Uncommon expansion of piperidine ring into hydroazocine ring in reactions of some piperidine β-acyl derivatives with acetylenecarboxylic acids esters

Cyclohexanone condensation with formaldehyde and methylamine led to the formation of 4ahydroxy-2-methyloctahydrospiro[isoquinoline-4,1'-cyclohexan]-2'-one whose structure was established by means of X-ray diffraction (XRD) analysis. This spiro compound reacted with acetylenecarboxylic acids esters with unexpected conversion of its piperidine ring into a hexahydroazocine cycle. The uncommon expansion reaction of the β-acyl-substituted piperidine ring into a hexahydroazocine cycle is confirmed by the analogous conversion of 4-hydroxy-1-methyl-4-phenylpiperidin-3-yl(phenyl)methanone into azocine derivative at treating with methyl propiolate.     

Cosmic-ray calibration of lead scintillation monitor with internal trigger

Cosmic-ray calibration of the 4-channel lead scintillation monitor with internal trigger shows that the consideration of only coinciding signals of counters placed in the monitor depth and detecting the final part of the high-energy photon shower, with signals of any other counters at the monitor top, detecting both the initial part of the high-energy photon shower and low-energy background photons, decreases the number of detected coincidences by a factor of 2–4. An increase in the number of such coincidences when using the monitor in the setup for studying neutral pion photoproduction on nuclei in the photon beam of the labeling system of the “PAKHRA” accelerator of the Lebedev Physical Institute makes it possible to separate the high-energy electromagnetic shower from the low-energy background and to monitor the beam photon energy.     

Modeling electrohydrodynamic flows in slightly conductive liquids

Mechanical Mathematics Department, Moscow State University, Moscow 117234. Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 36, No. 4, pp. 36–44, July–August, 1995.     

Perhydro[1,3,2]dioxaborinino[5,4-c]pyridine-A New Heterocyclic System

Russian Journal of Organic Chemistry -     

Oxygen electroreduction on a granulated layer of a copper-containing electron-ion exchanger

The reduction of dissolved oxygen from a flowing aqueous solution of sodium sulfite on a cathodically polarized granulated layer of a copper-containing electron-ion exchanger is studied. It is established that the polarizing current is distributed over the layer height nonuniformly. A peak current corresponding to the oxygen electroreduction is discovered. The peak shifts from the inlet into the granulated layer to the exit out of it, which is connected with the advance of the concentration front and with an increase in ohmic resistance due to partial oxidation of copper centers. The distribution of the polarizing current is analogous to the distribution of the limiting current of the oxygen reduction, which is determined from polarization curves. The reaching of a stationary position of the peak of the polarizing current and the oxygen reduction degree with time testifies to the onset of a stationary state, at which the current turns limiting and the balance between the arrival and electroreduction of oxygen is fulfilled.     

Synthesis of pyrrolidine and tetrahydroazonine derivatives from <Emphasis Type="Italic">N</Emphasis>-[bis(ethoxycarbonyl)methyl]tetrahydropyridinium bromide and methyl acetylenedicarboxylate

The reaction of N-methyl-N-(diethoxycarbonyl)methyltetrahydropyridinium bromide with dimethyl acetylenedicarboxylate in the presence of triethylamine at room temperature afforded 1,2-dimethyl 1-ethyl 2-[(3-vinyl-1-methyl-3-phenyl-2-ethoxycarbonyl)pyrrolidin-2-yl]-ethene-1,1,2-tricarboxylate in 25% yield. Its structure was proved by XRD analysis. At cooling to −20°C the pyrrolidine yield signifi cantly decreased and 3,4-dimethyl 2,2-diethyl 1-methyl-7-phenyl-1,5,8,9-tetrahydro-2H-azonine-2,2,3,4-tetratcarboxylate was obtained in 31% yield.     

Determination of the constants of electrochemical reactions and the ion mobility coefficients in weakly conducting liquids from an analysis of the current—voltage characteristics

The problem is considered of the passage of a direct current through a solution of a weak electrolyte in a two-dimensional cell. Allowance is made for the electrochemical reactions of dissociation and reconbination which take place in the electrolyte when the rate of dissociation of the molecules is regarded as dependent on the electric field intensity [1–3]. For electrolytes whose recombination coefficient is of the order of magnitude of the Langevin coefficient, theoretical current—voltage characteristics are given for the limiting cases of large and small values of the characteristic times for the ion concentrations to be changed by electrochemical reactions and the transport of ions by the electric field. A method of determining the dissociation rate, the recombination coefficient, and the ion mobility coefficients is proposed on the basis of comparison of the theoretical and experimental current—voltage characteristics.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 6. pp. 113–120, November–December, 1984.     

On the possibility of blowing a gas jet into a supersonic flow without formation of a three-dimensional boundary-layer separation zone

We consider the flow formed by the interaction of a supersonic flow and a transverse sonic or supersonic jet blown at right angles to the direction of the main flow through a nozzle whose exit section is in a flat wall. When a gas jet is blown through a circular opening [1] the pressure rises in front of the jet because of the stagnation of the oncoming flow. This leads to separation of the boundary layer formed on the wall in front of the blowing nozzle. The resulting three-dimensional separation zone leads to a sharp increase in the pressure and the heat fluxes to the wall in front of the blowing nozzle, which is undesirable in many modern applications. The aim of the present investigation was to find a shape of the exit section of the blowing nozzle for which there is no three-dimensional separation zone of the boundary layer in front of the blowing nozzle.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 3, pp. 162–165, May–June, 1979.     

Copper electrodeposition into ion-exchange materials

Electrodeposition of copper into spherical granules of ion-exchange materials KU-23 and KU-2 out of acid sulfate solutions is studied by a method of cyclic voltammetry. It is discovered that the discharge of copper ions in an ion-exchange matrix is characterized by a cathodic overvoltage that is higher than the overvoltage of the same process on a graphite substrate by 0.08 V, which is most probably connected with a limited mobility of ions localized at fixed groups [RSO ₃ ^? ]. The cyclic voltammogram exhibits an additional cathodic peak in the potential region corresponding to the reduction of single-charged copper ions that form as a result of their accumulation inside pores of the ion-exchange matrix during anodic dissolution of metal deposited previously. It is fixed microscopically that the process of deposition begins at the graphite substrate/ion-exchanger interface and passes into bulk upon the formation of an electron-conducting layer saturated with copper. Preliminary saturation of the ion-exchanger by copper deposited chemically facilitates uniform electrodeposition of copper over the entire volume of pores of the ion-exchange matrix.     

The chemical precipitation of nickel on ion exchangers and active carbons

The chemical precipitation of nickel in the form of poorly soluble precipitates in ion exchanger matrices and on active carbons from solutions of nickel chloride and chemical nickel plating electrolytes was studied. The sorption of nickel ions from a solution of nickel chloride occurs most effectively on Purolite D24002 macroporous chelate forming ion exchanger, KU-23-15/100 sulfo cation exchanger, and KU-2-8 gel sulfo cation exchanger. Nickel enters sulfo cation exchangers in the form of counterions, and is adsorbed on Purolite D24002 largely because of complex formation. The subsequent precipitation of nickel in the solid state in matrix pores liberates ionogenic centers, which allows repeated sorption cycles to be performed. After three chemical precipitation cycles under static conditions, the amount of nickel is higher by 170–250% than the ion exchange capacity of the sorbents. The electrolyte of chemical nickel plating contains nickel predominantly in the form of negatively charged and neutral complexes with glycine, which cannot form bonds with the matrices under study. It is therefore reasonable to perform sorption at decreased solution pH values.