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[ CAS No. 25016-20-0 ]

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Chemical Structure| 25016-20-0
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CAS No. :25016-20-0 MDL No. :MFCD00464254
Formula : C5H6N2O2 Boiling Point : 306.9°C at 760 mmHg
Linear Structure Formula :- InChI Key :-
M.W :126.11 g/mol Pubchem ID :573176
Synonyms :

Safety of [ 25016-20-0 ]

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:

Application In Synthesis of [ 25016-20-0 ]

  • Upstream synthesis route of [ 25016-20-0 ]
  • Downstream synthetic route of [ 25016-20-0 ]

[ 25016-20-0 ] Synthesis Path-Upstream   1~12

  • 1
  • [ 1621-91-6 ]
  • [ 77-78-1 ]
  • [ 16034-46-1 ]
  • [ 25016-20-0 ]
YieldReaction ConditionsOperation in experiment
38%
Stage #1: With sodium hydroxide In water at 40 - 80℃; for 2.75 h;
Stage #2: With hydrogenchloride In water
Dimethyl sulfate (236 g, 177 mL, 1.87 mol) was added dropwise over 45 min to a stirred solution of pyrazole-3-carboxylic acid (200 g, 1.78 mol) in 20percent aqueous sodium hydroxide (850 mL) at 40 °C. The reaction mixture was heated at 80 °C for 2 h, cooled to room temperature, filtered, the filtrate acidified to pH 1 with concentrated HCI, the precipitate filtered, washed with water, and dried under vacuum to yield 1-methylpyrazole-5-carboxylic acid (85 g, 38percent). The filtrate was concentrated in vacuo to 800 ML, extracted with chloroform (15X400 mL), the organic phase dried over anhydrous magnesium sulfate, concentrated in vacuo, and the residue recrystallized from isopropanol to yield 1-METHYLPYRAZOLE-3-CARBOXYLIC acid (74 g) as a white crystalline solid.
38%
Stage #1: With sodium hydroxide In water at 40 - 80℃; for 2 h;
Stage #2: With hydrogenchloride In water
A stirred solution of 3-methylpyrazole (82.1 g, 1.0 mol) in water (3.5 L) was heated to 70 °C. Potassium permanganate (111 g, 0.70 mol) was added in one portion, keeping the temperature near 70 °C. The reaction mixture was stirred for 1 h at 70 °C, and then a second portion of potassium permanganate (111 g) was added at 70 °C. After 1 h, a final portion of potassium permanganate (111 g) was added at 70 °C. The reaction mixture was stirred a further 2 h at 70 °C, and any unreacted oxidant was reduced by the dropwise addition of isopropanol. The reaction mixture was cooled to room temperature, filtered, the solid was rinsed with water, and the filtrate evaporated to 500 mL. The aqueous was chilled to 0 °C, acidified with concentrated HC1, filtered, the solid product washed with water, and dried under vacuum to provide pyrazole- 3-carboxylic acid as a white solid (64.4 g, 57percent). Dimethyl sulfate (236 g, 177 ML, 1.87 mol) was added dropwise over 45 min to a stirred solution of pyrazole-3-carboxylic acid (200 g, 1.78 mol) in 20percent aqueous sodium hydroxide (850 ML) at 40 °C. The reaction mixture was heated at 80 °C for 2 h, cooled to room temperature, filtered, the filtrate acidified to pH 1 with concentrated HC1, the precipitate filtered, washed with water, and dried under vacuum to yield 1-METHYLPYRAZOLE-5-CARBOXYLIC acid (85 g, 38percent). The filtrate was concentrated in vacuo to 800 ML, extracted with chloroform (15X400 mL), the organic phase dried over anhydrous magnesium sulfate, concentrated in vacuo, and the