alpha-Hydroxyalprazolam → 6-phenyl-8-chloro-4H-s-triazolo[4,3-a][1,4]benzodiazepine-1-carboxaldehyde

HRID 1414906Notes

Reaction equation

HRID 1414906 reaction equation
[C:1]1([C:7]2[C:13]3[CH:14]=[C:15]([Cl:18])[CH:16]=[CH:17][C:12]=3[N:11]3[C:19]([CH2:22][OH:23])=[N:20][N:21]=[C:10]3[CH2:9][N:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1>[O-2].[O-2].[Mn+4].C1C=CC=CC=1>[C:1]1([C:7]2[C:13]3[CH:14]=[C:15]([Cl:18])[CH:16]=[CH:17][C:12]=3[N:11]3[C:19]([CH:22]=[O:23])=[N:20][N:21]=[C:10]3[CH2:9][N:8]=2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

4

Reactant 1

HCID 162244alpha-Hydroxyalprazolam2×

Product 1

HCID 214860116-phenyl-8-chloro-4H-s-triazolo[4,3-a][1,4]benzodiazepine-1-carboxaldehyde

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalystHCID 241BenzeneSolvent

Procedure

A mixture of 1.3 g of 6-phenyl-8-chloro-4H-s-triazolo [4,3-a][1,4]benzodiazepine-1-methanol [cp., e.g. German `Offenlegungsschrift` No. 2,156,472, Belgian Pat. No. 775,558] , 3.4 g of manganese dioxide and 80 ml of benzene is refluxed for 2 hours. The reaction mixture is then filtered through a layer of silica gel, and the filtrate concentrated by evaporation. The residue is chromatographed through silica gel (Merck, 0.063 - 0.2 mm particle size) with various ethyl acetate/ethanol mixtures of increasing ethanol content as the eluant. The fractions eluted with ethyl acetate/ethanol (4:1) are combined and concentrated by evaporation. The residue is crystallised from ethyl acetate/petroleum ether to obtain 6-phenyl-8-chloro-4H-s-triazolo[4,3-a] [1,4]benzodiazepine-1-carboxaldehyde, M.P. 161°-163°.

Workup

  1. filtrationThe reaction mixture is then filtered through a layer of silica gel
  2. concentrationthe filtrate concentrated by evaporation
  3. customThe residue is chromatographed through silica gel (Merck, 0.063 - 0.2 mm particle size) with various ethyl acetate/ethanol mixtures of increasing ethanol content as the eluant
  4. washThe fractions eluted with ethyl acetate/ethanol (4:1)
  5. concentrationconcentrated by evaporation
  6. customThe residue is crystallised from ethyl acetate/petroleum ether

Sources & evidence

ORD record
ord-ebe97f1dc49447a3b1dc27d7a0db5031
Source dataset
uspto-grants-1977_01
Patent number
US04002764

Reaction notes

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