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CAS No. : | 247069-27-8 | MDL No. : | MFCD03412208 |
Formula : | C5H5F2N3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | GCIUCMRUMOAHKR-UHFFFAOYSA-N |
M.W : | 145.11 | Pubchem ID : | 10176199 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H319 | 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 |
---|---|---|
EXAMPLE 7AA solution of EXAMPLE 6 (83.2Kg) in triethyl orthoformate (SO.lKg) at reflux wasstirred for 0.5-1 hour, treated with acetic anhydride (103.5Kg), stirred for 12 hours and cooledto ambient temperature to provide a solution that was used immediately.EXAMPLE 7BThe solution of EXAMPLE 7A was treated with N-methylpyrrolidinone (210Kg),acetonitrile (161Kg) and water (3Kg), added to a suspension of EXAMPLE 4 (57.4Kg) in 1:1N-methylpyrrolidinone (210Kg) and acetonitrile (161Kg), stirred for 2 hours, added to water(662Kg) and filtered. The filtrant was washed with (2:1) acetonitrile/water and water anddried under vacuum at 60C to provide 119.5Kg of product. Mp 157-160C; 'H NMR(CDC13, 300 MHz) (E) 8 1.15 (t, 3H), 4.16 (q, 2H), 4.64 (br s, 2H), 6.90 (m, 1H), 7.22 (t,1H), 7.32 (m, 1H), 9.03 (d, 1H), 12.44 (bd, 1H); (Z) 8 1.03 (t, 3H), 4.11 (q, 2H), 4.60 (br s,2H), 6.90 (m, 1H), 7.20 (t, 1H), 7.48 (m, 1H), 8.90 (d, 1H), 11.17 (bd, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With formic acid;20% Pd(OH)2 on carbon; In Isopropyl acetate; water; at 50℃; for 2h; | A mixture of half-wet 20% palladium hydroxide on carbon (68.1 Kg) was treatedsequentially with 39.1% (w/w) EXAMPLE 3 in isopropyl acetate (410Kg total, 160KgEXAMPLE 3), isopropyl acetate (550Kg) and 88% formic acid (57Kg). The mixture wasstirred at 50C for 2 hours and filtered under nitrogen through diatomaceous earth (Celite)with isopropyl acetate (200Kg) rinsing. The filtrate was washed twice with 6% citric acidsolution having its pH adjusted to 4 with potassium hydroxide (water (200Kg)/citric acid(12Kg)/potassium hydroxide (2Kg)), 1M sodium bicarbonate solution (150Kg) and water(150Kg) and concentrated. The concentrate was treated with heptane(1005Kg) over 90minutes, and the solution was cooled to 0C and filtered. The filtrant was washed withheptane (220Kg) and dried under vacuum at 40C to provide 61.5Kg of product, which wasstored in an opaque container under nitrogen. H NMR (CDCls, 300 MHz) 8 7.03 (t, 1H),4.5-4.0 (brs, 4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With ammonium hydroxide; In ethanol; at 30℃; for 3h;Green chemistry; | In a 250 mL sealed four-neck reaction flask,15.1 g of 2,3,5,6-tetrachloropyridine prepared in Example 5 and 100 mL of ethanol were added.Add 15 grams of 22% ammonia water,The end of the drop,The mixture was stirred and controlled at 30 C for 3 hours, and the reaction was completed. The organic phase was evaporated under reduced pressure to give a pale-yellow solid (1,3,5,5,6-tetrafluoropyridine, 13.2 g, yield 91.0%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | In tert-butyl methyl ether; at 22℃; for 1 - 2h; | General procedure: A solution of 18-crown-6 (2.2 mmol) in methyl tert-butyl ether (5 mL) was added to a solution of polyhalogenated diaminopyridine (2.0 mmol) in the same solvent (5 mL). The mixture was kept for 1-2 h at room temperature (?22 C) upon stirring. The precipitate formed was filtered off, washed with a small amount of the cold solvent, dried in air to a constant weight, and recrystallized from CCl4. |
