Ethylenediamine → 3-(tert-Butyloxycarbonyl)-7-(pyrazin-2-yl)-2,3,4,5-tetrahydro-1H-3-benzazepine

HRID 33220Notes

Reaction equation

HRID 33220 reaction equation
[C:1]([C:4]1[CH:21]=[CH:20][C:7]2[CH2:8][CH2:9][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:11][CH2:12][C:6]=2[CH:5]=1)(=O)[CH3:2].[Se](=O)=O.[CH2:25]([NH2:28])[CH2:26][NH2:27].[OH-].[K+]>O1CCOCC1.O.C(O)C>[C:16]([O:15][C:13]([N:10]1[CH2:9][CH2:8][C:7]2[CH:20]=[CH:21][C:4]([C:1]3[CH:2]=[N:28][CH:25]=[CH:26][N:27]=3)=[CH:5][C:6]=2[CH2:12][CH2:11]1)=[O:14])([CH3:19])([CH3:18])[CH3:17]

Participants

8

Reactant 4

HCID 3301EthylenediamineHCID 14797Potassium HydroxideHCID 24007Selenium DioxideHCID 18173273tert-butyl 7-acetyl-2,3,4,5-tetrahydro-1H-3-benzazepine-3-carboxylate

Product 1

HCID 691794783-(tert-Butyloxycarbonyl)-7-(pyrazin-2-yl)-2,3,4,5-tetrahydro-1H-3-benzazepineYield 25.6%

Reagents, catalysts & solvents 3

HCID 702EthanolSolvent2×HCID 962WaterSolventHCID 312751,4-DioxaneSolvent2×

Procedure

To a stirred solution of 7-acetyl-3-(tert-butyloxycarbonyl)-2,3,4,5-tetrahydro-1H-3-benzazepine (12 g, 42 mmol) in dioxan (60 ml) was added selenium dioxide (4.61 g, 42 mmol) in dioxan (60 ml) and water (15 ml). The mixture was heated under reflux for 18 h., cooled and the solid residue filtered. The filtrate was evaporated in vacuo and the residue azeotroped with toluene to give an orange gum which was dissolved in ethanol and added dropwise to a stirred solution of ethylenediamine (3 g, 50 mmol) in ethanol at 0° C. After the addition was complete, KOH (2.6 g, 46 mmol) was added and the reaction heated under reflux for 3 h. The reaction mixture was then allowed to cool and evaporated in vacuo. The residue was partitioned between water and dichloromethane and the combined organic extracts dried and evaporated in vacuo to give a brown gum. Purification by silica gel chromatography (eluant 20% EtOAc:hexane) gave the title compound as a yellow oil (3.5 g).

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 18 h.
  3. temperaturecooled
  4. filtrationthe solid residue filtered
  5. customThe filtrate was evaporated in vacuo
  6. customthe residue azeotroped with toluene
  7. customto give an orange gum which
  8. additionAfter the addition
  9. temperaturethe reaction heated
  10. temperatureunder reflux for 3 h
  11. temperatureto cool
  12. customevaporated in vacuo
  13. customThe residue was partitioned between water and dichloromethane
  14. customthe combined organic extracts dried
  15. customevaporated in vacuo
  16. customto give a brown gum
  17. customPurification by silica gel chromatography (eluant 20% EtOAc:hexane)

Sources & evidence

ORD record
ord-84ea043f4c9140a5b6734ec0df09a85a
Source dataset
uspto-grants-2008_09
Patent number
US07429579B2

Reaction notes

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