Tert-Butyl nitrite → Ethyl 2-(2,3-dioxo-4,5-dihydro-1-benzazepin-1-yl)acetate

HRID 482778Notes

Reaction equation

HRID 482778 reaction equation
N(OC(C)(C)C)=[O:2].N[CH:9]1[CH2:15][CH2:14][C:13]2[CH:16]=[CH:17][CH:18]=[CH:19][C:12]=2[N:11]([CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:10]1=[O:26].ClC1C=CC=C(C(OO)=O)C=1>C(Cl)(Cl)Cl.C(O)(=O)C>[CH2:24]([O:23][C:21]([CH2:20][N:11]1[C:12]2[CH:19]=[CH:18][CH:17]=[CH:16][C:13]=2[CH2:14][CH2:15][C:9](=[O:2])[C:10]1=[O:26])=[O:22])[CH3:25]

Participants

6

Reactant 3

HCID 10906Tert-Butyl nitriteHCID 70297m-Chloroperbenzoic acidHCID 132435253-amino-1-ethoxycarbonylmethyl-2,3,4,5-tetrahydro-1H-[1]benzazepin-2-one

Product 1

HCID 13500724Ethyl 2-(2,3-dioxo-4,5-dihydro-1-benzazepin-1-yl)acetate

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6212ChloroformSolvent

Procedure

t-Butyl nitrite (31 ml) was added with stirring to a solution of 3-amino-1-ethoxycarbonylmethyl-2,3,4,5-tetrahydro-1H[1]-benzazepin-2-one (55 g) in chloroform (1000 ml) and acetic acid (2.8 ml). The reaction mixture was refluxed under nitrogen for 3.5 hours, and then cooled to 0°. While stirring was maintained, m-chloroperbenzoic acid (43.5 g) was added in five portions during 0.5 hour. The reaction mixture was allowed to warm to room temperature and stirred for an additional 1.5 hours. The reaction mixture was washed with saturated aqueous sodium bicarbonate (500 ml), concentrated aqueous ammonia (2×250 ml), and saturated brine (250 ml). The organic solution was dried over sodium sulfate, treated with charcoal, and evaporated under reduced pressure to give an oil which was triturated with ether to give 1-ethoxycarbonylmethyl-2,3,4,5-tetrahydro-1H[1]-benzazepin-2,3-dione, m.p. 112°-114°.

Workup

  1. temperatureThe reaction mixture was refluxed under nitrogen for 3.5 hours
  2. temperaturecooled to 0°
  3. temperaturewas maintained
  4. stirringstirred for an additional 1.5 hours
  5. washThe reaction mixture was washed with saturated aqueous sodium bicarbonate (500 ml), concentrated aqueous ammonia (2×250 ml), and saturated brine (250 ml)
  6. dry with materialThe organic solution was dried over sodium sulfate
  7. additiontreated with charcoal
  8. customevaporated under reduced pressure
  9. customto give an oil which
  10. customwas triturated with ether

Sources & evidence

ORD record
ord-9e9ce12a3ac146498aac02f1b267ac7b
Source dataset
uspto-grants-1986_03
Patent number
US04575503

Reaction notes

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