Reaction #1379898

Reaction equation

O-benzyl hydroxylamine hydrochloride

N,N-diisopropylethylamine

acryloyl chloride

→

N-benzyloxyacrylarnide

Yield 48.4%

N-benzyloxyacrylamide

Yield 48.4%

Solvents

dichloromethane

dichloromethane

Conditions

Workup

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

Procedure

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).

Source