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 1267045Notes

Reaction equation

HRID 1267045 reaction equation
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

Participants

6

Reactant 4

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

Product 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-carboxylateYield 90.3%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

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+).

Workup

  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

Sources & evidence

ORD record
ord-41727bf25ee949cd8f9a0703195743ff
Source dataset
uspto-grants-2003_04
Patent number
US06552017B1

Reaction notes

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