吡咯-IR法测定铝化β沸石的碱性

The basicities of aluminated zeolites βhave been investigated by FTIR spectra of chemisorbed pyrrole. The NH-stretching frequency of pyrrole adsorbed on the samples shifts towards lower wavenumber as the St/Al ratio is decreased and correlates well with the negative charge on the framework oxygen calculated from the Sanderson electronegativity equalization principle, revealing zeolite β to possess a stronger overall basicity after alumination and, therefore, the alumination to be an effective method to improve the basicity. It is also found that the heterogeneity of basic strength occurs and some stronger basic sites appear after alumination.     

Simultaneous operation of plural separation modes in capillary electrophoresis with a chemiluminescence detector possessing a micro-space area for reaction/detection

Analysis of alpha-amino acids, proteins, and phenolic compounds was simultaneously performed using three capillaries in capillary electrophoresis with chemiluminescence detection, taking advantage of the micro-space area for reaction/detection at the tip of the capillary. The three capillaries included usual, polymer-containing, and sodium docley sulfate (SDS)-containing migration buffers for separation. The eluted samples from the capillaries, which were inserted into the chemiluminescence detection cell, were mixed with chemiluminescence reagent at the tips of the capillaries to generate visible light. The specific micro-space area for reaction/detection at the tips of the capillaries enabled the simultaneous operation of the three separation modes in the present system.     

The thermodynamics of mixing C6 and C7 compounds with a bicyclic compound at infinite dilution

The activity coefficients at infinite dilution have been measured at 25°C for cyclohexane, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, benzene, n-hexane, 1-hexene, 1-hexyne, n-heptane, 1-heptene and 1-heptyne in decahydronaphthalene, bicyclohexyl, 1,2,3,4-tetrahydronaphthalene and cyclohexylbenzene. These results, together with previously determined H _m ^E and V _m ^E have been used to calculate the partial molar excess thermodynamic properties of mixing at infinite dilution.     

Structure and conformational features of tetrahydrothienothiepinoisoxazole as a novel heterocyclic system

The crystal and molecular structure of a novel heterocyclic system, 8-methyl-3,3a,4,5-tetrahydrothieno[3,2:6,7]thiepino[4,5-c]isoxazole, has been determined by X-ray analysis. The seven-membered ring has the boat conformation (B), while the isoxazoline cycle has the flat chair conformation (₃E). There are strong steric strains between the vicinal protons at the C(3a), C(3), and C(4) atoms.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1795–1797, October, 1994.     

Three-dimensional aromaticity in deltahedral boranes and carboranes

Methods derived from topology and graph theory indicate that the deltahedral boranes B _n H _n ^2– and the corresponding carboranes C₂B_n–2H _n (6 n 12) may be regarded as three-dimensional delocalized aromatic systems in which surface bonding and core bonding correspond to -bonding and -bonding, respectively, in planar polygonal two-dimensional hydrocarbons CinnH _n ^(n–6)+ (n=5/7). The two extreme types of topologies which may be used to model core bonding in deltahedral boranes and carboranes are the deltahedral (D _n ) topology based on the skeleton of the underlying deltahedron and the complete (K _n ) topology based on the corresponding complete graph. Analyses of the Hoffmann-Lipscomb LCAO extended Hückel computations, the Armstrong—Perkins—Stewart self-consistent molecular orbital computations, and SCF MOab initio GAUSSIAN-82 computations on B₆H₆ ^2– indicate that the approximation of the atomic orbitals by the sum of the molecular orbitals, as is typical in modernab initio computations, leads to significantly weaker apparent core bonding approximated more closely by deltahedral (D _n ) topology than by complete (K _n ) topology.This work was presented at the Workshop The Modern Problems of Heteroorganic Chemistry sponsored by the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (May 8–13, 1993).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1353–1360, August, 1993.     

Reactions of organic halides with organometallic compounds and terminal acetylenes catalyzed by palladium complexes

The results of the investigation of the cross-coupling of organometallic compounds and terminal acetylenes with organic halides catalyzed by transition metal complexes are generalized and analyzed. The influence of different factors on the rate and selectivity of catalytic cross-coupling is discussed. A detailed mechanism of the cross-coupling of Grignard reagents with organic halides is suggested. The cross-coupling reaction involving organotin compounds proceeds under very mild conditions in the presence of a ligand-free Pd catalyst. Examples of using catalytic cross-coupling of organic halides with organomagnesium, organozinc, and organotin compounds are presented.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2148–2167, September, 1996.     

Simple enzyme reactors suitable for the byproduct-free preparation of the aglycones of naturally occurring glycosides under mild conditions

Naringinase from Penicillium species—containing α-l-rhamnosidase and β-d-glucosidase activity—immobilized on silicate carriers can be used as a mild and effective means to cleave naturally occurring glycosides into their aglycones and sugar components. The procedure was tested with flavonoid-, anthraquinone-, and steroidglycosides. Since the solubility of such compounds is limited in aqueous solutions, a simple batch procedure has been developed to convert solid substrates suspended in only small amounts of buffer to the desired products with high yields.     

Deactivation,coating and performance of nickel capillary columns for GLC

Electroformed nickel tubing was deactivated by chemical vapor deposition of silicon from silane gas and subsequent treatment with cyclooctamethyltetrasiloxane (D4). Standard activity tests performed on the uncoated tube and also on columns coated with crosslinked and uncrosslinked, nonpolar stationary phase, show that good quality flexible columns can be prepared from nickel tubing. The inner surface of the silicon coated tube was characterized by Auger depth profile analysis.     

N- and O-Alkylation of 3-indolylcyclopropylacetic acid derivatives

2,2-Dimethyl-3-(2-methyl-3-indolyl)cyclopropylacetic acid, its amide and esters, and the corresponding alcohol, viz., the product of ester reduction by LiAlH₄, were synthesized. The chemoselectivity of N- and O-alkylation of these compounds was studied. Selective monoalkylation at the nitrogen atom of the heterocycle, O-alkylation to the side chain, or dialkylation at both nucleophilic sites can be carried out under conditions of phase-transfer catalysis. The N-acylation at the indole fragment of nitrile of this acid occurs only under the Vilsmeier—Haak formylation conditions.