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Product Details of [ 1314734-57-0 ]

CAS No. :1314734-57-0
Formula : C9H9BrN4O2
M.W : 285.10
SMILES Code : O=C(C1=NNC2=NC=C(Br)C=C21)N(OC)C

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Application In Synthesis of [ 1314734-57-0 ]

* 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 [ 1314734-57-0 ]

[ 1314734-57-0 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 916325-85-4 ]
  • [ 6638-79-5 ]
  • [ 1314734-57-0 ]
YieldReaction ConditionsOperation in experiment
92% Step 8[00182] To a solution of 5-bromo-lH-pyrazole[3,4-£]pyridine-3-carboxylic acid (VIII) (0.242 g, 1 mmol) in dry DMF (5 mL) was added CDI (0.178 g, 1.1 mmol) and heated for 3 h at 65C under nitrogen. The solution was cooled to room temperature and Nu,Omicron-dimethyl hydroxylamine hydrochloride (0.107 g, 1.1 mmol) was added to the solution. The solution was again heated for 3 h at 65C under nitrogen. The solution was cooled and the solvent was evaporated under reduced pressure. The residue was dissolved in DCM, washed successively with a 10% HC1 solution, a saturated NaHC03 solution and brine. The organic phase was dried over MgS04, filtered and concentrated under reduced pressure to produce 5-bromo-N-methoxy-N-methyl-lH-pyrazolo[3,4- £]pyridine-3-carboxamide (IX) as a white solid (260 mg, 0.91 mmol, 92%> yield). 1H NMR (CDC13) delta ppm 3.55 (s, 3H), 3.78 (s, 3H), 8.59 (d, J=3.01 Hz, 1 H), 8.67 (d, J=3.01 Hz, 1 H); ESIMS found for C9H9BrN402 mlz 285.4 (M+H).
92% To a solution of 5-bromo-1H-pyrazole[3,4-b]pyridine-3-carboxylic acid (XVIII) (0.242 g, 1 mmol) in dry DMF (5 mL) was added CDI (0.178 g, 1.1 mmol) and heated for 3 h at 65 C. under nitrogen. The solution was cooled to room temperature and N,O-dimethyl hydroxylamine hydrochloride (0.107 g, 1.1 mmol) was added to the solution. The solution was again heated for 3 h at 65 C. under nitrogen. The solution was cooled and the solvent was evaporated under reduced pressure. The residue was dissolved in DCM, washed successively with a 10% HCl solution, a saturated aqueous NaHCO3 solution and brine. The organic phase was dried over MgSO4, filtered and concentrated under reduced pressure to produce 5-bromo-N-methoxy-N-methyl-1H-pyrazolo[3,4-b]pyridine-3-carboxamide (XIX) as a white solid (260 mg, 0.91 mmol, 92% yield). 1H NMR (CDCl3) delta ppm 3.55 (s, 3H), 3.78 (s, 3H), 8.59 (d, J=3.01 Hz, 1H), 8.67 (d, J=3.01 Hz, 1H); ESIMS found for C9H9BrN4O2 m/z 285.4 (M+H).
92% Step 8 To a solution of 5-bromo-1H-pyrazole[3,4-b]pyridine-3-carboxylic acid (XVI) (0.242 g, 1 mmol) in dry DMF (5 mL) was added CDI (0.178 g, 1.1 mmol) and heated for 3 h at 65 C. under nitrogen. The solution was cooled to room temperature and N,O-dimethyl hydroxylamine hydrochloride (0.107 g, 1.1 mmol) was added to the solution. The solution was again heated for 3 h at 65 C. under nitrogen. The solution was cooled and the solvent was evaporated under reduced pressure. The residue was dissolved in DCM, washed successively with a 10% HCl solution, a saturated aqueous NaHCO3 solution and brine. The organic phase was dried over MgSO4, filtered and concentrated under reduced pressure to produce 5-bromo-N-methoxy-N-methyl-1H-pyrazolo[3,4-b]pyridine-3-carboxamide (XVII) as a white solid (260 mg, 0.91 mmol, 92% yield). 1H NMR (CDCl3) delta ppm 3.55 (s, 3H), 3.78 (s, 3H), 8.59 (d, J=3.01 Hz, 1H), 8.67 (d, J=3.01 Hz, 1H); ESIMS found for C9H9BrN4O2 m/z 285.4 (M+H).
92% To a solution of 5-bromo-1H-pyrazole[3,4-b]pyridine-3-carboxylic acid (XVI) (0.242 g, 1 mmol) in dry DMF (5 mL) was added CDI (0.178 g, 1.1 mmol) and heated for 3 h at 65C under nitrogen. The solution was cooled to room temperature and Nu,Omicron-dimethyl hydroxylamine hydrochloride (0.107 g, 1.1 mmol) was added to the solution. The solution was again heated for 3 h at 65C under nitrogen. The solution was cooled and the solvent was evaporated under reduced pressure. The residue was dissolved in DCM, washed successively with a 10%) HCl solution, a saturated aqueous NaHCO3 solution and brine. The organic phase was dried over MgSO4, filtered and concentrated under reduced pressure to produce 5-bromo-N-methoxy-N-methyl-1H-pyrazolo[3,4-6]pyridine-3-carboxamide (XVII) as a white solid (260 mg, 0.91 mmol, 92% yield). 1H NMR (CDCl3) delta ppm 3.55 (s, 3H), 3.78 (s, 3H), 8.59 (d, J=3.01Hz, 1H), 8.67 (d, J=3.01Hz, 1H); ESIMS found for C9H9BrN4O2 m/z 285.4 (M+H).
7.94 g <strong>[916325-85-4]5-bromo-1H-pyrazolo[3,4-b]pyridine-3-carboxylic acid</strong> ((III), 7.91 g, 32.7 mmol) and 1,1?- carbonyldiimidazole (5.83 g, 35.9 mmol) were stirred in 200 mL of DMF at 60C for 45 minutes. To the resulting suspension was added N,O-dimethylhydroxylamine hydrochloride (3.51 g, 35.9 mmol) and the mixture was stirred for 4 h at 65 C. Most of the solvent was removed under vacuum and to the residue half sat. NaHCO3-solution was added. The solids were collected by suction filtration, washed with water and dried at 110 C. Yield: 7.94 g, HPLC purity: 96 %, 1H NMR (200 MHz, DMSO) delta 14.46 (s, 1H), 8.62 (d, J = 20.4 Hz, 2H), 3.76 (s, 3H), 3.44 (s, 3H), [M-H]- = 283.0 / 285.0.

