Synthesis and properties of N-methylmorpholinium 4aryl-6-methyl-5-phenylcarbamoyl-3cyano-1,4dihydropyridine-2-thiolates. Molecular and crystalline structure of 2allylthio-6-methyl-5-phenylcarbamoyl-4-(2chlorophenyl)-3-cyano-1,4-dihydropyridine

By the condensation of an aromatic aldehyde, the anilide of acetoacetic acid, cyanothioacetamide, and Nmethylmorpholine, substituted N-methylmorpholinium 1,4-dihydropyridine-2-thiolates have been synthesized and subsequently used in the synthesis of the corresponding thiones, 2-alkylthiopyridines, thieno[2, 3b]pyridines, and disulfides. X-ray diffraction has been used to establish the structure of 2-allylthio-6-methyl-5phenylcarbamoyl-4-(2-chlorophenyl)-3-cyano-1, 4-dihydropyridine.T. G. Shevchenko Lugansk State Pedagogical Institute, Lugansk 348011. A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, Moscow 117813. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1243–1251, September, 1996. Original article submitted May 13, 1996.     

Stereoselective synthesis and structure of 3,4-trans-6-amino-4-aryl-3-carbamoyl-5-cyano-1,2,3,4-tetrahydropyridin-2(1H)-thiones

Condensation of thiocarbamoylacetamide with arylidenemalononitrile or the three-component condensation of thiocarbamoylacetamide with aldehydes and malononitrile in the presence of triethylamine occurred regioselectively to give triethylammonium-6-amino-4-aryl-3-carbamoyl-5-cyano-1,4-dihydropyridine-2-thiolates. Protonation of the latter occurred stereoselectively to give 3,4-trans-6-aryl-3-carbamoyl-5-cyano-1,2,3,4-tetrahydropyridin-2(1H)-thiones. The¹H NMR spectrum and single x-ray crystallography indicate that the dihydropyridine ring has he sofa conformation with trans-pseudodiaxial orientation of the Ar and CONH₂ groups and trans-pseudoequatorial orientation of atoms 3-H and 4-H.N. D. Zelinskii Organic Chemistry Institute, Russian Academy of Sciences, Moscow, 117913. A. N. Nesmeyanov Institute of Elementoorganic Chemistry, Russian Academy of Sciences, Moscow, 117813. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1376–1382, Octoberm 1996. Original article submitted June 10, 1996.     

Chemistry of 2-substituted benzimidazoles. 1. 5-Amino-2-methyl(aryl, arylalkyl, pyridyl)benzimidazoles

A series of 2-substituted benzimidazoles was synthesized. These products were consecutively converted into 5-nitro- and 5-amino-2-substituted benzimidazoles.Russian People's Friendship University, 117198 Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 493–500, April, 200.     

Synthesis,molecular, and crystalline structure of 3-benzoyl-1,2-di(ethylsulfonyl)indolizine

Reaction of pyridiniumbenzoyl methylide with (E)-1,2-di(ethylsulfonyl)-1,2-dichloroethene (which has four nucleophilic groups) occurs via a 1,3-dipolar stereo- and regio directed cycloaddition to give 3-benzoyl-1,2-di(ethylsulfonyl)indolizine the structure of which was established using x-ray crystallography. The rotation of the phenyl substituted by 72.6° relative to the indolizine ring plane and the geometry of the ethylsulfonyl groups can be explained by steric hindrance due to shortened intramolecular non-valence contacts.Deceased.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow 117813. N. D. Zelinski Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 950–954, July, 1996. Original article submitted May 5, 1996.     

Naphthomoles. 7. Synthesis of 4,11-dimethoxynaphtho[2,3-f]indole-5,10-dione and 4-methoxynaphtho[2,3-f]-indole-5,10-dione

4,11-Dimethoxynaphtho[2,3-f]indole-5,10-dione and 4-methoxynaphtho[2,3-f[indole-5,10-dione have been synthesized by the Leimgruber-Batcho reaction from 1,4-dimethoxy-2-methyl-3-nitroanthraquinone.Russian University of Chemical Technology, Moscow 125190. Center for Drug Chemistry, All-Russian Scientific Research Institute for Pharmaceutical Chemistry, Moscow 119815. Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 8, pp. 1050–1054, August, 1996. Original article submitted March 20, 1996.     

