Hydrazine → HCID 23568904, compound

HRID 2376225Notes

Reaction equation

HRID 2376225 reaction equation
[CH2:1]([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)[CH3:2].[NH2:26][NH2:27].C([O-])([O-])=O.[Cs+].[Cs+]>C1COCC1.C(OCC)(=O)C>[CH2:1]([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]1[CH:8]=[C:9]([C:11]2[CH:16]=[CH:15][C:14]([Br:17])=[CH:13][CH:12]=2)[N:27]([C:14]2[CH:15]=[CH:16][C:11]([CH3:9])=[CH:12][CH:13]=2)[N:26]=1)[CH3:2]

Participants

6

Reactant 3

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

Product 1

HCID 23568904HCID 23568904, compoundYield 115%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

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-5744a7d2cc57438b965ca571d76b2ffd
Source dataset
uspto-grants-2008_12
Patent number
US07465808B2

Reaction notes

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