Nitric Acid → 7-Hydroxy-8-nitro-1,2,4,5-tetrahydro-benzo[d]azepine-3-carboxylic acid tert-butyl ester

HRID 1668560Notes

Reaction equation

HRID 1668560 reaction equation
[N+:1]([O-:4])(O)=[O:2].[OH:5][C:6]1[CH:23]=[CH:22][C:9]2[CH2:10][CH2:11][N:12]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:13][CH2:14][C:8]=2[CH:7]=1.C(=O)(O)[O-].[Na+]>C(Cl)Cl>[OH:5][C:6]1[C:23]([N+:1]([O-:4])=[O:2])=[CH:22][C:9]2[CH2:10][CH2:11][N:12]([C:15]([O:17][C:18]([CH3:19])([CH3:21])[CH3:20])=[O:16])[CH2:13][CH2:14][C:8]=2[CH:7]=1

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 516892Sodium BicarbonateHCID 18173274tert-butyl 7-hydroxy-2,3,4,5-tetrahydro-1H-3-benzazepine-3-carboxylate

Product 1

HCID 589728117-Hydroxy-8-nitro-1,2,4,5-tetrahydro-benzo[d]azepine-3-carboxylic acid tert-butyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Nitric acid (70%, 3.44 ml) was added dropwise over 40 min with vigorous stirring to 1,1-dimethylethyl 7-hydroxy-1,2,4,5-tetrahydro-benzo[d]azepine-3-carboxylate (14.2 g) in DCM with cooling in an ice bath. After additional 5 min silica gel (15 g) and sodium bicarbonate powder (5 g) were added and stirring was continued for 1.5 h. The mixture was filtered through a layer (1 cm) of silica gel and the solids washed with EtOAc. The resulting solution was concentrated and submitted to column chromatography to provide the title compound as a yellow solid (8.54 g).

Workup

  1. temperaturewith cooling in an ice bath
  2. filtrationThe mixture was filtered through a layer (1 cm) of silica gel
  3. washthe solids washed with EtOAc
  4. concentrationThe resulting solution was concentrated

Sources & evidence

ORD record
ord-3bcfbfaee7f54d739a192a0fc4c3d402
Source dataset
uspto-grants-2011_08
Patent number
US07989444B2

Reaction notes

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