Methyl iodide → Tert-butyl 2-bromo-4,5-dimethyl-5,6,7,8,9,10-hexahydro-7,10-epiminocyclohepta[b]indole-carboxylate

HRID 2036730ノート

反応式

HRID 2036730 の反応式
[Br:1][C:2]1[CH:10]=[C:9]([CH3:11])[C:8]2[NH:7][C:6]3[CH2:12][CH:13]4[NH:17][CH:16]([C:5]=3[C:4]=2[C:3]=1[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:15][CH2:14]4.[H-].[Na+].I[CH3:28]>CN(C=O)C.C(OCC)(=O)C>[Br:1][C:2]1[CH:10]=[C:9]([CH3:11])[C:8]2[N:7]([CH3:28])[C:6]3[CH2:12][CH:13]4[NH:17][CH:16]([C:5]=3[C:4]=2[C:3]=1[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:15][CH2:14]4

参加物

6

反応物 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 67085300Tert-butyl 2-bromo-4-methyl-5,6,7,8,9,10-hexahydro-7,10-epiminocyclohepta[b]indole-carboxylate

生成物 1

HCID 67085249Tert-butyl 2-bromo-4,5-dimethyl-5,6,7,8,9,10-hexahydro-7,10-epiminocyclohepta[b]indole-carboxylate収率 80%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a solution of the product of step B (410 mg, 1.05 mmol) in DMF (3.5 ml) at 0° C., under nitrogen was added sodium hydride (60% dispersion in mineral oil, 51 mg, 2.09 mmol). The mixture was stirred for 45 min at 0-5° C. before iodomethane (0.13 mL, 2.09 mmol) was added. The mixture was stirred for a further 90 min then quenched with ice water. The mixture was diluted with ethyl acetate, washed with water, brine and dried over anhydrous sodium sulfate. Concentration in vacuo afforded a viscous oil which was dissolved in a minimal amount of ethyl acetate and precipitated by addition of hexanes. The separated solid was filtered and dried in vacuo to give tert-butyl 2-bromo-4,5-dimethyl-5,6,7,8,9,10-hexahydro-7,10-epiminocyclohepta[b]indole-carboxylate (340 mg, 80%) as an off-white solid. 1H NMR (CDCl3, 300 MHz): δ 7.43 (d, J=1.2 Hz, 1H), 6.94 (d, J=1.2 Hz, 1H), 5.05-5.30 (m, 1H), 4.52-4.70 (m, 1H), 3.80 (s, 3H), 3.15-3.47 (m, 1H), 2.69 (s, 3H), 2.43 (dd, J=15.9, 0.9 Hz, 1H), 2.23-2.30 (m, 1H), 2.08-2.22 (m, 1H), 1.85-1.95 (m, 1H), 1.58-1.64 (m, 1H), 1.39 (br s, 9H).

後処理

  1. additionwas added
  2. customthen quenched with ice water
  3. additionThe mixture was diluted with ethyl acetate
  4. washwashed with water, brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationConcentration in vacuo
  7. customafforded a viscous oil which
  8. customprecipitated by addition of hexanes
  9. filtrationThe separated solid was filtered
  10. customdried in vacuo

出典と根拠

ORDレコード
ord-7ecf305bf32c4c7aaa9cd25e7ff4c381
出典データセット
uspto-grants-2013_11
特許番号
US08575186B2

反応ノート

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