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 1764804

反応式

HRID 1764804 の反応式
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

参加物

6

反応物 4

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

生成物 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-carboxylate収率 90.3%

試薬・触媒・溶媒 1

HCID 6422Trifluoroacetic acid溶媒

実験手順

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+).

後処理

  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 magnesium sulfate
  7. customevaporated to dryness

出典と根拠

ORDレコード
ord-a609577cd78c4aceb24b9210c4242252
出典データセット
uspto-grants-2007_06
特許番号
USRE039680E1

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