Investigation of the stereodirection of the Ritter reaction. Crystaline and molecular structures of N-(2-phenethyl)-2,5-dimethyl-4-phenylpiperid-4-ol and N-(2-phenethyl)-2,5-dimethyl-4-phenyl-4-acetamidopiperidine

The stereodirection of the Ritter reaction of N-(2-phenethyl)-2,5-dimethyl-4-phenylpiperid-4-ol to the corresponding amide has been studied. X-ray analysis has shown that the reaction occurs with retention of the configuration about atom C₄ of the piperidine ring.A. L. Mndzhoyan Institute of Fine Organic Chemistry, Armenian Academy of Sciences, Yerevan 375014. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1384–1390, October 1994. Original article submitted September 28, 1994.     

Investigation of the stereodirection of the Ritter reaction. Crystalline and molecular structure of N-(2-phenethyl)-4-methylpiperid-4-ol and N-(2-phenethyl)-4-methyl-4-acetamido-piperidine

The stereodirection of the Ritter reaction of N-(2-phenethyl)-4-methylpiperid-4-ol to the corresponding amide has been studied. X-ray analysis has shown that the reaction occurs with retention of the configuration about atom C₄ of the piperidine ring. Attempts are made to explain the stereodirection of the direction.A. L. Mndzhoyan Institute of Fine Organic Chemistry, Armenian Academy of Sciences, Yerevan 375014. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1391–1396, October, 1994. Original article submitted September 28, 1994.     

Synthesis of 3-hydrazino-6-tert-butyl-1,2,4-triazolo[3,4-c]-1,2,4-triazin-5-one

3-Hydrazino-6-tert-butyl-1,2,4-triazolo[3,4,c]-1,2,4-triazin-5-one was synthesized by the reaction of a substituted 4-(N,N-dimethylcarbamoyl)-3-thioxo-1,2,4-triazine with hydrazine. The spectral characteristics and the proposed reaction mechanism are discussed.The Sumy State University, Sumy 244007. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1258–1260, September, 1994. Original article submitted September 14, 1994.     

Pyrimidotetrathiafulvalenes. 2. Trimethylsilylation of 5,-dioxo(4H, 6H)-1,3-dithiolo-[4,5-d]pyrimidine-2-selone and the use of the silylated product for the synthesis of 2,4-dioxopyrimidotetrathiafulvalenes

The trimethylsilylation of 5,7-dioxo(4H,6H)-1,3-dithiolo[4,5-d]pyrimidine-2-selone with bis(trimethylsilyl) acetamide enables pyrimido-tetrathiafulvalene derivatives to be prepared in benzene solution and increases the yield of the target compounds compared with the reaction of the unsilylated selone in DMF solution. The intermediate 2,4-bis(trimethyl-silyloxy)pyrimidotetrathisfulvalenes were sensitive to hydrolysis. The previously undescribed [2,4-dioxo(1H,3H)pyrimido]di-(methylthio)tetrathifulvalene has been obtained. The redox properties of the compounds obtained have been investigated by cyclic current-potential measurements.Riga Technical University, Riga LV-1658. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1285–1289, September, 1994. Original article submitted July 25, 1994.     

4-dialkyldithiocarbamoyl-5-nitropyrimidines. Synthesis,structure, properties

The reaction of 4-chloro-5-nitropyrimidines with sodium dialkyldithiocarbamates gives the corresponding 4-dialkyldithiocarbamoyl derivatives. On heating these derivatives the nitro group is displaced and disulfides are formed at position 5 of the pyrimidine ring. Transformation to 1,3-dithiolo[4,5-d]pyrimidines has been demonstrated.Center for Drug Chemistry, All-Russian Scientific Research Institute for Pharmaceutical Chemistry, Moscow 119815. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1420–1423, October 1994. Original article submitted September 6, 1994.     

Purines,pyrimidines, and condensed systems based on these compounds. 12. 1,3-Dimethylpyrimido[4,5-d]pyrimidine-2, 4-(1H,3H)dione: The first case of regioselective amination of condensed pyrimidines in position 2

1,3-Dimethylpyrimido[4,5-d]pyrimidine-2,4-(1H,3H)dione (l) reacts with alkylamides in liquid ammonia in the presence of an oxidizing agent such as KMnO₄ or Ag(C₅H₅N)₂MnO₄, giving 7-amino derivatives; but the interaction of (1) with methylamine gives a mixture of isomeric alkylaminated products. Subsequent hydrolysis of the 7-piperidino derivatives in an alkaline medium and then in an article medium gives 4-methylamino-2-piperidinopyrimidine with quantitative yield.For Communication 11, see [1].Rostov State University, Rostov-na-Donu 344104. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1249–1252, September, 1994. Original article submitted September 6, 1994.     

