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CAS No. : | 637336-53-9 | MDL No. : | MFCD04969986 |
Formula : | C6H9N3O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | UBOGPSNFKMAOPP-UHFFFAOYSA-N |
M.W : | 155.15 | Pubchem ID : | 7017722 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-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 |
---|---|---|
91.1% | With triethylamine; In aqueous hydrochloric acid; dichloromethane; N,N-dimethyl-formamide; | Step 4 Preparation of 1-methyl-4-(trityl-amino)-1H-pyrazole-3-carboxylic acid methyl ester A solution of <strong>[637336-53-9]4-amino-1-methyl-1H-pyrazole-3-carboxylic acid methyl ester</strong> (160 mg, 1.03 mmol) in N,N-dimethylformamide (1.0 mL) at 25 C. was treated with triethylamine (0.35 mL, 2.6 mmol) and triphenylmethylchloride (316 mg, 1.13 mmol). Additional N,N-dimethylformamide (2.0 mL) was added to the reaction to aid stirring. The reaction was stirred at 25 C. for 18 h. At this time, the reaction was concentrated in vacuo. The residue was dissolved in dichloromethane (50 mL) and then was washed with a IN aqueous hydrochloric acid solution (1*10 mL), a saturated aqueous sodium bicarbonate solution (1*10 mL), and a saturated aqueous sodium chloride solution (1*10 mL). The organics were dried over magnesium sulfate, filtered, and concentrated in vacuo to afford 1-methyl-4-(trityl-amino)-1H-pyrazole-3-carboxylic acid methyl ester (373 mg, 91.1%) as an off-white solid: 1H NMR (DMSO-d6, 300 MHz) delta7.25 (m, 16H), 3.74 (s, 3H), 3.53 (s, 3H). |
91.1% | With triethylamine; In DMF (N,N-dimethyl-formamide); at 25℃; for 18h; | (160 mg, 1.03 mmol) [IN N, N DIMETHYLFORMAMIDE] (1.0 mL) at [25 oC] was treated with triethylamine (0.35 mL, 2.6 mmol) and triphenylmethylchloride (316 mg, 1.13 mmol). Additional [N, N DIMETHYLFORMAMIDE] (2.0 mL) was added to the reaction to aid stirring. The reaction was stirred at [25 oC] for 18 h. At this time, the reaction was concentrated in vacuo. The residue was dissolved in dichloromethane (50 mL) and then was washed with a 1N aqueous hydrochloric acid solution [(1 X 10] mL), a saturated aqueous sodium bicarbonate solution [(1 X 10] mL), and a saturated aqueous sodium chloride solution [(1 X 10] mL). The organics were dried over magnesium sulfate, filtered, and concentrated in vacuo to afford [1-METHYL-4- (TRITYL-AMINO)-LH-PYRAZOLE-3-CARBOXYLIC] acid methyl ester (373 mg, 91.1%) as an off-white solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With palladium 10% on activated carbon; hydrogen; In methanol; at 20℃; for 4h; | 10% palladium/C (2.87 g, 2.7 mmol) was added to a stirred solution of methyl 1 -methyl- 4-nitro-1 H-pyrazole-3-carboxylate (p69, 7.15 g, 38.6 mmol) in methanol (250 ml_) and stirred at RT under H2 atmosphere for 4 hrs. The catalyst was filtered off and the solvent was evaporated under vacuum to afford methyl 4-amino-1 -methyl-1 H-pyrazole- 3-carboxylate (p70, 6 g, y= quant) as purple wax used as such in the next step. MS (/T7/z): 156.1 [MH]+ |
100% | With palladium on activated charcoal; hydrogen; In methanol; at 20℃; under 775.743 Torr; for 12h;Inert atmosphere; | To a solution of methyl 1-methyl-4-nitro-pyrazole-3-carboxylate (2 g, 10.8 mmol, CAS400877-57-8) in MeOH (20 mL) was added Pd/C (200 mg, 10% wt) under N2 atmosphere. The suspension was degassed and purged with H2 gas 3 times. The mixture was stirred under H2 (15 Psi) at rt for 12 hr. On completion, the reaction mixture was filtered and concentrated in vacuo to give the title compound (1.68 g, 100% yield) as a white solid. 1H NMR (400 MHz, CDCl3) delta 6.95 (s, 1H), 3.92 (s, 3H), 3.86 (s, 3H). |
96% | palladium; In methanol; | Step 3 Preparation of 4-amino-1-methyl-1H-pyrazole-3-carboxylic acid methyl ester A mixture of 1-methyl-4-nitro-1H-pyrazole-3-carboxylic acid methyl ester (500 mg, 2.7 mmol) and 10% palladium on carbon (50 mg) in methanol (25 mL) was subjected to 60 psi pressure of hydrogen gas in a Parr apparatus for 24 h. At this time, the reaction mixture was filtered through a pad of celite and washed with methanol. The filtrate was concentrated in vacuo to afford 4-amino-1-methyl-1H-pyrazole-3-carboxylic acid methyl ester (402 mg, 96%) as an off-white solid: 1H NMR (DMSO-d6, 300 MHz) delta7.10 (s, 1H), 4.65 (broad s, 2H), 3.73 (s, 3H), 3.72 (s, 3H). |