Synthesis of n2-alkyl(aryl,dialkyl, cycloalkyl)guanines

Novel N²-alkyl(aryl, dialkyl, cycloalkyl)guanines have been synthesized by treating 2-chloro-7-benzylhypozanthine with amines and debenzylation of the N²-substituted 7-benzylguanine products by means of palladium catalyzed hydrogenation.DeceasedCenter for the Chemistry of Medicinal Compounds. All Russian Chemico-Pharmaceutical Science Research Institute, Moscow, 119815. State Institute for Blood Substitutes and Medicinal Preparations, Moscow, 109044. Zaporozh'e State Medicinal Institute, Zaporozhe'e, 330074. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 391–394, March, 1996. Original article submitted January 6, 1996.     

Solid-phase synthesis of 1,2-benzophenazine and some fused imidazole derivatives

The solid-phase synthesis of 1,2-benzophenazine and various N-methylbenzimidazoles using o-diaminoarenes is very promising and permits the synthesis of 1-methyl-4,5-[b]naphtho-1H-imidazole, which could not be obtained by the condensation of o-diaminoarenes with paraformaldehyde using the standard liquid-phase method.M. V. Lomonosov Moscow State University, 119899, Moscow, Institute for Synthetic Polymer Materials, 117461, Moscow, and Institute of Physiologically Active Compounds, Russian Academy of Sciences, Chernogolovka, 1424432, Moscow Oblast. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 672–674, May, 1996. Original article submitted April 3, 1996.     

Basicity and structure of 5-hydroxybenzimidazoles in nitromethane

Examination of the acid-base properties of 5-hydroxybenzimidazoles has shown them to exist in nitromethane as the 5-hydroxy-tautomers. Substituents in the 2-position have a predominantly inductive effect on the basicity of the 3-nitrogen, rationalized as in other nitrogen heterocycles by the proximity of the substituents to the reaction center.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. The Research Institute for Intermediates and Dyes, 103787 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 421–425, February, 1992.     

Convenient method for synthesis of functionally substituted hexahydroquinolines. Molecular and crystal structure of 4-isopropyl-7,7-dimethyl-5-oxo-3-cyano-2-cyanomethylthio-1,4,5,6,7,8-hexahydroquinoline

We have obtained 2-alkylthio-7,7-dimethyl-5-oxo-4-ethyl(isopropyl)-3-cyano-1,4,5,6,7,8-hexahydroquinolines by reaction of 5,5-dimethylcyclohexane-1,3-dione, propionic (or isobutyric) aldehyde, cyanothioacetamide, and alkyl halides. We have established the structure of 4-isopropyl-7,7-dimethyl-5-oxo-3-cyano-2-cyanomethylthio-1,4,5,6,7,8-hexahydroquinoline by x-ray diffraction.T. G. Shevchenko Lugansk State Pedagogical Institute, Lugansk 348011. A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, Moscow 117813. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 785–792, June, 1997.     

New method for the synthesis of 1,2,3-triazole 1-oxides

A general method is proposed for the synthesis of 1,2,3-triazole 1-oxides using 3,4-dinitro- or 4-amino-3-nitrofuroxanes.Deceased.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913, Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 675–679, May, 1996. Original article submitted February 22, 1996. Resubmitted after revision April 5, 1996.     

Branched polycyclic tetrazole systems. 1. Synthesis and structure of 2-(5-tetrazolyl)ethyl derivatives of some CH-, OH-, and NH-acids

The cycloaddition of dimethylammonium azide to the nitrile groups of 2-cyanoethyl derivatives of CH-, OH-, and NH-acids leads to open-chain branched structures containing terminal NH-tetrazolyl groups. An x-ray diffraction structural analysis of tris[2-(5-tetrazolyl)ethyl]nitromethane revealed steric access of the equivalent NH-tetrazolyl rings of the branched system. In going from the branched nitrile substrates to the corresponding tetrazoles, the PMR spectra show a breakdown in the resolution of the multiplet components, which had not been observed previously for monocyclic 5-substituted tetrazoles. A dependence was found for the¹³C NMR chemical shifts on the pK_a values, reflecting the NH-acidity of the branched polycyclic tetrazoles in water. Dedicated to the memory of I. N. Goncharova. St. Petersburg State Technological Institute, 198013 St. Petersburg. V. A. éngel'gart Institute of Molecular Biology, Russian Academy of Sciences, 117984 Moscow. L. Ya. Karpov Physics and Chemistry Research Institute, 103062 Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1494–1501, November, 1997.     

