Calcium Carbonate → 6-Methylphthalide

HRID 2361331

Reaction equation

HRID 2361331 reaction equation
BrC[C:3]1[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][C:4]=1[C:5]([O:7][CH3:8])=[O:6].C(=O)([O-])[O-].[Ca+2]>O1CCOCC1.O>[CH3:13][C:10]1[CH:9]=[C:4]2[C:3]([CH2:8][O:7][C:5]2=[O:6])=[CH:12][CH:11]=1

Participants

5

Reactant 2

HCID 10112Calcium CarbonateHCID 57561371Methyl 2-(bromomethyl)-5-methylbenzoate

Product 1

HCID 6387566-MethylphthalideYield 29.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

A heterogeneous, colorless solution of methyl 2-(bromomethyl)-5-methylbenzoate and regioisomer (27.2 mmol) and calcium carbonate (16.33 g, 163 mmol) in 1,4-dioxane (194 mL) and water (194 mL) was refluxed. After 5 hr, the reaction was cooled to room temperature. The insolubles were filtered, and the filtrate was concentrated in vacuo. The residue was extracted with CH2Cl2 (2×200 mL). The organic layers were combined, dried over MgSO4, and concentrated in vacuo to give an oil which was purified by flash chromatography using an ISCO 220 g column eluting with 10-50% EtOAc/hexanes. Appropriate fractions were collected and concentrated in vacuo to give the desired product (1.205 g, 8.13 mmol, 29.9% yield) as a white solid.

Workup

  1. filtrationThe insolubles were filtered
  2. concentrationthe filtrate was concentrated in vacuo
  3. extractionThe residue was extracted with CH2Cl2 (2×200 mL)
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customto give an oil which
  7. customwas purified by flash chromatography
  8. washeluting with 10-50% EtOAc/hexanes
  9. customAppropriate fractions were collected
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-0a7e43c93e404ce69c8320c0993b98b6
Source dataset
uspto-grants-2014_04
Patent number
US08685969B2

Linked notes

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