Ethyl benzoylacetate → HCID 59301171, compound

HRID 2235825Notes

Reaction equation

HRID 2235825 reaction equation
[CH2:1]([O:3][C:4](=[O:14])[CH2:5][C:6](=[O:13])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)[CH3:2].O([C:17]([CH3:20])([CH3:19])[CH3:18])[K].Br[CH2:22][C:23]([CH2:25]Br)=[O:24].[CH2:27]1[CH2:31]OC[CH2:28]1>>[CH2:1]([O:3][C:4](=[O:14])[CH:5]([C:6](=[O:13])[C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=1)[CH2:22][C:23](=[O:24])[CH2:25][CH2:18][C:17]1[CH:20]=[CH:31][CH:27]=[CH:28][CH:19]=1)[CH3:2]

Participants

5

Reactant 4

HCID 7170Ethyl benzoylacetateHCID 8028TetrahydrofuranHCID 699521,3-Dibromo-2-propanoneHCID 178418922HCID 178418922, compound

Product 1

HCID 59301171HCID 59301171, compound

Procedure

Neat 3-oxo-3-phenyl-propionic acid ethyl ester (95%; 0.80 mL; 4.4 mmol) was added over 1.5 min to a soln of KO-t-Bu (1.0 M in THF; 4.40 mL; 4.4 mmol) in THF (4.4 mL) at 0° C. After 20 min, the above solid bromomethyl ketone (910 mg; 4.0 mmol) was added in one portion. After an additional 2 h, the r×n was quenched with aq. citric acid. The organic volatiles were removed on a rotary evaporator then the product extracted into EtOAc (25 mL). The soln was washed with water (2×8 mL), satd NaCl (1×8 mL), dried over MgSO4, filtered through a plug of silica with an EtOAc wash and concd. The product was purified by MPLC (silica; 0-->35% EtOAc in hexanes gradient) yielding a clear, colorless liquid (1.199 g; 97%). 1H NMR (CDCl3) δ 8.02 (m, 2H), 7.60 (m, 1H), 7.49 (m, 2H), 7.28 (m, 2H), 7.22-7.15 (m, 3H), 4.93 (dd, J=6.4, 7.6 Hz, 1H), 4.13 (q, J=7.2 Hz, 2H), 3.19 (dd, J=7.6, 18.4 Hz, 1H), 3.12 (dd, J=6.4, 18.0 Hz, 1H), 2.94-2.82 (m, 4H), 1.15 (t, J=7.0 Hz, 3H).

Workup

  1. waitAfter an additional 2 h
  2. customthe r×n was quenched with aq. citric acid
  3. customThe organic volatiles were removed on a rotary evaporator
  4. extractionthe product extracted into EtOAc (25 mL)
  5. washThe soln was washed with water (2×8 mL), satd NaCl (1×8 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered through a plug of silica with an EtOAc
  8. washwash
  9. customThe product was purified by MPLC (silica; 0-->35% EtOAc in hexanes gradient)
  10. customyielding a clear, colorless liquid (1.199 g; 97%)

Sources & evidence

ORD record
ord-95da71d5c97c407aa1b99d2a8fc43386
Source dataset
uspto-grants-2010_05
Patent number
US07714022B2

Reaction notes

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