Hydrochloric Acid → Ethyl 3-(4-bromophenyl)-3-oxopropanoate

HRID 2269302Notes

Reaction equation

HRID 2269302 reaction equation
[H-].[Na+].[C:3](=[O:10])([O:7][CH2:8][CH3:9])OCC.[Br:11][C:12]1[CH:17]=[CH:16][C:15]([C:18](=[O:20])[CH3:19])=[CH:14][CH:13]=1.Cl>C(OCC)C.C(O)C>[Br:11][C:12]1[CH:17]=[CH:16][C:15]([C:18]([CH2:19][C:3]([O:7][CH2:8][CH3:9])=[O:10])=[O:20])=[CH:14][CH:13]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 7466p-BromoacetophenoneHCID 7766Diethyl CarbonateHCID 24758Sodium hydride

Product 1

HCID 2757149Ethyl 3-(4-bromophenyl)-3-oxopropanoateYield 74.5%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
0 °C

Procedure

Sodium hydride (5.2 g, 0.21 mol) was suspended in dry diethyl ether and cooled to 0° C. Diethyl carbonate (17.7 g, 0.15 mol) was added and the contents were stirred for ten minutes, at which time dropwise addition of p-bromoacetophenone (19.9 g, 0.1 mol) in diethyl ether (50 mL) and ethanol (0.2 mL) was initiated. Addition was continued for twenty minutes; the solution was refluxed for three hours, cooled to room temperature and poured onto cold 10% aqueous hydrochloric acid (250 mL). The aqueous solution was extracted twice with diethyl ether (750 mL) and the combined extracts were washed successively with water (250 mL), brine (250 mL) and dried (MgSO4). The solvent was removed in vacuo and the residue was purified on silica gel, eluting with hexane/ethyl acetate (4/1), to afford 20.2 g (74%) of the title compound as an oil. 1HNMR (60MHz, CDCl3): δ1.2 (t,3H), 3.9 (s, 2H), 4.1 (q, 2H), 7.55 (d, J=7 Hz, 2H), 7.75 (d, J=2 Hz, 2H).

Workup

  1. additionAddition
  2. waitwas continued for twenty minutes
  3. temperaturethe solution was refluxed for three hours
  4. temperaturecooled to room temperature
  5. extractionThe aqueous solution was extracted twice with diethyl ether (750 mL)
  6. washthe combined extracts were washed successively with water (250 mL), brine (250 mL)
  7. dry with materialdried (MgSO4)
  8. customThe solvent was removed in vacuo
  9. customthe residue was purified on silica gel
  10. washeluting with hexane/ethyl acetate (4/1)

Sources & evidence

ORD record
ord-b545be3f6d6049dc9df28602dd657481
Source dataset
uspto-grants-2001_12
Patent number
US06329408B1

Reaction notes

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