Water → 4-[(4-Bromophenyl)(cyclopentylidene)methyl]phenol

HRID 229127

반응식

HRID 229127 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)[CH2:21][CH2:20][CH2:19][CH2:18]1.O>C1COCC1.[Zn].Cl[Ti](Cl)(Cl)Cl>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:17]2[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

7

반응물 3

HCID 962WaterHCID 8452CyclopentanoneHCID 4570728(4-Bromophenyl)(4-hydroxyphenyl)methanone

생성물 1

HCID 686545024-[(4-Bromophenyl)(cyclopentylidene)methyl]phenol수율 81%

시약·촉매·용매 3

HCID 23994Zinc촉매HCID 24193Titanium Tetrachloride촉매HCID 8028Tetrahydrofuran용매2회

실험 절차

To a stirred suspension of zinc powder (0.71 g, 10.9 mmoL) in anhydrous THF (15 mL) was slowly added, via syringe, TiCl4 (0.58 mL, 1.0 g, 5.3 mmoL) at RT under a nitrogen atmosphere. The stirred reaction mixture was heated at reflux under a nitrogen atmosphere for 2.5 h. To the refluxing reaction mixture was added a solution of (4-bromophenyl)(4-hydroxyphenyl)methanone (2) (0.408 g, 1.47 mmol) and cyclopentanone (0.38 mL, 0.36 g, 4.3 mmol) in THF (15 mL) and heating continued an additional 2 h. The reaction mixture was allowed to cool to room temperature and water (10 mL) slowly added. The reaction mixture was then filtered through a pad of Celite and the Celite pad washed with EtOAc. The filtrate was transferred to a separatory funnel and the organic layer was separated. The organic phase was washed with brine, dried (MgSO4), filtered, and the filtrate 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 0.391 g (81%) of compound 3 as a pale yellow solid. 1H NMR (400 MHz, DMSO-d6): δ 1.59 (m, 4H), 2.27 (m, 4H), 6.66 (d, J=8.5 Hz, 2H), 6.89 (d, J=8.4 Hz, 2H), 7.04 (d, J=8.4 Hz, 2H), 7.45 (d, J=8.4 Hz, 2H), 9.32 (s, 1H). HRMS (EI) Calcd for C18H17BrO: 328.0463 (M+.). Found: 328.0469.

후처리

  1. additionwas slowly added, via syringe
  2. customat RT
  3. customThe stirred reaction mixture
  4. temperaturewas heated
  5. temperatureat reflux under a nitrogen atmosphere for 2.5 h
  6. customTo the refluxing reaction mixture
  7. temperatureheating
  8. filtrationThe reaction mixture was then filtered through a pad of Celite
  9. washthe Celite pad washed with EtOAc
  10. customThe filtrate was transferred to a separatory funnel
  11. customthe organic layer was separated
  12. washThe organic phase was washed with brine
  13. dry with materialdried (MgSO4)
  14. filtrationfiltered
  15. concentrationthe filtrate concentrated in vacuo
  16. customto give the crude product
  17. 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-c9465aac4d184dea9d4244b21f041d30
출처 데이터셋
uspto-grants-2009_07
특허 번호
US07560589B2

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