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[ CAS No. 1150617-54-1 ]

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Chemical Structure| 1150617-54-1
Chemical Structure| 1150617-54-1
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CAS No. :1150617-54-1 MDL No. :MFCD12024534
Formula : C6H4BrN3 Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W :198.02 g/mol Pubchem ID :40152259
Synonyms :

Safety of [ 1150617-54-1 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P280-P305+P351+P338 UN#:N/A
Hazard Statements:H302 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 1150617-54-1 ]

  • Upstream synthesis route of [ 1150617-54-1 ]
  • Downstream synthetic route of [ 1150617-54-1 ]

[ 1150617-54-1 ] Synthesis Path-Upstream   1~10

  • 1
  • [ 1301214-71-0 ]
  • [ 1150617-54-1 ]
YieldReaction ConditionsOperation in experiment
77%
Stage #1: With potassium acetate; acetic anhydride; acetic acid In chloroform at 20℃; for 0.25 h;
Stage #2: With isopentyl nitrite In chloroform at 40 - 60℃;
Stage #3: With sodium hydroxide In methanol; water at 0 - 20℃;
To a solution of N-(5-bromo-2-methylpyridin-3-yl)acetamide (8.28 g, 36 mmol) in chloroform (550 mL) at ambient temperature was added potassium acetate (4.32 g, 43.6 mmol), acetic acid (2.5 mL, 43.6 mmol) and followed by acetic anhydride (6.86 mL, 72.6 mmol).
The mixture was stirred at ambient temperature for 15 minutes before being heated to 40° C.
IsoamyInitrite was then added dropwise.
The reaction was then stirred at 60° C. for 48 hours.
The reaction mixture was poured slowly into a saturated solution of sodium bicarbonate (500 mL) at 0° C.
The organic phase was retained and the aqueous phase extracted with dichloromethane (500 mL).
The combined organics were then concentrated to a brown oil which was dissolved in methanol (500 mL).
Aqueous sodium hydroxide (2 M, 500 mL) was added at 0° C. and the mixture stirred at ambient temperature for 1 hour before the methanol was removed in vacuo.
The aqueous mixture was then extracted with ethyl acetate (3*500 mL).
The combined organics dried over magnesium sulfate, and the solvent removed in vacuo to give 6-bromo-1H-pyrazolo[4,3-b]pyridine as a light brown solid (5.5 g, 27.9 mmol, 77percent).
1HNMR (400, CD3OD): δ ppm 8.55 (s, 1H), 8.24 (s, 1H), 8.21 (s, 1H).
77% With potassium acetate; acetic anhydride; isopentyl nitrite In chloroform; acetic acid at 20 - 60℃; To a solution of N-(5-bromo-2-methylpyridin-3-yl)acetamide (8.28 g, 36 mmol) in chloroform (550 mL) at ambient temperature was added potassium acetate (4.32 g, 43.6 mmol), acetic acid (2.5 mL, 43.6 mmol) and followed by acetic anhydride (6.86 mL, 72.6 mmol). The mixture was stirred at ambient temperature for 15 minutes before being heated to 40 °C. Isoamylnitrite was then added dropwise. The reaction was then stirred at 60 °C for 48 hours. The reaction mixture was poured slowly into a saturated solution of sodium bicarbonate (500 mL) at 0 °C. The organic phase was retained and the aqueous phase extracted with dichloromethane (500 mL). The combined organics were then concentrated to a brown oil which was dissolved in methanol (500 mL). Aqueous sodium hydroxide (2 M, 500 mL) was added at 0 °C and the mixture stirred at ambient temperature for 1 hour before the methanol was removed in vacuo. The aqueous mixture was then extracted with ethyl acetate (3 x 500 mL). The combined organics dried over magnesium sulfate, and the solvent removed in vacuo to give 6-bromo-1H-pyrazolo[4,3-b]pyridine as a light brown solid (5.5 g, 27.9 mmol, 77 percent). 1HNMR (400, CD3OD): ppm 8.55 (s, 1 H), 8.24 (s, 1 H), 8.21 (s, 1 H).
