Hydrazine → HCID 11754688, compound

HRID 1823224Notes

Reaction equation

HRID 1823224 reaction equation
C([O:3][C:4](=[O:25])[CH:5]([C:18]1[CH:19]=[C:20]([CH3:24])[CH:21]=[CH:22][CH:23]=1)[CH2:6][C:7]#[C:8][C:9]([C:11]1[CH:16]=[CH:15][C:14]([Br:17])=[CH:13][CH:12]=1)=O)C.[NH2:26][NH2:27].C([O-])([O-])=O.[Cs+].[Cs+]>C1COCC1.C(OCC)(=O)C>[Br:17][C:14]1[CH:13]=[CH:12][C:11]([C:9]2[N:27]([C:14]3[CH:15]=[CH:16][C:11]([CH3:9])=[CH:12][CH:13]=3)[N:26]=[C:7]([CH2:6][CH:5]([C:18]3[CH:19]=[C:20]([CH3:24])[CH:21]=[CH:22][CH:23]=3)[C:4]([OH:3])=[O:25])[CH:8]=2)=[CH:16][CH:15]=1

Participants

6

Reactant 3

HCID 9321HydrazineHCID 10796Cesium carbonate2×HCID 68878037HCID 68878037, compound

Product 1

HCID 11754688HCID 11754688, compoundYield 121.8%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

3-[5-(4-Bromo-phenyl)-1-β-tolyl-1H-pyrazol-3-yl]-2-m-tolyl-propionic acid ethyl ester. To a solution of 6-(4-bromo-phenyl)-6-oxo-2-m-tolyl-hex-4-ynoic acid ethyl ester (7.5 g, 19 mmol) in THF (40 mL) was added hydrazine (4.5 g, 28 mmol, 1.5 equiv) and Cs2CO3 (9.0 g, 28 mmol, 1.5 equiv). The reaction mixture was stirred at room temperature for 12 h. The resulting mixture was diluted with ethyl acetate (30 mL), and a satd aq solution of cesium carbonate (50 mL) was added. The resulting aqueous layer was back-extracted with ethyl acetate (2×30 mL). The combined organic layers were washed with satd aq NaHCO3 (50 mL) then brine (50 mL), and dried (MgSO4). The solvent was evaporated under reduced pressure, and the residue was purified by chromatography (silica gel, 25% ethyl acetate/hexanes) to afford the desired compound (5.5 g, 58%). TLC (silica gel, 3:7 EtOAc/hexanes): Rf=0.35. MS (ESI): mass calculated for C28H27BrN2O2, 502.13; m/z found, 503/505 [M+H]+. 1H NMR (400 MHz, CDCl3): 7.39 (d, J=10.7 Hz, 2H), 7.25-7.01 (m, 10H), 6.17 (s, 1H), 4.19-4.03 (m, 3H), 3.52 (dd, J=14.7, 9.6 Hz, 1H), 3.09 (dd, J=14.7, 6.0, 1H), 2.35 (s, 6H), 1.19 (t, J=7.1 Hz, 3H).

Workup

  1. extractionThe resulting aqueous layer was back-extracted with ethyl acetate (2×30 mL)
  2. washThe combined organic layers were washed with satd aq NaHCO3 (50 mL)
  3. dry with materialbrine (50 mL), and dried (MgSO4)
  4. customThe solvent was evaporated under reduced pressure
  5. customthe residue was purified by chromatography (silica gel, 25% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-1a391d5bb8d94828a0d24c059c1a4b56
Source dataset
uspto-grants-2006_05
Patent number
US07037931B2

Reaction notes

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