Iodine → 4-({3,5-Bis[(3,5-di-tert-butylphenyl)vinyl]phenyl}vinyl)toluene

HRID 495223ノート

反応式

HRID 495223 の反応式
[O-]CC.[Li+].[C:5]([C:9]1[CH:10]=[C:11]([CH:19]=[CH:20][C:21]2[CH:22]=[C:23]([CH:26]=[C:27]([CH:29]=[CH:30][C:31]3[CH:36]=[C:35]([C:37]([CH3:40])([CH3:39])[CH3:38])[CH:34]=[C:33]([C:41]([CH3:44])([CH3:43])[CH3:42])[CH:32]=3)[CH:28]=2)[CH:24]=O)[CH:12]=[C:13]([C:15]([CH3:18])([CH3:17])[CH3:16])[CH:14]=1)([CH3:8])([CH3:7])[CH3:6].[Cl-].[CH3:46][C:47]1[CH:54]=[CH:53][C:50]([CH2:51][PH3+])=[CH:49][CH:48]=1.II>C(OCC)C.C1(C)C=CC=CC=1>[C:5]([C:9]1[CH:10]=[C:11]([CH:19]=[CH:20][C:21]2[CH:22]=[C:23]([CH:24]=[CH:46][C:47]3[CH:54]=[CH:53][C:50]([CH3:51])=[CH:49][CH:48]=3)[CH:26]=[C:27]([CH:29]=[CH:30][C:31]3[CH:36]=[C:35]([C:37]([CH3:40])([CH3:39])[CH3:38])[CH:34]=[C:33]([C:41]([CH3:44])([CH3:43])[CH3:42])[CH:32]=3)[CH:28]=2)[CH:12]=[C:13]([C:15]([CH3:18])([CH3:17])[CH3:16])[CH:14]=1)([CH3:8])([CH3:7])[CH3:6]

参加物

7

反応物 4

HCID 807IodineHCID 179813694-Methylbenzylphosphonium chlorideHCID 23661847Lithium ethoxideHCID 540286873,5-Bis[2-(3,5-di-tert-butylphenyl)ethenyl]benzaldehyde

生成物 1

HCID 865927514-({3,5-Bis[(3,5-di-tert-butylphenyl)vinyl]phenyl}vinyl)toluene収率 64.4%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 3283Diethyl Ether溶媒

実験手順

Lithium ethoxide (1.0 M in ethanol, 15.0.mL, 15 mmol) was added to a stirred suspension of 3,5-bis[(3,5-di-tert-butylphenyl)vinyl]benzaldehyde (A) (WO99/9921935) (4.00 g, 7.48 mmol) and 4-methylbenzylphosphoniumchloride (8) (3.62 g, 8.98 mmol) in diethyl ether (40 mL), giving a clear orange solution which was stirred at room temperature for 2 h. The solution was washed with water (3×40 mL) and brine (40 mL), dried over anhydrous magnesium sulphate, filtered and the solvent removed, This residue was passed through a plug of silica with dichloromethane—light petroleum (1:4) as eluent to give a white solid, which was found by 1H NMR to be mainly cis isomer. The solid was heated with iodine (210 mg) and toluene (100 mL) at 100° C. under argon for 6 h and allowed to cool. The solution was washed with saturated aqueous sodium metabisulphite (50 mL) and brine (50 mL) and the solvent removed. The residue was recrystallised from a dichloromethane—hexanes mixture to leave 4-({3,5-bis[(3,5-di-tert-butylphenyl)vinyl]phenyl}vinyl)toluene (9) (3.00 g, 64%) as a white solid. δH(400 MHz, CDCl3) 1.40 (36 H, s, t-butyl), 2.39 (3 H, s, CH3), 7.13 and 7.22 (2 H, d, J 16, core vinyl H), 7.17 and 7.28 (4 H, d, J 16, branch vinyl H), 7.21 and 7.48 (4 H, AA′BB′, core phenyl H), 7.39 (2 H, dd, J 1.5, sp H), 7.43 (4 H, d, J 1.5, sp H), 7.59 (2 H, d, J 1, bp H) and 7.62 (1 H s, bp H).

後処理

  1. customgiving a clear orange solution which
  2. washThe solution was washed with water (3×40 mL) and brine (40 mL)
  3. dry with materialdried over anhydrous magnesium sulphate
  4. filtrationfiltered
  5. customthe solvent removed
  6. customto give a white solid, which
  7. temperatureto cool
  8. washThe solution was washed with saturated aqueous sodium metabisulphite (50 mL) and brine (50 mL)
  9. customthe solvent removed
  10. customThe residue was recrystallised from a dichloromethane—hexanes mixture

出典と根拠

ORDレコード
ord-e5b234f572924e66bf347b897c6d3f1b
出典データセット
uspto-grants-2009_05
特許番号
US07537842B2

反応ノート

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