77%
Stage #1: With potassium acetate; acetic anhydride; acetic acid In chloroform at 20 - 60℃; for 48.25 h;
Stage #2: With water; sodium hydroxide In methanol at 0 - 20℃;
To a solution of N-(5-bromo-2-methylpyridin-3-yl)acetamide (8.28 g, 36 mmol) in chloroform (550 mL) at ambient temperature was added potassium acetate (4.32 g, 43.6 mmol), acetic acid (2.5 mL, 43.6 mmol) and followed by acetic anhydride (6.86 mL, 72.6 mmol). The mixture was stirred at ambient temperature for 15 minutes before being heated to 40° C. Isoamylnitrite was then added dropwise. The reaction was then stirred at 60° C. for 48 hours. The reaction mixture was poured slowly into a saturated solution of sodium bicarbonate (500 mL) at 0° C. The organic phase was retained and the aqueous phase extracted with dichloromethane (500 mL). The combined organics were then concentrated to a brown oil which was dissolved in methanol (500 mL). Aqueous sodium hydroxide (2 M, 500 mL) was added at 0° C. and the mixture stirred at ambient temperature for 1 hour before the methanol was removed in vacuo. The aqueous mixture was then extracted with ethyl acetate (3.x.500 mL). The combined organics were dried over magnesium sulfate, filtered, and the solvent removed in vacuo to give 6-bromo-1H-pyrazolo[4,3-b]pyridine as a light brown solid (5.5 g, 77percent). 1HNMR (400 MHz, CD3OD, δ): 8.55 (s, 1H), 8.24 (s, 1H), 8.21 (s, 1H).
77%
Stage #1: With potassium acetate; acetic anhydride; acetic acid In chloroform at 20 - 40℃;
Stage #2: With tert.-butylnitrite In chloroform at 60℃; for 48 h;
Stage #3: With water; sodium hydroxide In methanol at 0 - 20℃;
To a solution of N-(5- bromo-2-methylpyridin-3-yl)acetamide (M-3) (8.3 g, 36 mmol) in chloroform (550 mL) at ambient temperature was added potassium acetate (4.3 g, 43.6 mmol), acetic acid (2.5 mL, 43.6 mmol) and followed by acetic anhydride (6.9 mL, 72.6 mmol). The mixture was stirred at ambient temperature for 15 minutes before being heated to 40 °C. Jert-butyl nitrite (6.5 mL, 54 mmol) was then added dropwise. The reaction was then stirred at 60 °C for 48 hours. The reaction mixture was poured slowly into a saturated solution of sodium bicarbonate (500 mL) at 0 °C. The organic phase was retained and the aqueous phase extracted with dichloromethane (500 mL). The combined organics were then concentrated to a brown oil which was dissolved in methanol (500 mL). Aqueous sodium hydroxide (2 M, 500 mL) was added at 0 °C and the mixture stirred at ambient temperature for 1 hour before the methanol was removed in vacuo. The aqueous mixture was then extracted with ethyl acetate (3 χ 500 mL). The combined organics dried over magnesium sulfate, and the solvent removed in vacuo to give the title compound as a light brown solid (5.5 g, 27.9 mmol, 77percent). 1HNMR (400, CD3OD): δ ppm 8.55 (s, 1H), 8.24 (s, 1H), 8.21 (s, 1H). LCMS (ESI) calc'd for C6H4BrN3 [M+H]+: 197.96, found: 198, 199.
77%
Stage #1: With potassium acetate; acetic anhydride; acetic acid In chloroform at 20℃; for 0.25 h;
Stage #2: With tert.-butylnitrite In chloroform at 40 - 60℃; for 48 h;
To a solution of N-(5-bromo-2-methylpyridin-3-yl)acetamide (M-3) (8.3 g, 36 mmol) in chloroform (550 mL) atambient temperature was added potassium acetate (4.3 g, 43.6 mmol), acetic acid (2.5 mL, 43.6 mmol) and followed by acetic anhydride (6.9 mL, 72.6 mmol). The mixture was stirred at ambient temperature for 15 minutes before being heated to 40 °C. Tert-butyl nitrite (6.5 mL, 54 mmol) was then added dropwise. The reaction was then stirred at 60 °C for 48 hours.The reaction mixture was poured slowly into a saturated solution of sodium bicarbonate (500 mL) at 0 °C. The organic phase was retained and the aqueous phase extracted with dichloromethane (500 mL). The combined organics were then concentrated to a brown oil which was dissolved in methanol (500 mL). Aqueous sodium hydroxide (2 M, 500 mL) was added at 0 °C and the mixture stirred at ambient temperature for 1 hour before the methanolwas removed in vacuo. The aqueous mixture was then extracted with ethyl acetate (3 x 500 mL). The combined organics were dried over magnesium sulfate, and the solvent removed in vacuo to give the title compound as a light brown solid (5.5 g, 27.9 mmol, 77percent). ‘HNMR (400, CD3OD): ö ppm 8.55 (s, 1H), 8.24 (s, 1H), 8.21 (s, 1H). LCMS (ESI) calc’d for C6H4BrN3 [M+H]: 197.96, found: 198, 199.

