Sulfuric Acid → Ethyl 7-bromo-4-hydroxy-1,1-dimethyl-2-oxo-naphthalene-3-carboxylate

HRID 2078168Notes

Reaction equation

HRID 2078168 reaction equation
OS(O)(=O)=O.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.[Br:20][C:21]1[CH:22]=[C:23]([C:27]([CH3:42])([CH3:41])[C:28]([CH:30]([C:36](OCC)=[O:37])[C:31]([O:33][CH2:34][CH3:35])=[O:32])=[O:29])[CH:24]=[CH:25][CH:26]=1>>[Br:20][C:21]1[CH:22]=[C:23]2[C:24]([C:36]([OH:37])=[C:30]([C:31]([O:33][CH2:34][CH3:35])=[O:32])[C:28](=[O:29])[C:27]2([CH3:41])[CH3:42])=[CH:25][CH:26]=1

Participants

4

Reactant 3

HCID 1118Sulfuric AcidHCID 14812Phosphorus oxide (P4O10)HCID 67099417Diethyl 2-(2-(3-bromophenyl)-2-methylpropanoyl)malonate

Product 1

HCID 67099405Ethyl 7-bromo-4-hydroxy-1,1-dimethyl-2-oxo-naphthalene-3-carboxylateYield 41.1%

Procedure

H2SO4 (60 mL, 710 mmol) was cooled to 0° C. and treated with P2O5 (20 g, 141 mmol). The mixture was brought to room temperature and added to diethyl 2-(2-(3-bromophenyl)-2-methylpropanoyl)malonate (17.44 g, 45 mmol). The reaction mixture was then stirred for 2 hours. Ice (H2O) was added, and the aqueous mixture was extracted with EtOAc (3×). The combined organic layers were washed with water (2×) and brine, dried (MgSO4), and concentrated in vacuo to give the crude compound as an orange oil. The crude oil was purified by silica flash chromatography (0-100% DCM/hexane) to give the desired compound as a white solid (6.27 g). MS (m/e)=339.1 (M+H)+.

Workup

  1. customwas brought to room temperature
  2. additionIce (H2O) was added
  3. extractionthe aqueous mixture was extracted with EtOAc (3×)
  4. washThe combined organic layers were washed with water (2×) and brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customto give the crude compound as an orange oil
  8. customThe crude oil was purified by silica flash chromatography (0-100% DCM/hexane)

Sources & evidence

ORD record
ord-1e44710e04044b1e969640f9878ee47b
Source dataset
uspto-grants-2011_04
Patent number
US07928139B2

Reaction notes

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