反应详情

温度

10 °C

A dry 100 mL three-neck round bottom flask equipped with a condenser, magnetic stir bar, thermometer, and a nitrogen inlet was charged with 5-bromoindene (99+% purity, 9.65 g, 50 mmol), diethyl ether (anhydrous, 60 mL), and phenylmagnesium bromide (18.0 mL 3M in diethyl ether, 54 mmol). The mixture was chilled to 10° C. and [1,2-bis(diphenylphosphino)ethane]nickel(II) chloride (0.1 g, 0.2 mmol) was added. The reaction mixture was warmed gradually to reflux. As the reaction progressed the clear solution became turbid from the precipitation of magnesium bromide by-product. After 4 hours at reflux the reaction mixture was quenched in chilled 5% aqueous HCl (200 mL). Additional diethyl ether (100 mL) was added and the organic phase was separated, water washed, and dried over anhydrous magnesium sulfate. Evaporation of diethyl ether followed by vacuum distillation (90° C./0.5 mm Hg) gave 5-phenylinene (8.4 g, 97% purity by GC) as pale yellow crysta1s. 1HNMR (CD2Cl2, 500 MHz) 50:50 mixture of isomers; δ7.72 (s, 1H); 7.62 (m, 5H); 7.52 (t, J=8 Hz, 2H); 7.43 (m, 6H); 7.32 (m, 2H); 6.93 (m, 2H); 6.61 (m, 2H); 3.47 (s, 2H); 3.44 (s, 2H).

1. customA dry 100 mL three-neck round bottom flask equipped with a condenser, magnetic stir bar
2. temperatureThe reaction mixture was warmed gradually
3. temperatureto reflux
4. customfrom the precipitation of magnesium bromide by-product
5. temperatureAfter 4 hours at reflux the reaction mixture
6. customwas quenched in chilled 5% aqueous HCl (200 mL)
7. additionAdditional diethyl ether (100 mL) was added
8. customthe organic phase was separated
9. washwater washed
10. dry with materialdried over anhydrous magnesium sulfate
11. customEvaporation of diethyl ether
12. distillationfollowed by vacuum distillation (90° C./0.5 mm Hg)
13. customgave 5-phenylinene (8.4 g, 97% purity by GC) as pale yellow crysta1s