Reaktion #430732

Reaktionsgleichung

4-(3-cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-(3-aminophenylethynyl)cyclohexane

4-(3-cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-(3-nitrophenylethynyl)cyclohexane

pyridinium p-toluenesulfonate

ammonium hydroxide

sodium carbonate

→

4-(3-cyclopentyloxy-4-methoxyphenyl)-4-(3-aminophenylethynyl)cyclohexan-1-one

Lösungsmittel

methanol

acetic acid

water

water

acetone

water

Water

methanol

dichloromethane

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.STIRRINGthe mixture was stirred for 0.5 h at room temperature and for 0.5 h at 45°-50°C.
2. 2
   Temperaturwas cooled to room temperature
3. 3
   workup.WAITAfter stiinng an additional 1 h
4. 4
   workup.STIRRINGstirring
5. 5
   workup.WAITwas continued for 2 h
6. 6
   FiltrationThe suspension was filtered through Celite®
7. 7
   Waschenwas washed well with dichloromethane
8. 8
   Sonstigethe extract was evaporated
9. 9
   workup.ADDITIONThe residue was diluted with dichloromethane
10. 10
    Waschenthe organic layer was washed with 5:95 ammonium hydroxide
11. 11
    Trocknenwater, was dried (potassium carbonate)
12. 12
    Sonstigewas evaporated
13. 13
    SonstigePurification by flash chromatography
14. 14
    Wascheneluting with 3:7 ethyl acetate
15. 15
    Sonstigehexanes, provided
16. 16
    Sonstigewas evaporated
17. 17
    workup.ADDITIONWater was added
18. 18
    Extraktionthe mixture was extracted three times with dichloromethane
19. 19
    Trocknenthe extract was dried (magnesium sulfate)
20. 20
    Sonstigewas evaporated
21. 21
    SonstigePurification by flash chromatography
22. 22
    Wascheneluting with 35:65 ethyl acetate

Vorschrift

To 4-(3-cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-(3-nitrophenylethynyl)cyclohexane (0.17 g, 0.35 mmol) in methanol (1 mL), acetic acid (1.2 mL) and water (1.2 mL) under an argon atmosphere was added titanium trichloride (0.3 g, 2 mmol). After stirring for 1.5 h at room temperature, titanium trichloride (0.3g, 2 mmol) and water (1.2 mL) were added, and the mixture was stirred for 0.5 h at room temperature and for 0.5 h at 45°-50°C., then was cooled to room temperature. Water (1.2 mL) and ammonium hydroxide (2.5 mL) were added. After stiinng an additional 1 h, methanol (17.5 mL), 5% sodium carbonate (17.5 mL) and dichloromethane (35 mL) were added, and stirring was continued for 2 h. The suspension was filtered through Celite®, was washed well with dichloromethane and the extract was evaporated. The residue was diluted with dichloromethane, the organic layer was washed with 5:95 ammonium hydroxide:water, was dried (potassium carbonate) and was evaporated. Purification by flash chromatography, eluting with 3:7 ethyl acetate:hexanes, provided a mixture of 4-(3-cyclopentyloxy-4-methoxyphenyl)-4-(3-anminophenylethynyl)-cyclohexan-1-one and 4-(3-cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-(3-aminophenylethynyl)cyclohexane (0.07 g). This mixture and a spatula-tip of pyridinium p-toluenesulfonate in acetone (4 mL) and water (1 mL) was refluxed for 3 days, then was evaporated. Water was added, the mixture was extracted three times with dichloromethane, the extract was dried (magnesium sulfate) and was evaporated. Purification by flash chromatography, eluting with 35:65 ethyl acetate:hexanes provided 4-(3-cyclopentyloxy-4-methoxyphenyl)-4-(3-aminophenylethynyl)cyclohexan-1-one as a colorless oil. 1H-NMR (400 MHz, CDCl3) δ 7.22 (d, J=2.2 Hz, 1H), 7.14 (m, 2H), 6.87 (m, 2H), 6.82 (d, J=2.8 Hz, 1H), 6.66 (dd, J=9.0, 2.4 Hz, 1H), 4.81 m, 1H), 3.85 (s, 3H), 3.7 (br, 2H), 3.04 (dt, J=14.3, 6.0 Hz, 2H), 2.47 (br d, J=14.6 Hz, 2H), 2.2-2.3 (m, 4), 1.8-2.0 (m, 6H), 1.61 (m, 2H).

Quelle