反应 #2713

ord-b76082d12d914f36b18aec03d29abfbc

反应方程式

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

反应条件

详细条件
See reaction.notes.procedure_details.

后处理

  1. 1
    workup.STIRRINGthe mixture was stirred for 5 hours
  2. 2
    洗涤washed with brine (10 mL)
  3. 3
    其他dried
  4. 4
    其他the solvent was removed by evaporation
  5. 5
    其他to obtain the E and Z olefinic compounds, which
  6. 6
    温度cooled to -50° C
  7. 7
    温度The reaction mixture was gradually warmed to -10° C. over 3hours
  8. 8
    其他quenched with methanol and water
  9. 9
    workup.ADDITIONThe reaction mixture was diluted with ethyl acetate (100 mL)
  10. 10
    洗涤The organic layer was washed with brine
  11. 11
    其他dried
  12. 12
    其他Solvent was removed under reduced pressure
  13. 13
    其他the residue purified by chromatography on silicagel

实验过程

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.

来源

DOI: 10.6084/m9.figshare.5104873.v1专利: US05728846uspto-grants-1998_03