1-(2-Chloro-4-nitrophenyl)-7,8-methylenedioxy-3,5-dihydro-2,3-benzodiazepin-4(4H)-one → 1-(4-Amino-2-chlorophenyl)-7,8-methylenedioxy-3,5-dihydro-2,3-benzodiazepin-4(4H)-one

HRID 442691Notes

Reaction equation

HRID 442691 reaction equation
[CH2:1]1[O:25][C:4]2=[CH:5][C:6]3[C:12]([C:13]4[CH:18]=[CH:17][C:16]([N+:19]([O-])=O)=[CH:15][C:14]=4[Cl:22])=[N:11][NH:10][C:9](=[O:23])[CH2:8][C:7]=3[CH:24]=[C:3]2[O:2]1.C(O)C.CC(C)=O.O>[Pd].C(O)C>[NH2:19][C:16]1[CH:17]=[CH:18][C:13]([C:12]2[C:6]3[CH:5]=[C:4]4[O:25][CH2:1][O:2][C:3]4=[CH:24][C:7]=3[CH2:8][C:9](=[O:23])[NH:10][N:11]=2)=[C:14]([Cl:22])[CH:15]=1

Participants

5

Reactant 2

HCID 540649381-(2-Chloro-4-nitrophenyl)-7,8-methylenedioxy-3,5-dihydro-2,3-benzodiazepin-4(4H)-oneHCID 86654442Ethanol acetone water

Product 1

HCID 541883761-(4-Amino-2-chlorophenyl)-7,8-methylenedioxy-3,5-dihydro-2,3-benzodiazepin-4(4H)-oneYield 21%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

To a suspension of 7,8-methylenedioxy-1-(2-chloro-4-nitrophenyl)-3,5-dihydro-2,3-benzodiazepin-4(4H)-one (1.4 g, 3.9 mmol) in 1:1:1 ethanol/acetone/water (45 mL) was added 5% Pd/C (106 mg) and HCO2NH4 (2.5 g, 40 mmol). The mixture was stirred at room temperature for 3 h and 15 mL of ethanol was added to the mixture which was then stirred at room temperature for three days. The catalyst was filtered out. The filtrate was extracted with EtOAc (100 mL). The organic phase was washed with water and brine, dried over Na2SO4 and concentrated in vacuo. The residue was purified by chromatography (1:4 hexane/EtOAc) to afford the title compound as a light yellow solid (0.27 g, 0.82 mmol, 21%), mp: 238°-240° C. 1H NMR (CDCl3) 8.34 (s, 1H), 7.41 (d, J=8.6, 1H), 6.81 (s, 1H), 6.69-6.67 (m, 3H), 6.02 (s, 2H), 3.92 (s, 2H), 3.42 (s, 2H).

Workup

  1. stirringwas then stirred at room temperature for three days
  2. filtrationThe catalyst was filtered out
  3. extractionThe filtrate was extracted with EtOAc (100 mL)
  4. washThe organic phase was washed with water and brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by chromatography (1:4 hexane/EtOAc)

Sources & evidence

ORD record
ord-e230b17544fb4d00a3bf027f2f01b34a
Source dataset
uspto-grants-1999_04
Patent number
US05891871

Reaction notes

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