Sodium Nitrite → Ethyl 7-chloro-5-(2-fluorophenyl)-α-(hydroxyimino)-3H-1,4-benzodiazepine-2-acetate

HRID 127489Notes

Reaction equation

HRID 127489 reaction equation
[CH2:1]([O:3][C:4](=[O:25])[CH:5]=[C:6]1[CH2:12][N:11]=[C:10]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[F:19])[C:9]2[CH:20]=[C:21]([Cl:24])[CH:22]=[CH:23][C:8]=2[NH:7]1)[CH3:2].[N:26]([O-])=[O:27].[Na+]>C(O)(=O)C>[CH2:1]([O:3][C:4](=[O:25])[C:5](=[N:26][OH:27])[C:6]1[CH2:12][N:11]=[C:10]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[F:19])[C:9]2[CH:20]=[C:21]([Cl:24])[CH:22]=[CH:23][C:8]=2[N:7]=1)[CH3:2]

Participants

4

Reactant 2

HCID 23668193Sodium NitriteHCID 70573318HCID 70573318, compound

Product 1

HCID 136435021Ethyl 7-chloro-5-(2-fluorophenyl)-α-(hydroxyimino)-3H-1,4-benzodiazepine-2-acetate

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

The crude 7-chloro-5-(2-fluorophenyl)-1,3-dihydro-2H-1,4-benzodiazepine-2-ylideneacetic acid ethyl ester obtained by reduction of 10 g. of the end produce of Example 15 as described above was dissolved in 40 ml. of glacial acetic acid. Sodium nitrite, 2.45 g., was added with stirring over a period of 5 minutes. Following the addition the mixture was stirred at room temperature for 15 minutes. The product started to crystallize and was further precipitated by addition of 50 ml. of water. The crystals were collected, washed with water, ethanol and ether to yield the end product. The analytical sample was recrystallized from tetrahydrofuran/ethanol to give pale yellow crystals with mp 230°-233°.

Workup

  1. customof the end produce of Example 15
  2. dissolutionabove was dissolved in 40 ml
  3. addition, was added
  4. additionthe addition the mixture
  5. stirringwas stirred at room temperature for 15 minutes
  6. customto crystallize
  7. customwas further precipitated by addition of 50 ml
  8. customThe crystals were collected
  9. washwashed with water, ethanol and ether
  10. customto yield the end product
  11. customThe analytical sample was recrystallized from tetrahydrofuran/ethanol
  12. customto give pale yellow crystals with mp 230°-233°

Sources & evidence

ORD record
ord-83a282e2ca92416989cc4d3108ba57ec
Source dataset
uspto-grants-1981_03
Patent number
US04256637

Reaction notes

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