Hexamethylenetetramine → 6-Chloro-5-fluoropyridine-3-carbaldehyde

HRID 2075170

Reaktionsgleichung

Reaktionsgleichung von HRID 2075170
Br[CH2:2][C:3]1[CH:4]=[C:5]([F:10])[C:6]([Cl:9])=[N:7][CH:8]=1.C1N2CN3CN(C2)CN1C3.C([O-])(O)=[O:22].[Na+]>C(O)(=O)C.O>[Cl:9][C:6]1[C:5]([F:10])=[CH:4][C:3]([CH:2]=[O:22])=[CH:8][N:7]=1

Komponenten

6

Edukt 3

HCID 4101HexamethylenetetramineHCID 516892Sodium BicarbonateHCID 592970785-(Bromomethyl)-2-chloro-3-fluoropyridine

Produkt 1

HCID 216981946-Chloro-5-fluoropyridine-3-carbaldehyde

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 176Acetic AcidLösungsmittelHCID 962WaterLösungsmittel

Versuchsvorschrift

A mixture of 5-(bromomethyl)-2-chloro-3-fluoropyridine (2.0 g, 8.91 mmol) and hexamethylenetetramine (2.75 g, 19.6 mmol) in 50% aqueous acetic acid (53 ml) was heated to reflux. After 1 hour, the mixture was cooled to room temperature, neutralized carefully with solid NaHCO3 (73.7 g), diluted with water (400 mL) and extracted with dichloromethane (2×100 mL). The combined organic extracts were dried over anhydrous sodium sulfate, concentrated on a rotary evaporator and purified by silica gel column chromatography (hexane/ethyl acetate) to afford 6-chloro-5-fluoronicotinaldehyde as pale-yellow solid: 1H NMR (400 MHz, CDCl3) δ 10.12 (d, J=2.4 Hz, 1H), 8.72 (d, J=1.6 Hz, 1H), 7.94 (dd, J=2.0, 8.0 Hz, 1H); 19F NMR (376 MHz, CDCl3) δ −116.3.

Aufarbeitung

  1. temperaturewas heated to reflux
  2. extractionextracted with dichloromethane (2×100 mL)
  3. dry with materialThe combined organic extracts were dried over anhydrous sodium sulfate
  4. concentrationconcentrated on a rotary evaporator
  5. custompurified by silica gel column chromatography (hexane/ethyl acetate)

Quellen und Nachweise

ORD-Eintrag
ord-8156c9d2572e4901b7511cb89bb774d6
Quelldatensatz
uspto-grants-2011_04
Patentnummer
US07919519B2

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