  • 2
  • [ 1262198-07-1 ]
  • [ 1314734-57-0 ]
  • (3-amino-2,4-difluorophenyl)-(5-bromo-1H-pyrazolo[3,4-b]pyridin-3-yl)methanone [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% To <strong>[1262198-07-1]3-bromo-2,6-difluoroaniline</strong> (3, 12.9 g, 61.9 mmol) in tetrahydrofuran (76.9 mL) was added 2M Isopropylmagnesium chloride in THF (30.9 mL, 61.9 mmol) dropwise at 0 C and stirred for 15 minutes at RT. After cooling to 0 C, chlorotrimethylsilane (7.85 mL, 61.9 mmol) was added, the mixture warmed to 25 C and stirred for 20 minutes. The suspension was cooled to 0 C and 2M Isopropylmagnesium chloride in THF (30.9 mL, 61.9 mmol) was added dropwise and stirred for 15 minutes at RT. After cooling to 0 C chlorotrimethylsilane (7.85 mL, 61.9 mmol) was added stirring continued for 20 minutes at 25 C. The suspension was cooled to 0 C again and 2M isopropylmagnesium chloride in THF (30.9 mL, 61.9 mmol) was added dropwise and the mixture was stirred for 10 minutes at 0 C (Solution A). (1001) Meanwhile 2M isopropylmagnesium chloride in THF (13.5 mL, 26.9 mmol) was added dropwise to a suspension of 5-bromo-N-methoxy-N-methyl-1H-pyrazolo[3,4-b]pyridine-3- carboxamide (4, 7.67 g, 26.9 mmol) in tetrahydrofuran (76.9 mL) at 0 C. The resulting suspension was stirred for 5 minutes and transferred to solution A. The reaction was stirred overnight at RT, conc. HCl (26.9 mL, 323 mmol) was added and stirred for 10 minutes. Water was added until the phases became clear. The mixture was neutralized with 2N NaOH, saturated with NaCl and extracted with THF. The extracts were washed with brine, dried over Na2SO4 and filtered. After evaporation of the solvent, the solids were stirred in 100 mL DCM collected by suction filtration and dried to yield 6.35 g a first crop as light yellow solid. The filtrate was evaporated, triturated with diethyl ether and DCM to obtain a second crop (0.41 g). Total yield (3-amino-2,4-difluorophenyl)-(5-bromo-1H-pyrazolo[3,4-b]pyridin-3-yl)methanone (5, 6.76 g, 19,1 mmol, 71% yield). (1002) Analytical data: (1003) 1H NMR (200 MHz, DMSO) δ 14.55 (s, 1H), 8.65 (dd, J = 5.2, 2.1 Hz, 2H), 7.13- 6.86 (m, 2H), 5.44 (s, 2H); (1004) 13C NMR (50 MHz, DMSO) δ 186.1, 153.5 (dd, J = 188, 9 Hz), 150.8, 150.3, 148.6 (dd, J = 191, 9 Hz), 141.1, 132.5, 126.1 (t, J = 17 Hz), 122.8 (dd, J = 12, 3 Hz), 116.2 (dd, J = 9, 3 Hz), 115.4, 115, 110.6 (dd, J = 19, 3 Hz); (1005) MS: [M-1]- = 351.2.
 

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