Reaktion #1379898

Reaktionsgleichung

O-benzyl hydroxylamine hydrochloride

N,N-diisopropylethylamine

acryloyl chloride

→

N-benzyloxyacrylarnide

Ausbeute 48.4%

N-benzyloxyacrylamide

Ausbeute 48.4%

Lösungsmittel

dichloromethane

dichloromethane

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONwas slowly added over a period of 1 hour to the cooled solution
2. 2
   SonstigeNext, the ice bath was removed
3. 3
   workup.WAITthe reaction mixture was left
4. 4
   Temperaturwarmed up gradually to room temperature
5. 5
   workup.ADDITIONWater (250 mL) was added to the reaction
6. 6
   Sonstigethe layers were separated
7. 7
   WaschenThe organic solution was washed with diluted hydrochloric acid (0.2N; 3×300 mL)
8. 8
   TrocknenThe organic layer was then dried over magnesium sulfate
9. 9
   Filtrationfiltered
10. 10
    Sonstigethe solvent removed under reduced pressure
11. 11
    SonstigeThe residue was purified by flash chromatography
12. 12
    workup.ADDITIONa mixture of hexane and ethyl acetate (70:30)
13. 13
    Waschento elute the product
14. 14
    SonstigeThe purification

Vorschrift

A solution of acryloyl chloride (3 mL; 3.342 g; 36.9 mmole) dissolved in dry dichloromethane (25 mL) was cooled at 0° C. with an ice bath. A mixture of O-benzyl hydroxylamine hydrochloride (6.4902 g; 40.66 mmole) and N,N-diisopropylethylamine (15.6 mL; 11.575 g; 89.56 mmole) in dry dichloromethane (110 mL) was slowly added over a period of 1 hour to the cooled solution. Next, the ice bath was removed, and the reaction mixture was left stirring overnight while its temperature warmed up gradually to room temperature. Water (250 mL) was added to the reaction and the layers were separated. The organic solution was washed with diluted hydrochloric acid (0.2N; 3×300 mL), a saturated sodium bicarbonate solution (1×200 mL), water (3×250 mL), and finally brine (1×250 mL). The organic layer was then dried over magnesium sulfate, filtered, and the solvent removed under reduced pressure. The residue was purified by flash chromatography using a mixture of hexane and ethyl acetate (70:30) to elute the product. The purification gave 3.165 g (48.4%) of N-benzyloxyacrylarnide (30) as a viscous colorless oil. 1H NMR (CDCl3; 300 MHz): 8.27 (bs, 1H, C6H5CH2ONHCOCH═CH2), 7.39 (s, 5H, C6H5CH2ONHCOCH═CH2), 6.41 (d, 1H, J=16.6 Hz, C6H5CH2ONHCOCH═CHtrans), 6.02 (m, 1H, C6H5CH2ONHCOCH═CH2), 5.72 (d, 1H, J=9.5 Hz, C6H5CH2ONHCOCH═CHcis), 4.93 ppm (bs, 2H, C6H5CH2ONHCOCH═CH2).

Quelle