Ethyl formate → 6-Hydroxymethylene-2-isopropyl-3-methoxy-cyclohex-2-enone

HRID 1609794Notes

Reaction equation

HRID 1609794 reaction equation
[H-].[Na+].[CH:3](OCC)=[O:4].[CH:8]([C:11]1[C:12](=[O:19])[CH2:13][CH2:14][CH2:15][C:16]=1[O:17][CH3:18])([CH3:10])[CH3:9].P([O-])([O-])(O)=O.[Na+].[Na+]>C1C=CC=CC=1>[OH:4][CH:3]=[C:13]1[C:12](=[O:19])[C:11]([CH:8]([CH3:10])[CH3:9])=[C:16]([O:17][CH3:18])[CH2:15][CH2:14]1

Participants

6

Reactant 4

HCID 8025Ethyl formateHCID 24203Sodium Phosphate, DibasicHCID 24758Sodium hydrideHCID 222601342-Isopropyl-3-methoxy-cyclohex-2-enone

Product 1

HCID 696592786-Hydroxymethylene-2-isopropyl-3-methoxy-cyclohex-2-enoneYield 60.1%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent2×

Procedure

To a suspension of sodium hydride (3.6 g, 60% suspension, 90 mmol) in benzene (100 mL), a mixture of ethyl formate (12.5 g) and 2-isopropyl-3-methoxy-cyclohex-2-enone (5g, 29.7 mmol) in benzene was added dropwise at 5° C. The reaction mixture was stirred at ice temperature for 1 hour, and at room temperature for 18 hours. The reaction mixture was cooled in an ice bath, and 10% sodium hydrogen phosphate solution (200 mL) was added dropwise. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate (2×50 mL). The combined organic layers were washed with brine and dried over anhydrous sodium sulfate. The solvent was removed in vacuo, and the resulting product was purified on a column of silica gel (Hex:EtOAc) to give the title compound as a thick viscous liquid (3.5 g, 60%). 1H NMR (CDCl3): δ 1.15 (d, 6H, 2×CH3), 2.35–2.6 (m, 4H, 2×CH2), 3.15 (m, 1H, CH), 3.8 (s, 3H, OCH3), 7.17 (d, 1H, ═CHOH).

Workup

  1. additionwas added dropwise at 5° C
  2. waitat room temperature for 18 hours
  3. temperatureThe reaction mixture was cooled in an ice bath
  4. customThe organic layer was separated
  5. extractionthe aqueous layer was extracted with ethyl acetate (2×50 mL)
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. customThe solvent was removed in vacuo
  9. customthe resulting product was purified on a column of silica gel (Hex:EtOAc)

Sources & evidence

ORD record
ord-f1bc8dc452ce407e932291979e5324e2
Source dataset
uspto-grants-2006_01
Patent number
US06982260B1

Reaction notes

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