tert-Butyl acrylate → HCID 67539111, compound

HRID 1192340Notes

Reaction equation

HRID 1192340 reaction equation
[CH2:1]([O:3][C:4](=[O:13])[CH2:5][C:6]1[CH:11]=[CH:10][C:9]([Cl:12])=[CH:8][CH:7]=1)[CH3:2].CC(C)([O-])C.[K+].[C:20]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])(=[O:23])[CH:21]=[CH2:22]>C1COCC1>[CH2:1]([O:3][C:4](=[O:13])[CH:5]([C:6]1[CH:11]=[CH:10][C:9]([Cl:12])=[CH:8][CH:7]=1)[CH2:22][CH2:21][C:20]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH3:2]

Participants

5

Reactant 3

HCID 15458tert-Butyl acrylateHCID 84177Ethyl (4-chlorophenyl)acetateHCID 23665647Potassium tert-butoxide

Product 1

HCID 67539111HCID 67539111, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

The (4-chlorophenyl)-acetic acid ethyl ester (9.52 g, 47.9 mmol) was dissolved in 80 mL of THF, cooled to 0° C., and treated with potassium tert-butoxide (538 mg, 4.79 mmol). The resulting orange solution was allowed to stir for 15 minutes at 0° C., then cooled to −78° C. The tert-butyl acrylate (7.72 mL, 52.7 mmol) was added in three equal portions over ten minutes. The solution was allowed to stir overnight warming slowly to room temperature. The reaction solution was concentrated in vacuo, and the residue was partitioned between ethyl acetate and saturated NH4Cl solution. The aqueous was extracted with ethyl acetate, and the organics were combined. The organic was washed with brine, separated, dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by chromatography (silica gel eluted with 9:1 hexanes:EtOAc) to afford the 2-(4-chlorophenyl)-pentanedioic acid 5-tert-butyl ester 1-ethyl ester in greater than 80% purity (9.00 g, 57%). 1H NMR (CDCl3, 400 MHz) δ 7.31-7.21 (m, 4H), 4.13 (q, J=7.6 Hz, 2H), 3.58 (t, J=8.0 Hz, 1H), 2.27 (m, 1H), 2.16 (t, J=7.2 Hz, 2H), 2.04 (m, 1H), 1.43 (s, 9H), 1.21 (t, J=7.6 Hz, 3H).

Workup

  1. temperaturecooled to −78° C
  2. stirringto stir overnight
  3. temperaturewarming slowly to room temperature
  4. concentrationThe reaction solution was concentrated in vacuo
  5. customthe residue was partitioned between ethyl acetate and saturated NH4Cl solution
  6. extractionThe aqueous was extracted with ethyl acetate
  7. washThe organic was washed with brine
  8. customseparated
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customThe residue was purified by chromatography (silica gel eluted with 9:1 hexanes:EtOAc)

Sources & evidence

ORD record
ord-03cef4d567f2491cbe529fcf815526d8
Source dataset
uspto-grants-2014_03
Patent number
US08680114B2

Reaction notes

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