Electrochemically induced processes in the formation of phosphorus acid derivatives. 2. The role of polymerization processes in the electrosynthesis of the esters of phosphorus acids from white phosphorus

The mechanism of the electrosynthesis of phosphate esters from white phosphorus was investigated. It was shown that the reaction takes place by two paths, i.e., monomeric (with the participation of dissolved phosphorus) and polymeric (with the participation of phosphorus on the surface of an emulsion drop). It was established that in an alcohol solution of tetraethylammonium iodide the main part of the final product is formed through an intermediate polymeric compound. It was noticed that by studying the dynamics of the accumulation of the dissolved product during electrolysis it is possible to trace the mechanism of reaction of the phosphorus at the individual stages of the process.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420028 Kazan'. V. I. Ul'yanov-Lenin Kazan' State University, 420028 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1328–1333, June, 1992.     

Structure of dysprosium monotartrate in aqueous solution from magnetic double refraction and molecular mechanics data

pH-Metering and magnetic double refraction are used to determine the molar constant of magnetic double refraction of dysprosium monotartrate DyH₂L⁺ (H₄L is tartaric acid). A molecular mechanics technique (Dashevskii-Plyamovatyi model) was used to model the structure of the ligand and hydrate surroundings of dysprosium(III) in DyH₂L⁺. Theoretical molar constants of magnetic double refraction calculated from the molecular mechanics data (CONKERR program) were compared with the experimental values; the most probable models of the surroundings of the dysprosium(III) are established.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences, 420062 Kazan'. V. I. Ul'yanov-Lenin Kazan' State University, 420008 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2232–2237, October, 1992.     

Synthesis and properties of triethylammonium 2,2,5-triphenyl-1,3,2,5-dioxaborataphosphorinane

The reaction of bis(hydroxymethyl)phenylphosphine with isobutyl diphenylborate in the presence of triethylamine leads to the formation of triethylammonium 2,2,5-triphenyl-1,3,2,5-dioxaborataphosphorinane (1). The reaction of compound 1 with electrophilic reagents (O, S, Se, CH₂O, RHal) leads to quaternization of the phosphorus atom, giving the corresponding phosphine oxides, sulfides, and selenides and P,B-containing betaines. In the reactions of compound 1 with amines aminomethylphosphines of the diazaphosphorinane and diazadiphosphacyclooctane series are formed. Ammonium 1,3,2,5-dioxaborataphosphorinanes dissociate in solutions and enter into ion exchange with phosphonium iodides, leading to phosphonium 1,3,2,5-dioxaborataphosphorinanes. The latter, in the case of the aminomethylphosphonium cation, undergo intramolecular rearrangement with the formation of P,B-containing betaines and aminomethylphosphines.Deceased.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1398–1405, June, 1992.     

Electrochemically induced processes of formation of phosphorus acid derivatives. 4. Synthesis of trialkyl phosphates from white phosphorus

The products of electrolysis in dipolar aprotic solvents on the background of tetraethylammonium iodide in the presence of white phosphorus are trialkyl phosphite (the primary product after splitting of all the P-P bonds in the phosphoric oligomers) and triaryl phosphate. It was found that the formation of triaryl phosphate from white phosphorus proceeds by way of electrochemical reduction of pentaaroxyphosphorane — an intermediate product of the reaction of triaryl phosphite with iodine and phenol. A strong dependence of the yields and distribution of the products on the composition of the electrolyte has been observed.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center of the Russian Academy of Sciences, 420083 Kazan'. V. I. Ul'yanov-Lenin Kazan' State University, 420008 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2039–2043, September, 1992.     

Electrochemical reduction of some compounds of two-coordinate phosphorus and arsenic in an aprotic medium

The electrochemical reduction of a series of compounds of two-coordinate phosphorus and arsenic with linear structure was investigated for the first time. The main polarographic characteristics indicate irreversibility of the electrode process and its complication by kinetic limitations. The products of controlled-potential electrolysis were analyzed, and schemes are presented for the electrochemical reduction, which consists in hydrogenation with cleavage of the P=E bond of most of the studied compounds (1,2, and4) and in cleavage of the C_Ar-P bond in sterically hindered compound3. The electrolysis products underwent further transformation in the presence of oxygen and moisture of air.DeceasedA. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1754–1760, August, 1992.     

