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Substituted acrylamides have found an extensive application in organic and medical chemistry; therefore, it is very important to get insight into their features such as electronic structure, spectral properties, and stereochemical transformations. A correct interpretation of the chemical behavior and biological activity of these heteroatomic systems is impossible without knowledge of the structure of stereodynamic forms and factors determining their relative stability. The structure and peculiarities of stereodynamic behavior of substituted acrylamides and their model compounds were studied by dynamic and multinuclear 1 H, 13 C, and 15 N nuclear magnetic resonance (NMR) spectroscopy in CDCl 3 and DMSO-d 6 solution. It has been established that acrylamides in solution are realized as Z- and E-isomers, with the E-rotamer being somewhat predominant. The obtained experimental values of the free activation energy of rotamers vary within 15-17 kcal/mol, depending on the stereochemical structure of the molecule. 15 N NMR spectroscopy is the most reliable and fastest method for determining the structural and stereochemical features of nitrogen-containing compounds., (© 2023 John Wiley & Sons Ltd.)

The effects of intramolecular and intermolecular coordination on (31)P nuclear shielding have been investigated in the series of tetracoordinated, pentacoordinated and hexacoordinated N-vinylpyrazoles and intermolecular complexes of N-vinylimidazole and 1-allyl-3,5-dimethylpyrazole with phosphorous pentachloride both experimentally and theoretically. It was shown that either intramolecular or intermolecular coordination involving phosphorous results in a dramatic (31)P nuclear shielding amounting to approximately 150 ppm on changing the phosphorous coordination number by one. A major importance of solvent effects on (31)P nuclear shielding of intramolecular and intermolecular complexes involving N → P coordination bond has been demonstrated. It was found that the zeroth-order regular approximation-gauge-including atomic orbital-B1PW91/DZP method was sufficiently accurate for the calculation of (31)P NMR chemical shifts, provided relativistic corrections are taken into account, the latter being of crucial importance in the description of (31)P nuclear shielding., (Copyright © 2012 John Wiley & Sons, Ltd.)

Several representatives of natural flavonoids and their synthetic nitro-derivatives have been investigated by polarography and electron paramagnetic resonance (EPR) spectroscopy under electrochemical reduction in acetonitrile, dimethylformamide (DMF), dimethylsulfoxide (DMSO) or 1,2-dimethoxyethane. All the compounds studied are reduced in the first stage by one-electron transfer, apart from flavanone, which accepts two electrons simultaneously. However, the primary radical anions were detected by EPR spectroscopy only for 4'-nitroflavone. It was shown that radical anions of other flavonoids quickly dimerized. The analysis of the temperature dependence of the hyperfine interaction constants and broadening of lines in EPR spectra of 4'-nitroflavone radical anions has shown that the distribution of spin density is due to both the change of polarity of the medium and rotation of the nitrophenyl moiety. The assignment of hyperfine structure constants for the 4'-nitroflavone radical anion was confirmed by density functional theory (DFT) calculations., (Copyright © 2011 John Wiley & Sons, Ltd.)

The non-degenerate tautomers of 3-nitro-1,2,4-triazole-5-one (NTO) radical anions were investigated for the first time by an ESR method during electrochemical reduction of NTO in an aprotic medium., (Copyright (c) 2009 John Wiley & Sons, Ltd.)

Benzotriazole nitro derivatives were prepared by nitration of the corresponding benzotriazoles and by methylation or cyclization of appropriate nitro-1,2-phenylenediamines. Structures and tautomerism of the nitrobenzotriazoles were studied by multinuclear (1)H, (13)C, (15)N, and 2D NMR spectroscopy and quantum chemistry., (2008 John Wiley & Sons, Ltd.)

The structure of novel phosphorus-containing N-vinylazoles prepared by action of phosphorus pentachloride has been studied by multinuclear (1)H, (13)C, (15)N, (31)P and two-dimensional (2D) NMR spectroscopy. N-vinyl-substituted 1,2-diazoles and 1,2,3-triazoles have undergone phosphorylation, exclusively, on double bond. N-vinylazoles-based hexa-coordinated phosphorus compounds have been synthesized for the first time. (31)P NMR spectroscopy provides the most convenient and unambiguous method for the investigation of E-Z-isomeric structures of phosphorylated enamines., (2008 John Wiley & Sons, Ltd.)

Novel 2-acetylamino-4-acetyl-5-aryl(heteryl)-1,3,4-thiadiazolines, 2-acetylamino-5-aryl(heteryl)-1,3,4-thiadiazoles, and some of their salts were prepared and studied by multinuclear 1H, 13C, 15N, 19F and 2D NMR spectroscopy. The acetylation of thiosemicarbazones is accompanied by ring closure to form the corresponding 1,3,4-thiadiazolines and 1,3,4-thiadiazoles. 15N NMR spectroscopy is a unique method for the identification of thiadiazole pyridinium salts., (Copyright 2007 John Wiley & Sons, Ltd.)

Configurational assignment of five carbon, silicon and germanium containing propynal oximes has been carried out by means of experimental measurements and high-level ab initio calculations of their 13C-1H, 13C-13C and 15N-1H spin-spin coupling constants. The title compounds were shown to exist in the nonequilibrium mixture of E and Z isomers with the energy difference of less than 0.3 kcal/mol calculated at the MP2/6-311G** level., (Copyright 2007 John Wiley & Sons, Ltd.)

Configurational assignment of seven azomethines obtained from the alpha-functionally substituted and nonsubstituted alpha,beta-unsaturated aldehydes has been performed on the basis of experimental measurements and the high-level ab initio calculations of their 1J(C,C) and 1J(C,H), involving the alpha-imino carbon that demonstrated the marked stereochemical dependence of both coupling constants upon the orientation of the nitrogen lone pair in the diverse isomers of the title azomethines., (Copyright 2005 John Wiley & Sons, Ltd.)

Carbon-carbon coupling constants have been experimentally measured using the INADEQUATE pulse sequence in the series of N-[1,2-bis(dialkylamino)-2-arylethylidene]arylsulfonamides obtained from N-(1-aryl-2,2,2-trichloroethyl)amides of arylsulfonic acids. Comparison of the experimental J(C,C) in this series with those calculated at the SOPPA (Second-Order Polarization Propagator Approach) level in the model aminosulfonylamidine provided an unambiguous assignment at the C=N bond of the eight-title aminosulfonylamidines to E-configuration, while the unknown J(C,C) couplings in their inaccessible diverse Z isomers have been predicted with high reliability. The established marked difference between J(C,C) of the corresponding carbon-carbon bonds in cis and trans orientations to the nitrogen lone pair in aminosulfonylamidines provides a powerful tool in the configurational assignment at the C=N bond in a wide series of the related systems containing the C=N-SO2R moiety.