Water → 4-[(4-Bromophenyl)(tetrahydro-4H-thiopyran-4-ylidene)methyl]phenol

HRID 2100049

Reaktionsgleichung

Reaktionsgleichung von HRID 2100049
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[CH:15]=[CH:14][C:13]([OH:16])=[CH:12][CH:11]=2)=O)=[CH:4][CH:3]=1.[S:17]1[CH2:22][CH2:21][C:20](=O)[CH2:19][CH2:18]1.O.C([O-])([O-])=O.[K+].[K+]>C1COCC1.Cl[Ti](Cl)(Cl)Cl.[Zn]>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:20]2[CH2:21][CH2:22][S:17][CH2:18][CH2:19]2)[C:10]2[CH:15]=[CH:14][C:13]([OH:16])=[CH:12][CH:11]=2)=[CH:4][CH:3]=1

Komponenten

8

Edukt 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 66173Tetrahydrothiopyran-4-oneHCID 4570728(4-Bromophenyl)(4-hydroxyphenyl)methanone

Produkt 1

HCID 686544294-[(4-Bromophenyl)(tetrahydro-4H-thiopyran-4-ylidene)methyl]phenolAusbeute 71 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 23994ZincKatalysatorHCID 24193Titanium TetrachlorideKatalysatorHCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

In a 3-neck round-bottomed flask equipped with a condenser and a nitrogen inlet, TiCl4 (0.51 mL, 4.67 mmol) was slowly added to a suspension of zinc powder (0.63 g, 9.60 mmol) in anhydrous THF (13 mL) at room temperature. The reaction was heated at reflux for 2.5 h. The reaction was taken out of the oil bath then a solution of (4-bromophenyl)(4-hydroxyphenyl)methanone (2)(0.35 g, 1.26 mmol) and tetrahydrothiopyran-4-one (0.44 g, 3.79 mmol) in anhydrous THF (13 mL) was added and the reaction mixture was heated at reflux for 2 h. The reaction mixture was cooled to room temperature and water (10 mL) added, via syringe, followed by addition of 10% aqueous K2CO3 (10 mL). The reaction mixture was filtered through a pad of Celite and the pad washed with EtOAc. The filtrate was transferred to a separatory funnel and the layers were separated. The organic layer washed with brine, dried (MgSO4), filtered, and the filtrate was concentrated to give an oil. The crude product was purified by flash column chromatography on silica gel using a hexanes:EtOAc gradient (100:0 to 75:25) to give compound 36 as a white powder (0.323 g, 71%). 1H NMR (400 MHz, DMSO-d6): δ 2.38-2.41 (m, 2H), 2.45-2.47 (m, 2H), 2.62-2.66 (m, 4H), 6.67 (d, J=8.5 Hz, 2H), 6.86 (d, J=8.5 Hz, 2H), 7.01 (d, J=8.2 Hz, 2H), 7.47 (d, J=8.3 Hz, 2H), 9.39 (s, 1H).

Aufarbeitung

  1. customIn a 3-neck round-bottomed flask equipped with a condenser and a nitrogen inlet
  2. temperatureThe reaction was heated
  3. temperatureat reflux for 2.5 h
  4. temperaturethe reaction mixture was heated
  5. temperatureat reflux for 2 h
  6. filtrationThe reaction mixture was filtered through a pad of Celite
  7. washthe pad washed with EtOAc
  8. customThe filtrate was transferred to a separatory funnel
  9. customthe layers were separated
  10. washThe organic layer washed with brine
  11. dry with materialdried (MgSO4)
  12. filtrationfiltered
  13. concentrationthe filtrate was concentrated
  14. customto give an oil
  15. customThe crude product was purified by flash column chromatography on silica gel using a hexanes

Quellen und Nachweise

ORD-Eintrag
ord-796265d408304dca9aab63af5d636bbf
Quelldatensatz
uspto-grants-2009_08
Patentnummer
US07569601B2

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