Interamination of some aminooxypyrimidines

Bis(pyrimidinyl)amines have been prepared by reaction of aminooxypyrimidines with aminooxypyrimidine hydrochlorides.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 169–173, January, 1992.     

Synthesis and heterocyclization of osazones of carbonyl-substituted glyoxals

Enolates of α-chloro-β-oxoaldehydes react with arylhydrazines in the presence of acetic acid, forming osazones of carbonyl-substituted glyoxals. The same osazones are obtained by the reaction of β-oxo-α-chlorenamines with arylhydrazines. Under conditions of acid catalysis, these osazones undergo intramolecular heterocyclization to the corresponding functionalized pyrazoles. Kazan' State Technological University. Kazan' 420015, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 190–193, February, 1998.     

Nucleophilic thiylation of limonene 8,9-oxide

Thioterpenols of the menthane series have been obtained by reactions of limonene 8,9-oxide with thiols and with isothiuronium salts.S. V. Kurashov Kazan' State Medical University, 420012, Kazan', ul. Butlerov, 49, Korp. B Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 197–200, March–April, 1999.     

Reactions of camphene oxide with sulfur-containing nucleophiles

Sulfur-containing derivatives of the camphene series have been obtained by the nucleophilic addition of isothiouronium salts and thiourea under the conditions of base catalysis.S. V. Kurashov Kazan' State Medical Institute, 420012 Kazan', ul. Butlerova, 12. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 244–246, March–April, 1994.     

Synthesis of 1,3,4,2,6-oxathiazadiphosphorines

Alkyl chlorides and 6-alkoxy-2,4-bis(diethylamino)-6-oxo-1,3,4,2,6-oxathiazadiphosphorines are the products of the reaction of tetraethyldiamidochlorophosphite with dialkylisothiocyanatophosphates. The structure of the oxathiazadiphosphorines was demonstrated by IR,¹H,¹³C,³¹P NMR, and mass spectroscopy and it was found that they are formed as a mixture of two geometric isomers.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific-Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1168–1171, May, 1992.     

Thiophene-2-aldehyde in the Darzens reaction

The reaction of the title compound with dichloroacetic acid esters in the presence of butyllithium gave esters of 3-thienyl-3-hydroxy-2,2-dichloropropionic acid.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center of the Russian Academy of Sciences, 420083 Kazan', Russia. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1870–1873, August, 1992.     

Reactions of mixed O,S-esters of acids of trivalent phosphorus with substituted 1-chloroacetylenes

The reactions of mixed O,S-esters oftert-butylthiophosphonous acid and dithiophosphorous acid with 1-chloro-2-organylacetylenes were studied. On the basis of them, a convenient method for the synthesis of thioesters of organylethynylthiophosphinic and dithiophosphonic acids, which are undescribed in the literature, was proposed. A difference was found in the chemical behavior of the methyl ester of S,S-diethyldithiophosphorous acid by comparison with the corresponding complete esters and thioesters of phosphorous acid in reactions with dichloroacetylene.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1635–1637, July, 1992.     

Reactions of camphene oxide with sulfur-containing nucleophiles

Sulfur-containing derivatives of the camphene series have been obtained by the nucleophilic addition of isothiouronium salts and thiourea under the conditions of base catalysis. S. V. Kurashov Kazan' State Medical Institute, 420012 Kazan', ul. Butlerova, 12. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 244–246, March–April, 1994.     

