Nitric Acid → 7-Nitro-2,3,4,5-tetrahydro-1H-benzo[D]azepine

HRID 1696536Notes

Reaction equation

HRID 1696536 reaction equation
[CH2:1]1[C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][C:6]=2[CH2:5][CH2:4][NH:3][CH2:2]1.[N+:12]([O-])([OH:14])=[O:13].[OH-].[Na+]>OS(O)(=O)=O>[N+:12]([C:9]1[CH:10]=[CH:11][C:6]2[CH2:5][CH2:4][NH:3][CH2:2][CH2:1][C:7]=2[CH:8]=1)([O-:14])=[O:13]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 14798Sodium HydroxideHCID 14002432,3,4,5-Tetrahydro-1H-benzo(d)azepine

Product 1

HCID 113100427-Nitro-2,3,4,5-tetrahydro-1H-benzo[D]azepineYield 46%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of 2,3,4,5-tetrahydro-1H-benzo[d]azepine dissolved in conc. H2SO4 (1.5 mL) was cooled to 0° C. and a mixture of concentrated H2SO4 (0.12 mL) and fuming HNO3 (0.06 mL) (also cooled to 0° C.) was added dropwise. After the addition was complete, the mixture was stirred for 15-30 min. The reaction mixture was poured onto 10 g of crushed ice, followed by the dropwise addition of 20% NaOH solution. The mixture was extracted with EtOAc (3×). The organic layer was washed with H2O, dried (Na2SO4), concentrated and under vacuum to afford 7-nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine as a brown liquid (0.12 g, 46% yield). LC-MS (EI) m/z: 193.0 (M+H+).

Workup

  1. temperaturealso cooled to 0° C.)
  2. additionwas added dropwise
  3. additionAfter the addition
  4. extractionThe mixture was extracted with EtOAc (3×)
  5. washThe organic layer was washed with H2O
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated and under vacuum

Sources & evidence

ORD record
ord-ba15d97bce804dc7bdae246dba0939b5
Source dataset
uspto-grants-2012_04
Patent number
US08163756B2

Reaction notes

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