반응 #1851986

반응 방정식

sodium hydroxide

Sodium cyanoborohydride

ethyl 2,3,9,10-tetrahydro-2-oxo-1H-pyrido[3′,4′:4,5]-pyrrolo[1,2,3-de]quinoxaline-8(7H)-carboxylate

ammonium hydroxide

→

ethyl (6bR,10aS)-2-oxo-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxaline-8(7H)-carboxylate

수율 90.3%

용매

trifluoroacetic acid

반응 조건

후처리

1. 1
   온도cooled in an ice-water bath, under nitrogen
2. 2
   workup.ADDITIONAfter the addition
3. 3
   workup.ADDITIONcontaining ice
4. 4
   추출The mixture was extracted with dichloromethane (2×)
5. 5
   세척the extract was washed with water
6. 6
   건조dried over magnesium sulfate
7. 7
   기타evaporated to dryness

실험 절차

Sodium cyanoborohydride (4.0 g; 65 mmol) was added, in small portions, to a vigorously stirred solution of ethyl 2,3,9,10-tetrahydro-2-oxo-1H-pyrido[3′,4′:4,5]-pyrrolo[1,2,3-de]quinoxaline-8(7H)-carboxylate (11.97 g, 40 mmol) in trifluoroacetic acid (125 mL) cooled in an ice-water bath, under nitrogen. After the addition was complete, the mixture was stirred for 30 min and then poured slowly into ammonium hydroxide (300 mL) containing ice followed by the addition of enough 1N sodium hydroxide to make the mixture basic. The mixture was extracted with dichloromethane (2×) and the extract was washed with water, dried over magnesium sulfate, and evaporated to dryness to yield 10.89 g (90%) of ethyl (6bR,10aS)-2-oxo-2,3,6b,9,10,10a-hexahydro-1H-pyrido[3′,4′:4,5]pyrrolo[1,2,3-de]quinoxaline-8(7H)-carboxylate as an off-white powder, m.p. 167-168° C. (dec., sinters at 70° C.). 1H NMR (CDCl3, 300 MHz) δ 1.28 (t, J=7 Hz, 3H), 1.81-1.95 (m, 2H), 3.13-3.22 (m,1H), 3.23-3.39 (m, 1H), 3.44 (d, J=14.7 Hz, 1H), 3.41-3.51(m, 1H), 3.80-3.95 (m, 1H), 3.98 (d, J=14.7 Hz, 2H), 4.16 (q, 2H), 6.59 (d, J=7.7 Hz, 1H), 6.74 (t, J=7.7 Hz, 1H), 6.83 (d, J=7.7 Hz, 1H), 8.17 (s, 1H) ppm. MS (CI): 302 (M+H+).

출처