Reaktion #2713

ord-b76082d12d914f36b18aec03d29abfbc

Reaktionsgleichung

Cc1ccc(C2=CC(C)(C)Oc3ccc(C=O)cc32)cc1
2,2-dimethyl-4(tol-4-yl)-chrom-3-en-6-al
Cc1ccc(C2=CC(C)(C)Oc3ccc(C=O)cc32)cc1
Compound Q
Cc1ccc(C2=CC(C)(C)Oc3ccc(C=O)cc32)cc1
2,2-dimethyl-4(tol-4-yl)-chrom-3-en-6-al
CCOC(=O)c1ccc(CCC(OC)(OC)P(=O)(OCC)OCC)cc1
ethyl 4-(diethoxyphosphoryl-3,3-dimethoxypropyl)benzoate
CCOC(=O)c1ccc(CCC(OC)(OC)P(=O)(OCC)OCC)cc1
Compound D
CCOC(=O)c1ccc(CCC(OC)(OC)P(=O)(OCC)OCC)cc1
ethyl 4-(diethoxyphosphoryl-3,3-dimethoxypropyl)benzoate
[Li][CH2]CCC
n-BuLi
[Cl][Sn]([Cl])([Cl])[Cl]
SnCl4
CCOC(=O)c1ccc(-c2ccc3cc4c(cc3c2)C(c2ccc(C)cc2)=CC(C)(C)O4)cc1
title compound
CCOC(=O)c1ccc(-c2ccc3cc4c(cc3c2)C(c2ccc(C)cc2)=CC(C)(C)O4)cc1
Ethyl-4-[2,2-dimethyl-4-(tol-4-yl)-benzo[1,2-g]-chrom-3-en-7-yl]benzoate

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    workup.STIRRINGthe mixture was stirred for 5 hours
  2. 2
    Waschenwashed with brine (10 mL)
  3. 3
    Sonstigedried
  4. 4
    Sonstigethe solvent was removed by evaporation
  5. 5
    Sonstigeto obtain the E and Z olefinic compounds, which
  6. 6
    Temperaturcooled to -50° C
  7. 7
    TemperaturThe reaction mixture was gradually warmed to -10° C. over 3hours
  8. 8
    Sonstigequenched with methanol and water
  9. 9
    workup.ADDITIONThe reaction mixture was diluted with ethyl acetate (100 mL)
  10. 10
    WaschenThe organic layer was washed with brine
  11. 11
    Sonstigedried
  12. 12
    SonstigeSolvent was removed under reduced pressure
  13. 13
    Sonstigethe residue purified by chromatography on silicagel

Vorschrift

To a cold (-78° C.) solution of ethyl 4-(diethoxyphosphoryl-3,3-dimethoxypropyl)benzoate (Compound D, 1.4 g, 3.6 mmol) in THF (9 mL) was added n-BuLi in hexane (1.6M solution, 2.8 mL). The mixture was gradually warmed to ambient temperature over 30 minutes and stirred for 5 minutes. To this mixture was added 2,2-dimethyl-4(tol-4-yl)-chrom-3-en-6-al (Compound Q, 260 mg, 0.93 mmol) in THF (1 mL) at ambient temperature and the mixture was stirred for 5 hours. The reaction mixture was diluted with ethyl acetate (100 mL) and washed with brine (10 mL) dried and the solvent was removed by evaporation. The residual material was subjected to flash chromatography on silicagel to obtain the E and Z olefinic compounds, which were dissolved in dichloromethane (5 mL) and cooled to -50° C. A solution of SnCl4 in dichloromethane (150 mg in 0.7 mL) was added to the olefinic compounds. The reaction mixture was gradually warmed to -10° C. over 3hours and then quenched with methanol and water. The reaction mixture was diluted with ethyl acetate (100 mL). The organic layer was washed with brine and dried. Solvent was removed under reduced pressure and the residue purified by chromatography on silicagel to afford the title compound as a white solid.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US05728846uspto-grants-1998_03