Gulnara K. Kadorkina

Sterically hindered inversion of nitrogen atoms in cyclic hydrazines:N,N′-dialkyl-1,3,4-oxadiazolidines; 1,3,4-thiadiazolidine; and 4,5-benzo-1,2,3,6-tetrahydropyridazine

N,N′-Diisopropyl-substituted 1,3,4-oxadiazolidine3c, 1,3,4-thiadiazolidine6, 4,5-benzo-1,2,3,6-tetrahydropyridazine8, and new 3,4-dialkyl-1,3,4-oxadiazolidines9–14 were synthesized and studied. The configurational stability of the N atoms does not change on going from compound3c to itsS-analog6 and decreases in the case of pyridazine8. 3,4-Di-tert-alkyl-1,3,4-oxadiazolidines3d and11–14 were found to be promising objectes for optical resolution.

Structure of products of the reaction of 2-cyanoaziridine with carbonyl compounds

The structure of azimexone (3), the product of the reaction of 2-cyanoaziridine with acetone, was confirmed on the basis of1H and13C NMR spectra. The formation of this product is accounted for by the α-aziridinoalkylating action of an intermediate containing a good leaving iminoyloxy group. Similar reactions were observed for 1-chloromethylaziridine and a 1-aziridinylmethylammonium salt (6), but not for 1-methoxymethylaziridine (7) and 1-aziridinemethanol.

Reactions of aziridine, its dimer, 2,2-dimethyl-aziridine dimer, and β,β-bis-N-aziridinoethylamine with aromatic aldehydes and dialdehydes

The reactions of aziridine, its dimer, 2,2-dimethylaziridine dimer, and the novel compound β,β-bis-N-aziridinoethylamine with aromatic aldehydes and dialdehydes have given novel compounds.

Chiroptical properties of the non-planar nitrosamine chromophore in N-nitrosaziridines

The sign of the long-wavelength Cotton effect in the circular dichroism (CD) spectra of N-nitrosaziridines, possessing a non-planar nitrosamine chromophore, is determined by the intrinsic chirality of the chromophore, as in the cases of N-acylaziridines and gauche-cyclopropylketones.

α,ω-Bis-N-aziridinoalkanes

By reactions of α,ω-diamines with 1,2-dihaloethanes there were synthesized α,ω-bis-N-aziridinoalkanes (la-g) and bis-N-aziridinoethyl ether (II). From 1,3-diaminopropane and dichloroethane bis-aziridine (III) was isolated in addition to (Ia). NMR spectra of the products were studied.

Geminal systems 34. Inhibited inversion of nitrogen and absence of bisaziridinomethylating ability in bisaziridinomethoxymethane

Conclusions1.Like monoaziridine analogs, bisaziridinomethoxymethane does not enter the amino-methylation reaction.2.In bisaziridinomethoxymethane, an inhibited inversion of the N atom that is usual for N-alkylaziridines was shown to occur.3.For the aziridines studied, a screening effect of the N-substituent relative to ring cis protons was found.

Asymmetric nitrogen. Communications 38. Optically active 1-hydroxyl-, 1-alkoxycarbonyloxy-, and 1-tosyloxy-2, 2-bis(trifluoromethyl)-aziridines

Conclusions1.Diastereomeric 1-alkoxycarbonyloxy-2,2-bis(trifluoromethyl)aziridines, which were separated by crystallization and chromatography, under the influence of phenylhydrazine acylates give optically active 1-hydroxy-2,2-bis(trifluoromethyl)aziridine, on the basis of which optically active 1-tosyloxy-2,2-bis(trifluoro-methyl)aziridine was obtained.2.The activation parameters of the epimerization of diastereomeric 1-alkoxycarbonyloxy-2,2-bis(trifluoromethyl)aziridines were found.