Water → 1,4-Benzodioxin,2,3-dihydro-6-(2-nitroethenyl)-

HRID 23198

Reaktionsgleichung

Reaktionsgleichung von HRID 23198
[O:1]1[C:6]2[CH:7]=[CH:8][C:9]([CH:11]=O)=[CH:10][C:5]=2[O:4][CH2:3][CH2:2]1.[N+:13]([CH3:16])([O-:15])=[O:14].C([O-])(=O)C.[NH4+].O>C(O)(=O)C>[N+:13]([CH:16]=[CH:11][C:9]1[CH:8]=[CH:7][C:6]2[O:1][CH2:2][CH2:3][O:4][C:5]=2[CH:10]=1)([O-:15])=[O:14]

Komponenten

6

Edukt 4

HCID 962WaterHCID 6375NitromethaneHCID 2481272,3-Dihydro-1,4-benzodioxin-6-carbaldehydeHCID 517165Ammonium Acetate

Produkt 1

HCID 241544511,4-Benzodioxin,2,3-dihydro-6-(2-nitroethenyl)-Ausbeute 61 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 176Acetic AcidLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

To 1,4-benzodioxane-6-carboxaldehyde (10.0 g, 60 mmol) in acetic acid (50 mL) was added nitromethane (6.3 mL, 1.9 eq.) and ammonium acetate (5.1 g, 1.1 eq.). After heating at 110° C. for 4 hours the mixture was cooled to ambient temperature, water (150 mL) was added, and the solid precipitate was collected by filtration. The solid was crystallized from methylene chloride-hexane (1:1, 45 mL) to obtain 7.6 g (61%) of 6-(2-nitroethenyl)-1,4-benzodioxane. To a portion of the solid (3.58 g) dissolved in MeOH-EtOH-AcOEt (1:1:1, 450 mL) was added 10% Pd/C (1.7 g) and concentrated HCl (3.3 mL, 2.3 eq). After shaking on a Parr hydrogenator at 45 psi for 5 hours, the catalyst was removed by filtration through Celite and washed with methanol. Evaporation of the filtrate gave 3.59 g (96%) of 1,4-benzodioxan-6-ethanamine, hydrochloride.

Aufarbeitung

  1. temperaturewas cooled to ambient temperature
  2. filtrationthe solid precipitate was collected by filtration
  3. customThe solid was crystallized from methylene chloride-hexane (1:1, 45 mL)

Quellen und Nachweise

ORD-Eintrag
ord-5fa2cf57bf4c466887c8db147b8a3ccb
Quelldatensatz
uspto-grants-2005_02
Patentnummer
US06849739B2

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