Acetic Acid → HCID 57323027, compound

HRID 2164575Notes

Reaction equation

HRID 2164575 reaction equation
[C:1]([O:4][CH:5]=[C:6]1[CH:12]2[CH:9]([C:10](Cl)(Cl)[C:11]2=[O:13])[CH:8]=[CH:7]1)(=[O:3])[CH3:2].C(O)(=O)C>C(Cl)Cl.[Zn]>[C:1]([O:4][CH:5]=[C:6]1[CH:12]2[CH:9]([CH2:10][C:11]2=[O:13])[CH:8]=[CH:7]1)(=[O:3])[CH3:2]

Participants

5

Reactant 2

HCID 176Acetic AcidHCID 57141998HCID 57141998, compound

Product 1

HCID 57323027HCID 57323027, compoundYield 63.2%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalyst3×HCID 6344DichloromethaneSolvent

Procedure

A mixture of 540 mg of 4-(acetoxymethylene)-7,7-dichloro-6-oxobicyclo[3.2.0]hept-2-ene, 600 mg of zinc dust and 10 mL of acetic acid was stirred at room temperature for 15 min under argon. An additional 500 mg of zinc was then added; the mixture was stirred between 75° and 80° for 1 hr. The temperature was raised to between 85° and 90° and after addition of 1 g of zinc dust the mixture was stirred for 1 hr. The cooled reaction mixture was diluted with methylene chloride, filtered and evaporated to dryness on a rotary evaporator. The product was purified by preparative thin layer chromatography on three 20×20×0.2 cm silica gel plates, eluting with methylene chloride-hexane (2:1), to afford 246 mg (63.0%) of 4-(acetoxymethylene)-6-oxobicyclo[3.2.0]hept-2-ene (cis, trans mixture) as an oil. NMR (220 MHz; CDCl3): δ2.02 (3 H, s), 2.05 (3H, s), 2.59 (1H, t, J=3.3), 2.68 (1H, t, J=3.3), 3.25 (2H, m), 3.50 (2H, m), 4.25 (1H, m), 4.55 (1H, m), 6.11 (3H, m), 6.43 (1H, d, J=5.5), 7.0 (1H, broad s), and 7.25 (1H broad s). A small amount of this mixture was successfully separated by preparative thin layer chromatography on a 0.25 mm silica gel plate. The mass spectra of the two components were identical. HRMS: Calcd for C10H10O3, 178.0630; found, 178.0617.

Workup

  1. stirringthe mixture was stirred between 75° and 80° for 1 hr
  2. temperatureThe temperature was raised to between 85° and 90°
  3. stirringwas stirred for 1 hr
  4. customThe cooled reaction mixture
  5. filtrationfiltered
  6. customevaporated to dryness on a rotary evaporator
  7. customThe product was purified by preparative thin layer chromatography on three 20×20×0.2 cm silica gel plates
  8. washeluting with methylene chloride-hexane (2:1)

Sources & evidence

ORD record
ord-d1ba9af8db0045e6a6b8188dd41a2054
Source dataset
uspto-grants-1985_03
Patent number
US04505905

Reaction notes

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