1256822-80-6|3-Bromo-5-fluoro-1H-pyrazolo[3,4-b]pyridine| Ambeed

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Quality Control of [ 1256822-80-6 ] Purity: 95% SDS Specification

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Product Details of [ 1256822-80-6 ]

CAS No. :	1256822-80-6
Formula :	C₆H₃BrFN₃
M.W :	216.01
SMILES Code :	FC1=CN=C(NN=C2Br)C2=C1
MDL No. :	MFCD18261249
InChI Key :	QKRFTNZERDLUQL-UHFFFAOYSA-N
Pubchem ID :	71251254

Safety of [ 1256822-80-6 ]

GHS Pictogram:
Signal Word:	Warning
Hazard Statements:	H302-H315-H319-H335
Precautionary Statements:	P261-P305+P351+P338

Application In Synthesis of [ 1256822-80-6 ]

* 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.

Downstream synthetic route of [ 1256822-80-6 ]

[ 1256822-80-6 ] Synthesis Path-Downstream 1~35

1
[ 38186-88-8 ]
[ 1256822-80-6 ]

References: [1]Patent: WO2012/83117,2012,A1 .
[2]Patent: WO2013/19828,2013,A1 .
[3]Patent: WO2012/83121,2012,A1 .

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[ 1256822-80-6 ]
[ 76-83-5 ]
[ 1383446-10-3 ]

Yield	Reaction Conditions	Operation in experiment
35%		3-Bromo-5-fluoro-1H-pyrazolo[3,4-b]pyridine (1.48 g, 6.85 mmol)Dissolved in anhydrous DMF (5mL), cooled to -15 C,NaH (0.33 g, 8.30 mmol, 60%) was slowly added thereto.The resulting mixture was stirred at -15 C for 30 minutes.Then triphenylchloromethane (2.31 g, 8.29 mmol) was added.The mixture was warmed to room temperature for 1 hour.Then, 1 M of dilute hydrochloric acid (100 mL) was added thereto to quench the reaction.The liquid phase was separated and the aqueous phase was extracted with ethyl acetate (100 mL×2).The combined organic phases were washed with brine (200 mL).Dry over anhydrous sodium sulfate, filter, and distill off the solvent under reduced pressure.The residue was purified by silica gel column chromatography(petroleum ether/ethyl acetate (v/v) = 20/1-15/1)The title compound was obtained as a pale yellow solid(1.09g, 35%).
	With potassium carbonate; In N,N-dimethyl-formamide; at 20℃;	Formation of 3-bromo-5-fluoro-l-triryl-lH-pyrazoIo[3,4-6]pyridine (5)A mixture of 3-bromo-5-fluoro-lH-pyrazolo[3,4-6]pyridine, 4, (0.97 g, 4.49 mmol) and K2CO3 (1.86 g, 13.47 mmol) in DMF (9.7 mL) was cooled to 0 C. Chlorodiphenylmethylbenzene (1.38 g, 4.94 mmol) was added. The mixture was stirred at room 'temperature overnight. The mixture was diluted into ethyl acetate (40 mL) and water (30 mL) and the layers were separated. The organic layer was washed with brine, dried over Na2SC>4, filtered and concentrated in vacuo. The product was purified by silica gel chromatography (40% ethyl acetate/hexanes) to afford 1.68 g of the desired product as a white solid: NMR (300 MHz, DMSO-i 6) delta 8.45 - 8.38 (m, 1 H), 8.04 (dd, J = 8.0, 2.7 Hz, 1 H), 7.35 - 7.16 (m, 15H); LCMS Gradient 10-90%, 0.1% formic acid, 5min, C18/ACN, Retention Time = 3.03 min (M+H) 459.46.
	With potassium carbonate; In N,N-dimethyl-formamide; at 0 - 20℃;	Formation of 3-bromo-5-fluoro-l-trityl-lH-pyrazolo[3,4-A]pyridine (5)A mixture of 3-bromo-5-fluoro- lH-pyrazolo[3,4-&]pyridine, 4, (0.97 g, 4.49 mmol) and K2C03 (1.86 g, 13.47 mmol) in DMF (9.7 mL) was cooled to 0 C. Chlorodiphenylmethylbenzene (1 .38 g, 4.94 mmol) was added. The mixture was stirred at room temperature overnight. The mixture was diluted with 40 mL of ethyl acetate and washed with 30 mL of water. The organic layer was washed with brine, dried over Na^SG^, filtered and concentrated in vacuo. The product was purified by silica gel chromatography (40% ethyl acetate/hexanes) to afford 1 .68 g of the desired product as a white solid: NMR (300 MHz, /6-DMSO) delta 8.45 - 8.38 (m, 1 H), 8.04 (dd, J = 8.0, 2.7 Hz, 1H), 7.35 - 7.16 (m, 15H); LC/MS Gradient 10-90%, 0.1 % formic 5min, C18/ACN, Retention Time = 3.03 min, (M+H) 459.46.

