反应详情

Placed in an oven-dried, three-necked flask was 1.615 g (5 mMol) of 1,1-dichloro-2,2-Bis-(p-methoxyphenyl) cyclopropane which was flushed with argon and sealed with a rubber septum. Using oven-dried syringes, 10 ml of chloroform, 0.32 g (4 mMol) of pyridine and 2.9 ml (20 mMol) of iodotrimethylsilane were injected into the flask in the order specified above (the chloroform and pyridine had been dried previously over anhydrous magnesium sulfate). The mixture turned yellow and a white precipitate was noted with the addition of iodotrimethylsilane. The mixture turned yellow and a white precipitate was noted with the addition of iodotrimethylsilane. The mixture was heated to reflux without stirring for 72 hours. Thin layer chromatography was performed with methylene chloride and a small amount of starting material still was present. Anhydrous methanol, dried with magnesium sulfate, in the amount of 2.5 ml was added and the mixture turned golden brown. It was cooled to room temperature and transferred to a round bottom flask with 10 ml of chloroform. The volatile components were removed on a rotary evaporator to yield a yellow solid which was dissolved in 50 ml of ether. The insoluble pyridium hydrochloride was filtered. The ether was evaporated to afford a yellow solid whose NMR and thin layer chromatography (with methylene chloride-acetone (95:5)) showed starting material along with some polar components. These components were separated by column chromatography on silica gel (125 g) with methylene chloride-acetone (95:5) as eluent. Unreacted starting material was eluted first and 0.4 g was recovered. Compound 1,1-dichloro-2-(p-methoxyphenyl)-2-(p-hydroxyphenyl) cyclopropane was eluted next and recrystallized in hexane with trace of ethanol to give colorless fine needles. The column was then washed with acetone, and compound 1,1-dichloro-2,2-Bis-(p-hydroxyphenyl) cyclopropane as a red brown solid was obtained upon evaporation of the solvent. This solid was recrystallized in chloroform to give a light pink solid.

1. customwas flushed with argon
2. customsealed with a rubber septum
3. dry with materialhad been dried previously over anhydrous magnesium sulfate)
4. additiona white precipitate was noted with the addition of iodotrimethylsilane
5. additiona white precipitate was noted with the addition of iodotrimethylsilane
6. temperatureThe mixture was heated
7. temperatureto reflux
8. dry with materialAnhydrous methanol, dried with magnesium sulfate, in the amount of 2.5 ml
9. additionwas added
10. customtransferred to a round bottom flask with 10 ml of chloroform
11. customThe volatile components were removed on a rotary evaporator
12. customto yield a yellow solid which
13. filtrationThe insoluble pyridium hydrochloride was filtered
14. customThe ether was evaporated
15. customto afford a yellow solid whose NMR
16. customThese components were separated by column chromatography on silica gel (125 g) with methylene chloride-acetone (95:5) as eluent
17. washwas eluted first
18. custom0.4 g was recovered
19. washCompound 1,1-dichloro-2-(p-methoxyphenyl)-2-(p-hydroxyphenyl) cyclopropane was eluted next
20. customrecrystallized in hexane with trace of ethanol
21. customto give colorless fine needles
22. washThe column was then washed with acetone