at 5℃; for 12h; | General procedure: b) A solution of 18-crown-6 (0.9 mmol) in one of the listed solvent (n-hexane, acetone, MeOH, t-BuOMe, CHCl3, CCl4, and DMAc, 25 mL) was added dropwise to a solution of arylenediamine (from 2.0 to 4.0 mmol) in the same solvent (25 mL). The mixture was kept at room temperature (~22 C) to evaporate 50-80% of the solvent volume, and at 5 C for 12 h. The precipitate formed was filtered off, washed with a small amount of the cold solvent, and dried in air to a constant weight. The chemical composition of the precipitate was analyzed using NMR spectroscopy. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
7.9 g | In acetonitrile; at 10 - 30℃; | (2) Compound A-2 (5 g, 20.3 mmol), triethylorthoformate (10 ml) and acetic anhydride (6 ml) were mixed and stirred, and the temperature was raised to 120-130C. The mixture was stirred for 4 hours, and the reaction was completely cooled down to 15 - The mixture was stirred at 25 C, added with water (30 ml) and ethyl acetate (30 ml) for 10 minutes. The mixture was extracted with liquid and the organic phase was dried over anhydrous sodium sulfate. The organic layer was concentrated under reduced pressure and dissolved in acetonitrile (20 ml). A mixture of diamino-3,5-difluoropyridine (3.2 g, 22.3 mmol) and acetonitrile (20 ml) was added dropwise, and the temperature was controlled at 10-30C for 1-2 hours. The reaction was complete, the temperature was lowered, an appropriate amount of water was added, filtered, and dried to give 7.9 g of Compound A-3, HPLC 97.4%, and Compound 12.3%. Yield 97%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium nitrite; In hexane; dimethyl sulfoxide; at 5 - 20℃; for 1h; | General procedure: To a solution of hexane (5 mL), DMSO (0.5 mL), and trifluoromethanesulfonicacid (0.54 mL, 6 mmol) at 5 C were sequentially added therespective aminopyridine 1a-j (2 mmol) and NaNO2 (0.35 g, 5 mmol)under stirring and the mixture was stirred for 10 min. An immediateemission of N2 bubbles was observed. In the case of diamino derivatives1k-n, double amounts of NaNO2 and TfOH were used. The resultingmixture was then stirred for 50 min at r.t. until the startingamine had been consumed as monitored by TLC. The reaction mixturewas poured into H2O and extracted with CH2Cl2 (2 × 25 mL). Thecombined organic extracts were dried (Na2SO4), filtered, and the solventwas removed under reduced pressure on a rotary evaporator.The product was purified by silica gel flash chromatography (eluent:CH2Cl2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | In 1-methyl-pyrrolidin-2-one; acetonitrile; at 20℃; for 6h; | General procedure: To a mixture of the above 5a, 5b, N-methylpyrrolidone (NMP, 80 mL) and acetonitrile (40 mL) was added a solution of <strong>[247069-27-8]3,5-difluoropyridine-2,6-diamine</strong> (29.80 g0.205 mol), NMP (30 mL) and acetonitrile (20 mL) in portions and stirred for 6 h at room temperature. The reaction mixture was poured into water (120 mL) and stirred for 2 h, and then filtered. The solid was collected by suction, washed with acetonitrile and water (v:v = 60:1), and dried in vacuo to give the title compounds 6a, 6b (37-53%, from 1a, 1b) as yellow solids. |
28.4 g | In 1-methyl-pyrrolidin-2-one; acetonitrile; at 20℃; for 1h; | To a three-necked flask was added compound 3 (20g, 0.071mol),triethylorthoformate (18.97mL, 0.11mol) and acetic anhydride (20.21mL, 0.21mol) wasstirred and heated to reflux (~ 139 ) 3h, falls at room temperature, the reactionliquid was NMP- acetonitrile (50mL-50mL) diluted with 1mL of distilled water was addedto prepare the compound 4 directly without separation into the next reaction. Threeneckedflask was added 2,6-diamino-3,5-difluoro-pyridine (11.38g, 0.078mol), NMPacetonitrile(50mL-50mL), stirred and dissolved at room temperature, the reactionsolution was added dropwise a step, droplets Bi reaction was stirred at room temperature1h. 160mL of distilled water was added dropwise to the reaction, the precipitated lightyellow solid was filtered, followed by acetonitrile - water (48mL-24mL), water (50mL)and washed beating, 60 deg.] C and dried in vacuo to give a yellow powder 28.4g,HPLC98.4%. |
