反应详情

A mixture of 2-bromo-7-iodo-9,9-didecylfluorene (52.13 g, 0.08 mol), diphenylamine (15.6 g, 0.0922 mol, 1.152 eq), potassium carbonate (25.5 g, 0.1844 mol), TDA-1 (5 mL), copper bronze (3.0 g, 0.05 g atom) and xylenes (75 mL) was brought to reflux, and 35 ml, of xylenes were distilled off to reach a reaction temperature of 160° C. The reaction was maintained at this temperature for 18 hours. Some more solvent was distilled off to reach a reaction temperature of 175° C., where the reaction was held for additional 6 hours. The mixture was then cooled, diluted with 100 mL toluene, filtered, the filtrate was concentrated, and the residue was transferred to a column of 600 g of silica gel. Elution with 750 mL hexanes returned a mixture of dibromo and bromoiodo fluorenes as an oil, 10.3 g. Elution with heptane-toluene, 1:1 gave the product, 33.48 g (61% yield, 77% yield on consumed bromoiodo fluorene), m.p. 66.8-69.2° C. Mass Spec. (m/z): 691, 693 (M+).

1. temperatureto reflux
2. distillation35 ml, of xylenes were distilled off
3. customa reaction temperature of 160° C
4. temperatureThe reaction was maintained at this temperature for 18 hours
5. distillationSome more solvent was distilled off
6. customa reaction temperature of 175° C., where
7. temperatureThe mixture was then cooled
8. additiondiluted with 100 mL toluene
9. filtrationfiltered
10. concentrationthe filtrate was concentrated
11. washElution with 750 mL hexanes
12. additiona mixture of dibromo and bromoiodo fluorenes as an oil, 10.3 g
13. washElution with heptane-toluene, 1:1
14. customgave
15. customthe product, 33.48 g (61% yield, 77% yield on consumed bromoiodo fluorene), m.p. 66.8-69.2° C