N-Hydroxyphthalimide → 4-Methoxymethoxybenzyloxyamine

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.

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

ORD 기록

ord-678548f54d434e2dbf999cf0d3a7dde1

출처 데이터셋

uspto-grants-2001_06

DOI

10.6084/m9.figshare.5104873.v1

특허 번호

US06251926B1