Potassium Carbonate → 4-[(4-Bromophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol

HRID 229137

반응식

HRID 229137 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.[CH3:17][C:18]1([CH3:27])[CH2:23][C:22]([CH3:25])([CH3:24])[CH2:21][C:20](=O)[CH2:19]1.C([O-])([O-])=O.[K+].[K+]>C1COCC1.[Zn].Cl[Ti](Cl)(Cl)Cl>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:20]2[CH2:21][C:22]([CH3:25])([CH3:24])[CH2:23][C:18]([CH3:27])([CH3:17])[CH2:19]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 11430Potassium CarbonateHCID 843993,3,5,5-TetramethylcyclohexanoneHCID 4570728(4-Bromophenyl)(4-hydroxyphenyl)methanone

생성물 1

HCID 686543984-[(4-Bromophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol

시약·촉매·용매 3

HCID 23994Zinc촉매HCID 24193Titanium Tetrachloride촉매HCID 8028Tetrahydrofuran용매2회

실험 절차

To a stirred suspension of zinc powder (23.4 g, 0.36 mol) in THF (300 mL) was slowly added TiCl4 (20 mL, 0.18 mol) via a syringe at room temperature under a nitrogen atmosphere. The reaction mixture was heated at reflux for 1 h. A solution of (4-bromophenyl)(4-hydroxyphenyl)methanone (2) (10.0 g, 0.036 mol) and 3,3,5,5-tetramethylcyclohexanone (16.7 g, 0.108 mol) in THF (100 mL) was added to the reaction mixture. The reaction mixture was heated at reflux with stirring under a nitrogen atmosphere for an additional 2 h. The reaction mixture was allowed to cool to room temperature. To the reaction mixture was poured into a 10% aqueous K2CO3 (1 L). 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 and the layers were separated. The aqueous phase was further extracted with EtOAc (4×250 mL). The combined organic phase was washed with brine (2×100 mL), dried (Na2SO4), filtered, and then filtrate was concentrated under reduced pressure to give the crude product as a gold-yellow oil. The crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (100:0 to 1:1) as an eluent to afford 10.45 g (73%) of compound 14 as a white solid. 1H NMR (300 MHz, CDCl3): δ 0.91 (s, 6H), 0.95 (s, 6H), 1.31 (s, 2H), 1.96 (s, 2H), 1.99 (s, 2H), 4.67 (s, 1H), 6.76 (d, J=8.7 Hz, 2H), 7.03 (d, J=6.0 Hz, 2H), 7.05 (d, J=6.0 Hz, 2H), 7.41(d, J=8.4 Hz, 2H). HRMS (EI) Calcd for C23H27BrO: 398.1245 (M+.). Found: 398.1248.

후처리

  1. customat room temperature
  2. temperatureThe reaction mixture was heated
  3. temperatureat reflux for 1 h
  4. temperatureThe reaction mixture was heated
  5. temperatureat reflux
  6. filtrationThe reaction mixture was filtered through a pad of Celite
  7. washthe pad was washed with EtOAc
  8. customThe filtrate was transferred to a separatory funnel
  9. customthe layers were separated
  10. extractionThe aqueous phase was further extracted with EtOAc (4×250 mL)
  11. washThe combined organic phase was washed with brine (2×100 mL)
  12. dry with materialdried (Na2SO4)
  13. filtrationfiltered
  14. concentrationfiltrate was concentrated under reduced pressure

출처 및 근거

ORD 기록
ord-af5be7b3a87c4fc182e384a39ba47574
출처 데이터셋
uspto-grants-2009_07
특허 번호
US07560589B2

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