Sulfuric Acid → 4-Hydroxymethyl-4-vinyltetrahydro-2-furanone

HRID 363500Notes

Reaction equation

HRID 363500 reaction equation
O(C[C:10]([CH2:19][O:20][Si](C(C)(C)C)(C)C)([CH:17]=[CH2:18])[CH2:11][C:12]([O:14][CH2:15]C)=[O:13])[Si](C(C)(C)C)(C)C.OS(O)(=O)=O>C1COCC1>[OH:20][CH2:19][C:10]1([CH:17]=[CH2:18])[CH2:15][O:14][C:12](=[O:13])[CH2:11]1

Participants

4

Reactant 2

HCID 1118Sulfuric AcidHCID 10598023Ethyl 3,3-bis[(tert-butyldimethylsiloxy)methyl]-4-pentenoate

Product 1

HCID 105587194-Hydroxymethyl-4-vinyltetrahydro-2-furanoneYield 88%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 7a (8.34 g, 20 mmol) in aqueous THF (60 mL, 1:1) was treated with concentrated H2SO4 (10 mL) and stirred at room temperature for 24 h. The mixture was concentrated under vacuum, diluted with water, and the aqueous layer was extracted with CHCl3. The combined organic layer was washed with H2O , dried (NaSO4) and concentrated. The residue was purified by flash column chromatography over silica gel with EtOAc/hexane (2:1) as eluant to give 8b (2.50 g, 88%) as an oil; IR (neat) 3452 (OH), 1777 (C=O), 1641 cm-1 ; 1H NMR (CDCl3) δ 2.51 (d of AB, J=17.4 Hz, 1 H, H-3a), 2.63 (d of AB, J=17.4 Hz, 1 H, H-3b), 3.62 (s, 2 H, CH2OH), 4.16 (d of AB, J=9.2 Hz, 1 H, H-5a), 4.32 (d of AB, J=9.2 Hz, 1 H, H-5b), 5.19 (d, J=17.5 Hz, 1 H, CH=CHH), 5.29 (d, J=10.8 Hz, 1 H, CH=CHH), 5.85 (dd, J=17.5, 10.8 Hz, 1 H, CH=CH2); 13C NMR (CDCl3) δ 35.94, 47.61, 65.56, 73.33, 116.18, 137.55, 176.97. Anal. Calcd for C7H10O3 : C, 59.14; H. 7.09. Found: C, 59.05; H, 7.09.

Workup

  1. concentrationThe mixture was concentrated under vacuum
  2. additiondiluted with water
  3. extractionthe aqueous layer was extracted with CHCl3
  4. washThe combined organic layer was washed with H2O
  5. dry with materialdried (NaSO4)
  6. concentrationconcentrated
  7. customThe residue was purified by flash column chromatography over silica gel with EtOAc/hexane (2:1) as eluant

Sources & evidence

ORD record
ord-f0951bcfd98842cf8b8923329b6fb109
Source dataset
uspto-grants-1999_02
Patent number
US05874464

Reaction notes

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