Ethanol → HCID 22749548, compound

HRID 1679292Notes

Reaction equation

HRID 1679292 reaction equation
[C:1]1([N:7]2[C:13]3[CH:14]=[CH:15][CH:16]=[CH:17][C:12]=3[NH:11][C:10](=[CH:18][N+:19]([O-])=O)[CH2:9][C:8]2=[O:22])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:23](O)[CH3:24]>[Ni].O1CCCC1>[CH3:23][C:24]1[N:11]2[C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=3[N:7]([C:1]3[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=3)[C:8](=[O:22])[CH2:9][C:10]2=[CH:18][N:19]=1

Participants

5

Reactant 2

HCID 702EthanolHCID 70605160HCID 70605160, compound

Product 1

HCID 22749548HCID 22749548, compound

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Raney nickel, 11 g, was added to a solution of 3.5 g (0.0118 m) of 5-phenyl-1,2,3,4-tetrahydro-2-nitromethylene-5H-1,5-benzodiazepin-4-one in 50 ml of tetrahydrofuran, and 150 ml of ethanol. The mixture was then hydrogenated at atmospheric pressure for a period of 20 hours. The catalyst was filtered off and washed with tetrahydrofuran and methylene chloride. The filtrate was evaporated and the remaining oil (3.1 g) was dissolved in 250 ml of xylene and 6.2 ml of triethylorthoacetate. After heating to reflux with stirring for 30 min, the reaction mixture was evaporated. The residue was dissolved in 200 ml of toluene and 19 g of activated manganese dioxide was added to the solution. The mixture was stirred and refluxed for 30 min. The manganese dioxide was filtered off and washed well with tetrahydrofuran and methylene chloride. The filtrate was evaporated, and the residue was crystallized from ethyl acetate to yield crystals with mp 217°-220°. For analysis, the material was recrystallized from methylene chloride/ethyl acetate to give colorless crystals with mp 221°-223°.

Workup

  1. filtrationThe catalyst was filtered off
  2. washwashed with tetrahydrofuran and methylene chloride
  3. customThe filtrate was evaporated
  4. dissolutionthe remaining oil (3.1 g) was dissolved in 250 ml of xylene
  5. temperatureAfter heating
  6. temperatureto reflux
  7. customthe reaction mixture was evaporated
  8. dissolutionThe residue was dissolved in 200 ml of toluene
  9. addition19 g of activated manganese dioxide was added to the solution
  10. stirringThe mixture was stirred
  11. temperaturerefluxed for 30 min
  12. filtrationThe manganese dioxide was filtered off
  13. washwashed well with tetrahydrofuran and methylene chloride
  14. customThe filtrate was evaporated
  15. customthe residue was crystallized from ethyl acetate
  16. customto yield crystals with mp 217°-220°
  17. customFor analysis, the material was recrystallized from methylene chloride/ethyl acetate
  18. customto give colorless crystals with mp 221°-223°

Sources & evidence

ORD record
ord-402f7d323fa14c7dbeff05dac5486911
Source dataset
uspto-grants-1978_03
Patent number
US04080323

Reaction notes

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