2-Methoxyethanol → HCID 90011233, compound

HRID 1481489Notes

Reaction equation

HRID 1481489 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([N:8]2[C:12]([C:13]([O:15][CH2:16]C)=O)=[CH:11][C:10]([CH:18]3[CH2:20][CH2:19]3)=[N:9]2)=[N:6][CH:7]=1.C1(C(=O)CC(=NOC)C(OCC)=[O:28])CC1.COCCO.BrC1C=C[C:45]([NH:48][NH2:49])=NC=1>C(O)(=O)C>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([N:8]2[C:12]([C:13]3[O:15][C:16](=[O:28])[N:48]([CH3:45])[N:49]=3)=[CH:11][C:10]([CH:18]3[CH2:20][CH2:19]3)=[N:9]2)=[N:6][CH:7]=1

Participants

6

Reactant 4

HCID 80192-MethoxyethanolHCID 115356995-Bromo-2-hydrazinopyridineHCID 76664812HCID 76664812, compoundHCID 90011477HCID 90011477, compound

Product 1

HCID 90011233HCID 90011233, compoundYield 33%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Step-3: Ethyl 1-(5-Bromopyridin-2-yl)-3-cyclopropyl-1H-pyrazole-5-carboxylate: To a stirred solution of ethyl 4-cyclopropyl-2-(methoxyimino)-4-oxobutanoate (420 mg, 1.97 mmol) in acetic acid:2-methoxyethanol (6 mL, 2:1) was added 5-bromo-2-hydrazinylpyridine (370 mg, 1.97 mmol) at room temperature. The resulting mixture was refluxed for 3 h. The reaction mixture was cooled to room temperature and the solvent was evaporated under vacuum. The crude product was purified by flash column chromatography (silica gel, ethyl acetate-hexanes system) to afford 220 mg (33%) of the title compound as pale yellow syrup. 1HNMR (400 MHz, CDCl3) δ 8.49 (d, J=2.0 Hz, 1H), 7.95 (dd, J=2.0 & 8.0 Hz, 1H), 7.58 (d, J=8.0 Hz, 1H), 6.56 (s, 1H), 4.30 (q, J=7.0 Hz, 2H), 2.04-1.98 (m, 1H), 1.29 (t, J=7.0 Hz, 3H), 1.02-0.97 (m, 2H), 0.83-0.79 (m, 2H); ESI-MS (m/z) 336, 338 [(MH)+, Br79,81].

Workup

  1. temperatureThe resulting mixture was refluxed for 3 h
  2. customthe solvent was evaporated under vacuum
  3. customThe crude product was purified by flash column chromatography (silica gel, ethyl acetate-hexanes system)

Sources & evidence

ORD record
ord-9995fb0805fb46948f48e551e0a76c47
Source dataset
uspto-grants-2016_08
Patent number
US09409898B2

Reaction notes

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