Phosphorus sulfide (P2S5) → 7-chloro-1,3-dihydro-3-methyl-5-phenyl-2H-1,4-benzodiazepine-2-thione

HRID 1789587Notes

Reaction equation

HRID 1789587 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:11][C:10](=O)[CH:9]([CH3:13])[N:8]=[C:7]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[C:6]=2[CH:20]=1.P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=[S:22]>N1C=CC=CC=1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:11][C:10](=[S:22])[CH:9]([CH3:13])[N:8]=[C:7]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[C:6]=2[CH:20]=1

Participants

4

Reactant 2

HCID 14817Phosphorus sulfide (P2S5)HCID 382377-chloro-3-methyl-5-phenyl-2,3-dihydro-1H-1,4-benzodiazepin-2-one

Product 1

HCID 126124347-chloro-1,3-dihydro-3-methyl-5-phenyl-2H-1,4-benzodiazepine-2-thioneYield 28.5%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

A stirred mixture of 7-chloro-1,3-dihydro-3-methyl-5-phenyl-2H-1,4 -benzodiazepin-2-one (10 g, 0.035 mol) in pyridine (300 ml), treated with P2S5 (8.0 g, 0.036 mol) was refluxed, under N2, for 2 hours then concentrated in vacuo. To remove the remaining pyridine the residue was combined with toluene twice with concentration after each addition. The remaining material was mixed with cold NaHCO3 and extracted twice with CH2Cl2. At this point a precipitate thought to be undissolved product formed between the two layers. This was filtered and washed with CH2Cl2 and H2O . The NaHCO3 layer was extracted with CH2Cl2 again. The combined CH2Cl2 extracts were washed with brine, dried over Na2SO4, and concentrated in vacuo. The residue was crystallized from EtOAc-Skelly B to give 3.0 g of the subtitled intermediate, mp 250°. The precipitate was also recrystallized from EtOAc-Skelly B to give 3.01 g of additional subtitled intermediate, mp 255°.

Workup

  1. temperaturewas refluxed, under N2, for 2 hours
  2. concentrationthen concentrated in vacuo
  3. customTo remove the remaining pyridine the residue
  4. concentrationwas combined with toluene twice with concentration
  5. additionafter each addition
  6. additionThe remaining material was mixed with cold NaHCO3
  7. extractionextracted twice with CH2Cl2
  8. customformed between the two layers
  9. filtrationThis was filtered
  10. washwashed with CH2Cl2 and H2O
  11. extractionThe NaHCO3 layer was extracted with CH2Cl2 again
  12. washThe combined CH2Cl2 extracts were washed with brine
  13. dry with materialdried over Na2SO4
  14. concentrationconcentrated in vacuo
  15. customThe residue was crystallized from EtOAc-Skelly B

Sources & evidence

ORD record
ord-4a7555b3ee7d41e19e75897c9406272c
Source dataset
uspto-grants-1987_08
Patent number
US04689413

Reaction notes

Loading…