反应 #2717

ord-4fc614d343484a3da54bc68b788f4a1f

反应方程式

Cc1ccc(C2=CC(C)(C)Oc3ccc(C=O)cc32)s1
2,2-dimethyl-4(5-methyl-thien-2-yl)-chrom-3-en-6-al
Cc1ccc(C2=CC(C)(C)Oc3ccc(C=O)cc32)s1
Compound S
Cc1ccc(C2=CC(C)(C)Oc3ccc(C=O)cc32)s1
2,2-dimethyl-4(5-methyl-thien-2-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)s2)=CC(C)(C)O4)cc1
title compound
CCOC(=O)c1ccc(-c2ccc3cc4c(cc3c2)C(c2ccc(C)s2)=CC(C)(C)O4)cc1
Ethyl-4-[2,2-dimethyl-4-(5-methyl-thien-2-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
    其他was recooled to -78° C.
  2. 2
    workup.STIRRINGThe mixture was stirred at ambient temperature for 2 hours
  3. 3
    洗涤washed with brine (10 mL)
  4. 4
    其他dried
  5. 5
    其他the solvent was removed by evaporation
  6. 6
    其他to obtain the E and Z olefinic compounds, which
  7. 7
    温度cooled to -78° C
  8. 8
    workup.STIRRINGThe resulting mixture was stirred for 30 minutes
  9. 9
    其他quenched with methanol, water
  10. 10
    workup.ADDITIONdiluted with ethyl acetate (100 mL)
  11. 11
    洗涤The organic layer was washed with brine
  12. 12
    其他dried
  13. 13
    其他Solvent was removed under reduced pressure
  14. 14
    其他purified by silicagel chromatography

实验过程

To a cold (-78° C.) solution of ethyl 4-(diethoxyphosphoryl-3,3-dimethoxypropyl)benzoate (Compound D, 690 mg, 1.75 mmol) in THF (8 mL) was added n-BuLi in hexane (1.6M solution, 1.1 mL). The mixture was gradually warmed to ambient temperature over 30 min and stirred for 5 minutes. The mixture was recooled to -78° C. and 2,2-dimethyl-4(5-methyl-thien-2-yl)-chrom-3-en-6-al (Compound S, 300 mg, 1.1 mmol) in THF (1 mL) was added to the reaction mixture. The mixture was stirred at ambient temperature for 2 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 material was subjected to flash chromatography on silica gel to obtain the E and Z olefinic compounds, which were dissolved in dichloromethane (5 mL) and cooled to -78° C. A solution of SnCl4 in dichloromethane (52 mg in 0.2 mL) was added to the olefinic compounds. The resulting mixture was stirred for 30 minutes, quenched with methanol, water and diluted with ethyl acetate (100 mL). The organic layer was washed with brine and dried. Solvent was removed under reduced pressure and purified by silicagel chromatography to afford the title compound as a white solid.

来源

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