Cyclohexanone → 4-[(4-Bromophenyl)(cyclohexylidene)methyl]phenol

HRID 229130

반응식

HRID 229130 반응식
[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.[C:17]1(=O)[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1>O1CCCC1.[Zn].Cl[Ti](Cl)(Cl)Cl>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:17]2[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]2)[C:10]2[CH:15]=[CH:14][C:13]([OH:16])=[CH:12][CH:11]=2)=[CH:4][CH:3]=1

참가 물질

6

반응물 2

HCID 7967CyclohexanoneHCID 4570728(4-Bromophenyl)(4-hydroxyphenyl)methanone

생성물 1

HCID 686545334-[(4-Bromophenyl)(cyclohexylidene)methyl]phenol수율 95%

시약·촉매·용매 3

HCID 23994Zinc촉매HCID 24193Titanium Tetrachloride촉매HCID 8028Tetrahydrofuran용매2회

실험 절차

To a 3-neck round-bottomed flask were added zinc powder (1.96 g, 30 mmol) followed by anhydrous THF (40 mL). To the stirred suspension was slowly added, via syringe, TiCl4 (1.6 mL, 2.77 g, 14.6 mmol) at room temperature. The reaction mixture was heated at reflux with stirring under a nitrogen atmosphere for 2 h. To the refluxing reaction mixture was added a solution of (4-bromophenyl)(4-hydroxyphenyl)methanone (2) (1.1 g, 3.61 mmol) and cyclohexanone (1.1 mL, 1.04 g, 10.6 mmol) in anhydrous tetrahydrofuran (40 mL). The stirred reaction mixture was heated at reflux under a nitrogen atmosphere for 2 h. The oil bath was removed and the reaction mixture was allowed to cool to room temperature. To the reaction mixture was slowly added water (24 mL) followed by 10% aqueous K2CO3 (24 mL). The reaction mixture was filtered through a pad of Celite and the pad was washed with EtOAc. The filtrate was transferred to a separatory funnel with the aid of water and EtOAc and the layers were separated. The organic phase was washed with brine, dried over MgSO4, filtered, and the filtrate was concentrated in vacuo to give the crude product. The crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (100:0 to 60:40) to give 1.17 g (95%) of compound 6 as an off-white solid. 1H NMR (400 MHz, DMSO-d6): δ 1.52 (m, 6H), 2.12 (m, 4H), 6.65 (d, J=8.4 Hz, 2H), 6.82 (d, J=8.4 Hz, 2H), 6.97 (d, J=8.3 Hz, 2H), 7.44 (d, J=8.3 Hz, 2H), 9.32 (s, 1H). HRMS (EI) Calcd for C19H19BrO: 342.0619 (M+.). Found: 342.0627.

후처리

  1. additionTo the stirred suspension was slowly added, via syringe
  2. customat room temperature
  3. temperatureThe reaction mixture was heated
  4. temperatureat reflux
  5. customTo the refluxing reaction mixture
  6. customThe stirred reaction mixture
  7. temperaturewas heated
  8. temperatureat reflux under a nitrogen atmosphere for 2 h
  9. customThe oil bath was removed
  10. filtrationThe reaction mixture was filtered through a pad of Celite
  11. washthe pad was washed with EtOAc
  12. customThe filtrate was transferred to a separatory funnel with the aid of water and EtOAc
  13. customthe layers were separated
  14. washThe organic phase was washed with brine
  15. dry with materialdried over MgSO4
  16. filtrationfiltered
  17. concentrationthe filtrate was concentrated in vacuo
  18. customto give the crude product
  19. customThe crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (100:0 to 60:40)

출처 및 근거

ORD 기록
ord-5d80c6e657764d81a723037ef0f023a0
출처 데이터셋
uspto-grants-2009_07
특허 번호
US07560589B2

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