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1,1-dimethylethyl 7-(4-amino-3-nitrophenyl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate → 1,1-dimethylethyl 7-(3,4-diaminophenyl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate

HRID 241178
Notes
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Reaction equation

HRID 241178 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[CH:10][C:11]3[O:17][CH2:16][CH2:15][N:14]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:13][C:12]=3[CH:25]=2)=[CH:4][C:3]=1[N+:26]([O-])=O.[H][H]>C(OCC)(=O)C.[Pd]>[NH2:26][C:3]1[CH:4]=[C:5]([C:8]2[CH:9]=[CH:10][C:11]3[O:17][CH2:16][CH2:15][N:14]([C:18]([O:20][C:21]([CH3:23])([CH3:22])[CH3:24])=[O:19])[CH2:13][C:12]=3[CH:25]=2)[CH:6]=[CH:7][C:2]=1[NH2:1]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 2

HCID 675056591,1-dimethylethyl 7-(4-amino-3-nitrophenyl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylateHCID 178418361HCID 178418361, compound

Product 1

HCID 668201741,1-dimethylethyl 7-(3,4-diaminophenyl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylateYield 6,774.2%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalyst
HCID 8857
Ethyl Acetate
Solvent

Procedure

To a solution of 1,1-dimethylethyl 7-(4-amino-3-nitrophenyl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate (Example 26, 1.35 g, 3.1 mmol) in ethyl acetate (30 mL) was added 5% palladium on carbon (wet). The resulting suspension was subjected to an atmosphere of hydrogen (40 psi) for 15 h. The catalyst was then removed by filtration through celite. The filtrate was concentrated to provide 1,1-dimethylethyl 7-(3,4-diaminophenyl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate (748 mg, 210 mmol, 68% yield) as an orange viscous syrup. MS (EI) for C20H25N3O3: 356 (MH+).

Workup

  1. customThe catalyst was then removed by filtration through celite
  2. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-ea881aa48fcb4f71a4eccf90a7b36cb6
Source dataset
uspto-grants-2014_02
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08648066B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes