Nitrogen → HCID 20188514, compound

HRID 1789588Notes

Reaction equation

HRID 1789588 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:11][C:10](=S)[CH:9]([CH3:13])[N:8]=[C:7](C3C=CC=CC=3)[C:6]=2[CH:20]=1.[C:21]1([CH2:27][C:28]([NH:30][NH2:31])=O)[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.N#N>C(O)CCC>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[C:28]([CH2:27][C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=4)=[N:30][N:31]=[C:10]3[CH:9]([CH3:13])[N:8]=[CH:7][C:6]=2[CH:20]=1

Participants

5

Reactant 3

HCID 947NitrogenHCID 70301Benzeneacetic acid, hydrazideHCID 126124347-chloro-1,3-dihydro-3-methyl-5-phenyl-2H-1,4-benzodiazepine-2-thione

Product 1

HCID 20188514HCID 20188514, compoundYield 48%

Reagents, catalysts & solvents 1

HCID 2631-ButanolSolvent

Procedure

A stirred mixture of 7-chloro-1,3-dihydro-3-methyl-5-phenyl-2H-1,4 -benzodiazepine-2-thione (3.0 g, 0.01 mol), phenyl acetic acid hydrazide (4.95 g, 0.033 mol) and butanol (150 ml) was refluxed for 16 hours while N2 was being bubbled through the mixture. The reaction mixture was concentrated under high vacuum, and the residue mixed with iced H2O. The product was filtered and dissolved in CH2Cl2. The CH2Cl2 was washed with dilute HCl and brine, dried over Na2SO4 and concentrated in vacuo. At this point it appeared that complete cyclization had not been achieved. Therefore, the residue was combined with acetic acid (100 ml) and refluxed for 2 hours under N2. The reaction mixture was concentrated in vacuo and the residue mixed with CH2Cl2 and H2O. The CH2Cl2 was washed with NaHCO3 and brine, dried over Na2SO4 and concentrated in vacuo. The material was crystallized from EtOAc-Skelly B to give 1.55 g, mp 195°-197° of the subtitled intermediate, which had a C:H:N:Cl ratio of 72.38:4.85:14.16:8.81. Calculated for C24H19N4Cl: 72.26:4.80:14.05:8.89.

Workup

  1. customwas being bubbled through the mixture
  2. concentrationThe reaction mixture was concentrated under high vacuum
  3. additionthe residue mixed with iced H2O
  4. filtrationThe product was filtered
  5. dissolutiondissolved in CH2Cl2
  6. washThe CH2Cl2 was washed with dilute HCl and brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated in vacuo
  9. temperaturerefluxed for 2 hours under N2
  10. concentrationThe reaction mixture was concentrated in vacuo
  11. additionthe residue mixed with CH2Cl2 and H2O
  12. washThe CH2Cl2 was washed with NaHCO3 and brine
  13. dry with materialdried over Na2SO4
  14. concentrationconcentrated in vacuo
  15. customThe material was crystallized from EtOAc-Skelly B

Sources & evidence

ORD record
ord-b4428ac60e6c496ca0f1e60747a77b73
Source dataset
uspto-grants-1987_08
Patent number
US04689413

Reaction notes

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