2-chloro-5-nitropyridine (Aldrich) in 600 mL of dimethyl sulfoxide under an inert atmosphere was added 100 g of anhydrous KF. The reaction was heated at 70C for 18 hours before cooling and diluting with 500 mL each of brine, ethyl acetate, and hexanes. This mixture was filtered through a pad of celite, the organic phase was separated, and the aqueous phase was extracted three times with equal volumes of ethyl acetate and hexanes. The pooled organic phases were washed with brine, dried with anhydrous sodium sulfate, and stripped of the solvents. This crude product was passed through a plug of silica gel with a gradient of 10-30percent ethyl acetate/hexanes and stripped to constant weight on a rotary evaporator to give 76 g (84percent) of 2-fluoro-5-nitropyridine as an oil, which was used in the following procedure. To 76 g of 2-fluoro-5-nitropyridine in 500 ml of ethyl acetate under nitrogen was added 100 g of Raney nickel which had been washed three times with ethanol and three times with ethyl acetate. The nitrogen was replaced with hydrogen and the reaction was allowed to proceed for 18 hours at 30 lb/in2. After the hydrogen atmosphere had been replaced by nitrogen, the reaction was filtered through celite and stripped of solvent. The product was purified by passing through a plug of silica gel with chloroform and recrystallized from chloroform to give 42 g (70percent) of 6-fluoro-pyridin-3-ylamine in two crops as white platelets: melting point 90-91C; mass spectrum (m/e): M+H 112.7. |
With potassium fluoride; In diethyl ether; water; benzene; | A mixture of 5-nitro-2-chloropyridine (2.0 g, 12.6 mmol) and anhydrous potassium fluoride (2.2 g, 38 mmol) in a combination of sulfalone (6 mL) and benzene (4 mL) was stirred at RT for 20 min. The benzene was then removed by distillation. The resulting mixture was heated at 150° C. for 12 h. The mixture was cooled to RT whereupon water (60 mL) was added. The desired product was separated from the solution via steam distillation. Extraction of the distillate with diethyl ether (2*10 mL) followed by drying (Na2SO4) and concentration gave 5-nitro-2-fluoropyridine as a water white oil (1.3 g, 73percent). |
With potassium fluoride; In diethyl ether; water; benzene; | A mixture of 5-nitro-2-chloropyridine (2.0 g, 12.6 mrnol) and anhydrous potassium fluoride (2.2 g, 38 mmol) in a combination of sulfalone (6 nmL) and benzene (4 mL) was stirred at RT for 20 min. The benzene was then removed by distillation. The resulting mixture was heated at 150° C. for 12 h. The mixture was cooled to RT whereupon water (60 mL) was added. The desired product was separated from the solution via steam distillation. Extraction of the distillate with diethyl ether (2*10 mL) followed by drying (Na2SO4) and concentration gave 5-nitro-2-fluoropyridine as a water white oil (1.3 g, 73percent). | |
119.4 g (83%) | With cesium fluoride; In 1,2-dimethoxyethane; | Method A Preparation of 2-Fluoro-5-nitropyridine A suspension of 160 g (1.01 mol) of 2-chloro-5-nitropyridine and 379 g of dry cesium fluoride was placed in a dry stainless steel bomb which was then charged with 1 L of anhydrous ethylene glycol dimethyl ether. The bomb was sealed, and the reaction was heated at 130° C. with vigorous stirring for 18 hours. The reactor was cooled, vented, and the contents suspended by vigorous agitation. The solids were collected by filtration, then washed well with dichloromethane. The resulting dark brown filtrate was concentrated at 45° C. to give a thick oily brown residue that was distilled through a 4-inch Vigreux column at 61° C./0.05 mm Hg (literature bp 86-87° C./7 mm Hg; Finger G. C. and Starr L. D., J. Am. Chem. Soc., 81:2674-2675 (1959)) to afford 119.4 g (83percent) of the product as a clear pale yellow oil, >96percent pure by gas chromatography (GC). Nuclear magnetic resonance spectroscopy (1H NMR) in deuterated chloroform (CDCl3): delta9.15 (dd, J=2.7, 0.7 Hz, 1H), 8.63 (td, J=7.7, 2.9 Hz, 1H), and 7.15 (dd, J=9.3, 3.4 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With 5%-palladium/activated carbon; hydrogen; sodium sulfate; In toluene; for 15h; | 0.282 g of 5% Pd / C and lOmmol of anhydrous sodium sulfate were added to a 100 mL round bottom flask containing 50 mmol of <strong>[456-24-6]5-nitro-2-fluoropyridine</strong> in 50 ml of toluene, then hydrogen gas was added and heated and stirred for 15 hours. After completion of the reaction, the mixture was cooled to room temperature, suction filtered, spin-evaporated, recrystallized and dried in vacuo to give 1.6806 g of 5-amino-2-fluoropyridine as a solid product in 75% yield. |
70% | With hydrogen;nickel; In ethyl acetate; for 18h; | To 100 g of 2-chloro-5-nitropyridine (Aldrich) in 600 mL of dimethyl sulfoxide under an inert atmosphere was added 100 g of anhydrous KF. The reaction was heated at 70 C. for 18 hours before cooling and diluting with 500 mL each of brine, ethyl acetate, and hexanes. This mixture was filtered through a pad of celite, the organic phase was separated, and the aqueous phase was extracted three times with equal volumes of ethyl acetate and hexanes. The pooled organic phases were washed with brine, dried with anhydrous sodium sulfate, and stripped of the solvents. This crude product was passed through a plug of silica gel with a gradient of 10-30% ethyl acetate/hexanes and stripped to constant weight on a rotary evaporator to give 76 g (84%) of <strong>[456-24-6]2-fluoro-5-nitropyridine</strong> as an oil, which was used in the following procedure. To 76 g of <strong>[456-24-6]2-fluoro-5-nitropyridine</strong> in 500 ml of ethyl acetate under nitrogen was added 100 g of Raney nickel which had been washed three times with ethanol and three times with ethyl acetate. The nitrogen was replaced with hydrogen and the reaction was allowed to proceed for 18 hours at 30 lb/in2. After the hydrogen atmosphere had been replaced by nitrogen, the reaction was filtered through celite and stripped of solvent. The product was purified by passing through a plug of silica gel with chloroform and recrystallized from chloroform to give 42 g (70%) of 6-fluoro-pyridin-3-ylamine in two crops as white platelets: melting point 90-91 C.; mass spectrum (m/e): M+H 112.7. |
70% | To 100 g of 2-chloro-5-nitropyridine (Aldrich) in 600 mL of dimethyl sulfoxide under an inert atmosphere was added 100 g of anhydrous KF. The reaction was heated at 70C for 18 hours before cooling and diluting with 500 mL each of brine, ethyl acetate, and hexanes. This mixture was filtered through a pad of celite, the organic phase was separated, and the aqueous phase was extracted three times with equal volumes of ethyl acetate and hexanes. The pooled organic phases were washed with brine, dried with anhydrous sodium sulfate, and stripped of the solvents. This crude product was passed through a plug of silica gel with a gradient of 10-30% ethyl acetate/hexanes and stripped to constant weight on a rotary evaporator to give 76 g (84%) of <strong>[456-24-6]2-fluoro-5-nitropyridine</strong> as an oil, which was used in the following procedure. To 76 g of <strong>[456-24-6]2-fluoro-5-nitropyridine</strong> in 500 ml of ethyl acetate under nitrogen was added 100 g of Raney nickel which had been washed three times with ethanol and three times with ethyl acetate. The nitrogen was replaced with hydrogen and the reaction was allowed to proceed for 18 hours at 30 lb/in2. After the hydrogen atmosphere had been replaced by nitrogen, the reaction was filtered through celite and stripped of solvent. The product was purified by passing through a plug of silica gel with chloroform and recrystallized from chloroform to give 42 g (70%) of 6-fluoro-pyridin-3-ylamine in two crops as white platelets: melting point 90-91C; mass spectrum (m/e): M+H 112.7. |
palladium on charcoal; In toluene; | Method A Preparation of 5-Amino-2-fluoropyridine A solution of 5 g (35 mmol) <strong>[456-24-6]2-fluoro-5-nitropyridine</strong> in 100 mL of toluene was hydrogenated over a mixture of 5% palladium on charcoal and anhydrous sodium sulfate until the uptake of hydrogen ceased. The solids were filtered off, the residue was washed with ethyl acetate, and the combined organic solutions were evaporated to give 3.7 (94%) of 5-amino-2-fluoropyridine as a white solid. Recrystallization from dichloromethane-hexanes gave the product mp 89-90 C. (literature mp 87-87.5 C.; Finger G. C., Starr L. D., Roe A., and Link W. J., J. Org. Chem., 27:3965-3968 (1967)). 1H NMR (CDCl3): delta7.62 (t, J=2.3 Hz, 1H), 7.11 (td, J=7.7, 3.0 Hz, 1H), 6.72 (dd, J=8.7, 3.3 Hz, 1H), and 3.74 (br s, 2H). | |
30.9 g (75%) | palladium-carbon; In ethanol; | 12b. 5-Amino-2-fluoropyridine <strong>[456-24-6]<strong>[456-24-6]2-Fluoro-5-nitropyridin</strong>e</strong> (52.35 g, 368 mmol, from step 12a) was combined with 5% Pd/C (100 mg) in EtOH (100 mL), and the mixture was stirred under a H2 atmosphere for 4 days. The mixture was filtered and concentrated, and the residue was chromatographed (silica gel;/EtOAc/hexane, 1:9 to 1:1) to afford 30.9 g (75%)of the title compound: 1 H NMR (DMSOd-6 300 MHz) delta6.74 (dd, J=3, 6 Hz, 1H), 7.11 (m, 1H), 7.26 (t, J=1 Hz, 1H); MS (CI/NH3) m/z: 113 (M+H)+, 130 (M+NH4)+. |
30.9 g (75%) | palladium-carbon; In ethanol; | 8c. 3-Amino-6-fluoropyridine <strong>[456-24-6]<strong>[456-24-6]2-Fluoro-5-nitropyridin</strong>e</strong> (52.4 g, 368 mmol, from Step 8b above) was combined with 5% Pd/C (100 mg, Aldrich) in EtOH (100 mL) and the mixture was stirred under a H2 atmosphere for 4 days. The mixture was filtered and concentrated. The crude product was chromatographed (silica gel; hexane/EtOAc, 9:1 to 1:1) to give 30.9 g (75%) of the title compound: 1 H NMR (DMSO-d6, 300 MHz) delta 6.74 (dd, J=3, 6 HzH, 1 H), 7.11 (m, 1 H), 7.26 (t, J=1 Hz, 1 H), MS (CI/NH3) m/z 113 (M+H)+, 130 (M+NH4)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76%Spectr. | With tetramethylammonium fluoride; In N,N-dimethyl-formamide; at 20℃; for 24h; | General procedure: General Procedure E: General Experimental Details for NMR Yields Reported in Figure 3. In a drybox, anhydrous NMe4F (18.6 mg, 0.2 jumol, 2 equiv) and the appropriate aryi chloride or nitroarene substrate (0.1 nimol, 1 equiv) were weighed into a 4 mL vial equipped with a micro stirbar. DMF (0.5 mL) was added, and the viai was removed from the drybox and stirred at room temperature unless otherwise noted for 24 hours. The reaction was cooled to room temperature and an internal standard (1, 3, 5-trifluorobenzene, 100 iL of a 0.5 M solution in toluene) was added. An aliquot was removed for analysis by 59F NMR spectroscopy and GCMS. |
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