1,2-Dimethoxyethane → 2-Hydroxy-4-(2-methoxypyridin-3-yl)benzaldehyde

HRID 470362

Reaktionsgleichung

Reaktionsgleichung von HRID 470362
NC1C=C(N2CCN(C)CC2)C=CC=1N.[CH3:16][O:17][C:18]1[C:23]([C:24]2[CH:48]=[CH:47][C:27]3NC(C4NC5C=CC(N6CCN(C)CC6)=CC=5N=4)=N[C:26]=3[CH:25]=2)=[CH:22][CH:21]=[CH:20][N:19]=1.[C:49](=O)([O-])[O-:50].[Na+].[Na+].C[O:56]CCOC>O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[OH:56][C:26]1[CH:25]=[C:24]([C:23]2[C:18]([O:17][CH3:16])=[N:19][CH:20]=[CH:21][CH:22]=2)[CH:48]=[CH:47][C:27]=1[CH:49]=[O:50]

Komponenten

7

Edukt 4

HCID 80711,2-DimethoxyethaneHCID 10340Sodium CarbonateHCID 27635454-(4-Methylpiperazino)-1,2-benzenediamineHCID 178494094HCID 178494094, Verbindung

Produkt 1

HCID 597844602-Hydroxy-4-(2-methoxypyridin-3-yl)benzaldehyde

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

Pd(PPh3)4 (9 g, 0.008 mol) was added to a degassed suspension of 4-bromo-2-hydroxybenzaldehyde (5, 34.2 g, 0.17 mol), 2-methoxypyridine-3-boronic acid (6, 28.5 g, 0.186 mol) and sodium carbonate (18.5 g) in 1,2-dimethoxyethane (420 mL) and water (140 mL) and heated at 80° C. for 16 h. The reaction mixture was cooled to room temperature and filtered through Celite. Celite was washed with chloroform (2×200 mL) and water (200 mL). The organic layer was separated and concentrated in vacuo to a residue which was re-crystallized from EtOAc/hexanes to obtain the desired 2-hydroxy-4-(2-methoxypyridin-3-yl)benzaldehyde (7a) after isolation by filtration (16.25 g). The filtrate from the recrystallization process was evaporated to dryness and the residue purified by flash chromatography (15% EtOAc/hexanes) to obtain the desired 2-hydroxy-4-(2-methoxypyridin-3-yl)benzaldehyde (11.87 g) in an overall yield of 28.12 g (72%). 1H NMR (C6D6) δ 11.06 (s, 1H), 9.95 (s, 1H), 8.18 (dd, J=4.98 Hz, 1.83 Hz, 1H), 7.29-7.71 (m, 2H), 7.60 (dd, J=7.29 Hz, 1.83 Hz, 1H), 7.08-6.96 (m, 2H), 3.99 (s, 3H).

Aufarbeitung

  1. temperatureThe reaction mixture was cooled to room temperature
  2. filtrationfiltered through Celite
  3. washCelite was washed with chloroform (2×200 mL) and water (200 mL)
  4. customThe organic layer was separated
  5. concentrationconcentrated in vacuo to a residue which
  6. customwas re-crystallized from EtOAc/hexanes

Quellen und Nachweise

ORD-Eintrag
ord-04601a0abf30400ea941fd56c3c87aed
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08629147B2

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