Synthesis, characterization, and quantum chemical calculation studies on 3-(3-nitrophenylsulfonyl)aniline

A novel partially reduced polynitro aromatic compound, 3-(3-nitrophenylsulfonyl)aniline (III), was found during the catalytic transfer hydrogenation of 3,3′-sulfonylbis(nitrobenzene) (I) to 3,3′-sulfonyldianiline (II). III was identified and characterized by elemental analysis, IR, 1H NMR, and X-ray single crystal diffraction. The optimized geometries of III calculated by DFT-B3LYP/6-31G* and HF/6-31G* closely resemble the crystal structure. The frontier orbital gap and the electrostatic potential isosurface map of III were calculated and compared with those of I. HF/6-31G* method is better than DFT-B3LYP/6-31G* method to predict the vibrational frequencies by the comparisons between the calculated results and the experimental data. The present study of III, in general, may lead to the better understanding of the mechanisms and intermediates of the reduction of polynitro aromatic compounds, especially the nitro groups at the different aromatic rings, and may also help in designing and synthesizing new partial reduction products for technological applications.

► A new partially reduced polynitro aromatic compound, 3-(3-nitrophenylsulfonyl)aniline, was found.
► It was prior identified during the catalytic transfer hydrogenation of 3,3’-sulfonylbis(nitrobenzene) to 3,3’-sulfonyldianiline.
► Then it was isolated and fully characterized by several techniques and X-ray crystallography.
► DFT-B3LYP/6-31G∗ and HF/6-31G∗ studies for the title compound were presented.
► The intra and intermolecular hydrogen bonds pattern is discussed in relation to the theoretical configuration of the isolated molecule.