Ethyl benzoylformate → HCID 11020409, compound

HRID 2229476Notes

Reaction equation

HRID 2229476 reaction equation
[C:1]([C:9]([O:11][CH2:12][CH3:13])=[O:10])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:14]([Si](C)(C)C)[CH:15]=[CH2:16].[Sn](Cl)(Cl)(Cl)Cl>C(Cl)Cl>[C:2]1([C:1]2([C:9]([OH:11])=[O:10])[CH2:16][CH2:15][CH2:14][O:8]2)[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1.[OH:8][C:1]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)([CH2:16][CH:15]=[CH2:14])[C:9]([O:11][CH2:12][CH3:13])=[O:10]

Participants

6

Reactant 3

HCID 15349Ethyl benzoylformateHCID 24287Tin tetrachlorideHCID 69808Allyltrimethylsilane

Product 2

HCID 11020409HCID 11020409, compoundYield 77.8%HCID 18467999phenyl tetrahydrofuran-2-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

The title compound was prepared according to a literature procedure (T. Akiyama, K. Ishikawa and S. Ozaki, Chemistry letters 1994, 627). To a solution of ethyl benzoylformate (2.5 g, 14.0 mmol) and allyl trimethylsilane (2.7 ml, 16.9 mmol) in 31 ml of methylene chloride (anhydrous) at −78° C. was added 1.6 ml of tin chloride (14.28 mmol) dropwise. The cooling bath was removed after the addition was complete. After the reaction mixture was stirred at room temperature for 5 min., TLC showed the reaction was complete. Triethylamine (3.5 ml) and water (150 ml) were added to quench the reaction. Extraction with ethyl acetate was complicated by the emulsion which was broken up by filtration through celite. The extracts were washed with brine, dried over MgSO4, filtered, and concentrated. The residue was purified by silica gel chromatography with methylene chloride/hexane=2.5:97.5 to afford 2-hydroxyl-2-phenyl-4-pentenoic acid, ethyl ester as an oil (1.2 g). 400 MHz 1H NMR (CDCl3): δ 7.59 (m, 2H); 7.29 (m, 3H); 5.79 (m, 1H); 5.13 (m, 2H); 4.23 (m, 2H); 2.96 (m, 1H); 2.74 (m, 1H); 1.26 (t, J=7.0 Hz, 3H).

Workup

  1. customThe cooling bath was removed
  2. additionafter the addition
  3. additionTriethylamine (3.5 ml) and water (150 ml) were added
  4. customto quench
  5. customthe reaction
  6. extractionExtraction with ethyl acetate
  7. filtrationwas broken up by filtration through celite
  8. washThe extracts were washed with brine
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe residue was purified by silica gel chromatography with methylene chloride/hexane=2.5:97.5

Sources & evidence

ORD record
ord-b5429494edb24047ae3bbd32a5be441d
Source dataset
uspto-grants-2002_07
Patent number
US06420418B1

Reaction notes

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