Hydrochloric Acid → 5-Hydroxy-2-(2-methoxyethoxy)isonicotinaldehyde

HRID 1484775Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1484775
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:8]([O:11]COC)=[CH:9][N:10]=1)[CH:6]=[O:7].Cl.[C:16]([O-])([O-])=[O:17].[K+].[K+].C1[CH2:26][O:25][CH2:24]C1>O>[OH:11][C:8]1[C:5]([CH:6]=[O:7])=[CH:4][C:3]([O:2][CH2:1][CH2:24][O:25][CH3:26])=[N:10][CH:9]=1.[OH:11][C:8]1[CH:9]=[N:10][C:3]([O:2][CH2:1][CH2:24][O:25][CH3:26])=[C:4]([CH:5]=1)[CH:16]=[O:17]

Komponenten

7

Edukt 4

HCID 313Hydrochloric AcidHCID 8028TetrahydrofuranHCID 11430Potassium CarbonateHCID 121807202-Methoxy-5-(methoxymethoxy)-4-pyridinecarboxaldehyde

Produkt 2

HCID 866907685-Hydroxy-2-(2-methoxyethoxy)isonicotinaldehydeAusbeute 60 %HCID 866907695-Hydroxy-2-(2-methoxyethoxy)nicotinaldehydeAusbeute 11 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

To a solution of 2-methoxy-5-(methoxymethoxy)isonicotinaldehyde (1.27 g, 5.29 mol) in THF (5 mL) was added HCl (3 N, 4 mL). The reaction was stirred at 50° C. for 1 h, cooled to RT, and diluted with water (5 mL). The mixture was neutralized to pH 7-8 with solid K2CO3 and the aqueous layer was extracted with EtOAc (100 mL) twice. The combined organic layers were dried over Na2SO4, concentrated, and purified on silica gel using a mixture of EtOAc and hexanes to give 5-hydroxy-2-(2-methoxyethoxy)isonicotinaldehyde (630 mg, 60%) and 5-hydroxy-2-(2-methoxyethoxy)nicotinaldehyde (120 mg, 11%). Data for 5-hydroxy-2-(2-methoxyethoxy)isonicotinaldehyde: 1H NMR (400 MHz, CDCl3) δ 9.98 (s, 1H), 9.50 (s, 1H), 8.07 (s, 1H), 7.02 (s, 1H), 4.51-4.39 (m, 2H), 3.81-3.72 (m, 2H), 3.47 (s, 3H). LRMS (M+H+) m/z 198.1. Data for and 5-hydroxy-2-(2-methoxyethoxy)nicotinaldehyde: NMR (400 MHz, CDCl3) δ 10.3 (s, 1H), 7.99 (d, J=3.2 Hz, 1H), 7.58 (d, J=3.2 Hz, 1H), 7.18-7.07 (br, 1H), 4.54 (dd, J=5.4, 3.7 Hz, 2H), 3.84 (dd, J=5.4, 3.7 Hz, 2H), 3.49 (s, 3H); MS (ESI) m/z 198.1 [M+H]+.

Aufarbeitung

  1. temperaturecooled to RT
  2. extractionthe aqueous layer was extracted with EtOAc (100 mL) twice
  3. dry with materialThe combined organic layers were dried over Na2SO4
  4. concentrationconcentrated
  5. custompurified on silica gel using
  6. additiona mixture of EtOAc and hexanes

Quellen und Nachweise

ORD-Eintrag
ord-450f55298953409caf5bc6746f8dbbf2
Quelldatensatz
uspto-grants-2016_08
Patentnummer
US09422279B2

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