2-Vinylpyridine → 4-Chloro-2-[2-(pyridin-2-yl)vinyl]benzyloxybenzene

HRID 1276338Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1276338
Br[C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[CH:17]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][N:20]=1)=[CH2:18].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C([O-])(=O)C.[Na+]>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(Cl)Cl.CCCCC>[Cl:8][C:6]1[CH:5]=[CH:4][C:3]([O:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[C:2]([CH:18]=[CH:17][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][N:20]=2)[CH:7]=1

Komponenten

8

Edukt 4

HCID 75212-VinylpyridineHCID 80271Tri-o-tolylphosphineHCID 517045Sodium AcetateHCID 115511251-(Benzyloxy)-2-bromo-4-chlorobenzene

Produkt 1

HCID 540628024-Chloro-2-[2-(pyridin-2-yl)vinyl]benzyloxybenzeneAusbeute 58 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 6228DimethylformamideLösungsmittelHCID 21877063Dichloromethane pentaneLösungsmittel

Versuchsvorschrift

124.4 g (417.8 mmol) of 2-Bromo-4-chlorobenzyloxybenzene, 54.8 ml (501.4 mmol) of 2-vinylpyridine, 4.69 g (20.9 mmol) palladium acetate, 25.4 g (83.6 mmol) tritolylphosphine, and 48 g (584.9 mmol) sodium acetate are heated together in 200 ml DMF at 165° C. (oil bath temperature) under nitrogen for 8 hours. The cooled mixture is evaporated to dryness in vacuo. The residue is then diluted with Et2O:DCM (3:1, 1 L) and washed with sodium carbonate solution (1M, 3×1 L). The aqueous washings are extracted with Et2O:DCM (3:1, 1L) and the combined organic extract dried using MgSO4, filtered through celite, and evaporated to dryness to leave an orange solid. Flash chromatography (SiO2, DCM:pentane 3:1) gave a yellow solid which was triturated with pentane (600 ml) to give the title compound as a pale yellow solid (77.5 g, 58%), m.p. 105.2-105.8° C. 6H (250 MHz, CDCl3) 8.60 (d, J=4.5 Hz, 1H), 7.96 (d, J=16.3 Hz, 1H), 7.64-7.60 (m, 2H), 7.46-7.34 (m, 7H), 7.24 (d, J=16.6 Hz, 1H), 7.18-7.11 (m, 1H), 6.95 (d, J=8.9 Hz, 1H), 5.16 (s, 2H).

Aufarbeitung

  1. customThe cooled mixture is evaporated to dryness in vacuo
  2. additionThe residue is then diluted with Et2O:DCM (3:1, 1 L)
  3. washwashed with sodium carbonate solution (1M, 3×1 L)
  4. extractionThe aqueous washings are extracted with Et2O:DCM (3:1, 1L)
  5. extractionthe combined organic extract
  6. customdried
  7. filtrationfiltered through celite
  8. customevaporated to dryness
  9. customto leave an orange solid
  10. customwas triturated with pentane (600 ml)

Quellen und Nachweise

ORD-Eintrag
ord-606a043451e840bbaf4829b273cbc08c
Quelldatensatz
uspto-grants-2000_12
Patentnummer
US06166041

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