96% | With hydrogen;palladium 10% on activated carbon; In methanol; under 3102.97 Torr; for 24h; | A mixture of [1-METHYL-4-NITRO-LH-PYRAZOLE-3-CARBOXYLIC] acid methyl ester (500 mg, 2.7 mmol) and 10% palladium on carbon [(50] mg) in methanol [(25] mL) was subjected to 60 psi pressure of hydrogen gas in a Parr apparatus for 24 h. At this time, the reaction mixture was filtered through a pad of celite and washed with methanol. The filtrate was concentrated in vacuo to afford [4-AMINO-1-METHYL-LH-PYRAZOLE-3-] carboxylic acid methyl ester (402 mg, 96%) as an off-white solid |
95% | With hydrogen;palladium 10% on activated carbon; In methanol; under 30402.0 Torr; | 240 mg (1.30 mM) of the compound obtained in Preparative Example 7 was dissolved in 5 ml of methanol, to which 24 mg of 10% palladium/charcoal was added dropwise, and the resulting mixture was stirred under hydrogen pressure of 40 atm for 30 minutes. After the reaction was terminated, the resulting reaction solution was filtered through cellite, and distilled under reduced pressure, to obtain 191 mg (95%) of the title compound.1H NMR (300 MHz, CDCl3) delta 3.86 (s, 3H), 3.92 (s, 3H), 6.91 (s, 1H).Mass: 155 (M+) |
95% | With palladium on activated charcoal; In methanol; at 25℃; for 1h; | A solution of methyl 1-methyl-4-nitro-1H-pyrazole-3-carboxylate (1.0 g, 5.41 mmol) and Pd/C (200 mg) in MeOH (60 mL) was stirred for 1 hour at 25C. Pd/C was filtered out and the filtrate was concentrated to give desired compound as a white solid (800 mg, 95%). |
95% | With hydrogen;palladium 10% on activated carbon; In methanol; under 30402.0 Torr; for 0.5h; | 240 mg (1.30 mM) of the compound obtained in Preparative Example 7 was dissolved in 5 ml of methanol, to which 24 mg of 10% palladium/ EPO <DP n="28"/>charcoal was added dropwise, and the resulting mixture was stirred under hydrogen pressure of 40 atm for 30 minutes. After the reaction was terminated, the resulting reaction solution was filtered through cellite, and distilled under reduced pressure, to obtain 191 mg (95%) of the title compound.1H NMR(SOOMHZ, CDCl3) delta 3.86(s, 3H), 3.92(s, 3H), 6.91(s, IH). Mass : 155(M+) |
84% | With hydrogen;palladium 10% on activated carbon; In methanol; at 20℃;Inert atmosphere; | A solution of 1-methyl-4-nitro-1H-pyrazole-3-carboxylic acid methyl ester (4.8 g, 25.94 mmol) in dry MeOH (100 ml) was thoroughly purged with argon, treated with 10% Pd-C (2.7 g, 2.59 mmol), and again purged with argon. Then the reaction mixture was hydrogenated under a balloon pressure of hydrogen at rt for overnight. The reaction mixture was filtered through a bed of celite. The filtrate was concentrated and dried to give the title compound as gray - whitesolid (3.4 g, 84%), which was used in the next reaction step without further purification. |
84% | With hydrogen;palladium 10% on activated carbon; In methanol; at 20℃;Inert atmosphere; | A solution of l-methyl-4-nitro-lH-pyrazole-3-carboxylic acid methyl ester (4.8 g, 25.94 mmol) in dry MeOH (100ml) was thoroughly purged with argon, treated with 10% Pd-C (2.7 g, 2.59 mmol), and again purged with argon. Then the reaction mixture was hydrogenated under a balloon pressure of hydrogen at rt for overnight. The reaction mixture was filtered through a bed of celite. The filtrate was concentrated and dried to give the title compound as gray-white solid (3.4 g, 84%), which was used in the next reaction step without further purification. |
With palladium 10% on activated carbon; hydrogen; In methanol; under 2068.65 Torr; for 1h; | Methyl-4-nitro-lH-pyrazole-3-carboxylate (5.0 g, 27.01 mmol)Added to a hydrogenation reaction flask containing 50mL of methanol,Pd / C (10%, 0.5 g) was added,40psi hydrogen pressure reaction 1.0h,TLC test showed that the reaction was completed,Suction filtration, Pd / C filtration, and concentrated under reduced pressure to give the crude product (3.72 g, 88.7%),The crude product was used without purification in the next reaction administered. | |
