反应详情

温度

2 °C

3,5-bis(phenylethynyl)benzil (65.6 grams, 0.16 mole) prepared in the manner of Example 1,1,3-diphenylacetone (37.8 grams, 0.18 mole), 2-propanol (583 milliliters) and toluene (218 milliliters), were added to a 2 liter glass four neck Morton reactor containing a magnetic stirring bar. The reactor was additionally outfitted with chilled (2° C.) condenser, a thermometer with thermostatically controlled heating mantle and a subsurface tube for sparging with nitrogen. Under a nitrogen atmosphere, an addition funnel was loaded with tetrabutylammonium hydroxide (1M in methanol) (5.46 milliliters) diluted into 2-propanol (97 milliliters) which had been sparged with nitrogen. This addition funnel was then attached to the reactor under dynamic nitrogen flow. Sparging and heating of the stirred slurry commenced, and after 42 minutes, once a reflux (80° C.) was achieved, a clear light yellow colored solution had formed. At this time, the sparge tube was move up out of the solution in the reactor to provide nitrogen overhead, then dropwise solution of the catalyst commenced, inducing the formation of a dark red color. After 92 minutes at reflux, 44 milliliters of the catalyst solution had been added and HPLC analysis indicated that full conversion of the 3,5-bis[phenylethynyl)benzil reactant had been achieved, with minimum formation of coproducts. After a cumulative 101 minutes at reflux, the heating mantle was removed from the reactor, additional 2-propanol was added (413 milliliters), then an ice bath was placed under the reactor and the stirred contents were maintained therein for the next 39 minutes until a temperature of 5° C. was achieved. The product was recovered via filtration through a coarse flitted glass funnel. The product cake on the funnel was washed with two portions (50 milliliters) of 2-propanol, giving a clear filtrate with the second wash. Drying in a vacuum oven to provided 79.66 grams (85.3 percent isolated yield) of 4-(3,5-bis(phenylethynyl)-phenyl)-2,3,5-triphenylcyclopentadienone (unsymmetrically substituted 3,5-AAB monomer) as a dark red purple colored crystalline product. HPLC analysis revealed the presence of the desired product at 100 area percent.

1. additioncontaining a magnetic stirring bar
2. temperaturea thermometer with thermostatically controlled heating mantle and a subsurface tube
3. customfor sparging with nitrogen
4. customUnder a nitrogen atmosphere, an addition funnel was loaded with tetrabutylammonium hydroxide (1M in methanol) (5.46 milliliters)
5. additiondiluted into 2-propanol (97 milliliters) which
6. customhad been sparged with nitrogen
7. customThis addition funnel was then attached to the reactor under dynamic nitrogen
8. customSparging
9. temperatureheating of the stirred slurry
10. temperatureonce a reflux (80° C.)
11. customa clear light yellow colored solution had formed
12. customto provide nitrogen overhead
13. temperatureAfter 92 minutes at reflux
14. temperatureAfter a cumulative 101 minutes at reflux
15. customthe heating mantle was removed from the reactor, additional 2-propanol
16. additionwas added (413 milliliters)
17. customan ice bath was placed under the reactor
18. temperaturethe stirred contents were maintained
19. customfor the next 39 minutes
20. customuntil a temperature of 5° C.
21. filtrationThe product was recovered via filtration through a coarse flitted glass funnel
22. washThe product cake on the funnel was washed with two portions (50 milliliters) of 2-propanol
23. customgiving a clear filtrate with the second wash
24. customDrying in a vacuum oven