V. Yu. Petukhova

Reaction of 1,2-dialkyldiaziridines with ketenes as a new approach to cyclic and linear systems containing the N— C—N fragment

The reaction of 1,2-dialkyldiaziridines with ketenes proceeds through the N—N bond cleavage to form three types of structures containing the N—C—N fragment, viz., 1,3-dialkylimidazolidin-4-ones, 3,5-diacyl-3,5-diazahept-1-enes, and β-lactams. The reaction pathway depends on the reaction conditions and the structures of the starting compounds.

Generation and metathesis of azomethine imines in reaction of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes with het(aryl)methylidenemalononitriles

A new metathesis reaction of azomethine imines is found. Catalytic or thermal diaziridine ring opening of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes leads to azomethine imines reacting further with het(aryl)methylidenemalononitriles to give in situ new azomethine imines inaccessible by common synthetic methods. New azomethine imines are detected as pyrazolines formed via a 1,4-H shift and trapped by the [3+2] cycloaddition with various dipolarophiles to yield 1,5-diazabicyclo[3.3.0]octane derivatives bearing pharmacophoric heterocycles, e.g. furan, nitrofuran, thiophene, and indole. The best results are achieved in the Et2O·BF3-catalyzed reactions in ionic liquids.

Synthesis and structure of 1-[ω-(3,3-dialkyldiaziridin-1-yl)alkyl]-3,3-dialkyldiaziridines

A method for the synthesis of 1-[ω-(3,3-dialkyldiaziridin-1-yl)alkyl]-3,3-dialkyldiaziridines based on the reaction of ketoxime O-arenesulfonates with alkylenediamines was developed. Diastrereomers (the racemic and meso forms) of 1-[2-(3,3-dimethyldiaziridin-1-yl)ethyl]-3,3-dimethyldiaziridine were isolated. The structure of the meso form was confirmed by X-ray diffraction analysis.

Synthesis and structures of complexes ofN-(2-aminoethyl)diaziridines with transition metal salts

A series of complexes ofN-(2-aminoethyl)diaziridines with transition metal salts (Zn2+, Cd2+, Ni2+, Co2+, Mn2+, or Fe2+) were synthesized. Their structures were established by IR and NMR spectroscopy. The structure of bis[1,2-bis(2-aminoethyl)diaziridine]cadmium(II) diperehlorate was confirmed by X-ray diffraction analysis.

Reaction of O-substituted hydroxylamines with aldimines and primary aliphatic amines in the synthesis of diaziridines

Conclusions1.We have studied the synthesis of diaziridines from aldehydes by the reaction of O-mesitylsulfonyl-, O-mesitoyl-,O-(2,4-dinitrophenyl)- and O-picrylhydroxylamines with N-ethylidene-n-butylamine, and with a butylamine-acetaldehyde mixture. For this purpose, only the first two aminating reagents are suitable.2.Two other aminating reagents, viz., O-(2,4-dinitrophenyl)- and O-picrylhydroxylamines, can aminate aldimines at the N atom.3.The difference in reactivity of the two pairs of aminating reagents is determined by the greater nucleophilic properties of O-mesitylsulfonyl- and O-mesitoylhydroxylamines, as compared with O-(2,4-dinitrophenyl)- and O-picrylhydroxylamines.4.These aminating reagents do not aminate butylamine to butylhydrazine, but are decomposed by its alkalinity to yield the respective acids.

Synthesis of 1,3,5-triazabicyclo[3.1.0]hexanes containing the fragments of α-amino acids and their esters at the N(3) atom

With 3,3-pentamethylene-1,2H-diaziridine as an example, it was shown that 3,3-dialkyl-1,2H-diaziridines can undergo cyclocondensation with α-amino acids and their esters to give the corresponding N(3)-substituted 1,3,5-triazabicyclo[3.1.0]hexanes, including pure enantiomers.

Diastereoselective synthesis of substituted 1,3,6-triazabicyclo[3.1.0]hexanes

A general method was developed for the synthesis of substituted 1,3,6-triazabicyclo[3.1.0]hexanes via intramolecular aminomethylation of the NH group of the diaziridine ring by the reactions of 3-aminomethyl-1,3-dimethyldiaziridine with aliphatic, aromatic, and heteroaromatic carbonyl compounds. These reactions with aldehydes proceeded diastereoselectively to form mixtures of two racemates, viz., 1R*,2R*,5R*,6R* and 1R*,2S*,5R*,6R*, in a ratio of (3—20) : 1, the predominant diastereomer being isolated in all cases. The reactions with symmetrical ketones gave rise exclusively to the (1R*,5R*,6R*) racemate. The predominant diastereomer 1R*,2R*,5R*,6R*-2-(2-bromothien-5-yl)-1,3,6-triazabicyclo[3.1.0]hexane crystallized as a conglomerate. The structure of one of its enantiomers was established by X-ray diffraction analysis.

Synthesis of unsubstituted 1,3,5-triazabicyclo[3.1.0]hexane

Unsubstituted 1,3,5-triazabicyclo[3.1.0]hexane has been syntesized for the first time by treating a Henry solution with NaOCl.