Reaction of 1,2- and 1,3-dicarbonyl compounds with 1,3-diamines: some new 1,4-diazepines

Abstract

Glyoxal sodium hydrogen sulphite addition compound reacts with 2,4-diaminopentane dihydrochloride to yield 5,7-dimethylhexahydro-l,4-diazepin-2-one, but glyoxal monohydrate reacts with 1.3-diaminopropane and 2.4-diaminopentane under alkaline conditions to produce more complex substances. Cyclohexane-I ,2-dione condenses with 1.3-diaminopropane to form 2.3.4.6.7.8-hexahydro-I H -I ,5-benzodiazepine, but di-imines formed from two molecules of dicarbonyl compound and one of diamine result from the reactions of 1.3-diaminopropane with benzil, camphorquinone, and isatin. Complex products are obtained from o-quinones and diaminopropane. 1,3-diketones and 1.3-diamines react to produce open-chain compounds formed from two molecules of ketone and one of amine. 2,3-Dihydro-I H-1.4-diazepine is apparently formed from malonaldehyde and ethylenediamine, but 1.2-diaminocyclohexane reacts with malonaldehyde to give 1,2-bis(2-formylvin~lamino~cycl o hexane.

Synthesis and DNA Strand Breakage Activity of Some 1,4-Diazepines.

“…To obtain further information on pyrazine analogues, we investigated the reaction of 1,3-propanediamine (PD) with a-dicarbonyl compounds. In this paper, we describe the synthesis of 6,7-dihydro-5H-1,4-diazepines (2b-d) 9,10) and a related 1,4-diazepine-type compound 2Јe 8) in a one-pot reaction and evaluate their DNA breakage activities.…”

“…6) By contrast, simple monocyclic 1,4-diazepines have received less attention, with the exception of the 2,3-dihydro-1H-1,4-diazepine system. 7) Regarding the 6,7-dihydro-5H-1,4-diazepine (2) system as well as the corresponding unsaturated system, the preparation of these analogues is known to be difficult 8) and occasionally unsuccessful. To obtain further information on pyrazine analogues, we investigated the reaction of 1,3-propanediamine (PD) with a-dicarbonyl compounds.…”

Assignment of the Liposidomycin Diazepanone Stereochemistry

“…Searching in 1988 for literature precedent for the synthesis of 1,4-diazepan-2-ones, we were unable to find a method suitable for making the liposidomycin diazepanone itself. The reaction of 1,3-diamines with glyoxal to give simple diazepanones had been demonstrated, and when the symmetrical partners N , N ‘-dimethylpropane-1,3-diamine ( 5 ) and the sodium bisulfite adduct of glyoxal ( 6 ) were heated together at reflux, the expected 1,4-dimethyl-1,4-diazepan-2-one 7 was formed in modest yield (Scheme ). The harsh conditions of this reaction, however, might well cause epimerization or elimination of the substituents of more elaborated diazepanones such as 3 and 4 , even if appropriate asymmetrical partner reagents could be identified.…”

Electronic Excited States of the Cyclic 1,4-Diaza-1,3-diene (Cyclic α-Diimine) System. Photochemical Reactions of 2H-Isoimidazole, 5,6-Dihydropyrazine, and 1,4-Diazepine Derivatives

“…The diazeThe cyclic 1,4-diaza-1,3-dienes used in this pine 11 was prepared in like manner from benzil study were readily prepared by condensation of and 1,3-propanediamine with little of the difficulthe a-diketone with the appropriate amine. The ty experienced by others (14). The analytical and syntheses of isoimidazoles (2, 12) and 5,6-dihy-spectral data for these compounds are given in For personal use only.…”