Tetrahydrofuran → 2-(aminomethyl)-5-bromo-2,3,4,9-tetrahydro-1H-carbazole-8-carboxamide

HRID 1811137Notes

Reaction equation

HRID 1811137 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][C:12]([C:15]([NH2:17])=[O:16])=[C:11]2[C:3]=1[C:4]1[CH2:5][CH2:6][CH:7]([CH:18]=O)[CH2:8][C:9]=1[NH:10]2.C([O-])(=O)C.[NH4+:24].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C1COCC1>C(Cl)Cl>[NH2:24][CH2:18][CH:7]1[CH2:6][CH2:5][C:4]2[C:3]3[C:11](=[C:12]([C:15]([NH2:17])=[O:16])[CH:13]=[CH:14][C:2]=3[Br:1])[NH:10][C:9]=2[CH2:8]1

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 517165Ammonium AcetateHCID 5049666Sodium triacetoxyborohydrideHCID 866429585-bromo-2-formyl-2,3,4,9-tetrahydro-1H-carbazole-8-carboxamide

Product 1

HCID 666059472-(aminomethyl)-5-bromo-2,3,4,9-tetrahydro-1H-carbazole-8-carboxamideYield 13%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Step 3 A solution of crude 5-bromo-2-formyl-2,3,4,9-tetrahydro-1H-carbazole-8-carboxamide (1 g, 3.11 mmol) in DCM (20 mL) was treated with ammonium acetate (3.60 g, 46.7 mmol) and sodium triacetoxyborohydride (0.990 g, 4.67 mmol) at rt and stirred for 10 min. THF (2 mL) was added to try to dissolve the starting material, but no reaction was observed after 1 h. The mixture was concentrated and the residue was dissolved in DMSO (10 mL). Additional sodium triacetoxyborohydride (500 mg) was added and the mixture was stirred at rt overnight. The mixture was diluted with water and the precipitate was removed by filtration. The filtrate was treated with 1 M aqueous sodium hydroxide and extracted three times with EtOAc. The combined organic phases were washed with water, dried and concentrated to provide 2-(aminomethyl)-5-bromo-2,3,4,9-tetrahydro-1H-carbazole-8-carboxamide as a white solid (130 mg, 13%), used without further purification. Mass spectrum m/z 322, 324 (M+H)+.

Workup

  1. dissolutionto dissolve the starting material
  2. waitno reaction was observed after 1 h
  3. concentrationThe mixture was concentrated
  4. dissolutionthe residue was dissolved in DMSO (10 mL)
  5. additionAdditional sodium triacetoxyborohydride (500 mg) was added
  6. stirringthe mixture was stirred at rt overnight
  7. additionThe mixture was diluted with water
  8. customthe precipitate was removed by filtration
  9. additionThe filtrate was treated with 1 M aqueous sodium hydroxide
  10. extractionextracted three times with EtOAc
  11. washThe combined organic phases were washed with water
  12. customdried
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-c2a4e14b25f640018112feab68accac5
Source dataset
uspto-grants-2013_01
Patent number
US08362065B2

Reaction notes

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