Comparative analysis of the applicability of AM1 and CNDO/2 methods for quantitative prediction of the35Cl NQR frequencies of RC-Cl compounds

The³⁵Cl NQR frequencies of a series of RC-Cl compounds were calculated by the AM1 and CNDO/2 methods in the Townes-Dailey approximation. It was shown that neither of these methods can be directly used for the quantitative prediction of NQR frequencies, and their use in the correlation approach is only possible in narrow series. The AM1 method gives better results for saturated compounds.Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1078–1082, May, 1992.     

Electrochemically induced processes in the formation of phosphorus acid derivatives. 1. Synthesis of trialkyl phosphates from white phosphorus

An electrochemical method, based on the joint action of nucleophilic and electrophilic reagents on P₄, is proposed in order to utilize white phosphorus in the formation of the esters of phosphorus acids. The action of alkoxide ions on white phosphorus in an alcohol medium in the presence of iodine generated at the anode leads to the formation of phosphate esters. A scheme in which the intermediate products are dialkyl and trialkyl phosphites and the side product is dialkyl alkylphosphonate is proposed for the process.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420028 Kazan'. V. I. Ul'yanov-Lenin Kazan State University, 420028 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1322–1328, June, 1992.     

New routes for the synthesis of 2,5-disubstituted 4-formylthiazoles

New 2,5-disubstituted 4-formylthiazoles have been obtained by the reaction of acetal-containing -chloroxiranes or their rearrangement products, chloroketones, with thioamides and N-allylurea.Kazan' State Technological University, Kazan' 420015, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 124–129, January, 1998.     

Dealkylation ofpara-nitrophenyldimethyl thiophosphate in micellar and liquid-crystalline media of then-decylammonium chloride-n-decylamine-water system

The kinetics of decomposition of p-nitrophenyldimethyl thiophosphate (1) were investigated spectrophotometrically in the n-decylammonium chloride-n-decylamine-water system (DAC-DA-H₂O), in which micellar or lamellar liquid-crystalline phases are formed as a function of the concentration of components. It was shown that1 is dealkylated in both phases. An increase in the surface charge density of associates decreases the rate of dealkylation. The activation energy in the lamellar phase is significantly higher than in the micellar phase.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1042–1048, May, 1992.     

Molecular structure of 6,6-dimethyl-2-dimethylamino-2-oxo-4,5; 7,8-dibenzo-1,3,6,2-dioxasilaphosphocin and 2-methyl-2,6-dioxo-4,5; 7,8-dibenzo-1,3,2-dioxaphosphocin

An x-ray structural investigation of the synthesized title compounds (1) and (2) has been performed. The heterocycle of 1 has a boat-chair conformation with the P²=O² bond in the axial position. The heterocycle of 2 has a distorted-boat conformation with the C⁶=O carbonyl in the plane of one of the fused benzene rings. The P²=O² bond is in a pseudoequatorial position.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 329–334, February, 1992.     

Reactivity of heterocyclic compounds in nitration. 8. Nitration of 3-hydroxypyridine and its substituted forms

Nitration of 3-hydroxypyridine and its substituted forms has been studied under various conditions. It is shown that, depending on the reaction temperature and the nitrating agent, the end products of the synthesis can be 3-hydroxy-2,6-dinitropyridine or 3-hydroxy-2,4,6-trinitropyridine. The possibility of substitutional nitration of iodine derivatives of 2- and 3-hydroxypyridine is demonstrated.For Communication 7, see [1].Kazan' State Technological University, Kazan' 420015, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 958–961, July, 1998.     

Structural kinetic rules governing the thermal decomposition of pyridine N-oxides

The Arrhenius parameters of the thermal composition of pyridine N-oxides in the liquid phase have been determined. The conclusion has been reached that the formation of an oxaziridine activated complex can be considered as the initial act of the thermolysis. A correlation has been found to exist between the rate constants of the thermal decomposition and the calculated values of the fractional electron charge at the oxygen of the N-oxide, and the length of the N- O bonds.Kazan' State Technological University, Kazan' 420015. Biisk Liceum of the Altai Region, Biisk 659322. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 644–646, May, 1994. Original article submitted April 4, 1994.