Reaction of 3,3-dichloropentane-2,4-dione with aromatic aldehydes under the conditions of Darzens reaction

3,3-Dichloropentane-2,4-dione reacts with aromatic aldehydes under the conditions of Darzens reaction to give 4-acetoxy-4-aryl-3,3-dichlorobutan-2-ones, the products of insertion into the -C-C bond. The reaction of ethyl dichloroacetylacetate with benzaldehyde yields a derivative of tricyclo[5.1.0.0^3,5]octane, rather than 2,6-bis(1-chlorobenzylidene)cyclohexane-1,4-dione, as the by-product.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1294–1298, July, 1995.     

Condensation of methyl 2-chloro-3-(3-nitrophenyl)-2,3-epoxypropionate with 1,2-phenylene diamine

It is established that the -chloroepoxide methyl 2-chloro-3-(3-nitrophenyl)-2, 3-epoxypropionate, in contrast to its a-chloroketone isomer methyl 3-(3-nitrophenyl-3-chloro-2-oxopropionate, forms 2-(3-nitrophenyl-3methoxycarbonylquinoxaline in reaction with 1,2-phenylene diamine, whereas the condensation of the achloroketone with 1,2 phenylene diamine gives 3-(-chloro-3-nitrophenyl)-2-oxo-1,2-dihydroquinoxaline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1105-1108, August, 1994.     

Synthesis of a symmetrical dithiirane

The reaction of p-xylene with epichlorohydrin in the presence of aluminum chloride gave 1,4-dimethyl-2,5-bis(1-chloro-2-hydroxypropyl)benzene, which serves as the starting compound for the synthesis of the corresponding symmetrical dithiirane.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1319–1321, October, 1985.     

Combined application of 2D NMR correlation methods and ab initio chemical shift calculations to the structure determination of new heterocyclic compounds

The combined use of 2D NMR correlation methods and ab initio chemical shift calculations is efficient and, in some cases, virtually the only way to determine the structures of new organic compounds. This approach enabled us to establish the structure of the major unusual product of the three-component reaction of imidazo[1,5-a]quinoxalin-4-one, bis(2-chloroethyl)amine hydrochloride, and potassium carbonate in DMF. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2172–2179, December, 2006. Dedicated to Professor A. V. Il’yasov on the occasion of his 70th birthday.     

Condensation of Aniline and o-Hydroxyaniline with 1,2-Dibromoethane

Russian Journal of Organic Chemistry -     

Highly Selective Ion-Sensitive Electrodes Based on Dibenzo-Crown Ethers Containing Functional Groups for the Determination of Potassium in Biological Fluids

The electrochemical properties of membranes based on dibenzo-crown ethers bearing hydroxyl and chloromethyl groups in polyether rings were studied. These substances were tested as membrane ionophores for ion-selective electrodes (ISEs) reversible to potassium ion. The developed ISEs were used for determining potassium in blood plasma samples. The generalized results of determining potassium in the blood of different patients with cardiovascular diseases revealed quantitative regularities that allowed the diseases to be diagnosed early.     

Local environment and dynamics of PO4 tetrahedra in Na-Al-PO3 glasses and melts

Glasses and melts in the system (NaPO3)(1-x)(Al(PO3)3)x were studied with the aim of obtaining information about the structure on the next larger scale beyond the PO4 group. Magic angle spinning NMR was applied to the pure NaPO3 glass and Raman scattering to systems with x = 0.00, 0.03, 0.06, 0.15, and 0.60 in the temperature range T = 300-1100 K. Comparison of the 31P chemical shift between glass and crystalline forms revealed that polymerization of the metaphosphate into tricyclophosphatelike (PO3)3(3-) rings is the dominant structure, ca. 80%, formed by the twofold vertex-joined PO4 groups in the glass. In the Raman study we focused on the prominent polarized band at ca. 1170 cm(-1) which is due to the symmetric breathing mode of the tetrahedral PO4 group. This band was decomposed into a few Gaussian lines. These component lines could be identified using the NMR results: two narrow components are due to PO4 groups in the tricyclophosphatelike rings, which have either a Na or an Al counterion and a third broad component is due to chain-polymerized (PO3(-))n. The variations of the component lines (peak positions, widths, and intensities) with respect to x and T are presented. We derive the shifts of the symmetric breathing mode frequency which are caused by Na or Al counterions, by ring closure, by x > 0, etc. The relative intensities of the narrow and broad components in the 1170-cm(-1) band of the Raman spectra are discussed. The amount of ring-to-chain transformation on addition of Al3+, and as functions of T and x, is derived. Indications for ordering on a next larger scale, derivable from Raman, NMR, and thermodynamics, are compared.     

Synthesis of monoethers by addition of aliphatic diols to bicyclo[2.2.1]hept-2-enes

Addition of aliphatic diols to bicyclo[2.2.1]hept-2-ene and its 5-alkyl-substituted derivatives in the presence of naphthalene-1,5-disulfonic acid leads to the formation of the corresponding bicyclo[2.2.1]hept-2-yl monoethers in high yields.     

Synthesis of some new derivatives of dithiene-and oxathienecarboxylic acids

Substituted anilides of 1,4-dithiene- and oxathienecarboxylic acids were synthesized. It was shown that the reaction of 3-phenyl-1,4-dithi-2-ene-2-carboxyl chloride with 2-aminopyridines, depending on the base used and the reaction conditions, leads to the formation of N-[3-phenyl-2-(1,4-dithi-2-en)ylcarbonyl]2-amino-pyridine and/or N,N-bis[3-phenyl-2-(1,4-dithi-2-en)-ylcarbonyl]pyridonimine. The data of IR, UV, and PME spectroscopy were used to confirm the structure of the synthesized compounds.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Science Center, Russian Academy of Sciences. Kazan 420083. Translated fro, Khimiya Geterotskiklicheskikh Soedinenii, No. 9, pp. 1191–1196, September, 1994. Original article submitted May 10, 1994.