1-Butanol → 1-methyl-8-chloro-6-phenyl-4H-s-triazolo-[4,3-a][1,5]benzodiazepin-5-one

HRID 616590Notes

Reaction equation

HRID 616590 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:11][C:10](=S)[CH2:9][C:8](=S)[N:7]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[C:6]=2[CH:20]=1.[C:21]([NH:24][NH2:25])(=O)[CH3:22].C([OH:30])CCC.CO>C(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[C:21]([CH3:22])=[N:24][N:25]=[C:10]3[CH2:9][C:8](=[O:30])[N:7]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[C:6]=2[CH:20]=1

Participants

6

Reactant 4

HCID 2631-ButanolHCID 887MethanolHCID 14039AcetohydrazideHCID 203679948-chloro-1-phenyl-1H-1,5-benzodiazepin-2,4-(3H,5H)-dithione

Product 1

HCID 122643201-methyl-8-chloro-6-phenyl-4H-s-triazolo-[4,3-a][1,5]benzodiazepin-5-one

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

A solution of 3 g. (0.01 mole) of 8-chloro-1-phenyl-4-thio-1H-1,5-benzodiazepin-2,4-(3H,5H)-dione and 8-chloro-1-phenyl-1H-1,5-benzodiazepin-2,4-(3H,5H)-dithione and 2 g. (0.024 mole) of acethydrazide in 300 ml. of n-butanol is refluxed for 24 hours. During this period nitrogen is bubbled through the reaction mixture. The solution is evaporated to dryness in vacuo and the residue is treated with cold water which gives 2.7 g. of yellow material. This material was found by thin layer chromatography (SiO2, 10% methanol; 90% chloroform) to be a mixture of three compounds and was chromatographed on 300 g. of silica gel using 3% methanol:97% chloroform as an eluting solvent. Fractions 12-19 (100 ml. each) were combined and concentrated giving 1.2 g. of product. This was recrystallized from absolute ethanol giving 800 mg. of white 8-chloro-1-methyl-6-phenyl-4H-s-triazolo[4,3 -a][1,5]benzodiazepin-5(6H)-one as white crystalline product of melting point 297°-298° C.

Workup

  1. customDuring this period nitrogen is bubbled through the reaction mixture
  2. customThe solution is evaporated to dryness in vacuo
  3. additionthe residue is treated with cold water which
  4. customgives 2.7 g
  5. additiona mixture of three compounds
  6. customwas chromatographed on 300 g
  7. concentrationconcentrated
  8. customgiving 1.2 g
  9. customThis was recrystallized from absolute ethanol giving 800 mg

Sources & evidence

ORD record
ord-1dad5f0e2e8e46499e327249bd60143f
Source dataset
uspto-grants-1978_02
Patent number
US04075202

Reaction notes

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