Reaktion #1596820

Reaktionsgleichung

3-(quinolin-2-yl)phenol

4′-iodo-2-nitrobiphenyl

K3PO4

→

desired product

Ausbeute 101.1%

2-(3-(quinolin-2-yl)phenoxy)-9H-carbazole

Ausbeute 101.1%

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigeequipped with a magnetic stir bar
2. 2
   SonstigeThe vessel was evacuated
3. 3
   workup.ADDITIONback-filled with nitrogen
4. 4
   workup.ADDITIONThen solvent DMSO (32 mL) was added under nitrogen
5. 5
   SonstigeAfter bubbling with nitrogen for 20 minutes
6. 6
   Sonstigewas monitored by TLC and about 22 hours
7. 7
   Sonstigewas consumed completely
8. 8
   TemperaturThen the mixture was cooled to ambient temperature
9. 9
   workup.ADDITIONdiluted with water
10. 10
    Extraktionextracted with ethyl acetate three times
11. 11
    WaschenThe combined organic layer was washed with water three times
12. 12
    Trocknendried over sodium sulfate
13. 13
    Filtrationfiltered
14. 14
    Waschenwashed with ethyl acetate
15. 15
    EinengenThe filtrate was concentrated
16. 16
    Sonstigethe residue was purified through column chromatography on silica gel

Vorschrift

3-(quinolin-2-yl)phenol (3.68 g, 15.30 mmol, 1.0 eq), 4′-iodo-2-nitrobiphenyl (5.97 g, 18.36 mmol, 1.2 eq), CuI (0.15 g, 0.77 mmol, 0.05 eq), picolinic acid (0.19 g, 1.53 mmol, 0.1 eq) and K3PO4 (6.50 g, 30.60 mmol, 2.0 eq) were added to a dry pressure vessel equipped with a magnetic stir bar. The vessel was evacuated and back-filled with nitrogen. The evacuation and back-fill procedure was repeated twice. Then solvent DMSO (32 mL) was added under nitrogen. After bubbling with nitrogen for 20 minutes, the mixture was heated to 80-90° C. in an oil bath. The reaction was monitored by TLC and about 22 hours later the starting material 3-(quinolin-2-yl)phenol was consumed completely. Then the mixture was cooled to ambient temperature and diluted with water, extracted with ethyl acetate three times. The combined organic layer was washed with water three times and dried over sodium sulfate, and filtered and washed with ethyl acetate. The filtrate was concentrated and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (10:1-5:1-3:1) as an eluent to obtain the desired product as a sticky brown liquid (5.98 g), which was used directly for the next step. A solution of PPh3 (11.19 g, 42.6 mmol) and the sticky brown liquid (5.95 g) obtained in the last step in 1,2-dichlorobenzene (28.4 mL) was stirred at a temperature of 175-185° C. in oil bath and for 21 hours under nitrogen, cooled and the solvent was removed by distillation under high vacuum. The residue was purified through column chromatography on silica gel using hexane and ethyl acetate (10:1-5:1-3:1) as an eluent to obtain the desired product 2-(3-(quinolin-2-yl)phenoxy)-9H-carbazole, which was further purified through recrystallization in ethyl acetate and hexane to get pure product as a white solid (4.45 g) in 75% total yield for the four steps. 1H NMR (DMSO-d6, 400 MHz): δ 6.96 (dd, J=8.4, 2.4 Hz, 1H), 7.13 (d, J=2.4 Hz, 1H), 7.16 (d, J=7.6 Hz, 1H), 7.21 (dd, J=8.4, 2.4 Hz, 1H), 7.35 (d, J=8.0 Hz, 1H), 7.46 (d, J=8.0 Hz, 1H), 7.57-7.61 (m, 2H), 7.74-7.77 (m, 1H), 7.99-8.03 (m, 3H), 8.05-8.09 (m, 2H), 8.14 (d, J=5.6 Hz, 1H), 8.16 (d, J=5.2 Hz, 1H), 8.46 (d, J=9.2 Hz, 1H), 11.23 (s, 1H).

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