2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 8-Chloro-2-methyl-6-phenyl-4H-pyrazolo[1,5-a][1,4]benzodiazepine

HRID 66236

Reaction equation

HRID 66236 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[N:12]=[C:13]([CH3:15])[CH:14]=[C:10]3[C:9](=O)[NH:8][CH:7]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)[C:6]=2[CH:23]=1.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>C1COCC1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[N:12]=[C:13]([CH3:15])[CH:14]=[C:10]3[CH2:9][N:8]=[C:7]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)[C:6]=2[CH:23]=1

Participants

4

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 123778928-Chloro-2-methyl-5,6-dihydro-4-oxo-6-phenyl-4H-pyrazolo[1,5-a][1,4]benzodiazepine

Product 1

HCID 123778938-Chloro-2-methyl-6-phenyl-4H-pyrazolo[1,5-a][1,4]benzodiazepine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 2.52 g. (7.8 mmol) of the end product of Example 16 in 75 ml. dry THF was reduced with 3.12 ml. (31.2 mmol) of BMS according to the procedure described above in 6, Method B. The crude product from this reduction was then treated with 2.15 g. (9.4 mmol) of DDQ according to the oxidation procedure described above in Example 8. The crude oxidation product was chromatographed on a 29 × 20 cm column of silica gel packed in benzene and eluted first with 3% EtOAc in benzene and then 5% EtOAc in benzene. Recrystallization from CH3OH/H2O of the material isolated from the column yielded the analytically pure end product as colorless needles: mp 105°-107°.

Workup

  1. customThe crude oxidation product was chromatographed on a 29 × 20 cm column of silica gel
  2. washeluted first with 3% EtOAc in benzene
  3. customRecrystallization from CH3OH/H2O of the material
  4. customisolated from the column
  5. customyielded the analytically pure end product as colorless needles

Sources & evidence

ORD record
ord-37ac342721a2430aa03c43144fd54248
Source dataset
uspto-grants-1978_12
Patent number
US04130716

Linked notes

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