反应详情

A 1.7 M solution of t-butyllithium in pentane (300 mL, 0.510 mol) was added under argon to a stirred suspension of p-iodotoluene (56.04 g, 0.257 mol) in ether (150 mL) at -78° C. The mixture was allowed to warm to room temperature over 1 h. The resulting solution of tolyllithium was added to a solution of 1,10-phenanthroline monohydrate (8.50 g, 0.043 mol) in toluene (100 mL). The resulting dark red solution was stirred under argon for 48 h. The reaction was carefully quenched with water (300 mL) and extracted with CH2Cl2 (3×150 mL). The combined organic layers were dried (Na2SO4) and evaporated to a volume of 500 mL under reduced pressure. The solution of crude product was oxidized by stirring with activated MnO2 (60 g). An additional portion of MnO2 (30 g) was added to the reaction after 1 h to ensure complete oxidation. After a total of 2 h, anhydrous MgSO4 (40 g) was added, and the mixture was filtered. The MnO2 /MgSO4 was washed with CH2Cl2 (300 mL), and the solvent was concentrated to a volume of 50 mL, when a crystalline solid formed. The solution was cooled in ice and filtered. The light yellow product crystals were filtered, washed with one portion of cold toluene (20 mL), and dried. Yield 8.63 g 56%). 1H NMR (CDCl3) δ8.38 (d, J=8.1 Hz, 4H), 8.29 (d, J=8.5 Hz, 2H), 8.13 (d, J=8.4 Hz, 2H), 7.77 (s, 2H), 7.40 (d, J=8.1 Hz, 4H), 2.47 (s, 6H).

1. customThe reaction was carefully quenched with water (300 mL)
2. extractionextracted with CH2Cl2 (3×150 mL)
3. dry with materialThe combined organic layers were dried (Na2SO4)
4. customevaporated to a volume of 500 mL under reduced pressure
5. stirringby stirring with activated MnO2 (60 g)
6. additionAn additional portion of MnO2 (30 g) was added to the reaction after 1 h
7. additionAfter a total of 2 h, anhydrous MgSO4 (40 g) was added
8. filtrationthe mixture was filtered
9. washThe MnO2 /MgSO4 was washed with CH2Cl2 (300 mL)
10. concentrationthe solvent was concentrated to a volume of 50 mL, when a crystalline solid
11. customformed
12. temperatureThe solution was cooled in ice
13. filtrationfiltered
14. filtrationThe light yellow product crystals were filtered
15. washwashed with one portion of cold toluene (20 mL)
16. customdried