Functionally substituted azines. 1. Synthesis and reactions of 2-(N-cyano-N-carbethoxmethylamino)-4,6-dimethylpyrimidine

Treatment of 2-(N-potassium-N-cyanamino)-4,6-dimethylpyrimidine with ethyliodoacetate produces 2-(N-cyano-N-carbethoxymethylamino)-4,6-dimethylpyrimidine. Alkaline hydrolysis of the last gives 2-(3-potassium-2,4-dioxoimidazolidinyl-1)-4,6-dimethylpyrimidine. Ammonolysis and hydrazinolysis give imino- or amino-imidazolidinylpyrimidine, respectively.Armenian Agricultural Institute, Erevan 375009. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1239–1241, September, 1994. Original article submitted August 9, 1994.     

2-[2-(Dimethylamino)vinyl]-6-pentafluorophenyl-4-phenylpyrylium perchlorate and its hydrolysis products: Synthesis and isomerism

2-(2-(Dimethylamino)vinyll-6 pentafluorophenyl-4-phenylpyryliunt perchlorate has been synthesized and it was shown that it is readily converted into 2-fornrylntethylene-6-pentafluorophenyl-4-phenyl-2H-pyran on chromatography on alkaline Al₂O₃. The stereoisornerism of the synthesized compounds has been studied by PMR spectroscopy.Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences (SO RAN) Novosibirsk 630090. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1188–1194, September, 1996. Original article submitted March 29, 1996.     

Molecular structure of 1-phenyl-2-chloro-3-(meta-nitrophenyl)-2,3-epoxypropanone

X-ray analysis was used to determined the structure of 1-phenyl-2-chloro-3-(m-nitrophenyl)-2,3-epoxypropanone, obtained by reacting phenacyl dihydrochloride with metanitrobenzaldehyde under Darzen's reaction conditions. The bulky m-nitrophenyl and benzoyl substituents were located in the trans position relative to the chloroepoxide fragment, which was found to stabilize when the m-nitrophenyl substituent was introduced.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Kazan 420083. Translated from Khimiya Geterotsiklicheskikh Soedinennii, No. 9, pp. 1172–1175, September, 1994. Original article submitted May 5, 1994.     

Ethyl 3,3-diamino-2-(2-p-tolylpyrimidin-4-yl)acrylate,a new representative of hetarylketene aminals

A new representative of hetarylketene aminals, ethyl 3,3-diamino-2-(2-p-tolylpyrimidin-4-yl)acrylate, was synthesized by the reaction ofp-toluamidine with the condensation product of dimethylformamide dimethyl acetal and the difluoroboron chelate of acetyl(ethoxycarbonyl)ketene (N-benzoyl)aminal. This synthesis is an example of pyrimidine ring assembly using the methodology based on transformations of chelate complexes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1638–1640, September, 1994.This research was partially supported by the International Science Foundation (Grant No. M5QOOO).     

2-(4-Cyanophenyl)-5-aryloxazoles

2-(4-Cyanophenyl)-5-aryloxazoles have been obtained by dyhydration of 4-(5-aryloxazolyl-2)benzamides with thionyl chloride in DMFA, then the spectral and luminescent properties of the former have been investigated. Introduction of the cyano group into the 2-phenyl radical of 2,5-diphenyloxazole leads to significant bathochromic and bathofluoric effects.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1265–1266, September, 1986.     

Mass spectroscopic study of 9-amino- and 9-alkyl(dialkyl,spiro)-1-and 4-azafluorenes

Elimination of a substituent from the 9-position appears to be the main pathway for decomposition of 9-amino-4-azafluorenes. An amine type fragmentation pattern has been observed as well. Decomposition of 9-spiro-4-azafluorenes occurs via cleavage of the radical bound to the three-membered ring. 9-Alkyl-(dialkyl)-1- and 4-azafluorenes also readily lose a substituent in position 9. The observed pathways and principles allow one to determine the nature of the substituent in the 9-position and also to differentiate 1-azafluorenes from 4-azafluorenes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1241–1246, September, 1987.     

Electrophilic substitution in a series of isomeric α-, β-, and γ-hydroxypyridines (review)

The principles of orientation and the mechanism of electrophilic substitution in a series of isomeric 2-, 3-, and 4-hydroxypyridines are examined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1155–1170, September, 1976.     