residue recrystallized from isopropanol to yield 1-METHYLPYRAZOLE-3-CARBOXYLIC acid (74 g) as a white crystalline solid. A suspension of the acid (90 g, 0.71 mol) and DMF (1 drop) in thionyl chloride (250 ML) was stirred at reflux under nitrogen for 2 h. The solvent was evaporated from the reaction mixture, the residue azeotroped with toluene (3X200 mL), diluted into toluene (250 mL), added to a suspension of Pd-C (10 wtpercent, 9.3 g) in toluene (500 ML), and the mixture stirred at reflux for 8 h with a gentle flow of hydrogen gas through the suspension. After cooling to room temperature, the suspension was filtered through celite, washed with toluene, and concentrated in vacuo. The residue was fractionally distilled under vacuum to provide the title compound (50 g, 63percent) as a low melting white solid (bp = 92 °C COMMAT; 8 MMHG).
Reference: [1] J. Gen. Chem. USSR (Engl. Transl.), 1982, vol. 52, # 11, p. 2291 - 2296[2] Zhurnal Obshchei Khimii, 1982, vol. 52, # 11, p. 2592 - 2598
[3] J. Gen. Chem. USSR (Engl. Transl.), 1982, vol. 52, # 11, p. 2291 - 2296[4] Zhurnal Obshchei Khimii, 1982, vol. 52, # 11, p. 2592 - 2598
[5] Patent: WO2004/58702, 2004, A2, . Location in patent: Page 30-31; 24
[6] Patent: WO2004/58763, 2004, A1, . Location in patent: Page 39-40
  • 2
  • [ 1621-91-6 ]
  • [ 77-78-1 ]
  • [ 16034-46-1 ]
  • [ 25016-20-0 ]
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2007, vol. 17, # 5, p. 1369 - 1375
  • 3
  • [ 25016-20-0 ]
  • [ 6647-98-9 ]
Reference: [1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1980, vol. 29, # 5, p. 778 - 784[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1980, # 5, p. 1071 - 1077
[3] Russian Chemical Bulletin, 2014, vol. 63, # 2, p. 360 - 367[4] Izv. Akad. Nauk, Ser. Khim., 2014, # 2, p. 360 - 367
[5] Russian Chemical Bulletin, 2013, vol. 62, # 4, p. 1044 - 1051[6] Izv. Akad. Nauk, Ser. Khim., 2013, vol. 62, # 4, p. 1043 - 1050,8
  • 4
  • [ 25016-20-0 ]
  • [ 27258-32-8 ]
YieldReaction ConditionsOperation in experiment
63%
Stage #1: for 2 h; Heating / reflux
Stage #2: With hydrogen In toluene for 8 h; Heating / reflux
A suspension of the acid (90 g, 0.71 mol) and DMF (1 drop) in thionyl chloride (250 mL) was stirred at reflux under nitrogen for 2 h. The solvent was evaporated from the reaction mixture, the residue azeotroped with toluene (3X200 mL), diluted into toluene (250 mL), added to a suspension OF PD-C (10 wtpercent, 9.3 g) in toluene (500 mL), and the mixture stirred at reflux for 8 h with a gentle flow of hydrogen gas through the suspension. After cooling to room temperature, the suspension was filtered through celite, washed with toluene, and concentrated in vacuo. The residue was fractionally distilled under vacuum to provide the title compound (50 g, 63percent) as a low melting white solid (bp = 92 °C COMMAT; 8 mmHg)
Reference: [1] Patent: WO2004/58702, 2004, A2, . Location in patent: Page 31; 24
  • 5
  • [ 25016-20-0 ]
  • [ 89179-62-4 ]
YieldReaction ConditionsOperation in experiment
59%
Stage #1: With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 0 - 30℃; for 2 h;
Stage #2: With ammonia In dichloromethane at 0℃; for 0.5 h;
