Anellierte 2,4‐Benzodiazepine 1. Mitteilung

Abstract

Durch die Auswahl geeigneter Substrate wurde mit der Quecksilber(II)‐ED‐TA‐Dehydrierung ein neuer Syntheseweg für die Stoffklasse kondensierter 2,4‐Benzodiazepine mit Amidin‐, Acylaminal‐ und Hydroximinoaminal‐Partialstruktur gefunden. Bei Verwendung des gewählten Oxidationsmittels konnte hier erstmalig eine Nachbargruppenbeteiligung δ‐ständiger nucleophiler Zentren beobachtet werden.

Oximes of Seven-Membered Heterocyclic Compounds Containing Two Heteroatoms

“…Thus, reaction of 1-phenyl-5-methyl-8-chloro-1,2,4,5-tetrahydro-2,4-dioxo-3H-1,5-benzodiazepine 9 with tert-amyl nitrite in the presence of tertBuOK in tert-BuOH affords oxime 10 in 85% yield [9]. Treatment of (Z)-2-piperidinomethyl benzamidoxime (11) with ethylenediaminetetraacetic acid disodium salt in ethanol in the presence of HgO leads to formation of the oxime of benzodiazepinone 12 in 75% yield [11]. Reaction of benzene-1,2-diamine (13) and 4,4,4-trifluoro-2-[(Z)-hydroxyimino]-3-oxobutyric acid ethyl ester in diethyl ether affords oxime 14 in 80% yield [12].…”

Synthesis of Novel Pyrido[1,2-b][2,4]Benzodiazepine Derivatives

“…2 In another example, the diazepine ring was added to a pyridine by using 2-bromomethylbenzoic acid derivatives. 1,[3][4][5] We now describe a new method for the synthesis of pyrido [1,2-b] [2,4]benzodiazepines which is based on the reaction of [2-(bromomethyl)phenyl](phenyl) methanone (о-bromomethylbenzophenone, 1) derivatives with 2-aminopyridines (2). Substances of type 1 are α-bromoacetophenone 7 viniloges, 6 which suggests the possibility of a cyclisation that is similar to the Chichibabin synthesis.…”

One-Pot Synthesis of 2,4-Benzodiazepin-1-ones Using Benzotriazole Methodology

“…Synthetic interest has so far focused on 1,4-benzodiazepines, 1,5-benzodiazepines, and 2,3-benzodiazepines . Published synthetic routes to 2,4-benzodiazepines are scarce: 2,4-benzodiazepin-1,3-diones are formed by the palladium-catalyzed intramolecular cyclization of 1-butyl-1( o -iodobenzyl)-3-phenylurea, and there is one reported synthesis of 2,3-benzodiazepin-1-one from 2-[(dimethylamino)methyl]benzamide . We now describe a one-pot synthesis of 2, 4-benzodiazepin-1-ones utilizing benzotriazole strategy.…”