Substituted and fused spiro[benzo-2-azepine-3,1′-cyclohexanes]

5-Methyl-4,5-dihydro-3H-spiro[benzo-2-azepine-3,1-cyclohexane] N-oxide was rear- ranged into 5-methyl-1-oxo-1,2,4,5-tetrahydro-3H-spiro[benzo-2-azepine-3,1-cyclohexane]. The latter was used for the synthesis of spiro{triazolo[3,4-a]- and-tetrazolo[5,1-a]benzo-2- azepinecyclohexanes}.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1647–1651, August, 2004.     

Synthesis of the esters of 1-alkyl-2-aminoindolyl-3-acetic acids by the kost reaction

The reaction of the esters of N-alkyl-N-phenylhydrazinocarbonylpropionic acids with phosphorus oxychloride in dioxane or with phosgene in benzene leads to the formation of the esters of 1-alkyl-2-aminoindolyl-3-acetic acids and of the corresponding N-alkyl-N-phenylaminosuccinimides.All-Russian Center for the Safety of Biologically Active Substances (ARC BAS), Kupavna, Moscow Oblast 142450. Translated from Khimiya Geterots iklicheskikh Soedinenii, No. 11, pp. 1502–1506, November, 1995. Original article submitted September 2, 1995.     

Potential energy of the smoothed surface of a molecule in its interaction with a solvent

A procedure was developed for calculating the potential of the smoothed surface of a solute molecule in its interaction with the solvent. The potential map of the smoothed surface was calculated for a series of molecules, including those containing various heteroatoms. A method was suggested for calculating the averaged potential of the solute molecule surface, taking into account the dynamics of solvation. The total energy of interaction of a solute molecule with the surrounding solvent was estimated.     

Oxidation of 1-aminobenzimidazoles. Synthesis and properties of 1,1′-azobenzimidazoles

1-Amino-2-R-benzimidazoles are oxidized by lead tetraacetate to give, depending on the substituent in the 2-position, either to 1,1-azobenzimidazoles (R=H, CH₃, C₆H₅, Cl, N(CH₃)₂) or 3-R-benzo-1,2,4-triazines (R=NH₂, NHCH₃, NHC₆H₅, OH). The factors affecting the course of the reaction are discussed. The physicochemical properties of the 1,1-azobenzimidiazoles obtained have been examined.For preliminary communication, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1486–1499, November, 1989.     

Spiropyrans and spirooxazines. 3. Synthesis of photochromic 5′-(4,5-diphenyl-1,3-oxazol-2-yl)-spiro[indoline-2,3′-naphtho[2,3-<Emphasis Type="Italic">b</Emphasis>]pyran]

The reaction of 2-hydroxy-3-(4,5-diphenyl-1,3-oxazol-2-yl)-1-naphthaldehyde with 1,2,3,3-tetramethyl-3H-indolium perchlorate afforded photochromic spiro[indoline-2,3′-naphthopyran] containing a 4,5-diphenyloxazole group in position 5′ of the naphthopyran fragment. The merocyanine form of the spiropyran gave complexes with bivalent heavy cations.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 693–697, March, 2005.     

Chlorotrimethylsilane-promoted synthesis of 1,2,4-triazolopyrimidines from 3,5-diamino-1,2,4-triazoles and pentane-2,4-diones

An efficient synthesis of 2-amino-1-R-[1,2,4]triazolo[1,5-a]- pyrimidinium or 3-amino-2-R-[1,2,4]triazolo[4,3-a]pyrimidi- nium chloride derivatives by heterocyclization of 3,5-diamino- 1-R-1,2,4-triazoles (R = Alk or Ar) with pentane-2,4-diones was developed. The process is promoted by chlorotrimethyl- silane which plays the dual role of carbonyl-activating agent and water scavenger.     

Study of Light Neutron-Rich Nuclei Using a Multilayer Semiconductor Setup

The characteristics of two modifications of the semiconductor (s.c.d.) setup consisting of telescopes on the basis of silicon detectors are presented. These settings allow performing a precision measurement of energy in a large dynamic range (from a few to hundreds of MeV) and particle identification in a wide range of masses. The issues of measurement of the characteristics of s.c.d. telescopes and their impact on the quality of the obtained experimental data are considered. Considerable attention is paid to the use of created semiconductor devices for the search for and spectroscopy of light exotic nuclei on the accelerators of PNPI (Gatchina) and LANL (Los Alamos).     

Acceleration of an ion-electron flow in a plane gap

Steady-state flows of ions and electrons in a plane gap are considered in the self-consistent 1D problem. The flows in the same direction are considered, and it is shown that the ion velocity can exceed the velocity of ion sound.     

Ionic Pd/NHC Catalytic System Enables Recoverable Homogeneous Catalysis: Mechanistic Study and Application in the Mizoroki–Heck Reaction

N-Heterocyclic carbene (NHC) ligands are ubiquitously utilized in catalysis. A common catalyst design model assumes strong M–NHC binding in this metal–ligand framework. In contrast to this common assumption, we demonstrate here that lability and controlled cleavage of the M−NHC bond (rather than its stabilization) could be more important for high-performance catalysis at low catalyst concentrations. The present study reveals a dynamic stabilization mechanism with labile metal–NHC binding and [PdX₃]⁻[NHC-R]⁺ ion pair formation. Access to reactive anionic palladium intermediates formed by dissociation of the NHC ligands and plausible stabilization of the molecular catalyst in solution by interaction with the [NHC-R]⁺ azolium ion is of particular importance for an efficient and recyclable catalyst. These ionic Pd/NHC complexes allowed for the first time the recycling of the complex in a well-defined form with isolation at each cycle. Computational investigation of the reaction mechanism confirms a facile formation of NHC-free anionic Pd in polar media through either Ph–NHC coupling or reversible H–NHC coupling. The present study formulates novel ideas for M/NHC catalyst design.