反应详情

温度

110 °C

Into a 100 ml. round bottom flask fitted with a condenser, thermometer, magnetic stirring bar, and a Drierite filled drying tube is charged 18.4 g (0.200 mole) norbornadiene, 30.6 g (0.200 mole) isobutyl 2-cyanoacrylate (inhibited with excess sulfur dioxide), and 0.1 g hydroquinone monomethyl ether (MEHQ). The solution is stirred and heated under a nitrogen atmosphere to 110°C. After 15 minutes at 100°C., the solution became cloudy, more viscous, and the reflux rate diminished. The mixture is then heated to 150°C. and maintained at this temperature for 24 hours. The solution is cooled to room temperature, diluted with 200 ml. hexane, filtered to remove polymeric solids, and the filtrate solvent stripped to a dark orange syrupy residue. The lattter is dissolved in 200 ml. acetone and to the resultant solution is added 800 ml. of an aqueous solution containing 96 g. of potassium permanganate and 96 g. magnesium sulfate. After several minutes, the excess potassium permanganate is destroyed by bubbling sulfur dioxide gas into the solution. The manganese dioxide precipitate is filtered and the solids washed thoroughly with acetone. After dilution of the filtrate with one-half of its volume with water, the product is extracted into chloroform. The extract is backwashed with 3 × 500 ml. water, dried over anhydrous magnesium sulfate, filtered, and solvent stripped under reduced pressure to give 27.2 g (56% theory) of crude adduct. Distillation affords 24.0 g (49% theory) of the pure norbornadiene/isobutyl 2-cyanoacrylate adduct, b.p. 110°-112°C. (0.4 mm), a colorless liquid.

1. customround bottom flask fitted with a condenser
2. customdrying tube
3. temperatureThe mixture is then heated to 150°C.
4. temperaturemaintained at this temperature for 24 hours
5. temperatureThe solution is cooled to room temperature
6. additiondiluted with 200 ml
7. filtrationhexane, filtered
8. customto remove polymeric solids
9. dissolutionThe lattter is dissolved in 200 ml
10. additionacetone and to the resultant solution is added 800 ml
11. additionof an aqueous solution containing 96 g
12. waitAfter several minutes
13. customthe excess potassium permanganate is destroyed
14. customby bubbling sulfur dioxide gas into the solution
15. filtrationThe manganese dioxide precipitate is filtered
16. washthe solids washed thoroughly with acetone
17. extractionAfter dilution of the filtrate with one-half of its volume with water, the product is extracted into chloroform
18. dry with materialwater, dried over anhydrous magnesium sulfate
19. filtrationfiltered
20. customto give 27.2 g (56% theory) of crude adduct
21. distillationDistillation