Amidoalkylation of mono- and dimercapto-pyrimidines

Reaction of 2- and 4-mercapto- and 2,4-dimercaptopyrimidines with N-(1-chloroalkyl)amides of carboxylic acids and N-acylimines forms only the S-substituted products.Institute of Bioorganic Chemistry and Petroleum Chemistry, Ukraine Academy of Sciences, Kiev 253660. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1234–1238, September, 1994. Original article submitted August 4, 1994.     

Intramolecular cyclization of hydrazides of (2-alkylthio-3,4-dihydro-6-methyl-4-oxo-3-pyrimidml)acetic acids to 1,2,3,4-tetrahydropyrimido[2,1-c]-1,2,4-triazine-3,6-diones

A method has been developed for the synthesis of 1,2,3,4-tetrahydropyrimido[2, 1-c]-1,2,4-triazine-3,6-diones by intramolecullar cyclization of hydrazides of (2-alkylthio-3,4-dihydro-6-methyl-4-oxo-3-pyrimidinyl)acetic acids in benzylamine.Vilnius University, Vilnius 2734. Translated Born Khimiya Geterotsiklicheskikh Soedinenii, No, 7, pp. 967–970, July, 1994. Original article submitted April 4, 1994.     

Synthesis and tautomerism of 2-[3(5)-aryl(methyl)pyrazol-4-yl]-1-benzimidazoles

An efficient method has been developed for the synthesis of 2-[3(5)-aryl(methyl)pyrazol-4-yl]-1H-benzimidazoles by cyclocondensation of 2-acylmethyl-1H-benzimidazoles benzoylhydrazones with DMF dimethylacetal. The tautomerism of the compounds obtained via migrations of a proton between the pyrazole nitrogen atoms has been studied by ¹H NMR. The more stable tautomers have electron acceptor aryl substituents placed at position 3 of the pyrazole ring and electron donor aryl substituents or a methyl at position 5. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1370–1377, September, 2006.     

Synthesis and some properties of planar 4-diphenylphosphino-1,3,2-dioxaborinanes

Fused 1,3,2-dioxaborinanes, derivatives of 4-diphenylphosphino- and 4-diphenylphosphoryl-4H-1, 3-dioxa-2-boraphenanthrenes, and their complexes with amines have been synthesized. According to X-ray diffraction data, the complex of 2-phenyl-4-diphenylphosphoryl-4H-1, 3-dioxa-2-boraphenanthrene with butylamine exists as a dimer due to the formation of intermolecular hydrogen bonds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1649–1655, September, 1994.The present work was financially supported by the International Science Foundation (grant No. RHBOOO).     

Synthesis of 2-alkyl(aryl,hetaryl)-4-methyl-1,2,3,4-tetrahydroquinolines

We have developed a preparative, three stage of synthesis of substituted 1,2,3,4-tetrahydroquinolines. Treatment of N-aryl-imines with allylmagnesium bormide gave N-aryl-N-alkenylamines which were cyclized to the tetrahydroquinolines. The configurations and conformations of the 4-methyl-1,2,3,4-tetra-hydroquinolines containing different 2- substituents have been determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 73–78, January, 1994.     

Synthesis,nature of electronic transitions,and absorption spectra of the dye based on 4-(methyl-1-{2-[4-(1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)phenyl]-2-oxoethyl}pyridinium bromide

The reaction of 3-(4-bromoacetylphenyl)-1-methylquinolin-2(1Н)-one with pyridine and 4-methylpyridine has afforded the corresponding pyridinium salts. Condensation of 4-methyl-1-{2-[4-(1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)phenyl]-2-oxoethyl}pyridinium bromide with 4-dimethylaminobenzaldehyde has given a new biscyanine dye, 1-{1-[4-(1,2-dihydro-1-methyl-2-oxo-3-quinolinyl)benzoyl]-2-[4-(dimethylamino)-phenyl]ethynyl}-4-{2-[4-(dimethylamino)phenyl]ethynyl}pyridinium bromide. Its electronic spectrum has been analyzed, and quantum-chemical simulation of spatial and electronic structure of its possible isomers has been performed.     

Kinetics of the decay of nitroxyl radicals during polymerization of a complex of acrylamide with bismuth nitrate

Kinetics of the decay of nitroxyl radicals during spontaneous polymerization of complexes of acrylamide (AAm) with Bi^III nitrate has been studied by ESR. From a comparison of the experimental and calculated kinetic curves, the initiation rate constant of polymerization has been determined. The approach proposed is suitable for determining the main kinetic characteristics of other polymerizable nonparamagnetic AAm complexes with metal nitrates.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1572–1575, September, 1994.This work was carried out with the financial support of the Russian Foundation for Basic Research (Project No93-03-4162).