2-Bromo-3,4,5-trimethoxybenzaldehyde → 2,6'-Diformyl-4,2',3',4'-tetramethoxybiphenyl-3-yl methanesulfonate

HRID 1925091Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1925091
Br[C:2]1[C:9]([O:10][CH3:11])=[C:8]([O:12][CH3:13])[C:7]([O:14][CH3:15])=[CH:6][C:3]=1[CH:4]=[O:5].[CH3:16][S:17]([O:20][C:21]1[C:26]([O:27][CH3:28])=[CH:25][CH:24]=[C:23](Br)[C:22]=1[CH:30]=[O:31])(=[O:19])=[O:18]>CN(C=O)C.C(OCC)(=O)C.[Cu]>[CH3:16][S:17]([O:20][C:21]1[C:22]([CH:30]=[O:31])=[C:23]([C:2]2[C:3]([CH:4]=[O:5])=[CH:6][C:7]([O:14][CH3:15])=[C:8]([O:12][CH3:13])[C:9]=2[O:10][CH3:11])[CH:24]=[CH:25][C:26]=1[O:27][CH3:28])(=[O:19])=[O:18]

Komponenten

6

Edukt 2

HCID 7780032-Bromo-3,4,5-trimethoxybenzaldehyde2×HCID 866380403-Bromo-2-formyl-6-methoxyphenyl methanesulfonate2×

Produkt 1

HCID 866380392,6'-Diformyl-4,2',3',4'-tetramethoxybiphenyl-3-yl methanesulfonateAusbeute 44 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 23978CopperKatalysatorHCID 6228DimethylformamideLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
165 °C

Versuchsvorschrift

To a suspension of copper bronze (0.646 g, 10 mmol) in anhydrous DMF (2 mL) was added a solution of 2-bromo-3,4,5-trimethoxybenzaldehyde (0.80 g, 2.91 mmol) and 3-bromo-2-formyl-6-methoxyphenyl methanesulfonate (0.30 g, 0.97 mmol) in anhydrous DMF (1 mL) and the suspension was stirred at 165° C. for 3 hours. TLC indicated the presence of unreacted 3-bromo-2-formyl-6-methoxyphenyl methanesulfonate and a further portion of 2-bromo-3,4,5-trimethoxybenzaldehyde (100 mg) was added. After a further 1 hour at 165° C. the reaction was complete and the reaction mixture was cooled and diluted with ethyl acetate (20 mL). The resulting suspension was filtered through Celite® (3 g) and the filtrate concentrated in vacuo. The residue was chromatographed over silica gel (70 g), eluting with hexane-ethyl acetate (gradient 2:1 to 1:1), followed by crystallisation (ethyl acetate) yielded 2,6′-diformyl-4,2′,3′,4′-tetramethoxybiphenyl-3-yl methanesulfonate (180 mg, 44%); m.p. 130-131° C.; Elemental Analysis Found: C, 53.7; H, 4.8; S, 7.8 (C19H20O9S requires C, 53.77; H, 4.75; S, 7.56%); NMR Spectrum δH (300 MHz, CDCl3) 10.18 (1H, s, 2-CHO), 9.63 (1H, s, 6′-CHO), 7.36 (1H, s, 5′-H), 7.26 (1H, d, J 8.4 Hz, 6-H), 7.15 (1H, d, J 8.4 Hz, 5-H), 4.03 (3H, s, OCH3), 3.98 (3H, s, OCH3), 3.57 (3H, s, OCH3), 3.43 (3H, s, SCH3); NMR Spectrum δC (100 MHz, CDCl3) 50.2, 56.5, 56.9, 61.2, 61.5, 106.2, 116.8, 127.5, 130.0, 130.7, 131.0, 132.1, 139.8, 147.6, 151.1, 152.6, 154.0, 189.3, 190.5; νmax/cm−1 (thin film) 2934, 2843, 1701, 1682, 1588, 1561, 1480, 1371, 1336, 1285, 1169, 1111, 1072; m/z (ES) 447 (MNa+, 100%), 379 (5); Rf (hexane-ethyl acetate 1:2) 0.20.

Aufarbeitung

  1. waitAfter a further 1 hour at 165° C. the reaction was complete
  2. temperaturethe reaction mixture was cooled
  3. filtrationThe resulting suspension was filtered through Celite® (3 g)
  4. concentrationthe filtrate concentrated in vacuo
  5. customThe residue was chromatographed over silica gel (70 g)
  6. washeluting with hexane-ethyl acetate (gradient 2:1 to 1:1)
  7. customfollowed by crystallisation (ethyl acetate)

Quellen und Nachweise

ORD-Eintrag
ord-9a81f1660c944904a0d61a899e1b7eef
Quelldatensatz
uspto-grants-2012_05
Patentnummer
US08178578B2

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