Dioxane sulfuric acid → 5-(Hydroxymethyl)-1,3-dihydro-2-benzofuran-1-one

HRID 1907039Notes

Reaction equation

HRID 1907039 reaction equation
BrC[C:3]1[CH:13]=[C:12]([CH2:14]Br)[CH:11]=[CH:10][C:4]=1[C:5]([O:7][CH2:8]C)=[O:6].[O:16]1CCOCC1.S(=O)(=O)(O)O>C(Cl)Cl>[OH:16][CH2:14][C:12]1[CH:11]=[C:10]2[C:4](=[CH:3][CH:13]=1)[C:5](=[O:6])[O:7][CH2:8]2

Participants

4

Reactant 2

HCID 19613996Dioxane sulfuric acidHCID 67127237HCID 67127237, compound

Product 1

HCID 124468605-(Hydroxymethyl)-1,3-dihydro-2-benzofuran-1-one

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A suspension of 2 (22.1 g, 65.7 mmol) in 700 mL of a 1:1 mixture of dioxane/sulfuric acid (1M) was heated under reflux for 20 h. After cooling to room temperature, the mixture was poured into 200 mL of DCM. The phases were separated and the aqueous phase was extracted with DCM (5×200 mL). The combined organic layers were washed with saturated NaHCO3 (3×200 mL) and brine (1×200 mL) and were dried over MgSO4. The solvent was removed in vacuo to yield 8.70 g (83%) of pure 3 as a colorless solid: 1H-NMR (400 MHz, DMSO-d6): δ 4.65 (s, 2H), 5.39 (s, 2H), 5.47 (br s, 1H), 7.51 (d, J=7.8 Hz, 1H), 7.60 (s, 1H), 7.78 (d, J=7.7 Hz, 1H); 13C-NMR (100 MHz, DMSO-d6): δ 62.4, 69.7, 120.0, 123.3, 124.5, 126.9, 147.5, 149.7, 170.5; MS (Cl+ (NH3)) m/z=165.0 (M+H+, 100), 182.0 (M+NH4+, 49).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 20 h
  3. customThe phases were separated
  4. extractionthe aqueous phase was extracted with DCM (5×200 mL)
  5. washThe combined organic layers were washed with saturated NaHCO3 (3×200 mL) and brine (1×200 mL)
  6. dry with materialwere dried over MgSO4
  7. customThe solvent was removed in vacuo

Sources & evidence

ORD record
ord-384d6b62a4854af68aaad86cd757b8e7
Source dataset
uspto-grants-2013_12
Patent number
US08597631B2

Reaction notes

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