Unusual heterocyclization of chalcone podands with 3-amino-1,2,4-triazole

A new type of intramolecular cyclization of 1,5-bis[2-(E-3-oxo-3-phenylprop-1-enyl)-phenoxy]-3-oxapentane with 3-aminotriazole promoted by potassium ions was discovered. A cascade mechanism for the formation of crownophane with 4,7-dihydro[1,2,4]triazolo[1,5-a]-pyrimidine fragment was suggested. Effects of oligooxyethylene fragment of the chalcone podand and acid-base catalysis on the selectivity of the cyclocondensation processes and degree of oxidation of triazolopyrimidine fragments were studied. The product structures were confirmed by IR, ¹H and ¹³C NMR spectroscopy and X-ray diffraction study.     

Pre-organization of diarylideneacetonyl crownophanes in single crystals to photochemical transformations

Specific features of crystal packings and pre-organization of diarylideneacetonyl crownophane molecules to solid-phase photochemical transformations were studied on the basis of X-ray diffraction data using methods of simulation of molecular crystal packings. The tendency of the most part of the synthesized macrocyclic E,E-isomers to the formation of homochiral crystals (P2₁2₁2₁) was revealed, while (23E,26E)-11,12,14,15-tetrahydro-8H-dinaphtho-[2,1-k:1′,2′-r][1,4,7,10]tetraoxacyclononadecine-23,26-dien-25(9H)-one is prone to polymorphism. A phenomenon of solid-phase stereospecific photochemical dimerization of molecules according to the syn-head-to-tail type without crystal destruction (single crystal—single crystal transformation) was found for one of the modifications of this crownophane.     

Structure, 1H and 13C NMR spectra, and biological activity of the antibiotic INA-1278 related to irumamycin and produced by the experimental Streptomyces sp. strain No. 1278

The screening for novel antibiotic producers by selection methods revealed the Streptomyces sp. strain No. 1278 producing the antibiotic INA-1278, which exhibits antimicrobial and antifungal activities. This compound was isolated from the liquid culture by extraction with organic solvents and purified by chromatographic methods. The structure of this antibiotic was studied by mass spectrometry and ¹H and ¹³C NMR spectroscopy. An analysis of the results of the investigation indicate that the compound INA-1278 is structurally related to the antibiotic irumamycin, which has been studied earlier. However, the novel antibiotic may differ from irumamycin in the configurations of some asymmetric centers, which were not established at the present stage of our research.     

Reactions of 4-acyl-1-alkoxyaryl-5-aryl-3-hydroxy-2,5-dihydro-1H-pyrrol-2-ones with nucleophilic reagents

4-Acetyl-1-alkoxyaryl-5-aryl-3-hydroxy-2,5-dihydro-1H-pyrrol-2-ones reacted with amines to give 1-alkoxyaryl-5-aryl-4-(1-R-aminoethylidene)pyrrolidine-2,3-diones. Reactions of amines with 4-benzoyl-substituted analogs involve nucleophilic attack on the C³ atom in the heteroring to produce the corresponding 3-R-amino-1-alkoxyaryl-5-aryl-4-benzoyl-2,5-dihydro-1H-pyrrol-2-ones. Reactions of the title compounds with hydrazine hydrate, regardless on the substituent on C₄, afforded 4-aryl-3-methyl(phenyl)-5-[2(4)-methoxyphenyl]-4,6-dihydropyrrolo[3,4-c]pyrazol-6-ones.     

Mass spectrometric characterization of peptides containing different oxidized tryptophan residues

The term reactive oxygen species refers to small molecules that can oxidize, for example, nearby proteins, especially cysteine, methionine, tryptophan, and tyrosine residues. Tryptophan oxidation is always irreversible in the cell and can yield several oxidation products, such as 5-hydroxy-tryptophan (5-HTP), oxindolylalanine (Oia), kynurenine (Kyn), and N-formyl-kynurenine (NFK). Because of the severe effects that oxidized tryptophan residues can have on proteins, there is a great need to develop generally applicable and highly sensitive techniques to identify the oxidized residue and the oxidation product. Here, the fragmentation behavior of synthetic peptides corresponding to sequences recently identified in three skeletal muscle proteins as containing oxidized tryptophan residues were studied using postsource decay and collision-induced dissociation (CID) in matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF)/TOF mass spectrometry (MS) and CID in an electrospray ionization (ESI) double quadrupole TOF-MS. For each sequence, a panel of five different peptides containing Trp, 5-HTP, Kyn, NFK, or Oia residue was studied. It was always possible to identify the modified positions by the y-series and also to distinguish the different oxidation products by characteristic fragment ions in the lower mass range by tandem MS. NFK- and Kyn-containing peptides displayed an intense signal at m/z 174.1, which could be useful in identifying accordingly modified peptides by a sensitive precursor ion scan. Most importantly, it was always possible to distinguish isomeric 5-HTP and Oia residues. In ESI- and MALDI-MS/MS, this was achieved by the signal intensity ratios of two signals obtained at m/z 130.1 and 146.1. In addition, high collision energy CID in the MALDI-TOF/TOF-MS also permitted the identification of these two isomeric residues by their v- and w-ions, respectively.     

Electrocyclic reaction of crown-containing 2-styrylbenzothiazoles

The photoinduced electrocyclic transformation of 15-crown-5-containing 2-styrylbenzothiazoles into condensed benzothiazoloquinoline derivatives was discovered. The process is accompanied by the formation of a C-N bond and elimination of a hydrogen atom. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1290–1292, May, 2005.     

Longitudinal development of giant air showers and problem of estimating the energy of primary-cosmic-ray particles

The attenuation length for the charged-particle density at a distance of 600 m from the shower axis may differ from that adopted in experimental investigations by 40–50%. This casts some doubt on experimental estimates previously obtained for the energy of primary-cosmic-ray particles in the region of ultrahigh energies.     

Novel synthesis of benzocrown ethers formylated in the benzene ring

Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, p. 996, May, 1993.     

Structure of orthophosphoric Acid-N,N-dimethylformamide complexes

Ab initio calculations weere used to obtain the characteristics of the most stable configurations of the (H₃PO₄)₂, DMFA-H₃PO₄, and DMFA-(H₃PO₄)₂ complexes in a vacuum. The changes in the geometric parameters in this series of complexes were analyzed and the energies of intermolecular interactions were estimated. The DMFA-(H₃PO₄)₂ complex was found to be most stable. It was established that the hydrogen bond between the DMFA and H₃PO₄ molecules is formed with the participation of both lone pairs of the oxygen atom of the DMFA molecule.     

Peroxyl radical acceptors released by polymer materials into the gas phase

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 973–974, April, 1991.