Step 3: To solution of step 2 intermediate (6.0 g, 47.6 mmol) in CH2CI2 (50 mL) were added oxalyl chloride (6.12 mL, 71.4 mmol) and catalytic amount of DMF (0.5 mL) at 0°C. The RM was stirred at rt for 2 h. The RM was concentrated under reduced pressure and residue was diluted with CH2CI2. NH3 gas was passed through RM at 0°C for 30 min. After that the RM was concentrated under reduced pressure and residue was suspended in THF (50 ml) and filtered. The filtrate was concentrated under reduced pressure to yield the desired compound (3.5 g, 59percent). LC-MS (Method 3): m/z [M+H]+ = 126 (MW calc. = 125.13); R, = 0.76 min.
Reference: [1] Patent: WO2015/22073, 2015, A1, . Location in patent: Page/Page column 90; 91
[2] Patent: WO2014/139150, 2014, A1,
[3] Patent: WO2014/150114, 2014, A1,
  • 6
  • [ 17827-61-1 ]
  • [ 25016-20-0 ]
YieldReaction ConditionsOperation in experiment
98% With lithium hydrochloride monohydrate In tetrahydrofuran; methanol; water at 0 - 30℃; for 3 h; Step 2: To a solution of step 1 intermediate (7.0 g, 50 mmol) in a mixture of THF (20 mL) and MeOH (20 mL) was added a solution of LiOH H20 (4.2 g, 100 mmol) in water (20 mL) at 0°C. The RM was stirred at rt for 3 h. The RM was concentrated and subsequently diluted with water. The aqueous layer was acidified with sat. NaHS04 solution up to pH~4-5 and extracted with EtOAc. The combined organic layers were dried and concentrated under reduced pressure to yield the desired product (6.2 g, 98percent). LC-MS (Method 3): m/z [M+H]+ = 127.2 (MW calc. 126.11); R, = 0.44 min.
Reference: [1] Patent: WO2015/22073, 2015, A1, . Location in patent: Page/Page column 90; 91
[2] Journal of Antibiotics, 1995, vol. 48, # 11, p. 1336 - 1344
  • 7
  • [ 1621-91-6 ]
  • [ 77-78-1 ]
  • [ 16034-46-1 ]
  • [ 25016-20-0 ]
YieldReaction ConditionsOperation in experiment
38%
Stage #1: With sodium hydroxide In water at 40 - 80℃; for 2.75 h;
Stage #2: With hydrogenchloride In water
Dimethyl sulfate (236 g, 177 mL, 1.87 mol) was added dropwise over 45 min to a stirred solution of pyrazole-3-carboxylic acid (200 g, 1.78 mol) in 20percent aqueous sodium hydroxide (850 mL) at 40 °C. The reaction mixture was heated at 80 °C for 2 h, cooled to room temperature, filtered, the filtrate acidified to pH 1 with concentrated HCI, the precipitate filtered, washed with water, and dried under vacuum to yield 1-methylpyrazole-5-carboxylic acid (85 g, 38percent). The filtrate was concentrated in vacuo to 800 ML, extracted with chloroform (15X400 mL), the organic phase dried over anhydrous magnesium sulfate, concentrated in vacuo, and the residue recrystallized from isopropanol to yield 1-METHYLPYRAZOLE-3-CARBOXYLIC acid (74 g) as a white crystalline solid.
38%
Stage #1: With sodium hydroxide In water at 40 - 80℃; for 2 h;
Stage #2: With hydrogenchloride In water
A stirred solution of 3-methylpyrazole (82.1 g, 1.0 mol) in water (3.5 L) was heated to 70 °C. Potassium permanganate (111 g, 0.70 mol) was added in one portion, keeping the temperature near 70 °C. The reaction mixture was stirred for 1 h at 70 °C, and then a second portion of potassium permanganate (111 g) was added at 70 °C. After 1 h, a final portion of potassium permanganate (111 g) was added at 70 °C. The reaction mixture was stirred a further 2 h at 70 °C, and any unreacted oxidant was reduced by the dropwise addition of isopropanol. The reaction mixture was cooled to room temperature, filtered, the solid was rinsed with water, and the filtrate evaporated to 500 