Kinetics and products of the reaction of diazo compounds with SO2

Data were obtained on the composition of products and kinetics of the reaction of SO₂ with Ph(R)CN₂ (R=Ph, Me) in solutions of isooctane, 1,4-di-oxane, and ethanol at 295 K. A mechanism was proposed for the process in accordance with which the sulfene being formed participates in concurrent reactions with the starting reagents. The relative rate constants for the process stages were determined.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2496–2500, November, 1990.     

29Si NMR study of the surface of pyrogenic silica modified by methylchlorosilanes

Cross-polarization ²⁹Si NMR spectra have been used for aerosil modified by methylchlorosilanes to identify surface organosilicon compounds and their reactions during hydrolysis and methanolysis.Translated from Teoreticheskaya i Eksperimental'naya Khimiya, No. 3, pp. 378–383, May–June, 1986.     

The mechanism of oxidation of indoxyl and its analogs to indigo and indigoides

Conclusions Intermediate formation of 3-oxynaphthenyl-2 radical during oxidation of 3-oxythionaphthene to thioindigo was demonstrated by the inhibitor method. The 1:1 recombination product of this radical and diphenylpicrylhydrazyl was isolated. It is assumed that the postulated oxidation mechanism is general for compounds possessing a methylene group bonded to an electron-donating X group and an electron-accepting C=O group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1168–1170, May, 1970.     

Topochemical investigations of peptide systems

The basic principles of the topochemical approach to the investigation of the structure-function relation in peptide systems are formulated. This approach makes use of the new possibility of transforming natural peptides, consisting in the modification of the molecule as a whole and utilization of the resultant analogs to elucidate the boundaries of the stereoelectronic complementarity of the biologically active peptide to the corresponding receptor. In particular, on the example of depsipeptide antibiotics and their topochemical analogs the fruitfulness of using such compounds as tools in elucidating the physicochemical basis of functioning of biological membranes is shown. The topochemical principle has also been applied in preparing specific competitive inhibitors of proteolytic enzymes, whose study may shed light on the nature of the forces binding the substrate to the contact site of the corresponding enzyme.     

Retention of analgin and anesthesin on sorbents with different polarities: The analysis of bellalgin tablets by high-performance liquid chromatography

The effects of acetonitrile and potassium dihydrogen phosphate concentrations in a mobile phase and the pH of the mobile phase on the retention of analgin (dipyrone) and anesthesin (benzocaine) on Symmetry C18 and Nova-Pak CN HP sorbents with grafted octadecylsilanol and nitrile groups, respectively, were studied. It was found that, under identical conditions, retention on the sorbent with grafted nitrile groups was weaker. A rapid and cost-effective procedure was developed for the determination of analgin and anesthesin in the analysis of Bellalgin tablets.     

Structure,tautomerism, and transformations of β-(3-nitro-2-pyridyl)- and β-(3-nitro-4-pyridyl)pyruvic acid esters

It was shown by means of IR, UV, and PMR spectra that -(3-nitro-2-pyridyl)pyruvic acid esters are practically completely enolized in the crystal state and in solution; ethyl -(3-nitro-4-pyridyl)pyruvate has an enol structure in the crystalline state and in pyridine solution but exists as a mixture of keto and enol forms in low-polarity solvents.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 389–393, March, 1974.     

Gas-discharge plasma initiated in air by a radiation pulse

Formation of a nonequilibriuin gas-discharge plasma in air under the action of radiation at a wavelength of 10.6 with a duration of 10^–6 sec is considered. It is shown that the air discharge occurs under nonequilibrium conditions by formation of an autoionization complex with subsequent oscillatory excitation of molecules. The molecular distribution function over oscillatory degrees of freedom is found in the diffusion approximation. The electron temperature and concentration in the breakdown plasma are calculated with consideration of multistep ionization of molecules and dissociative recombination of charged particles. Results are compared with experiment.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 9–13, February, 1985.     

A new synthesis of ampicillin and related investigations

Quaternization of (S)-α-bromophenylacetic acid amide (8) with hexamethylentetramine (hexamine) preceded with ca. 80% inversion of configuration. Accordingly, starting from the trimethylsilylester of N-(S)-(α-bromo-α-phenylacetyl)-6-aminopenicillanic acid (4) quaternization with hexamine and subsequent hydrolysis afforded N-(R)-α-phenylglycyl-6-aminopenicillanic acid (1, ampicillin). Some other model reactions have been investigated.