Ethanol → 8-chloro-1-methyl-6-phenyl-3,3a,4,6-tetrahydro-5H-imidazo[1,5-a][1,5]benzodiazepin-5-one

HRID 1679290Notes

Reaction equation

HRID 1679290 reaction equation
[Cl:1][C:2]1[CH:23]=[CH:22][C:5]2[NH:6][C:7](=[CH:18][N+:19]([O-])=O)[CH2:8][C:9](=[O:17])[N:10]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=3)[C:4]=2[CH:3]=1.[CH2:24](O)[CH3:25]>CN(C)C=O.[Ni]>[Cl:1][C:2]1[CH:23]=[CH:22][C:5]2[N:6]3[C:24]([CH3:25])=[N:19][CH2:18][CH:7]3[CH2:8][C:9](=[O:17])[N:10]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=3)[C:4]=2[CH:3]=1

Participants

5

Reactant 2

HCID 702EthanolHCID 706056287-Chloro-5-phenyl-1,2,3,4-tetrahydro-2-nitromethylene-5H-1, 5-benzodiazepin-4-one

Product 1

HCID 227495508-chloro-1-methyl-6-phenyl-3,3a,4,6-tetrahydro-5H-imidazo[1,5-a][1,5]benzodiazepin-5-one

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 6228DimethylformamideSolvent

Procedure

7-Chloro-5-phenyl-1,2,3,4-tetrahydro-2-nitromethylene-5H-1, 5-benzodiazepin-4-one 18.3 g (.055 mole) was dissolved in 300 ml of dimethylformamide by gentle heating on a steam bath. The solution was cooled to room temperature and 400 ml of ethanol and 55 g of Raney nickel were added. The mixture was hydrogenated at atmospheric pressure for 21 hours. The catalyst was filtered off and washed well with tetrahydrofuran and methylene chloride. The filtrate was evaporated and the residue was dissolved in 325 ml of xylene, and 40 ml of triethyl orthoacetate was added to the solution which was then refluxed for 1 hour. The mixture was evaporated and the residue was crystallized from ethyl acetate to yield end product with mp 248°-251°. The analytical sample was recrystallized from methylene chloride/ethyl acetate to give colorless crystals with mp 250°-252°.

Workup

  1. temperatureby gentle heating on a steam bath
  2. filtrationThe catalyst was filtered off
  3. washwashed well with tetrahydrofuran and methylene chloride
  4. customThe filtrate was evaporated
  5. dissolutionthe residue was dissolved in 325 ml of xylene
  6. addition40 ml of triethyl orthoacetate was added to the solution which
  7. temperaturewas then refluxed for 1 hour
  8. customThe mixture was evaporated
  9. customthe residue was crystallized from ethyl acetate
  10. customto yield end product with mp 248°-251°
  11. customThe analytical sample was recrystallized from methylene chloride/ethyl acetate
  12. customto give colorless crystals with mp 250°-252°

Sources & evidence

ORD record
ord-a4017303fe664ef4b1c5575a162d1332
Source dataset
uspto-grants-1978_03
Patent number
US04080323

Reaction notes

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