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

HRID 2085893Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2085893
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]

Komponenten

7

Edukt 4

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

Produkt 1

HCID 536686613,5-Bis[3',5'-bis(3'',5-''-di-t-butylstyryl)styryl]benzaldehydeAusbeute 277,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

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

Reaktionsbedingungen

Temperatur
130 °C

Versuchsvorschrift

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; CDCl3) 1.41 (72 H, s, t-Bu), 7.20 and 7.32 (8 H, d, J 16, G-2 vinyl H), 7.34 and 7.38 (4 H, d, J 16.5, G-1 vinyl H), 7.42 (4 H, dd, J 2, sp H), 7.46 (8 H, d, J 2, sp H), 7.67 (4 H, s, G-1 bp H), 7.69 (2 H, s, G-1 bp H), 8.00 (3 H, s, cp H) and 10.14 (1 H, s, CHO) which is identical to that reported.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-309b1d1010604ec9be03c7b65f54ecaf
Quelldatensatz
uspto-grants-2004_04
Patentnummer
US06720093B2

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