Sodium Carbonate → 3,5-Bis[3',5'-bis(3'',5-''-di-t-butylstyryl)styryl]benzaldehyde

HRID 411934Notes

Reaction equation

HRID 411934 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[C:8](Br)[CH:9]=1)[CH:5]=O.[C:11]([C:15]1[CH:16]=[C:17]([CH:44]=[C:45]([C:47]([CH3:50])([CH3:49])[CH3:48])[CH:46]=1)[CH:18]=[CH:19][C:20]1[CH:21]=[C:22]([CH:25]=[C:26]([CH:28]=[CH:29][C:30]2[CH:35]=[C:34]([C:36]([CH3:39])([CH3:38])[CH3:37])[CH:33]=[C:32]([C:40]([CH3:43])([CH3:42])[CH3:41])[CH:31]=2)[CH:27]=1)[CH:23]=[CH2:24])([CH3:14])([CH3:13])[CH3:12].[C:51](=[O:54])([O-])[O-].[Na+].[Na+].[C:57]([C:61]1(C)[C:66](O)=[C:65](C(C)(C)C)[CH:64]=[CH:63][CH2:62]1)([CH3:60])([CH3:59])[CH3:58]>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:36]([C:34]1[CH:35]=[C:30]([CH:31]=[C:32]([C:40]([CH3:43])([CH3:42])[CH3:41])[CH:33]=1)[CH:29]=[CH:28][C:26]1[CH:25]=[C:22]([CH:21]=[C:20]([CH:19]=[CH:18][C:17]2[CH:44]=[C:45]([C:47]([CH3:50])([CH3:49])[CH3:48])[CH:46]=[C:15]([C:11]([CH3:14])([CH3:12])[CH3:13])[CH:16]=2)[CH:27]=1)[CH:23]=[CH:24][C:2]1[CH:9]=[C:8]([CH:7]=[C:4]([CH:5]=[CH:23][C:22]2[CH:25]=[C:26]([CH:28]=[CH:29][C:63]3[CH:62]=[C:61]([C:57]([CH3:60])([CH3:58])[CH3:59])[CH:66]=[C:65]([C:32]([CH3:40])([CH3:33])[CH3:31])[CH:64]=3)[CH:27]=[C:20]([CH:19]=[CH:18][C:17]3[CH:16]=[C:15]([C:11]([CH3:14])([CH3:13])[CH3:12])[CH:46]=[C:45]([C:47]([CH3:50])([CH3:49])[CH3:48])[CH:44]=3)[CH:21]=2)[CH:3]=1)[CH:51]=[O:54])([CH3:37])([CH3:39])[CH3:38]

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 6220773,5-DibromobenzaldehydeHCID 538517063,5-Bis(3',5'-di-t-butylstyryl)styreneHCID 666371922,6-Di-t-butylcresol

Product 1

HCID 536686613,5-Bis[3',5'-bis(3'',5-''-di-t-butylstyryl)styryl]benzaldehydeYield 277.7%

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 (8.21 g, 31.1 mmoles), 3,5-bis(3′,5′-di-t-butylstyryl)styrene (41.4 g, 77.7 mmoles), anhydrous sodium carbonate (6.59 g, 62.2 mmoles), trans-di(μ-acetato)-bis[o-(di-o-tolylphosphino)benzyl]dipalladium (II) (58.3 mg, 0.062 mmoles, 0.1 mole %), 2,6-di-t-butylcresol (1.71 g, 7.77 mmoles) and anhydrous N,N-dimethylacetamide (100 mL) was degassed extremely thoroughly whilst stirring under oil-pump vacuum, purging with argon. The reaction mixture was then heated under argon at 130° C. for 17 hours. After further addition of anhydrous N,N-dimethylacetamide (100 mL), the reaction mixture was degassed for a second time and then heated at 130° C. for a further 5.5 hours. Further anhydrous N,N-dimethylacetamide (100 mL) was then added and the reaction was continued for a further 1 hour. The resulting sludge was washed with distilled water (3×250 mL) and dissolved in dichloromethane (1500 mL). The organic fraction was washed with distilled water (500 mL), dried over anhydrous sodium sulphate and evaporated to give a cream solid. The crude product was recrystallized from dichloromethane/pet. ether (60-80) three times before chromatography on flash silica using chloroform-pet.ether (60-80) (2:3) as the eluent gave a white solid of 3,5-bis[3′,5′-bis(3″,5-″-di-t-butylstyryl)styryl]benzaldehyde (25.2 g, 69%); δH(500 MHz; CDCl1) 1.41 (72H, s, t-Bu), 7.20 and 7.32 (8H, d, J 16, G-2 vinyl H), 7.34 and 7.38 (4H, d, J 16.5, G-1 vinyl H), 7.42 (4H, dd, J 2, sp H), 7.46 (8H, d, J 2, sp H), 7.67 (4H, s, G-1 bp H), 7.69 (2H, s, G-1 bp H), 8.00 (3H, s, cp H) and 10.14 (1H, s, CHO) which is identical to that reported.

Workup

  1. customwas degassed extremely thoroughly
  2. custompurging with argon
  3. additionAfter further addition of anhydrous N,N-dimethylacetamide (100 mL)
  4. customthe reaction mixture was degassed for a second time
  5. temperatureheated at 130° C. for a further 5.5 hours
  6. additionFurther anhydrous N,N-dimethylacetamide (100 mL) was then added
  7. washThe resulting sludge was washed with distilled water (3×250 mL)
  8. dissolutiondissolved in dichloromethane (1500 mL)
  9. washThe organic fraction was washed with distilled water (500 mL)
  10. dry with materialdried over anhydrous sodium sulphate
  11. customevaporated
  12. customto give a cream solid
  13. customThe crude product was recrystallized from dichloromethane/pet. ether (60-80) three times before chromatography on flash silica

Sources & evidence

ORD record
ord-07338c8d96594366b8420fa9e2c96ea7
Source dataset
uspto-grants-2003_05
Patent number
US06558818B1

Reaction notes

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