1.68 g

With potassium carbonate; In N,N-dimethyl-formamide; at 0 - 20℃;

Formation of 3-bromo-5-fluoro-l-trityl-lH-pyrazolo[3,4-6]pyridine (134a)A mixture of 3-bromo-5-fluoro-lH-pyrazolo[3,4-¾]pyridine, 133a, (0.97 g, 4.49 mmol) and K2CO3 (1.86 g, 13.47 mmol) in DMF (9.7 mL) was cooled to 0 C. Chlorodiphenylmethylbenzene (1.38 g, 4.94 mmol) was added. The mixture was stirred at room temperature overnight. The mixture was diluted into ethyl acetate (40 mL) and water (30 mL) and the layers were separated. The organic layer was washed with brine, dried over Na2S04, filtered and concentrated in vacuo. The product was purified by silica gel chromatography (40% ethyl acetate/hexanes) to afford 1.68 g of the desired product as a white solid: 1H NMR (300 MHz, DMSO- 6) delta 8.45 - 8.38 (m, 1H), 8.04 (dd, J = 8.0, 2.7 Hz, 1H), 7.35 - 7.16 (m, 15H); LCMS Gradient 10-90%, 0.1% formic acid, 5 minutes, C18/ACN, Retention Time = 3.03 minutes (M+H) 459.46.

References: [1]Patent: CN108276401,2018,A .Location in patent: Paragraph 0633; 0642; 0643.
[2]Patent: WO2012/83121,2012,A1 .Location in patent: Page/Page column 79.
[3]Patent: WO2012/83117,2012,A1 .Location in patent: Page/Page column 107.
[4]Patent: WO2013/19828,2013,A1 .Location in patent: Page/Page column 102-104.

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[ 75302-64-6 ]
[ 1256822-80-6 ]

References: [1]Patent: WO2012/83117,2012,A1 .
[2]Patent: WO2013/19828,2013,A1 .
[3]Patent: WO2012/83121,2012,A1 .

4
[ 791644-48-9 ]
[ 1256822-80-6 ]

References: [1]Patent: WO2012/83117,2012,A1 .
[2]Patent: WO2013/19828,2013,A1 .
[3]Patent: CN108276401,2018,A .
[4]Patent: WO2012/83121,2012,A1 .

5
[ 1034667-22-5 ]
[ 1256822-80-6 ]