Reference: [1] Patent: US2011/111046, 2011, A1, . Location in patent: Page/Page column 16
[2] Patent: WO2011/58473, 2011, A1, . Location in patent: Page/Page column 33; 34
[3] Patent: US2012/108619, 2012, A1, . Location in patent: Page/Page column 30
[4] Patent: WO2014/26327, 2014, A1, . Location in patent: Page/Page column 89
[5] Patent: WO2014/28589, 2014, A2, . Location in patent: Page/Page column 108; 109
[6] Patent: WO2012/87782, 2012, A1,
[7] Patent: WO2015/91889, 2015, A1,
[8] Patent: US2015/175619, 2015, A1,
[9] Patent: WO2016/57834, 2016, A1,
  • 2
  • [ 1383735-65-6 ]
  • [ 1150617-54-1 ]
YieldReaction ConditionsOperation in experiment
86% With water; sodium hydroxide In tetrahydrofuran; methanol at 27℃; for 5 h; To a solution of 1 -(6-bromo- 1 H-pyrazolo [4,3-b]pyridin- 1 -yl)ethanone (1.4 g, 5.9 mmol) in tetrahydrofuran (20 mL) and methanol (15 mL) was added a solution of sodium hydroxide (0.71 g, 18 mmol) in water (5 mL) at 27 °C. After 5 h, the reaction was neutralized with hydrogen chloride acid (2 mol/L, 10 mL), and the resulting mixture was extracted withethyl acetate (3 x 50 mL). The collected organic extracts were concentrated in vacuo. Purification by flash column chromatography (1 5—30percent ethyl acetate in petroleum ether) afforded 6-bromo-1H-pyrazolo[4,3-b]pyridine (1.0 g, 86percent yield). 1H NMR (400 MHz, Chloroform-d) ö: 10.46 (brs, 1 H), 8.58 (s, 1 H), 8.25 (s, 1 H), 7.98 (s, 1 H).
86% With water; sodium hydroxide In tetrahydrofuran; methanol at 27℃; for 5 h; Inert atmosphere To a solution of 1-(6-bromo-1H-pyrazolo[4,3-b]pyridin-1-yl)ethanone (1.4 g, 5.9 mmol) in tetrahydrofuran (20 mL) and methanol (15 mL) was added a solution of sodium hydroxide (0.71 g, 18 mmol) in water (5 mL) at 27° C.
After 5 h, the reaction was neutralized with hydrogen chloride acid (2 mol/L, 10 mL), and the resulting mixture was extracted with ethyl acetate (3*50 mL).
The collected organic extracts were concentrated in vacuo.
Purification by flash column chromatography (15→30percent ethyl acetate in petroleum ether) afforded 6-bromo-1H-pyrazolo[4,3-b]pyridine (1.0 g, 86percent yield).
1H NMR (400 MHz, Chloroform-d) δ 10.46 (brs, 1H), 8.58 (s, 1H), 8.25 (s, 1H), 7.98 (s, 1H).
Reference: [1] Patent: WO2015/91889, 2015, A1, . Location in patent: Page/Page column 78
[2] Patent: US2015/175619, 2015, A1, . Location in patent: Paragraph 0241; 0242
[3] Patent: WO2012/87782, 2012, A1, . Location in patent: Page/Page column 75
[4] Patent: WO2016/57834, 2016, A1, . Location in patent: Paragraph 000573
  • 3
  • [ 914358-73-9 ]
  • [ 1150617-54-1 ]
Reference: [1] Journal of Medicinal Chemistry, 2017, vol. 60, # 10, p. 4458 - 4473
[2] Patent: US2010/125089, 2010, A1, . Location in patent: Page/Page column 89
[3] Patent: US2011/111046, 2011, A1,
[4] Patent: WO2011/58473, 2011, A1,
[5] Patent: WO2012/87782, 2012, A1,
[6] Patent: WO2014/26327, 2014, A1,
[7] Patent: WO2014/28589, 2014, A2,
[8] Patent: WO2015/91889, 2015, A1,
[9] Patent: US2015/175619, 2015, A1,
[10] Patent: WO2016/57834, 2016, A1,
[11] Patent: US2012/108619, 2012, A1,
  • 4
  • [ 669066-93-7 ]
  • [ 1150617-54-1 ]
YieldReaction ConditionsOperation in experiment
275 mg With hydrazine hydrate In ethylene glycol at 140℃; for 23 h; To a solution of the compound [172-1] obtained in the process (1) (426 mg) in ethylene glycol (2.1 mL) was added hydrazine monohydrate (197 µL) at room temperature, and then the reaction mixture was stirred at 140°C for 23 hours. After cooling to room temperature, to the reaction mixture was added water, and extracted with a mixed solution of chloroform/isopropanol (volume ratio 10/1). The obtained organic layer was washed with brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to give the titled compound (275 mg) as a yellow solid. 1H-NMR (400 MHz, CDCl3) δ: 10.17 (1H, br), 8.65 (1H, d, J = 1.7 Hz), 8.31 (1H, s), 8.04 (1H, s). ESI-MS found: 198 [M+H]+
