Hydrazine hydrate (1:1) → 8-chloro-1-[(aminooxy)methyl]6-phenyl-4H-s-triazolo[4,3-a][1,4]benzodiazepine

HRID 436556Notes

Reaction equation

HRID 436556 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[C:12]([CH2:15][O:16][N:17]4C(=O)C5=CC=CC=C5C4=O)=[N:13][N:14]=[C:10]3[CH2:9][N:8]=[C:7]([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)[C:6]=2[CH:34]=1.O.NN>C(O)C>[NH2:17][O:16][CH2:15][C:12]1[N:11]2[C:5]3[CH:4]=[CH:3][C:2]([Cl:1])=[CH:34][C:6]=3[C:7]([C:28]3[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=3)=[N:8][CH2:9][C:10]2=[N:14][N:13]=1

Participants

4

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 126124258-chloro-6-phenyl-1-[(phthalimidooxy)methyl]-4H-s-triazolo[4,3-a][1,4]benzodiazepine

Product 1

HCID 126124268-chloro-1-[(aminooxy)methyl]6-phenyl-4H-s-triazolo[4,3-a][1,4]benzodiazepine

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
70 °C

Procedure

A stirred suspension of 8-chloro-6-phenyl-1-[(phthalimidooxy)methyl]-4H-s-triazolo[4,3-a][1,4]benzodiazepine (9.4 g., 0.02 mole) in absolute ethanol (100 ml.) was treated with hydrazine hydrate (1.45 ml.) and warmed, under nitrogen, at a bath temperature at 70° C. for 3 hours. The mixture was cooled in an ice bath and filtered. The solid was washed with ethanol and methylene chloride. The combined filtrate was concentrated in vacuo; the residue was mixed with water and extracted with methylene chloride. The extract was washed with water, dried over anhydrous sodium sulfate and concentrated. The residue was dissolved in chloroform-ethyl-acetate and filtered through a small pad of silica gel. The filtrate was crystallized from methanol-ethylacetate to give 1-[(aminooxy)methyl]-8-chloro-6-phenyl-4H-s-triazolo-[4,3-a][1,4]benzodiazepine in three crops: 1.95 g. of melting point 190°-191.5° C.; 0.89 g. of melting point 183°-186° C.; 0.285 g. of melting point 183°-186° C. The analytical sample had a melting point 191°-192° C.

Workup

  1. temperatureThe mixture was cooled in an ice bath
  2. filtrationfiltered
  3. washThe solid was washed with ethanol and methylene chloride
  4. concentrationThe combined filtrate was concentrated in vacuo
  5. additionthe residue was mixed with water
  6. extractionextracted with methylene chloride
  7. washThe extract was washed with water
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationconcentrated
  10. dissolutionThe residue was dissolved in chloroform-ethyl-acetate
  11. filtrationfiltered through a small pad of silica gel
  12. customThe filtrate was crystallized from methanol-ethylacetate

Sources & evidence

ORD record
ord-722cf0d58a1f459eb8712057338dcdb4
Source dataset
uspto-grants-1977_02
Patent number
US04009175

Reaction notes

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