Nitromethane → 5-(2-Nitro-ethyl)-2-phenoxy-pyridine

HRID 77889

Reaktionsgleichung

Reaktionsgleichung von HRID 77889
[O:1]([C:8]1[N:13]=[CH:12][C:11]([CH:14]=O)=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N+:16]([CH3:19])([O-:18])=[O:17].C([O-])(=O)C.[NH4+].[BH4-].[Na+]>C(O)(=O)C>[N+:16]([CH2:19][CH2:14][C:11]1[CH:10]=[CH:9][C:8]([O:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[N:13][CH:12]=1)([O-:18])=[O:17]

Komponenten

6

Edukt 4

HCID 6375NitromethaneHCID 517165Ammonium AcetateHCID 27765006-PhenoxynicotinaldehydeHCID 4311764Sodium borohydride

Produkt 1

HCID 576263415-(2-Nitro-ethyl)-2-phenoxy-pyridineAusbeute 55 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 176Acetic AcidLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To a solution of 6-phenoxy-pyridine-3-carbaldehyde (1.12 g, 5.62 mmol) described in Manufacturing Example 40-1-2 in acetic acid (10 mL) were added nitromethane (1.52 mL, 28.1 mmol) and ammonium acetate (866 mg, 11.2 mmol) under nitrogen atmosphere, which was stirred for 3 hours at 100° C. After being cooled to room temperature, the reaction solution was partitioned into water and ethyl acetate. The organic layer was separated, washed with saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under a reduced pressure. The resulting residue was dissolved in dimethyl sulfoxide (17 mL) and acetic acid (3 mL). Sodium borohydride (336 mg, 8.43 mmol) was added to this solution at room temperature while cooling appropriately, and stirred for 30 minutes at room temperature. The reaction solution was partitioned by addition of sodium hydrogencarbonate, water and ethyl acetate. The organic layer was separated, washed with water and saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under a reduced pressure. The residue was purified by NH silica gel column chromatography (heptane:ethyl acetate=3:1) to obtain the title compound (753 mg, 55%).

Aufarbeitung

  1. temperatureAfter being cooled to room temperature
  2. customthe reaction solution was partitioned into water and ethyl acetate
  3. customThe organic layer was separated
  4. washwashed with saturated aqueous sodium chloride
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated under a reduced pressure
  8. dissolutionThe resulting residue was dissolved in dimethyl sulfoxide (17 mL)
  9. temperaturewhile cooling appropriately
  10. stirringstirred for 30 minutes at room temperature
  11. customThe reaction solution was partitioned by addition of sodium hydrogencarbonate, water and ethyl acetate
  12. customThe organic layer was separated
  13. washwashed with water and saturated aqueous sodium chloride
  14. dry with materialdried over anhydrous magnesium sulfate
  15. filtrationfiltered
  16. concentrationThe filtrate was concentrated under a reduced pressure
  17. customThe residue was purified by NH silica gel column chromatography (heptane:ethyl acetate=3:1)

Quellen und Nachweise

ORD-Eintrag
ord-86d60cb3e24e41ab90a74f8ceb8b54c4
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08841327B2

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