275 mg With hydrazine hydrate In ethylene glycol at 140℃; for 23 h; (2) Synthesis of 6-bromo-1H-pyrazolo[4,3-b]pyridine [47-2] (hereinafter referred to as a compound [47-2]) To a solution of the compound [47-1] (426 mg) in ethylene glycol (2.1 mL) was added hydrazine monohydrate (197 µL) at room temperature, and the mixture was stirred at 140°C for 23 hours. After cooling to room temperature, water was added to the reaction mixture, and the mixture was extracted with a mixed solution of chloroform/isopropanol (volume ratio 10/1). The obtained organic layer was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to give the titled compound (275 mg) as a yellow solid. 1H-NMR (400 MHz, CDCl3) δ: 10.17 (1H, br), 8.65 (1H, d, J = 1.7 Hz), 8.31 (1H, s), 8.04 (1H, s). ESI-MS found: 198 [M + H]+
Reference: [1] Patent: EP2669270, 2013, A1, . Location in patent: Paragraph 0952-0953
[2] Patent: EP2878594, 2015, A1, . Location in patent: Paragraph 0585; 0586
  • 5
  • [ 911434-04-3 ]
  • [ 1150617-54-1 ]
Reference: [1] Patent: US2011/111046, 2011, A1,
[2] Patent: WO2011/58473, 2011, A1,
[3] Patent: WO2012/87782, 2012, A1,
[4] Patent: WO2016/57834, 2016, A1,
[5] Patent: US2012/108619, 2012, A1,
  • 6
  • [ 911434-05-4 ]
  • [ 1150617-54-1 ]
Reference: [1] Patent: US2011/111046, 2011, A1,
[2] Patent: WO2011/58473, 2011, A1,
[3] Patent: WO2012/87782, 2012, A1,
[4] Patent: WO2014/26327, 2014, A1,
[5] Patent: WO2014/28589, 2014, A2,
[6] Patent: WO2015/91889, 2015, A1,
[7] Patent: US2015/175619, 2015, A1,
[8] Patent: WO2016/57834, 2016, A1,
[9] Patent: US2012/108619, 2012, A1,
  • 7
  • [ 67443-38-3 ]
  • [ 1150617-54-1 ]
Reference: [1] Patent: US2011/111046, 2011, A1,
[2] Patent: WO2011/58473, 2011, A1,
[3] Patent: WO2012/87782, 2012, A1,
[4] Patent: WO2016/57834, 2016, A1,
[5] Patent: US2012/108619, 2012, A1,
  • 8
  • [ 886373-28-0 ]
  • [ 1150617-54-1 ]
Reference: [1] Patent: EP2669270, 2013, A1,
[2] Patent: EP2878594, 2015, A1,
  • 9
  • [ 1150617-54-1 ]
  • [ 74-88-4 ]
  • [ 1150617-56-3 ]
YieldReaction ConditionsOperation in experiment
35%
Stage #1: With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 0.5 h;
Stage #2: at 20℃; for 0.5 h;
To a solution of 6-bromo-1H-pyrazolo[4,3-b]pyridine (400 mg, 2.02 mmol) in DMF (10 mL) at 0 oC was added 60percent NaH in mineral oil (80.8 mg, 2.02 mmol) and the mixture was stirred at rt for 30 mm. A solution of Mel (287 mg, 2.02 mmol) in DMF (5 mL) was added and the mixture was stirred at rt for 30 mm. Then the mixture was poured into water and extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2504, filtered and concentrated under reduced pressure. The residue was purified by preparative reverse-phase HPLC to give 6-bromo-1-methyl-1H-pyrazolo[4,3-b]pyridine as a white solid (150 mg, 35percent). 1HNMR (300 MHz, DMSO-d6) 8.58-8.60 (m, 2H), 8.30-8.3 1 (m, 1H), 4.06 (s, 3H).
Reference: [1] Patent: WO2015/31613, 2015, A1, . Location in patent: Paragraph 000176
[2] Patent: US2013/281433, 2013, A1, . Location in patent: Paragraph 0854
[3] Patent: WO2016/57834, 2016, A1, . Location in patent: Paragraph 000574
  • 10
  • [ 1150617-54-1 ]
  • [ 74-88-4 ]
  • [ 1150617-56-3 ]
Reference: [1] Patent: WO2016/198400, 2016, A1, . Location in patent: Page/Page column 100; 101
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