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

HRID 2085893노트

반응식

HRID 2085893 반응식
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]

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

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

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온도
130 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-309b1d1010604ec9be03c7b65f54ecaf
출처 데이터셋
uspto-grants-2004_04
특허 번호
US06720093B2

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