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

HRID 495223Notes

Reaction equation

HRID 495223 reaction equation
[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]

Participants

7

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-e5b234f572924e66bf347b897c6d3f1b
Source dataset
uspto-grants-2009_05
Patent number
US07537842B2

Reaction notes

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