反应 #68721

反应方程式

4-Bromo-2-methylphenol

4,4′-(bicyclo[2.2.1]hept-5-en-2-ylmethylene)bis(2-methylphenol)

Triethylamine

formic acid

→

4,4′-((5-(4-hydroxy-3-methylphenyl)bicyclo[2.2.1]heptan-2-yl)methylene)-bis(2-methylphenol)

收率 54.0%

溶剂

ethyl acetate

DMF

反应条件

后处理

1. 1
   其他equipped
2. 2
   其他reaction vessel
3. 3
   其他to give a suspension
4. 4
   其他During, the course of the reaction
5. 5
   其他rose to 82° C.
6. 6
   其他After the initial exothermic reaction
7. 7
   其他The cooled reaction mixture
8. 8
   洗涤washed with water (160 mL)
9. 9
   其他to remove DMF
10. 10
    干燥The organic layer was dried over anhydrous MgSO4
11. 11
    其他The crude mixture was purified by preparative TLC

实验过程

Under a nitrogen atmosphere, 4-Bromo-2-methylphenol (4.69 g, 25.1 mmol), (tris-o-tolylphosphine)2PdCl2 (0.377 g; 0.480 mmol), and 4,4′-(bicyclo[2.2.1]hept-5-en-2-ylmethylene)bis(2-methylphenol) (5.14 g; 16.0 mmol) were charged to an appropriately sized and equipped reaction vessel. DMF (80 mL) was added to this reactant mixture to give a suspension. Triethylamine (11.0 mL, 78.9 mmol) and formic acid (2.30 mL, 60.9 mmol) were added to this suspension and then heated to 75° C. in an oil bath. The reaction mixture turned from its original orange suspension to pale yellow and became clear. During, the course of the reaction, the temperature of the reaction mixture rose to 82° C. and turned darker, and a gas evolved very slowly. After the initial exothermic reaction ceased, the reaction mixture was stirred overnight at 75° C. After this time, the reaction mixture was a clear, pale yellow solution with black particles. The cooled reaction mixture was diluted with ethyl acetate (80 mL) and washed with water (160 mL) to remove DMF. The organic layer was dried over anhydrous MgSO4. The crude mixture was purified by preparative TLC using a hexanes/ethyl acetate mixture (50:50) as developer to afford 3.7 g of 4,4′-((5-(4-hydroxy-3-methylphenyl)bicyclo[2.2.1]heptan-2-yl)methylene)-bis(2-methylphenol) (54% yield). The identity of the product as PP429 was confirmed by LC-MS (ESI) and proton NMR.

来源