Ammonium Chloride → Methyl 4-amino-12-cyclohexyl-6,7-dihydro-5-oxa-7a-azadibenzo[a,e]azulene-9-carboxylate

HRID 1012335Notes

Reaction equation

HRID 1012335 reaction equation
[CH:1]1([C:7]2[C:8]3[CH:27]=[CH:26][C:25]([C:28]([O:30][CH3:31])=[O:29])=[CH:24][C:9]=3[N:10]3[C:16]=2[C:15]2[CH:17]=[CH:18][CH:19]=[C:20]([N+:21]([O-])=O)[C:14]=2[O:13][CH2:12][CH2:11]3)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[Cl-].[NH4+]>O1CCCC1.C(O)C.O>[NH2:21][C:20]1[C:14]2[O:13][CH2:12][CH2:11][N:10]3[C:16](=[C:7]([CH:1]4[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]4)[C:8]4[CH:27]=[CH:26][C:25]([C:28]([O:30][CH3:31])=[O:29])=[CH:24][C:9]=43)[C:15]=2[CH:17]=[CH:18][CH:19]=1

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 23152429Methyl 12-cyclohexyl-4-nitro-6,7-dihydro-5-oxa-7a-azadibenzo[a,e]azulene-9-carboxylate

Product 1

HCID 23152437Methyl 4-amino-12-cyclohexyl-6,7-dihydro-5-oxa-7a-azadibenzo[a,e]azulene-9-carboxylateYield 93.5%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of methyl 12-cyclohexyl-4-nitro-6,7-dihydro-5-oxa-7a-azadibenzo[a,e]azulene-9-carboxylate (9.94 g, 23.6 mmol) in tetrahydrofuran (85 ml), ethanol (170 ml) and water (42.5 ml) were added ammonium chloride (6.31 g, 118 mmol) and reduced iron (6.60 g, 118 mmol), and the mixture was stirred at 100° C. for 2 hr. After filtration of the reaction solution, saturated aqueous sodium hydrogen carbonate solution was added to the filtrate, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtration, the solvent was concentrated under reduced pressure to give a solid. The obtained solid was washed with a mixed solvent (hexane:ethyl acetate-20:1). The solid was collected by filtration to give methyl 4-amino-12-cyclohexyl-6,7-dihydro-5-oxa-7a-azadibenzo[a,e]azulene-9-carboxylate (8.62 g, yield 93%).

Workup

  1. filtrationAfter filtration of the reaction solution, saturated aqueous sodium hydrogen carbonate solution
  2. additionwas added to the filtrate
  3. extractionthe mixture was extracted with ethyl acetate
  4. washThe organic layer was washed with saturated brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationAfter filtration
  7. concentrationthe solvent was concentrated under reduced pressure
  8. customto give a solid
  9. washThe obtained solid was washed with a mixed solvent (hexane:ethyl acetate-20:1)
  10. filtrationThe solid was collected by filtration

Sources & evidence

ORD record
ord-03900796561940fa97aacce2ac381237
Source dataset
uspto-grants-2011_07
Patent number
US07977331B1

Reaction notes

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