Chemical Bond in Metal Azides and Their Reactivity

Results of experimental investigations into the processes of slow and explosive decomposition of metal azides and the corresponding phenomenological models are analyzed. The energy-band structure and the valence electron density for actual crystallographic planes as well as the hypothetical electron density of the first unoccupied band of KN₃ and AgN₃ are calculated by the density functional method with the use of pseudopotentials. It is demonstrated that the anion-cation chemical bond in KN₃ is predominantly ionic in character, whereas a significant covalent component in AgN₃ is caused by Ag d-states. From the character of distribution of the valence and hypothetical electron densities it follows that the exciton and vibron decomposition mechanisms are improbable. The chain process is also improbable for alkali metal azides, because the gap energy for them is E _g 8 eV, which is close to the energy of azide ion decomposition Q 9–12 eV; the chain process is probable for AgN₃, because E _g(AgN₃) 3 eV. The chain process in AgN₃ is also favored by intense delocalization of the valence electron density through the hybridization of the Ag d-state and the N p-state, which causes a relatively high hole mobility.     

Structure and Reactivity of Glycosides: IV. Koenigs-Knorr Synthesis of Aryl β-D-Glucopyranosides Using Phase-Transfer Catalysts

A series of acetylated aryl -D-glucopyranosides were prepared in 12-63% yields from tetra-O- acetyl--D-glycopyranosyl bromide and phenols containing acyl, formyl, and hydroxy substituents, and also from sterically hindered phenols in the two-phase system chloroform-aqueous alkali in the presence of triethylbenzylammonium chloride. Hydroxyethylated sucrose and dibenzo-18-crown-6 do not behave as phasetransfer catalysts in glycosylation of phenols.     

Raising the Coefficient of Turbulent Diffusion in the Reaction Zone as Means To Improve Technical and Economical Parameters of Polymer Production

Use of a new type of apparatus, high-output small-size tubular turbulent reactors of mainly dif- fuser-confuser design, in very fast processes, including polymerization, is considered. The turbulent diffusion coefficient D _t and its distribution over the apparatus volume were calculated as functions of the confuser divergence angle . The calculations were confirmed by experimental data. New reactor designs for a number of processes of large-tonnage polymer production were proposed and put into practice.     

Interpenetrating polymer networks based on diisocyanates and polar monomers

Compatible interpenetrating polymer networks systems (IPS) have been obtained by two-stage polymerization of a mixture of diisocyanates (M₁) with various different polar monomers (M₂) initiated by catalytic systems based on tertiary amines. In the first stage, a polyisocyanate network (P₁) is formed and then M₂ is polymerized on a regenerated active centre with the formation of a linear polymer (L₂) specially arranged in P₁. The essential features of the formation of IPS of this type are considered. Some physico-mechanical and thermal characteristics are reported.     

Chemical transformations in sodium chloride aqueous solutions under the action of low-temperature contact glow-discharge plasma

Changes in the composition of aqueous NaCl solutions during the course of their treatment with glow-discharge plasma in a gas-liquid plasma-chemical reactor have been studied. A mathematical model involving the steps of oxidation of water molecules and chloride ions and the steps of reduction of their chemical conversion products has been developed. For the first time, it has been found that the hydrogen peroxide content of the solution monotonically decreases with the concentration of NaCl and a change in chlorite, chlorate, and perchlorate concentrations has the appearance of an undulating curve with a maximum at c(NaCl) = 3 g/L. The predominant accumulation of hypochlorite ions in the solution has been detected only in the case of the plasma treatment of the NaCl solutions with concentrations higher than 5 g/L.     

Investigation of Functionalized α‐Chloroalkyllithiums for a Stereospecific Reagent‐Controlled Homologation Approach to the Analgesic Alkaloid (−)‐Epibatidine

Four putative functionalized α‐chloroakyllithiums RCH₂CHLiCl, where R=CHCH₂ ( 18 a ), CCH ( 18 b ), CH₂OBn ( 18 c ), and CH[O(CH₂)₂O] ( 18 d ), were generated in situ by sulfoxide–lithium exchange from α‐chlorosulfoxides, and investigated for the stereospecific reagent‐controlled homologation (StReCH) of phenethyl and 2‐chloropyrid‐5‐yl ( 17 ) pinacol boronic esters. Deuterium labeling experiments revealed that α‐chloroalkyllithiums are quenched by proton transfer from their α‐chlorosulfoxide precursors and it was established that this effect compromises the yield of StReCH reactions. Use of α‐deuterated α‐chlorosulfoxides was discovered to ameliorate the problem by retarding the rate of acid‐base chemistry between the carbenoid and its precursor. Carbenoids 18 a and 18 b showed poor StReCH efficacy, particularly the propargyl group bearing carbenoid 18 b , the instability of which was attributed to a facile 1,2‐hydride shift. By contrast, 18 d , a carbenoid that benefits from a stabilizing interaction between O and Li atoms gave good StReCH yields. Boronate 17 was chain extended by carbenoids 18 a , 18 b , and 18 d in 16, 0, and 68 % yield, respectively; α‐deuterated isotopomers D ‐ 18 a and D ‐ 18 d gave yields of 33 and 79 % for the same reaction. Double StReCH of 17 was pursued to target contiguous stereodiads appropriate for the total synthesis of (?)‐epibatidine ( 15 ). One‐pot double StReCH of boronate 17 by two exposures to (S)‐D ‐ 18 a (≤66 % ee), followed by work‐up with KOOH, gave the expected stereodiad product in 16 % yield (d.r.～67:33). The comparable reaction using two exposures to (S)‐D ‐ 18 d (≤90 % ee) delivered the expected bisacetal containing stereodiad (R,R)‐DD ‐ 48 in 40 % yield (≥98 % ee, d.r.=85:15). Double StReCH of 17 using (S)‐D ‐ 18 d (≤90 % ee) followed by (R)‐D ‐ 18 d (≤90 % ee) likewise gave (R,S)‐DD ‐ 48 in 49 % yield (≥97 % ee, d.r.=79:21). (R,S)‐DD ‐ 48 was converted to a dideuterated isotopomer of a synthetic intermediate in Corey’s synthesis of 15 .     

The Interaction of O2, NO,and N2O with Surface Defects of Dispersed Titanium Dioxide

A combined study of intrinsic structural defects in reduced TiO₂ was performed using mass spectrometry, optical diffuse-reflectance spectroscopy, and UV photoelectron spectroscopy (UPS). It was found that the reduction of TiO₂ resulted in the appearance of absorption in the region 0.50 h 3.50 eV (400 2500 nm), which is formed by absorption due to free electrons (a continuum at h 1.50 eV), local centers—Ti³⁺ ions (a band at 2.00 eV), and oxygen vacancies (bands at 1.17, 2.81, and 2.55 eV). The spectrum of induced occupied electronic states in the forbidden gap and the position of oxygen vacancy levels with respect to the Fermi level were determined by UPS. The absorption of reduced TiO₂ was stable on the sample to T = 800 K in a vacuum; however, it weakened in contact with O₂, NO, and N₂O molecules beginning at T = 300 K (surface sites) and T 400 K (subsurface sites) as a result of filling oxygen vacancies with atomic oxygen in the course of dissociative adsorption. The adsorption complexes formed by the interaction of O₂, NO, and N₂O with defects were analyzed by temperature-programmed desorption. The distribution of sites over the energies of oxygen binding was found with the use of a nonuniform surface model, and specific oxygen adsorption species were revealed. It was found that the irradiation of TiO₂ activates the formation and decay of sites and results in the formation of specific O₂ and N₂O adsorption species.