Dimethylformamide → HCID 178486406, compound

HRID 2112510Notes

Reaction equation

HRID 2112510 reaction equation
[Br:1][C:2]1[C:3]([O:21][CH3:22])=[CH:4][C:5]2[NH:11][C:10](=S)[CH2:9][N:8]=[C:7]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=3[Cl:19])[C:6]=2[CH:20]=1.CO[C:25](OC)([N:27](C)C)[CH3:26].C[N:33](C)C=O>>[Br:1][C:2]1[C:3]([O:21][CH3:22])=[CH:4][C:5]2[N:11]=[C:10]3[NH:33][NH:27][C:25]([CH3:26])=[C:9]3[N:8]=[C:7]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=3[Cl:19])[C:6]=2[CH:20]=1

Participants

4

Reactant 3

HCID 6228DimethylformamideHCID 878351,1-Dimethoxyethyl(dimethyl)amineHCID 57642331HCID 57642331, compound

Product 1

HCID 178486406HCID 178486406, compound

Procedure

A mixture of 1.8 g (0.00455 mole) of 7-bromo-5-(2-chlorophenyl)-1,3-dihydro-8-methoxy-2H-1,4-benzodiazepin-2-thione (IId), 2.26 mL of 1,1-dimethoxy-N,N-dimethyl-ethanamine and 20 mL of dimethylformamide was stirred at room temperature for 1.5 hours, then at 110° C. for 5 hours. The mixture was cooled and concentrated under reduced pressure. The crude intermediate, IIId, was stirred with a solution of 0.713 mL of anhydrous hydrazine, 9 mL of methanol and 24 mL of dichloromethane for 26 hours and then partitioned between ethyl acetate and water. The ethyl acetate layer was washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. Chromatography on silica gel, eluting with ethyl acetate yielded 0.690 g of 7-bromo-5-(2-chlorophenyl)-1,2-dihydro-8-methoxy-3-methyl-pyrazolo[3,4-b][1,4]benzodiazepine (IVd). Recrystallization from dichloromethane provided the crystalline 7-bromo-5-(2-chlorophenyl)-1,2-dihydro-8-methoxy-3-methyl-pyrazolo[3,4-b][1,4]benzodiazepine (IVd), mp 210-211° C. MH+/Z=417.

Workup

  1. waitat 110° C. for 5 hours
  2. temperatureThe mixture was cooled
  3. concentrationconcentrated under reduced pressure
  4. stirringThe crude intermediate, IIId, was stirred with a solution of 0.713 mL of anhydrous hydrazine, 9 mL of methanol and 24 mL of dichloromethane for 26 hours
  5. custompartitioned between ethyl acetate and water
  6. washThe ethyl acetate layer was washed with water
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. washChromatography on silica gel, eluting with ethyl acetate

Sources & evidence

ORD record
ord-6bbb82da6ea844888844ee59dce4e250
Source dataset
uspto-grants-2009_04
Patent number
US07524840B2

Reaction notes

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