1-Aryl-2-nitro-3-trichloromethylaziridines: synthesis and structure

Abstract

A two step method was developed for the synthesis of new polyfunctional aziridines involving the addition of aromatic amines to 1 bromo 3,3,3 trichloro 1 nitropropene and the dehydro bromination of the resulting adducts. The 1 H and 13 C NMR spectroscopic and X ray diffrac tion studies showed that 1 aryl 2 nitro 3 trichloromethylaziridines are stereohomogeneous and have the geometry, such that the nitro and aryl substituents are in the trans positions with respect to the trichloromethyl group. The chemical bonding in the crystal and the gas phase was investigated based on high resolution X ray diffraction analysis of the electron density distribution and quantum chemical calculations.

Chemistry of Nitroaziridines

“…Subsequent cyclization using potassium acetate affords N-arylated nitroaziridines (12) ( Table 2). 16 According to the X-ray crystallographic data, the nitro group and aromatic ring are in trans positions with respect to the trichloromethyl group to avoid the steric hindrance. This…”

Highly Selective Detection of Nerve‐Agent Simulants with BODIPY Dyes

“…Similarly, addition of amines to gem ‐halonitroalkenes affords the corresponding nitroaziridines by means of a two‐step Michael addition/cyclization sequence. For example, in 2009 Berestovistkaya and co‐workers reported the synthesis of polyfunctional aziridines through addition of aromatic amines to 1‐bromo‐3,3,3‐trichloro‐1‐nitropropene ( 54r ) and dehydrobromination of the resulting adducts 54. Treatment of 54r with aromatic amines in anhydrous methanol at room temperature affords anilines 61 in 46–77 % yields.…”

The “Hockey Sticks” Effect Revisited: The Conformational and Electronic Properties of 3,7-Dithia-1,5-diazabicyclo[3.3.1]nonane from the QTAIM Perspective

“…The applicability of such comparisons has been proved in the case of hydrocarbon compounds, and the comparative analysis of atoms’ energies has been used to investigate the sources of the strain in cycloalkanes. , Further progress in the comparative analysis of atomic electronic populations and energies offered deeper insights into the nature and energy of intra- and intermolecular interactions. One of the most notable results obtained by such approach is the classification of various hydrogen bonding interactions, including weak ones such as C–H···O and H···H, , but it has been shown to be a useful tool for the conformational analysis as well. − In our recent charge density studies, , the same approach has been successfully applied to explore the LP–X–C–Y (where X and Y are heteroatoms and LP is a lone pair) stereoelectronic interactions (further SEI) in various systems. It has been shown that such interactions, which usually lead to an increase in the relative stability of the conformation with the antiperiplanar disposition of a lone pair and a polar bond (the so-called generalized anomeric effect, Scheme ), are accompanied by a decrease in energy and increase of electronic populations of the atoms X and Y and comparable opposite changes of both for the atom C …”

“…One of the most notable results obtained by such approach is the classification of various hydrogen bonding interactions, including weak ones such as CÀH 3 3 3 O 6 and H 3 3 3 H, 7,8 but it has been shown to be a useful tool for the conformational analysis as well. 9À11 In our recent charge density studies, 12,13 the same approach has been successfully applied to explore the LPÀXÀCÀY (where X and Y are heteroatoms and LP is a lone pair) stereoelectronic interactions (further SEI) in various systems. It has been shown that such interactions, which usually lead to an increase in the relative stability of the conformation with the antiperiplanar disposition of a lone pair and a polar bond (the so-called generalized anomeric effect, 14 Scheme 1), are accompanied by a decrease in energy and increase of electronic populations of the atoms X and Y and comparable opposite changes of both for the atom C. 12 The changes in energies of the atoms X, Y, and C have been shown to be more pronounced for stronger SEI that allows for direct comparison of effects of SEI on individual atoms with contributions from other intra-and intermolecular interactions.…”