Water → ethyl 5,6,7,8-tetrahydro-11-bromomethyl-8-oxo-4H-azocino [3.2.1-hi]indole-2-carboxylate

HRID 650086Notes

Reaction equation

HRID 650086 reaction equation
CC1C=CC=C2C=1C=C(C(OCC)=O)N2.[CH3:16][C:17]1[CH:25]=[CH:24][C:23]2[C:26](=[O:31])[CH2:27][CH2:28][CH2:29][CH2:30][N:21]3[C:22]=2[C:18]=1[CH:19]=[C:20]3[C:32]([O:34][CH2:35][CH3:36])=[O:33].[Br:37]N1C(=O)CCC1=O.O>C(Cl)(Cl)(Cl)Cl.N(C(C)(C)C#N)=NC(C)(C)C#N>[Br:37][CH2:16][C:17]1[CH:25]=[CH:24][C:23]2[C:26](=[O:31])[CH2:27][CH2:28][CH2:29][CH2:30][N:21]3[C:22]=2[C:18]=1[CH:19]=[C:20]3[C:32]([O:34][CH2:35][CH3:36])=[O:33]

Participants

7

Reactant 4

HCID 962WaterHCID 67184N-bromobutanimideHCID 12529972Ethyl 4-methyl-1H-indole-2-carboxylateHCID 70237721Ethyl 5,6,7,8-tetrahydro-11-methyl-8-oxo-4H-azocino [3.2.1-hi]indole-2-carboxylate2×

Product 1

HCID 70238124ethyl 5,6,7,8-tetrahydro-11-bromomethyl-8-oxo-4H-azocino [3.2.1-hi]indole-2-carboxylate

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

In accordance with the process described in Example 22(a)-(c) except for using ethyl 4-methyl-1H-indole-2-carboxylate as a starting material, ethyl 5,6,7,8-tetrahydro-11-methyl-8-oxo-4H-azocino[3.2.1-hi]indole-2-carboxylate (m.p. 98° C., recrystallized from isopropyl alcohol) was synthesized. Ethyl 5,6,7,8-tetrahydro-11-methyl-8-oxo-4H-azocino[3.2.1-hi]indole-2-carboxylate (2.50 g, 8.76 mmol) was then dissolved in carbon tetrachloride (80 ml) and N-bromosuccinimide (1.72 g, 9.64 mmol) and 2,2′-azobisisobutyronitrile (43 mg) were added therein under refluxing condition to heat at reflux for 2 hours. The reaction mixture was poured into water and extracted with chloroform. The extract was washed with saturated sodium chloride solution and dried over magnesium sulfate. The solvent was distilled off and the obtained residue was purified with silica gel column chromatography (eluated with ethyl acetate/n-hexane=1/10) to give ethyl 5,6,7,8-tetrahydro-11-bromomethyl-8-oxo-4H-azocino[3.2.1-hi]indole-2-carboxylate (3.12 g).

Workup

  1. customwas synthesized
  2. temperatureunder refluxing condition
  3. temperatureto heat
  4. temperatureat reflux for 2 hours
  5. extractionextracted with chloroform
  6. washThe extract was washed with saturated sodium chloride solution
  7. dry with materialdried over magnesium sulfate
  8. distillationThe solvent was distilled off
  9. customthe obtained residue was purified with silica gel column chromatography (eluated with ethyl acetate/n-hexane=1/10)

Sources & evidence

ORD record
ord-0c80873a781b4948ab86b839d659bdcf
Source dataset
uspto-grants-2001_08
Patent number
US06271251B1

Reaction notes

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