Synthesis of aromatic derivatives of 1,5-benzodiazepine in the reaction of 4-nitro-o-phenylenediamine with chalcone dibromides

The reaction of 4-nitro-o-phenylenediamine with 4-nitro-4-R-chalcone dibromides affords the corresponding -(2-amino-4-nitroanilino)chalcones; x-ray diffraction data indicate that these are the Z-isomers. Experiments have been perfortned to determine the conditions required for cyclization of these compounds into 2, 4-diaryl7(8)-nitro-1, 5-benzodiazepines. In the solid phase or in ethanol solutions, these latter compounds exist primarily in the 3H tautomeric form; but in DMSO solutions, the 1H form predominates.Khar'kov State University, Khar'kov 310077. Institute of Heteroorganic Chemistry, Russian Academy of Sciences, Moscow 117813. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 950–958, July, 1995. Original article submitted June 30, 1994; revision submitted April 3, 1995.Deceased     

Effect of the conditions of hydro-(organo-thermal treatment on the surface composition of oxide vanadium—Phosphorus catalysts

It was shown that hydrothermal, organothermal (with substitution of water by an organic solvent), and vacuum treatment allows altering the surface composition of V-P-Bi-O catalysts of oxidation of n-butane. The effect of the nature of the solvent, temperature, and duration of modification on the surface properties was examined. It was found that all types of treatment increase the P/V surface ratio (except for treatment in tetrahydrofuran) and decrease the Bi/V ratio (except for treatment in water). Increasing the temperature and sample modification time causes reduction of vanadium and an increase in the concentration of phosphorus on the surface. The effect of a change in the surface composition of the samples on the catalytic properties was examined and it was shown that an increase in the surface concentration of phosphorus increases the selectivity of formation of maleic anhydride. Treatment in 1-butanol, phosphoric acid, and in a vacuum are the most promising with respect to increasing the efficiency of catalysts in oxidation of butane.Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 31, No. 4, pp. 250–253, July–August, 1995.     

Pyrazolyc 3-hydroxychromones: Regulation of ESIPT reaction by the “flavonol-like” intramolecular hydrogen bonding to carbonyl group oxygen,which dominates over the “alternative” H-bond to heterocyclic nitrogen

Two isomeric pyrazole derivatives of 3-hydroxychromone (3HC) with and without the possibility of the multiple intramolecular hydrogen bonds formation were compared theoretically and experimentally with the aim to find out whether the excited state intramolecular proton transfer (ESIPT) reaction follows the traditional to the most of 3HCs “flavonol-like” direction towards the CO group oxygen or an “alternative” direction towards the heterocyclic nitrogen atom.Quantum-chemical modeling and comparative study of the experimental spectral parameters of the title compounds indicated the preferential realization of “flavonol-like” ESIPT to oxygen channel.The 3HC systems with the “alternative” intramolecular hydrogen bond to nitrogen were characterized as low fluorescent and practically unable to ESIPT with participation of the nitrogen containing heterocyclic unit.     

Spectrophotometric study of 5-arylidene- and 5-(5-arylfurfurylidene)rhodanines

5-Arylidenerhodanines and the previously undescribed 5-[5-(4-R-phenyl)furfurylidene]rhodanines were synthesized by the Andreasch method. It is assumed that Fermi resonance appears in the IR spectra of some of these compounds in the region of carbonyl absorption; bands of associated N-H bonds were identified. It is shown that in the case of 4-N(CH₃)₂-benzylidenerhodanine the long-wave band in the electronic spectra is a bathochromically shifted band of the same nature as the band in the spectra of 5-arylidenerhodanine derivatives with weak donor groups. The introduction of an arylfurfurylidene grouping gives rise to a substantial bathochromic shift of the absorption band of their molecules.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1490–1494, November, 1977.     

New steroid α,β-unsaturated ketones as chiral components of induced cholesteric liquid crystal systems

New (E)-16-arylidene derivatives of 3β-hydroxyandrost-5-en-17-one and their acetates containing different substituents in the arylidene fragment were synthesized. The ability of the synthesized chiral compounds to induce helical supramolecular ordering (their helical twisting power) upon the introduction into the nematic liquid crystal (LC) 4-cyano-4′-pentylbiphenyl (5CB) and into multicomponent mixtures E63 and LC-1289 characterized by a wide mesophase interval. The dependence of the helical twisting power of the studied chiral additives (CAd) on their molecular structure was analyzed. The highest helical twisting power (44.6–67.1 μm⁻¹) was revealed for the synthesized acetates. It was found that the composites based on LC-1289 and E63 containing the studied CAd in very low concentrations (≤10–11 mol.%) have selective light reflection in the visible spectral region. The helical twisting power of the studied α,β-unsaturated ketones is determined by the combined influence of the anisotropy of polarizability of CAd molecules and specific features of their molecular shape.     

Aziridinyl ketones and their cyclic anils. 10. 2,4,6-Triaryl-1,3-diazabicyclo[3.1.0]hex-3-enes

2,4,6-Triaryl-1,3-diazabicyclo[3.1.0]hex-3-enes were prepared by the reaction of ,-dibromochalcones with aromatic aldehydes and ammonia. The exo- and endo-isomers were isolated and characterized. X-ray structural analysis of the endo-6-(4-nitrophenyl)-2,4-diphenyl derivative was performed.See [1] for Communication 9.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1060–1066, August, 1991.     

Aziridinyl ketones and their heteroanalogs. 5. Synthesis and structures of 2-aryl-3-aroylaziridines

A number of trans- and cis-isomeric 1-R-2-aryl-3-aroylaziridines were synthesized, and their IR spectra were studied. Intramolecular hydrogen bonding is realized in the trans isomers when R = H, and they exist in the only possible conformation (intermediate between a gauche and a cisoid conformation). cis-Isomers II (R = alkyl) exist in solutions in the form of two conformers, viz., gauche and cisoid conformers, and the gauche conformer is thermodynamically preferable.See [1] for Communication A.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 11, pp. 1489–1494, November, 1980.