4-Aminophenol → HCID 53399142, Verbindung

HRID 1993537Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1993537
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.[H-].[Na+].[H][H].[N+]([C:16]1[CH:21]=[CH:20][N+:19]([O-])=[CH:18][CH:17]=1)([O-])=O.[Si]([C:27]#[N:28])(C)(C)C.CN(C)C(Cl)=O>O1CCOCC1.O>[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][C:16]2[CH:21]=[CH:20][N:19]=[C:18]([C:27]#[N:28])[CH:17]=2)=[CH:4][CH:3]=1

Komponenten

9

Edukt 6

HCID 4034-AminophenolHCID 6598Dimethylcarbamoyl ChlorideHCID 143004-Nitropyridine N-oxideHCID 24758Sodium hydrideHCID 82115Trimethylsilyl cyanideHCID 178418361HCID 178418361, Verbindung

Produkt 1

HCID 53399142HCID 53399142, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

4-Amino-phenol (2.54 g, 22.8 mmol, 1.1 equiv) is added in one portion to a suspension of NaH (60% free-flowing powder moistened with oil, 1.25 g, 31.2 mmol, 1.5 equiv) in dioxane abs. (30 mL), under an argon atmosphere. When hydrogen evolution subsides, 4-nitro-pyridine N-oxide (3 g, 20.8 mmol) is added in one portion. The resulting dark mixture is heated to 100° C. (oil bath temperature) for 22 h and then allowed to cool to rt. Me3SiCN (3.5 mL, 27.0 mmol, 1.3 equiv) is added. After 5 min, the reaction mixture is cooled with a 10° C. water bath and N,N-dimethylcarbamoyl chloride (2.5 mL, 27.0 mmol, 1.3 equiv) Is added dropwise. The reaction mixture is allowed to warm to rt. When the reaction becomes exothermic, the water bath (10° C.) is applied for a few minutes. The reaction mixture is allowed to warm to rt, stirred for 1 h, quenched by addition of MeOH (30 mL), and concentrated in vacuo. After addition of CH2Cl2 to the residue, the resulting suspension is filtered through a glass sintered funnel (washing with copious amount of the same solvent). The filtrate is concentrated in vacuo and the residue is purified by silica gel (200 g) column chromatography (CH2Cl2/Et2O, 90/10) to afford the title compound as a brownish solid: ES-MS: 211.9 [M+H]+; single peak at tR=4.86 min (System 2); Rf=0.44 (CH2Cl2/Et2O, 80/20).

Aufarbeitung

  1. temperatureto cool to rt
  2. temperaturethe reaction mixture is cooled with a 10° C. water bath
  3. temperatureto warm to rt
  4. temperatureto warm to rt
  5. customquenched by addition of MeOH (30 mL)
  6. concentrationconcentrated in vacuo
  7. additionAfter addition of CH2Cl2 to the residue
  8. filtrationthe resulting suspension is filtered through a glass sintered funnel (
  9. washwashing with copious amount of the same solvent)
  10. concentrationThe filtrate is concentrated in vacuo
  11. customthe residue is purified by silica gel (200 g) column chromatography (CH2Cl2/Et2O, 90/10)

Quellen und Nachweise

ORD-Eintrag
ord-1c7a0784447f4864a8de60011cda41e2
Quelldatensatz
uspto-grants-2010_01
Patentnummer
US07652022B2

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