Sodium Carbonate → 3,5-Bis[2-(3,5-di-tert-butylphenyl)ethenyl]benzaldehyde

HRID 411933Notes

Reaction equation

HRID 411933 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[C:8](Br)[CH:9]=1)[CH:5]=[O:6].[C:11]([C:15]1[CH:16]=[C:17]([CH:20]=[C:21]([C:23]([CH3:26])([CH3:25])[CH3:24])[CH:22]=1)[CH:18]=[CH2:19])([CH3:14])([CH3:13])[CH3:12].[C:27](=O)([O-])[O-].[Na+].[Na+].[C:33]([C:37]1([CH3:48])[C:42](O)=[C:41]([C:44]([CH3:47])([CH3:46])[CH3:45])[CH:40]=[CH:39][CH2:38]1)([CH3:36])([CH3:35])[CH3:34]>CC1C(P(C2C([CH2-])=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1.CC1C(P(C2C([CH2-])=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1.CC(O)=O.CC(O)=O.[Pd].[Pd].CN(C)C(=O)C>[C:11]([C:15]1[CH:16]=[C:17]([CH:20]=[C:21]([C:23]([CH3:26])([CH3:25])[CH3:24])[CH:22]=1)[CH:18]=[CH:19][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([CH:27]=[CH:38][C:39]2[CH:48]=[C:37]([C:33]([CH3:36])([CH3:35])[CH3:34])[CH:42]=[C:41]([C:44]([CH3:46])([CH3:45])[CH3:47])[CH:40]=2)[CH:9]=1)[CH:5]=[O:6])([CH3:14])([CH3:12])[CH3:13]

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 6220773,5-DibromobenzaldehydeHCID 109219283,5-Di-t-butylstyreneHCID 666371922,6-Di-t-butylcresol

Product 1

HCID 540286873,5-Bis[2-(3,5-di-tert-butylphenyl)ethenyl]benzaldehydeYield 139%

Reagents, catalysts & solvents 2

HCID 11104995trans-Bis(acetato)bis[2-[bis(2-methylphenyl)phosphino]benzyl]dipalladium(II)CatalystHCID 31374DimethylacetamideSolvent

Conditions

Temperature
130 °C

Procedure

A mixture of 3,5-dibromobenzaldehyde (31.7 g, 120 mmoles), 3,5-di-t-butylstyrene (65.0 g, 301 mmoles), anhydrous sodium carbonate (31.9 g, 301 mmoles), trans-di(μ-acetato)-bis[o-(di-o-tolylphosphino)benzyl]dipalladium (II) (244 mg, 0.26 mmoles, 0.1 mole %), 2,6-di-t-butylcresol (13.3 g, 60 mmoles) and anhydrous N,N-dimethylacetamide (130 mL) was degassed thoroughly whilst stirring under oil-pump vacuum, purging with argon. The reaction mixture was then heated under argon at 130° C. for 26.5 h. After cooling, ether (250 mL) and hydrochloric acid (1.5 M, 150 mL) were added carefully. A suspension remained in the organic layer, which was washed with distilled water (5×125 mL) and evaporated. The combined aqueous layers were extracted with ether (100 mL) and this organic extract was washed with distilled water (4×30 mL) and combined with the main organic fraction. The crude product was triturated thoroughly with cold pet. ether (40-60), filtered and recrystallized from dichloromethane/pet. ether (60-80) to give colourless crystals of 3,5-bis(3′,5′-di-t-butylstyryl)benzaldehyde (44.61 g, 69%), m.p. 217-219° C. (Found: C, 87.7; H, 9.7. C39H50O requires C, 87.6; H, 9.4%); νmax (CHCl3)/cm−1 1698s (C═O), 1596s (C═C) and 964s (C═C—H trans); λmax (CHCl3)/nm 316 (log ε/dm3 mol−1 cm−1 4.65); δH(500 MHz; CDCl3) 1.41 (36H, s, t-Bu), 7.20 and 7.34 (4H, d, J 16, vinyl H), 7.43 (2H, dd, J 2, sp H), 7.44 (4H, d, J 2, sp H), 7.94 (1H, m, cp H), 7.95 (2H, d, J 1.5, cp H) and 10.11 (1H, s, CHO); m/z (APCI+) 535 (M+, 100%).

Workup

  1. customwas degassed thoroughly
  2. custompurging with argon
  3. temperatureAfter cooling
  4. additionether (250 mL) and hydrochloric acid (1.5 M, 150 mL) were added carefully
  5. washwas washed with distilled water (5×125 mL)
  6. customevaporated
  7. extractionThe combined aqueous layers were extracted with ether (100 mL)
  8. extractionthis organic extract
  9. washwas washed with distilled water (4×30 mL)
  10. customThe crude product was triturated thoroughly with cold pet. ether (40-60)
  11. filtrationfiltered
  12. customrecrystallized from dichloromethane/pet. ether (60-80)

Sources & evidence

ORD record
ord-b913bc42de764caf8350632e43ba52ca
Source dataset
uspto-grants-2003_05
Patent number
US06558818B1

Reaction notes

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