Yield	Reaction Conditions	Operation in experiment
55%	With tert.-butylnitrite; In Bromoform; at 20 - 90℃; for 3h;	5-Fluoro-1H-pyrazolo[3,4-b]pyridin-3-amine (1.87 g, 12.30 mmol)Dissolved in tribromomethane (20 mL), and the resulting solution was stirred at room temperature.Then tert-butyl nitrite (5.3 mL, 49.20 mmol) was added thereto.The resulting mixture was warmed to 60 C and stirred for 1 hour.Then, the temperature was raised to 90 C for 2 hours, the reaction was stopped, and the mixture was cooled to room temperature.The reaction solution was concentrated under reduced pressure, and the obtained residue was applied to silica gel column chromatography.(PE/EA(v/v)=10/1) was purified to give the title compound as a white solid.(1.45g, 55%).
	With tert.-butylnitrite; Bromoform; at 61 - 90℃; for 2h;	Formation of 3-bromo-5-fluoro-lH-pyrazolo[3,4-Z>] pyridine (4)To a mixture of 5-fluoro-lH-pyrazolo[3,4-0]pyridin-3-arnine, 3, (0.88 g, 5.79 mmol) in bromoform (8.8 mL) was added /eri-butyl nitrite (1.38 mL, 1 1.57 mmol). This mixture was heated to 61 C for 1 h and then heated to 90 C for an additional hour. The mixture was cooled to room temperature and bromoform was removed under reduced pressure. The resulting crude - residue was purified by silica gel chromatography (5-50% ethyl acetate/hexanes) to afford 970 mg of the desired product as a white solid: NMR (300 MHz, DMSO-i/6) delta 14.22 (s, 1 H), 8.67 (dd, J = 2.7, 1.9 Hz, 1 H), 8.07 (dd, J = 8.2, 2.7 Hz, 1 H); LCMS Gradient 10-90%, 0.1% formic acid, 5min, C18/ACN, Retention Time = 2.42 min (M+H) 216.1 1.
	With tert.-butylnitrite; Bromoform; at 61 - 90℃; for 2h;	Formation of 3-bromo-5-fluoro-lH-pyrazolo[3,4-A]pyridine (4)To the miture of 5-fluoro-lH-pyrazolo[3,4-6]pyridin-3-amine, 3, (0.88 g, 5.79 mmol) in bromoform (8.8 mL) was added ter/-butyl nitrite ( 1.38 mL, 1 1.57 mmol). This mixture was heated to 61 C for 1 h and then heated to 90 C for an additional hour. The mixture was cooled to room temperature and bromoform was removed under reduced pressure. The resulting crude residue was purified by silica gel chromatography (5-50% ethyl acetate/hexanes) to afford 970 mg of the desired product as a white solid: NMR (300 MHz, DMSO) delta 14.22 (s, 1 H), 8.67 (dd, J = 2.7, 1.9 Hz, 1 H), 8.07 (dd, J = 8.2, 2.7 Hz, 1 H); LC/MS Gradient 10-90%, 0.1 % formic 5min, C 18/ACN, Retention Time = 2.42 min, (M+H) 216.1 1.

970 mg

With tert.-butylnitrite; Bromoform; at 61 - 90℃; for 2h;

Formation of 3-bromo-5-fluoro-lH-pyrazolo[3,4-6]pyridine (133a)To a mixture of 5-fiuoro-lH-pyrazolo[3,4-¾]pyridin-3-amine, 132a, (0.88 g, 5.79 mmol) in bromoform (8.8 mL) was added fert-butyl nitrite (1.38 mL, 11.57 mmol). This mixture was heated to 61 C for 1 h and then heated to 90 C for an additional hour. The mixture was cooled to room temperature and bromoform was removed under reduced pressure. The resulting crude residue was purified by silica gel chromatography (5-50%> ethyl acetate/hexanes) to afford 970 mg of the desired product as a white solid: 1H NMR (300 MHz, DMSO- 6) delta 14.22 (s, 1H), 8.67 (dd, J = 2.7, 1.9 Hz, 1H), 8.07 (dd, J = 8.2, 2.7 Hz, 1H); LCMS Gradient 10-90%, 0.1% formic acid, 5 minutes, C18/ACN, Retention Time = 2.42 minutes (M+H) 216.11.

References: [1]Patent: CN108276401,2018,A .Location in patent: Paragraph 0633; 0638; 0639.
[2]Patent: WO2012/83121,2012,A1 .Location in patent: Page/Page column 79.
[3]Patent: WO2012/83117,2012,A1 .Location in patent: Page/Page column 107.
[4]Patent: WO2013/19828,2013,A1 .Location in patent: Page/Page column 102-103.

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[ 1256822-80-6 ]
[ 1383485-63-9 ]