Sodium Hydroxide → ethyl (10R,15S)-3-oxo-1,4,12-triazatetracyclo[7.6.1.05,16.010,15]hexadeca-5,7,9(16)-triene-12-carboxylate

HRID 1267045

Reaktionsgleichung

Reaktionsgleichung von HRID 1267045
C([BH3-])#N.[Na+].[O:5]=[C:6]1[CH2:15][N:14]2[C:16]3[CH2:21][CH2:20][N:19]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH2:18][C:17]=3[C:12]3[C:13]2=[C:8]([CH:9]=[CH:10][CH:11]=3)[NH:7]1.[OH-].[NH4+].[OH-].[Na+]>FC(F)(F)C(O)=O>[O:5]=[C:6]1[CH2:15][N:14]2[C@H:16]3[CH2:21][CH2:20][N:19]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH2:18][C@H:17]3[C:12]3[C:13]2=[C:8]([CH:9]=[CH:10][CH:11]=3)[NH:7]1

Komponenten

6

Edukt 4

HCID 14798Sodium HydroxideHCID 14923Ammonium HydroxideHCID 5003444Sodium cyanoborohydrideHCID 22036738Lumat-004

Produkt 1

HCID 20578971ethyl (10R,15S)-3-oxo-1,4,12-triazatetracyclo[7.6.1.05,16.010,15]hexadeca-5,7,9(16)-triene-12-carboxylateAusbeute 90,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6422Trifluoroacetic acidLösungsmittel

Versuchsvorschrift

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 magesium 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+).

Aufarbeitung

  1. temperaturecooled in an ice-water bath, under nitrogen
  2. additionAfter the addition
  3. additioncontaining ice
  4. extractionThe mixture was extracted with dichloromethane (2×)
  5. washthe extract was washed with water
  6. dry with materialdried over magesium sulfate
  7. customevaporated to dryness

Quellen und Nachweise

ORD-Eintrag
ord-41727bf25ee949cd8f9a0703195743ff
Quelldatensatz
uspto-grants-2003_04
Patentnummer
US06552017B1

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