Effect of Water Vapor on Chromatographic Characteristics of the Cyclodextrin-Containing Stationary Liquid Phase in Capillary Gas Chromatography

The effects of the presence of water vapor in the carrier gas and the temperature on the retention of achiral and chiral compounds, enantioselectivity, and performance of an open-tubular column with a cyclodextrin-containing phase were studied. The use of a carrier gas containing water vapor in the determination of optically active isomers, such as camphor, slightly increases the retention factor. A substantial improvement of performance characteristics of the column was found: for hydroxy compounds, the column performance increased by two to three times and the peak symmetry improved by more than twice.     

Pathways of Intramolecular Cyclization of Phosphorylated Ureas and Thioureas: A Theoretical Study

The stability of phosphorylated ureas and thioureas containing various substituents at the P and N atoms and the stability of their cyclization products, the corresponding diazaphospholidines and/or oxaza(thiaza)phospholines, was evaluated by PM3, MNDO, and DFT calculations. The thermal effects of cyclizations involving phosphorylated ureas (or thioureas) and of separate steps of their synthesis were calculated. According to the calculations, diazaphospholidine structures are preferably formed from substituted ureas and thiazaphospholine structures, from their thio analogs; formation of five-membered heterorings with the P-N bond is thermodynamically preferable as compared to their six-membered analogs.     

Synthesis of 6R(β)-tritylaminopenicillanic-3R(β)-alcohol,a versatile stereoisomer of natural β-lactams

In an attempt to rationalize a synthesis of penicillin analogs modified at C(3), we have isolated the 3R(β)-carbinolamide derivative 4a. The trityl substituent on N(6′) seems to be responsible for the inversion of configuration which occurs at C(3) during the acid hydrolysis of the isocyanate intermediate. An hydrogen bond is formed on the β-face of the bell-shaped bicyclic skeleton between the N(6′)-nitrogen lone pair and the C(3) hydroxyl group. On standing, the carbinolamide analog slowly isomerizes to its expanded bicyclic isomer 4b , but the starting material may be easily recovered by treatment with acid. The postulated intermediate during isomerization, i.e., the open aldehyde form, does not accumulate. Substitutions of the hydroxyl group at C(3) lead to a variety of compounds with the biologically active 3S(α) configuration. These may be used to study the importance of the carboxyl group of penicillins in their interaction with β-lactamases at the molecular level.     

Kinetics and Mechanism of Palladium Electrodeposition from Alkaline Solutions of Palladium(II) Bisethylenediamine Complexes

The electroreduction kinetics of Pd(en)²⁺ ₂ complexes (0.01 M) is studied on a rotating disk electrode of Pd by recording CVA at 25, 50, and 70°C in solutions of pH 12–13 at ethylenediamine concentrations of 0.03–1.0 M. Established is a diffusion nature of limiting currents, from which diffusion coefficients for Pd(en)²⁺ ₂ complexes are calculated. The Pd electrode capacitance, determined by a pulsed galvanostatic method, is used for taking into account the true surface areas of electrolytic Pd deposits. Parameters of the slow electrochemical stage, which involves Pd(en)²⁺ ₂ complexes, are determined. The temperature dependence of the rate constant of cathodic reduction of Pd(en)²⁺ ₂ complexes is used for calculating an apparent activation energy. An electroreduction mechanism of Pd(en)²⁺ ₂ complexes on a Pd electrode is discussed.     

Isomerization of α-acetylenic ketones

A method is suggested for isomerization of -acetylenic ketones with migration of the oxo group from position 1 to position 3 and of the triple bond from position 2 to position 1 of the ketoacetylenic fragment; it consists of addition of Et₂NH at the triple bond of the ketone, conversion of the adduct to the imminium salt with POCl₃, followed by alkaline hydrolysis. The isomerization is achieved in one preparative stage without isolation of intermediate compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2094–2098, September, 1990.     

Choline esters of alkylenebisphosphonic acids

The reaction of the acid chlorides of alkylenebisphosphonic acids with ethylene glycol and ethylene chlorohydrin gave ethylene glycol and -chloroethyl esters of alkylenebisphosphonic acids. The quaternization of these products leads to choline esters of alkylenebisphosphonic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1424–1429, June, 1990.     

Bromination of 3-acyl-2-aminoindoles

Unlike 3-acylindoles, 3-acyl-2-aminoindoles display high selectivity on being electrophilically attacked in the benzene ring, and are substituted at the 6-position. At the same time, an unco-subsitution of the acyl group takes place (to the greatest extent — the formyl group). Direct bromination of 3-acyl- and 3-cyano-2-aminoindoles provides the 6-bromo- and 6,4-dibromo-2-aminoindoles and their derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 486–490, April, 1990.     

A spin-dependent unitary group approach to many-electron systems

In this article we derive a segment-level formula for the matrix elements of the U(2n) generators in a basis symmetry adapted to the subgroup U(n) × U(2) (i.e., spin-orbit basis), for the representations appropriate to many-electron systems. This enables the direct evaluation of the matrix elements of spin-dependent Hamiltonians.     

Halogenation of isoflavones using thionyl and sulphuryl chlorides

The reactions of thionyl and sulphuryl chlorides on isoflavones have been found to give a number of new chloroisoflavones and isoflavanones, whose structures have been elucidated on the basis of their spectral analytical data.     

On the behavior of α-brominated dimethyl o-benzenediacetate toward nitrogen nucleophiles. Part II. Reaction of dimethyl α-bromo-o-benzenediacetate with hydrazines

Dimethyl α-bromo-o-benzenediacetate ( 1 ) condensed with hydrazine and acetylhydrazine to give respectively 1-carbomethoxy-2-amino-1,4-dihydro-3-(2H)isoquinolinone (2) and its N-acetyl derivative ( 9 ). Replacement of the bromine atom of 1 with the N-1-methylhydrazino ( 3 ) and the N-1-phenylhydrazino ( 5 ) groups occurred by allowing 1 to react respectively with methylhydrazine and phenylhydrazine. In the latter case alkylation by 1 at the N-2 also occurred which led to the formation of the 2-phenylaminoisoquinolinone ( 8 ). Derivatives 3 and 5 smoothly cyclized to the 1-earbomethoxy-5(H)-1,2,3,4-tetrahydro-2,3-benzodiazepin-4-ones 4 and 6 . A series of derivatives of 2 were also pharmacologically tested as antiinflammatory and CNS depressant agents.