7.3 g | In acetonitrile; at 10 - 30℃; | (2) Compound W-2 (5 g, 17.8 mmol), triethylorthoformate (8 ml) and acetic anhydride (6 ml) were mixed and stirred, and the temperature was raised to 120-130C. The mixture was stirred for 4 hours, and the reaction was completely cooled down to 15C. The mixture was stirred at 25 C, added with water (30 ml) and ethyl acetate (30 ml) for 10 minutes. The mixture was extracted with liquid and the organic phase was dried over anhydrous sodium sulfate. The organic layer was concentrated under reduced pressure and dissolved in acetonitrile (20 ml). A mixture of <strong>[247069-27-8]2,6-diamino-3,5-difluoropyridine</strong> (3.1 g, 21.4 mmol) and acetonitrile (20 ml) was added dropwise, and the temperature was adjusted to 10-30 C for 1-2 hours. The reaction was complete, the temperature was lowered, an appropriate amount of water was added, filtered, and dried to give 7.3 g of Compound W-4, HPLC 97.1%, and Compound 2 2.5%. Yield 94.1%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | In 1-methyl-pyrrolidin-2-one; acetonitrile; at 20℃; for 6h; | General procedure: To a mixture of the above 5a, 5b, N-methylpyrrolidone (NMP, 80 mL) and acetonitrile (40 mL) was added a solution of <strong>[247069-27-8]3,5-difluoropyridine-2,6-diamine</strong> (29.80 g0.205 mol), NMP (30 mL) and acetonitrile (20 mL) in portions and stirred for 6 h at room temperature. The reaction mixture was poured into water (120 mL) and stirred for 2 h, and then filtered. The solid was collected by suction, washed with acetonitrile and water (v:v = 60:1), and dried in vacuo to give the title compounds 6a, 6b (37-53%, from 1a, 1b) as yellow solids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.58% | Ethyl 2,4,5-trifluorobenzoylacetate (20.0 g, 0.081 mol) was added to a 250 mL reaction flask.Triethylorthoformate (21.6 mL, 0.130 mol), acetic anhydride (32.5 mL, 0.344 mol), stirring,Heating was started and the temperature of the feed was raised to 130 C. for 4.0 hours.After the reaction was completed, the solvent was distilled off under reduced pressure to obtain an oily liquid.Add 70 mL of N-methylpyrrolidone to make the oily liquidThe solution was dissolved, <strong>[247069-27-8]3,5-difluoro-2,6-diaminopyridine</strong> (13.8 g, 0.095 mol) was added, and the feed solution was warmed to 50C.Stir and stir for 1.5h. After the addition of anhydrous lithium chloride (6.12 g, 0.146 mol), DBU (11.37 g, 0.075 mol) was added, and the reaction temperature was controlled at 35 C. for 2.0 h.3-Hydroxyazetidine hydrochloride (8.45 g, 0.077 mol) was added, DBU (26.82 g, 0.176 mol) was slowly added, and the temperature was 35 C. for 2.5 h.After the reaction is complete, transfer to a 500 mL reaction flask and add 25 mL of ethyl acetate.Slowly add 145 mL of 10% citric acid solution.After the addition was completed, the temperature was adjusted to 20C, and the crystals were crystallized for 4.0 hours. The crystals were collected, and the mixture was collected by suction filtration. The cake was collected and dried in an oven at 60C to obtain 38.35 g of the intermediate I. The yield was 93.58%. |
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