Acetic Acid → HCID 15729047, compound

HRID 374114Notes

Reaction equation

HRID 374114 reaction equation
[CH2:1]([N:8]1[CH2:14][CH:13]([N+:15]([O-])=O)[CH2:12][N:11]([CH3:18])[CH2:10][CH:9]1[CH3:19])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:20](O)(=[O:22])[CH3:21]>C(O)C.[Ni]>[C:20]([NH:15][CH:13]1[CH2:14][N:8]([CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[CH:9]([CH3:19])[CH2:10][N:11]([CH3:18])[CH2:12]1)(=[O:22])[CH3:21]

Participants

5

Reactant 2

HCID 176Acetic AcidHCID 15729046HCID 15729046, compound

Product 1

HCID 15729047HCID 15729047, compound

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent

Conditions

Temperature
25 °C

Procedure

1-Benzyl-2,4-dimethyl-6-nitrohexahydro-1H-1,4-diazepine (5.1 g) is dissolved in ethanol (100 ml) and acetic acid (5 ml) and hydrogenated over Raney-nickel (about 1 g) at 25° C. After the calculated amount of the hydrogen is absorbed, the catalyst is filtered off. The filtrate is evaporated under reduced pressure. The residue is dissolved in chloroform (100 ml), and acetic anhydride (4.0 g) is added to the solution. The reaction mixture is stirred for 2 hours at 25° C., diluted with aqueous sodium hydroxide solution, and extracted with chloroform. The organic layer is washed successively with water, aqueous sodium hydroxide solution, and saturated aqueous sodium chloride solution, and dried over magnesium sulfate. The solvent is evaporated under reduced pressure, the residue is chromatographed on silica gel with elution of chloroform-methanol (9:1). Fractions containing the object compound are pooled and evaporated under reduced pressure to give 6-acetylamino-1-benzyl-2,4-dimethylhexahydro-1H-1,4-diazepine (1.8 g) as an oil. The above compound is dissolved in 10% hydrochloric acid (20 ml) and is refluxed for 2 hours. After cooling, the reaction mixture is basified with aqueous sodium hydroxide solution and extracted with chloroform. The organic layer is washed successively with water and saturated aqueous sodium chloride solution, and dried over magnesium sulfate. The solvent is evaporated under reduced pressure to give the title compound (1.5 g).

Workup

  1. customat 25° C
  2. customAfter the calculated amount of the hydrogen is absorbed
  3. filtrationthe catalyst is filtered off
  4. customThe filtrate is evaporated under reduced pressure
  5. dissolutionThe residue is dissolved in chloroform (100 ml)
  6. additionacetic anhydride (4.0 g) is added to the solution
  7. additiondiluted with aqueous sodium hydroxide solution
  8. extractionextracted with chloroform
  9. washThe organic layer is washed successively with water, aqueous sodium hydroxide solution, and saturated aqueous sodium chloride solution
  10. dry with materialdried over magnesium sulfate
  11. customThe solvent is evaporated under reduced pressure
  12. customthe residue is chromatographed on silica gel with elution of chloroform-methanol (9:1)
  13. additionFractions containing the object compound
  14. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-a78d72b279394e83b84c9b085dbd3220
Source dataset
uspto-grants-1992_11
Patent number
US05166341

Reaction notes

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