mL. The aqueous was chilled to 0 °C, acidified with concentrated HC1, filtered, the solid product washed with water, and dried under vacuum to provide pyrazole- 3-carboxylic acid as a white solid (64.4 g, 57percent). Dimethyl sulfate (236 g, 177 ML, 1.87 mol) was added dropwise over 45 min to a stirred solution of pyrazole-3-carboxylic acid (200 g, 1.78 mol) in 20percent aqueous sodium hydroxide (850 ML) at 40 °C. The reaction mixture was heated at 80 °C for 2 h, cooled to room temperature, filtered, the filtrate acidified to pH 1 with concentrated HC1, the precipitate filtered, washed with water, and dried under vacuum to yield 1-METHYLPYRAZOLE-5-CARBOXYLIC acid (85 g, 38percent). The filtrate was concentrated in vacuo to 800 ML, extracted with chloroform (15X400 mL), the organic phase dried over anhydrous magnesium sulfate, concentrated in vacuo, and the residue recrystallized from isopropanol to yield 1-METHYLPYRAZOLE-3-CARBOXYLIC acid (74 g) as a white crystalline solid. A suspension of the acid (90 g, 0.71 mol) and DMF (1 drop) in thionyl chloride (250 ML) was stirred at reflux under nitrogen for 2 h. The solvent was evaporated from the reaction mixture, the residue azeotroped with toluene (3X200 mL), diluted into toluene (250 mL), added to a suspension of Pd-C (10 wtpercent, 9.3 g) in toluene (500 ML), and the mixture stirred at reflux for 8 h with a gentle flow of hydrogen gas through the suspension. After cooling to room temperature, the suspension was filtered through celite, washed with toluene, and concentrated in vacuo. The residue was fractionally distilled under vacuum to provide the title compound (50 g, 63percent) as a low melting white solid (bp = 92 °C COMMAT; 8 MMHG).
Reference: [1] J. Gen. Chem. USSR (Engl. Transl.), 1982, vol. 52, # 11, p. 2291 - 2296[2] Zhurnal Obshchei Khimii, 1982, vol. 52, # 11, p. 2592 - 2598
[3] J. Gen. Chem. USSR (Engl. Transl.), 1982, vol. 52, # 11, p. 2291 - 2296[4] Zhurnal Obshchei Khimii, 1982, vol. 52, # 11, p. 2592 - 2598
[5] Patent: WO2004/58702, 2004, A2, . Location in patent: Page 30-31; 24
[6] Patent: WO2004/58763, 2004, A1, . Location in patent: Page 39-40
  • 8
  • [ 694-48-4 ]
  • [ 25016-20-0 ]
Reference: [1] J. Gen. Chem. USSR (Engl. Transl.), 1982, vol. 52, # 11, p. 2291 - 2296[2] Zhurnal Obshchei Khimii, 1982, vol. 52, # 11, p. 2592 - 2598
[3] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1980, vol. 29, # 5, p. 778 - 784[4] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1980, # 5, p. 1071 - 1077
[5] Journal of Antibiotics, 1995, vol. 48, # 11, p. 1336 - 1344
  • 9
  • [ 124-38-9 ]
  • [ 151049-87-5 ]
  • [ 25016-20-0 ]
Reference: [1] Journal of Heterocyclic Chemistry, 1992, vol. 29, # 5, p. 1357 - 1359
  • 10
  • [ 1621-91-6 ]
  • [ 77-78-1 ]
  • [ 16034-46-1 ]
  • [ 25016-20-0 ]
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2007, vol. 17, # 5, p. 1369 - 1375
  • 11
  • [ 25016-20-0 ]
  • [ 84547-86-4 ]
Reference: [1] J. Gen. Chem. USSR (Engl. Transl.), 1982, vol. 52, # 11, p. 2291 - 2296[2] Zhurnal Obshchei Khimii, 1982, vol. 52, # 11, p. 2592 - 2598
  • 12
  • [ 25016-20-0 ]
  • [ 84547-62-6 ]
Reference: [1] J. Gen. Chem. USSR (Engl. Transl.), 1982, vol. 52, # 11, p. 2297 - 2303[2] Zhurnal Obshchei Khimii, 1982, vol. 52, # 11, p. 2598 - 2605
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