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.     

Acids and their functionally substituted esters fromAmaranthus cruentus seed oil

The acid composition of seed oil ofAmaranthus cruentus and the synthesis of their glycidyl and pyridinecontaining esters are studied. It is demonstrated that 67% of the total acids are C₁₈-polyunsaturated linoleic and linolenic. A new method for preparing glycidyl esters of C₁₈-unsaturated carboxylic acids is developed by reacting their salts with ECG in an aprotic medium to produce the corresponding glycidyl esters. The reaction of the glycidyl esters and pyridine salts with carboxylic and phosphonic acids produces the propanolpyridine esters of the acids that combine the properties of the acids and pyridinium salts and are promising in the search for biologically active compounds.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 217–219, May–June, 2000.     

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.     

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.     

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.     

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.     

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.     

Rapid analysis of the anisotropic EPR spectra of polycrystalline and amorphous systems formed by species with orthorhombic symmetry of the g value

Kazan' Physicotechnical Institute. Translated from Zhurnal Strukturnoi Khimii, Vol. 29, No 3, pp. 49–52, May–June, 1988.     

Reaction of organozinc reagents formed in reaction of dibromomalonic acid dialkyl esters and zinc, with 2-arylmethylenemalonic acid dinitriles and 3-aryl-2-cyanopropenoic acid methyl esters

Organozinc compounds, obtained from dibromomalonic acid dialkyl esters and zinc, react with 2-arylmethylmalonic acid dinitriles and 3-aryl-2-cyanopropenoic acid methyl esters forming 3-aryl-2,2-dicyanocyclopropane-1,1-dicarboxylic acid dialkyl esters and 3-aryl-2-cyanocyclopropane-1,1,2-tricarboxylic acid trimethyl esters. ¹H and ¹³C NMR, ³ J _CH constants are considered.     

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.     

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.     

Efficient synthesis of 2,6-disubstituted-5-hydroxy-3-oxo-2,3-dihydro-pyridazine-4-carboxylic acid ethyl esters

A general procedure is described for the preparation of 6-substituted-5-hydroxy-3-oxo-2,3-dihydro-pyridazine-4-carboxylic acid ethyl esters (6-substituted-5-hydroxy-3(2H)-pyridazinone-4-carboxylic acid ethyl esters). These compounds are shown to undergo selective alkylation at the 2-position in moderate to good yields (19-77%) to afford 2,6-disubstituted-5-hydroxy-3-oxo-2,3-dihydro-pyridazine-4-carboxylic acid ethyl esters (2,6-disubstituted-5-hydroxy-3(2H)-pyridazinone-4-carboxylic acid ethyl esters).     

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.     

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.     

Reactions of 4-chloroacetoacetic esters with thioureas

Several heterocyclic acetic acids and esters were synthesized by allowing the appropriate thiourea, ethylenethiourea or trimethylenethiourea to react with 4-chloroacetoacetic esters, followed by acid hydrolysis to the hydrochlorides of the free acids. Both esters and acids of 2-aminothiazole-4-acetic acid, 5,6-dihydro-imidazo[2,1-b]thiazole-3-acetic acid and 6,7-dihydro-5H-thiazolo[3,2-c]pyrimidine-3-acetic acid were obtained.     

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.     

X-ray crystallographic investigation of S-methyl N-diisopropoxythiophosphorylbenzimidothioate and S-cyanomethyl N-diisopropoxythiophosphorylbenzimidothioate

Institute of Physiologically Active substances, Academy of Sciences of the USSR. Kazan' State University. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 3, pp. 80–84, May–June, 1991.     

Monoterpenoids (3-carene and α-terpinene) in electrophilic disulfide addition reactions

The reactions of 3-carene and α-terpinene with dialkyl disulfides have been studied. S. V. Kurashov Kazan' State Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 624–626, September–October, 1990.     

Reduction of 3-substituted 2-methylquinolines with sodium tetrahydroborate

Reduction of esters of 2-metylquinoline-3-carboxylic acids and their perchlorates gave esters of 1,4-dihydro-2-methylquinoline-3-carboxylates, while derivatives of 1,2-dihydroquinoline were formed in the case of 1,2-dimethyl-3-ethoxycarbonyl-7-methoxyquinolinium perchlorate. Reduction of esters of 2-methylquinoline-3-carboxylic acid, 1,2-dimethyl-3-ethoxycarbonyl-1-methoxyquinolinium perchlorate and 3-acetyl-2-methyl-quinoline with sodium tetrahydroborate in acetic acid gave esters of 1,2-dimethyl- and 2-methyl-1,2,3,4-tetrahydroquinoline-3-carboxylic acid and 3-acetyl-2-methyl-1,2,3,4-tetrahydroquinoline.Latvian Institute of Organic Synthesis, Riga, LV-1006. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1383–1390, October, 1996. Original article submitted October 11, 1995.     

Oxidations of some α-amino acids under mitsunobu reaction conditions

Reactions of α-amino acids with azodicarboxylates and Ph₃P results in oxidation at the α-carbon. N-acyl or carbamoyl amino acid esters give azodicarobxylate adducts, whereas free α-amino acid esters are converted to the corresponding α-keto esters.