Heterocyclic variants of the 1,5‐benzodiazepine system. VI. Derivatives of 2‐methylthio‐4‐(p‐r‐phenyl)‐3H‐1,5‐benzodiazepines

Abstract

Ethyl 3‐[3H‐1,5‐benzodiazepin‐2‐yl]carbazates II were prepared in moderate yields from the title compounds and ethyl carbazate. The compounds II were easily transformed into 1H‐s‐triazolo[4,3‐a][1,5]benzodiazepin‐1‐ones III via a one‐step procedure. Reaction of triazolo‐1,5‐benzodiazepinones III with sodium hydride in methyl iodide gave a mixture of products from which were isolated two compounds IV and V. The structure of all products was confirmed by ir, 1H nmr and mass spectrometry.

Éthyl 5-méthylthio-3-(4-nitrophényl)-3a-phényl-3a,4-dihydro-3H-[1,2,4]triazolo[4,3-a][1,5]benzodiazépine-1-carboxylate

“…De  veloppant nos travaux de recherche concernant la synthe Á se des de  rive  s de benzodiaze  pines (Baouid et al, 1994(Baouid et al, , 1996Benelbaghdadi et al, 1997Benelbaghdadi et al, , 1998Essaber et al, 1998), nous de  crivons ici le comportement de la N-p-nitrophe  nyl-Ce  thoxycarbonylnitrilimine ge  ne  re  e in situ a Á partir de la N-pnitrophe  nylhydrazono--bromoglyoxylate d'e  thyle (Huisgen & Koch, 1955;Sharp & Hamilton, 1946) en pre  sence de la trie  thylamine vis-a Á-vis de la 2-me  thylthio-4-phe  nyl-3H-1,5benzodiaze  pine (Nardi et al, 1973;Cortes et al, 1991). Cette condensation dipolaire conduit a Á un seul cycloadduit avec un bon rendement.…”

Synthesis of 1,3,3a,5‐tetraaryl‐3a,4,5,6‐tetrahydro‐3H‐1,2,4‐triazolo[4,3‐a] [1,5]benzodiazepines

“…Although several synthetic methods have been developed for 1,2,4-triazole-fused 1,5-benzodiazepine derivatives [13][14][15][16], in connection with our investigation of the cycloaddition reactions of 1,5-benzodiazepines and 1,5-benzothiazepines, we have tested the 1,3-dipolar cycloaddition of 1,5-benzodiazepines with a nitrileimine for synthesis of 1,2,4-triazolo [4,3-a] [1,5]benzodiazepines (Scheme 1).…”

“…Up to now, much attention has been paid to the synthesis of 1,2,4-triazolo [1,4]benzodiazepines by various methods [9][10][11][12]. However, only a few of the 1,2,4-triazole- fused 1,5-benzodiazepine derivatives have been reported [13][14][15][16]. In recent years, our working group has synthesized numerous 1,5-benzothiazepine and 1,5-benzodiazepine tricyclic derivatives and studied their stereostructures and spectral properties due to their biological and pharmaceutical importance [17][18][19][20].…”

1,1-Dichloro-3-méthylthio-1a-phényl-1,1a,2,9-tétrahydroaziridino[2,1-d][1,5]benzodiazépine

“…Dans le but de de  velopper ces recherches vers de nouveaux syste Á mes tri ou te  trahe  te  rocycliques, ayant des structures analogues a Á celles des benzodiaze  pines actives (De Sarro et al, 1996) et pouvant pre  senter des activite  s pharmacologiques inte  ressantes, nous avons soumis la 2-me  thylthio-4-phe  nyl-1,5benzodiaze  pine (Cortes et al, 1991;Nardi et al, 1973) a Á l'action du dichlorocarbe Á ne. La me  thode de pre  paration conduisant a Á un seul produit de cycloaddition est de  crite dans la partie expe  rimentale.…”