8.57 g | With palladium 10% on activated carbon; hydrogen; In methanol; at 20℃; under 2327.23 Torr; for 6h; | B) Methyl 4-amino-1-methyl-1H-pyrazole-3-carboxylate To a solution of methyl 1-methyl-4-nitro-1H-pyrazole-3-carboxylate (10 g) in methanol (200 mL), palladium-carbon (10%) (2 g) was added, and the mixture was stirred at room temperature for 6 hours in a hydrogen atmosphere (45 psi). Palladium-carbon was filtered off, and then, the filtrate was concentrated to obtain the title compound (8.57 g). 1H NMR (400 MHz, CDCl3) delta 3.86 (3H, s), 3.92 (3H, s), 4.08 (2H, brs), 6.96 (1H, s). |
With palladium 10% on activated carbon; hydrogen; In methanol; at 20℃; for 4h; | 10% palladium/C (2.87 g, 2.7 mmol) was added to a stirred solution of methyl 1-methyl- 4-nitro-1 H-pyrazole-3-carboxylate (p129, 7.15 g, 38.6 mmol) in methanol (250 ml_) and stirred at RT under H2 atmosphere for 4 hrs. The catalyst was filtered off and the solvent was evaporated under vacuum to afford methyl 4-amino-1-methyl-1 H-pyrazole- 3-carboxylate (p130, 6 g, y= quant) as purple wax used as such in the next step. MS (/T7/z): 156.1 [MH]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With triethylamine; In tetrahydrofuran;Inert atmosphere; | Preparative Example 9 4-(2-bromoacetylamino)-1-methyl-1H-pyrazole-3-carboxylic acid methyl ester 160 mg (1.03 mM) of the compound obtained in Preparative Example 8 was dissolved in 3 ml of tetrahydrofuran, to which 0.11 ml (1.24 mM) of bromo acetylbromide and 0.22 ml (1.55 mM) of triethylamine were added dropwise, and the resulting mixture was stirred under a nitrogen atmosphere for a day. The solvent was distilled off under reduced pressure, and the resultant was extracted with ethyl acetate and brine. The organic solvent layer was dried over anhydrous sodium sulfate, filtered, and then distilled under reduced pressure. The resulting impure compound was purified by column chromatography (hexane:ethyl acetate=1:1), to obtain 100 mg (69%) of the title compound. 1H NMR (300 MHz, CDCl3) delta 3.79 (s, 3H), 3.99 (s, 3H), 4.03 (s, 2H), 8.20 (s, 1H), 9.95 (br, NH). Mass: 275 (Br79+), 277 (Br81) |
69% | With triethylamine; In tetrahydrofuran; for 24h; | 160 mg (1.03 mM) of the compound obtained in Preparative Example 8 was dissolved in 3 ml of tetrahydrofuran, to which 0.11 ml (1.24 mM) of bromo acetylbromide and 0.22 ml (1.55 mM) of triethylamine were added dropwise, and the resulting mixture was stirred under a nitrogen atmosphere for a day. The solvent was distilled off under reduced pressure, and the resultant was extracted with ethyl acetate and brine. The organic solvent layer was dried over anhydrous sodium sulfate, filtered, and then distilled under reduced pressure. The resulting impure compound was purified by column chromatography (hexane : ethyl acetate = 1 : 1), to obtain 100 mg(69%) of the title compound.1H NMR(300MHz, CDCl3) delta 3.79(s, 3H), 3.99(s, 3H), 4.03(s, 2H), 8.20(s, IH), 9.95(br, NH).Mass : 275(Br79+), 277(Br81) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | To a stirred solution of A-2 (600 mg, 2.34 mmol) in DMF (10 ml) was added EDCI (672 mg, 3.51 mmol) and HOBt (538 mg, 3.51 mmol) at 25 C. Stirring was continued for 10 min. 4-Amino-1-methyl-1H-pyrazole-3-carboxylic acid methyl ester (362 mg, 2.35 mmol) and triethylamine (0.8 ml, 5.35 mmol) were subsequently added to the above solution. The reaction mixture was stirred at 25 C. overnight, then quenched with water (8 ml), and extracted with CH2Cl2. The combined organic layers were washed with brine, dried (Na2SO4), filtered, and evaporated. The crude product thus obtained was purified by column chromatography over silica gel (2% MeOH /CH2Cl2) to provide the title compound (642 mg, 69%) as yellow sticky solid. | |
69% | To a stirred solution of A-2 (600 mg, 2.34 mmol) in DMF (10ml) was added EDCI (672 mg, 3.51 mmol) and HOBt (538 mg, 3.51 mmol) at 25C. Stirring was continued for 10 min. 4- Amino-l-methyl-lH-pyrazole-3-carboxylic acid methyl ester (362 mg, 2.35 mmol) and triethylamine (0.8 ml, 5.35 mmol) were subsequently added to the above solution. The reaction mixture was stirred at 25C overnight, then quenched with water (8 ml), and extracted with CH2C12. The combined organic layers were washed with brine, dried (Na2S04), filtered, and evaporated. The crude product thus obtained was purified by column chromatography over silica gel (2% MeOH/CH2Cl2) to provide the title compound (642 mg, 69%) as yellow sticky solid. |
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