Cyclohexanone → 4-[(4-Bromo-3-methylphenyl)(cyclohexylidene)methyl]phenol

HRID 229179ノート

反応式

HRID 229179 の反応式
[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][C:3]=1[CH3:17].[C:18]1(=O)[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]1>C1COCC1.[Ti](Cl)(Cl)(Cl)Cl.[Zn]>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:18]2[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]2)[C:10]2[CH:15]=[CH:14][C:13]([OH:16])=[CH:12][CH:11]=2)=[CH:4][C:3]=1[CH3:17]

参加物

6

反応物 2

HCID 7967CyclohexanoneHCID 68654843(4-Bromo-3-methylphenyl)(4-hydroxyphenyl)methanone

生成物 1

HCID 686545224-[(4-Bromo-3-methylphenyl)(cyclohexylidene)methyl]phenol収率 85%

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

Titanium tetrachloride (2.70 mL, 24.5 mmol) was added dropwise to a suspension of zinc powder (3.24 g, 49.5 mmol) in anhydrous THF (60 mL) at RT. After refluxing for 1 h, a mixture of 66 (1.78 g, 6.11 mmol) and cyclohexanone (1.80 g, 18.3 mmol) dissolved in THF (20 mL) was added dropwise. Refluxing was continued for 30 min. The reaction mixture was cooled to RT and filtered through Celite. Water (250 mL) was added and the mixture was extracted with Et2O (3×100 mL). The combined ethereal extracts were washed with water (200 mL), brine (200 mL), and dried over MgSO4. Concentration followed by flash chromatography (20:1 to 5:1 hexanes:EtOAc) afforded 1.85 g (85%) of 67 as an orange solid. 1H NMR (400 MHz, CDCl3): δ 1.58 (m, 6H), 2.20 (m, 4H), 2.32 (s, 3H), 5.95 (br s, 1H), 6.73 (d, J=8.4 Hz, 2H), 6.79 (dd, J=8.1 Hz, 2.0 Hz, 1H), 6.95 (m, 3H), 7.40 (d, J=8.1 Hz, 1H).

後処理

  1. temperatureAfter refluxing for 1 h
  2. additionwas added dropwise
  3. temperatureRefluxing
  4. filtrationfiltered through Celite
  5. additionWater (250 mL) was added
  6. extractionthe mixture was extracted with Et2O (3×100 mL)
  7. washThe combined ethereal extracts were washed with water (200 mL), brine (200 mL)
  8. dry with materialdried over MgSO4
  9. concentrationConcentration

出典と根拠

ORDレコード
ord-d5899242af304aa981aed3fababa5a74
出典データセット
uspto-grants-2009_07
特許番号
US07560589B2

反応ノート

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