N-Hydroxyphthalimide → 4-Methoxymethoxybenzyloxyamine

HRID 2299742Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2299742
[N:1](C(OCC)=O)=NC(OCC)=O.[CH3:13][O:14][CH2:15][O:16][C:17]1[CH:24]=[CH:23][C:20]([CH2:21][OH:22])=[CH:19][CH:18]=1.ON1C(=O)C2=CC=CC=C2C1=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1>[CH3:13][O:14][CH2:15][O:16][C:17]1[CH:24]=[CH:23][C:20]([CH2:21][O:22][NH2:1])=[CH:19][CH:18]=1

Komponenten

6

Edukt 4

HCID 10665N-HydroxyphthalimideHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 116079844-Methoxymethoxybenzylalcohol

Produkt 1

HCID 110522924-MethoxymethoxybenzyloxyamineAusbeute 58 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

Diethyl azodicarboxylate (40% toluene solution, 142 g) was added dropwise to a solution of 4-methoxymethoxybenzylalcohol (50.0 g), N-hydroxyphthalimide (44.1 g) and triphenylphosphine (83.7 g) in tetrahydrofuran (900 ml) at room temperature and stirred for 1 hour. The reaction mixture was concentrated. In order to remove triphenylphosphine oxide, the residue was subjected to silica gel chromatography to obtain crystals from an ethyl acetate-hexane (1:5, v/v)-eluted fraction. The crystals were washed with ethyl acetate-hexane (1:5, v/v) and then dissolved in tetrahydrofuran (200 ml) and ethanol (50 ml). To this solution was added hydrazine monohydrate (33.7 ml) and heated under reflux for 3 hours. The reaction mixture was cooled to room temperature, an aqueous solution of potassium carbonate was added and extracted with ethyl acetate. The ethyl acetate layer was washed with an aqueous saturated solution of sodium chloride, dried (MgSO4) and concentrated. Isopropyl ether was added to the residue and filtered to remove insolubles. The filtrate was concentrated to obtain 4-methoxymethoxybenzyloxyamine (28.9 g, yield 58%) as a colorless oil.

Aufarbeitung

  1. concentrationThe reaction mixture was concentrated
  2. customIn order to remove triphenylphosphine oxide
  3. customto obtain crystals from an ethyl acetate-hexane (1:5, v/v)-eluted fraction
  4. washThe crystals were washed with ethyl acetate-hexane (1:5
  5. dissolutionv/v) and then dissolved in tetrahydrofuran (200 ml)
  6. additionTo this solution was added hydrazine monohydrate (33.7 ml)
  7. temperatureheated
  8. temperatureunder reflux for 3 hours
  9. additionan aqueous solution of potassium carbonate was added
  10. extractionextracted with ethyl acetate
  11. washThe ethyl acetate layer was washed with an aqueous saturated solution of sodium chloride
  12. dry with materialdried (MgSO4)
  13. concentrationconcentrated
  14. additionIsopropyl ether was added to the residue
  15. filtrationfiltered
  16. customto remove insolubles
  17. concentrationThe filtrate was concentrated

Quellen und Nachweise

ORD-Eintrag
ord-109d2cc3f5fb4743af6151f53a07c855
Quelldatensatz
uspto-grants-2002_12
Patentnummer
US06495581B1

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