Water → 1-(3-Methylene-2,3-dihydro-1-benzoxepin-7-yl)ethanone

HRID 1791061Notes

Reaction equation

HRID 1791061 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:20]([C:23]1[CH:24]=[CH:25][C:26]([O:31][CH2:32][C:33]([CH2:35]I)=[CH2:34])=[C:27]([CH:30]=1)[CH:28]=O)(=[O:22])[CH3:21].C[O-].[Na+].O>C(#N)C.CO>[CH2:34]=[C:33]1[CH:35]=[CH:28][C:27]2[CH:30]=[C:23]([C:20](=[O:22])[CH3:21])[CH:24]=[CH:25][C:26]=2[O:31][CH2:32]1

Participants

7

Reactant 4

HCID 962WaterHCID 11776TriphenylphosphineHCID 10942334Sodium MethoxideHCID 220422815-Acetyl-2-{[2-(iodomethyl)-2-propenyl]oxy}benzaldehyde

Product 1

HCID 220422551-(3-Methylene-2,3-dihydro-1-benzoxepin-7-yl)ethanoneYield 58%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6342AcetonitrileSolvent

Procedure

973 mg (3.575 mmol) of triphenylphosphine are added under argon to 1.118 g (3.25 mmol) of 5-acetyl-2-{[2-(iodomethyl)-2-propenyl]oxy}benzaldehyde in solution in 30 ml of acetonitrile. The medium is brought to reflux and is stirred for 14 hours. After cooling the solution, 0.743 ml (3.25 mmol) of a 25% solution of sodium methoxide in methanol is added. The medium is stirred at ambient temperature for 3 hours and then water is added. After concentrating the solution under vacuum, dichloromethane is added. The phases are then separated and the aqueous phase is extracted with dichloromethane. The combined organic phases are washed, are then dried and are finally concentrated under vacuum. The crude reaction product is purified by chromatography on silica gel (ethyl acetate/heptane 10/90) to give 377 mg (58%) of 1-(3-methylene-2,3-dihydro-1-benzoxepin-7-yl)ethanone in the form of a white solid; 1H NMR (300 MHz, CDCl3): 7.86 (d, J=2.1 Hz, 1H), 7.75 (dd, J=2.1 Hz and 8.4 Hz, 1H), 7.03 (d, J=8.4 Hz, 1H), 6.51 (d, J=11.7 Hz, 1H), 6.38 (d, J=11.7 Hz, 1H), 5.28 and 5.11 (2s, 2H), 4.61 (s, 2H), 2.56 (s, 3H).

Workup

  1. temperatureto reflux
  2. additionis added
  3. stirringThe medium is stirred at ambient temperature for 3 hours
  4. concentrationAfter concentrating the solution under vacuum, dichloromethane
  5. additionis added
  6. customThe phases are then separated
  7. extractionthe aqueous phase is extracted with dichloromethane
  8. washThe combined organic phases are washed
  9. customare then dried
  10. concentrationare finally concentrated under vacuum
  11. customThe crude reaction product
  12. customis purified by chromatography on silica gel (ethyl acetate/heptane 10/90)

Sources & evidence

ORD record
ord-790f5a2328ca4e0baebd073feb8f231d
Source dataset
uspto-grants-2006_07
Patent number
US07071340B2

Reaction notes

Loading…