Triethylamine → (+)-5-(o-fluorophenyl)-1,3-dihydro-3-methyl-7-nitro-2H-1,4-benzodiazepin-2-thione

HRID 437335Notes

Reaction equation

HRID 437335 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[C:14]2[CH:15]=[C:16]([N+:19]([O-:21])=[O:20])[CH:17]=[CH:18][C:13]=2[NH:12][C:11](=O)[CH:10]([CH3:23])[N:9]=1.P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=[S:25].C(N(CC)CC)C>O1CCOCC1>[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[C:14]2[CH:15]=[C:16]([N+:19]([O-:21])=[O:20])[CH:17]=[CH:18][C:13]=2[NH:12][C:11](=[S:25])[CH:10]([CH3:23])[N:9]=1

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 14817Phosphorus sulfide (P2S5)HCID 20542078(+)-5-(o-fluorophenyl)-1,3-dihydro-3-methyl-7-nitro-2H-1,4-benzodiazepin-2-one

Product 1

HCID 21428189(+)-5-(o-fluorophenyl)-1,3-dihydro-3-methyl-7-nitro-2H-1,4-benzodiazepin-2-thione

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

32 g of (+)-5-(o-fluorophenyl)-1,3-dihydro-3-methyl-7-nitro-2H-1,4-benzodiazepin-2-one are dissolved in 450 ml of absolute dioxane and treated with 21 g of phosphorus pentasulfide and 15 ml of triethylamine. The mixture is heated to reflux for 20 minutes, cooled with ice and concentrated on a rotary evaporator. The residue is treated with 10% bicarbonate solution and ethyl acetate and the ethyl acetate phase is washed twice with 10% bicarbonate solution, dried with sodium sulfate, filtered and concentrated. Crystallisation of the residue from ethanol yields racemate. By concentration of the mother liquor, there is obtained crude (+)-5-(o-fluorophenyl)-1,3-dihydro-3-methyl-7-nitro-2H-1,4-benzodiazepin-2-thione which exhibits a rotation of [α]25D =+319.1° (in methylene chloride, 1%).

Workup

  1. temperatureThe mixture is heated
  2. temperatureto reflux for 20 minutes
  3. temperaturecooled with ice
  4. concentrationconcentrated on a rotary evaporator
  5. additionThe residue is treated with 10% bicarbonate solution and ethyl acetate
  6. washthe ethyl acetate phase is washed twice with 10% bicarbonate solution
  7. dry with materialdried with sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customCrystallisation of the residue from ethanol
  11. customyields racemate

Sources & evidence

ORD record
ord-4194b2f47df24ca0a92ae5c532e10e47
Source dataset
uspto-grants-1977_06
Patent number
US04031078

Reaction notes

Loading…