Cycloheptanone → 4,4'-(Cycloheptylidenemethylene)diphenol

HRID 229260

反応式

HRID 229260 の反応式
[OH: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)[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1.C([O-])([O-])=O.[K+].[K+]>C1COCC1.[Zn].Cl[Ti](Cl)(Cl)Cl>[C:17]1(=[C:8]([C:10]2[CH:15]=[CH:14][C:13]([OH:16])=[CH:12][CH:11]=2)[C:5]2[CH:6]=[CH:7][C:2]([OH:1])=[CH:3][CH:4]=2)[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1

参加物

7

反応物 3

HCID 10400CycloheptanoneHCID 11430Potassium CarbonateHCID 691504,4'-Dihydroxybenzophenone

生成物 1

HCID 115874204,4'-(Cycloheptylidenemethylene)diphenol

試薬・触媒・溶媒 3

HCID 23994Zinc触媒HCID 24193Titanium Tetrachloride触媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a stirred suspension of zinc powder (15.0 g, 0.23 mol) in THF (300 mL) was slowly added TiCl4 (12.5 mL, 0.115 mol) via a syringe at room temperature under a nitrogen atmosphere. The reaction mixture was heated at reflux for 1 h. A solution of bis(4-hydroxyphenyl)methanone (4.9 g, 0.023 mol) and cycloheptanone (7.74 g, 0.07 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. 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 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 50:50) as an eluent to afford 6.75 g (99%) of the title compound 189 as a white solid. 1H NMR (DMSO-d6): δ 9.21 (s, 2H), 6.84 (d, J=6.3 Hz, 4H), 6.63 (d, J=6.3 Hz, 4H), 2.19 (br s, 4H), 1.48 (br s, 8H). LCMS (ESI): m/z 294 (M+H)+.

後処理

  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. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-049324f85a98486aafdf7c4499e05084
出典データセット
uspto-grants-2009_07
特許番号
US07560589B2

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