Potassium Cyanide → Cyclopropylmethyl 8-chloro-9-oxo-12,12a-dihydro-9H,11H-azeto[2,1-c]imidazo[1,5-a][1,4]benzodiazepine-1-carboxylate

HRID 1154429Notes

Reaction equation

HRID 1154429 reaction equation
[Cl:1][C:2]1[C:7]2[C:8](=[O:23])[N:9]3[CH2:22][CH2:21][C@H:10]3[C:11]3[N:12]([CH:13]=[N:14][C:15]=3[C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:6]=2[CH:5]=[CH:4][CH:3]=1.[C-]#N.[K+].O[CH2:28][CH:29]1CC1>>[Cl:1][C:2]1[C:7]2[C:8](=[O:23])[N:9]3[CH2:22][CH2:21][C@H:10]3[C:11]3[N:12]([CH:13]=[N:14][C:15]=3[C:16]([O:18][CH2:19][CH:20]3[CH2:29][CH2:28]3)=[O:17])[C:6]=2[CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 3

HCID 9032Potassium CyanideHCID 75644CyclopropanemethanolHCID 54398902HCID 54398902, compound

Product 1

HCID 146197Cyclopropylmethyl 8-chloro-9-oxo-12,12a-dihydro-9H,11H-azeto[2,1-c]imidazo[1,5-a][1,4]benzodiazepine-1-carboxylate

Procedure

A mixture of 8.0 g (24 mmol) of ethyl (S)-8-chloro-12,12a-dihydro-9-oxo-9H,11H-azeto[2,1-c]imidazo[1,5-a][1,4]benzodiazepine-1-carboxylate, 0.5 g (7.7 mmol) of potassium cyanide and 60 ml of hydroxymethyl-cyclopropane is stirred at 130° for 5 hours, during this time a small amount of solvent being distilled off four times by the application of a slight vacuum. The mixture is subsequently evaporated in vacuo, the residue is partitioned between water and methylene chloride and the aqueous phase is extracted twice with methylene chloride. The combined organic extracts are washed three times with saturated sodium chloride solution, dried over magnesium sulphate and evaporated. The crude product is crystallized from ethyl acetate and there is obtained cyclopropylmethyl (S)-8-chloro-12,12a-dihydro-9-oxo-9H,11H-azeto[2,1-c]imidazo[1,5-a][1,4]benzodiazepine-1-carboxylate of decomposition point 183°-185° (partially racemized).

Workup

  1. distillationbeing distilled off four times by the application of a slight vacuum
  2. customThe mixture is subsequently evaporated in vacuo
  3. customthe residue is partitioned between water and methylene chloride
  4. extractionthe aqueous phase is extracted twice with methylene chloride
  5. washThe combined organic extracts are washed three times with saturated sodium chloride solution
  6. dry with materialdried over magnesium sulphate
  7. customevaporated
  8. customThe crude product is crystallized from ethyl acetate

Sources & evidence

ORD record
ord-4ea1fa1c43004d2898551bb14dfb3a41
Source dataset
uspto-grants-1984_12
Patent number
US04489003

Reaction notes

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