Pyrrolophenoxathiin dioxides. 1. Synthesis of 3H-pyrrolo[2,3-c]phenoxathiin 11,11-dioxide and 1h-pyrrolo[3,2-b]phenoxathiin 10,10, dioxide by the fischer reaction

Cyclization of the 2 phenoxathiin 10,10-dioxide hydrazone of ethyl pyruvate in ethyl polyphosphate results in the concurrent formation of the respective cyclic esters of both angular and linear structures. The parent compounds of a new condensed heterocyclic system of pyrrolophenoxathiin dioxides are synthesized from the latter.Georgian Technical University, Tbilisi 380075. D. I. Mendeleev Russian Chemical Engineering University, Moscow 125047. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 409–412, March, 1996. Original article submitted July 1, 1995.     

Synthesis of 2,6-diamino-3,5-dicyano-4-ethyl-4H-thiopyran and its recyclization to 6-amino-3,5-dicyano-4-ethylpyridine-2(1H)-thione

The triple condensation of propionaldehyde, malononitrile, and cyanothioacetamide gives 2,6-diamino-3,5-dicyano-4-ethyl-4H-thiopyran, which recyclizes to give 6-amino-3, 5-dicyano-4-ethylpyridine-2(1H)-thione. This thione was used to synthesize substituted 2-alkylthiopyridines and the corresponding thieno[2,3-b]pyridines.T. G. Shevchenko Lugansk State Pedagogical Institute, 348011 Lugansk. N. D. Zelinski Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1099–1103, August, 1996. Original article submitted May 13, 1996.     

Reactions of 5-methylene-1,3-dioxolan-2-ones with amines. Synthesis of 2-oxazolidinones

The reaction of 5-methylene-1,3-dioxolan-2-ones with aromatic or aliphatic amines as well as with the sodium salts of amino acids leads to 4-hydroxy-2-oxazolidinones. The reaction conditions depend on the basicity of the amines. The use of o-phenylenediamine in this reaction leads to the formation of a new heterocyclic system.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow; Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 241–251, February, 1999.     

Synthesis and transformations of 6-amino-3,5-dicyano-4ethylpyridine-2(1H)-thione

The condensation of propionaldehyde with cyanothioacetamide gives 6-amino-3,5-dicyano-4-ethylpyridine-2(1H)-thione, which was used to obtain substituted 2-alkylthiopyridines, 2-ethylthio-6- ethylaminopyridine, and pyrazolo[3,4-b]pyridine.T. G. Shevchenko Lugansk State Pedagogical Institute, 348011 Lugansk. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Science, 117913 Moscow. Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 8, pp. 1094–1098, August, 1996. Original article submitted March 4, 1996; revision submitted July 1, 1996.     

Complexes of cobalt(2+) chloride with hydrochlorides of N-(1,2,4-triazol-5-yl)- and N-(tetrazol-5-yl)benzamidines

We have synthesized complex compounds of Co(2+) chloride with hydrochlorides of N-(1,2,4-triazol-5-yl)benzamidine and N-(tetrazol-5-yl)benzamidine. According to magnetochemistry and electron spectroscopy data, the ligands are coordinated in a bidentate fashion with the N atom of the amidine group and the N atom of the heterocycle with formation of the tetrahedral chromophore CoN₂Cl₂.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2311–2315, October, 1992.     

Synthesis of 2-(3-hydroxyacetonyl)malonic aldehyde and its derivatives. Their reactions with 5-aminotetrazole

2-(3-Hydroxyacetonyl)malonic aldehyde and its derivatives were prepared for the first time by the hydrolysis of 2-substituted 2,5-dimethoxy-4-formyltetrahydrofuranes. Their interaction with 5-aminotetrazole gave functionally substituted 6-tetrazolo[1,5-a]pyrimidines.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Hexagon Chemistry Consultants, DK-1460 Copenhagen. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, 807–810, June, 1997.     

Asymmetric synthesis of organoelemental analogs of natural compounds. 7. (2R,3S)-2-amino-3-hydroxy-5-phosphonovaleric acid

The reaction of the Ni(II) complex of the Schiff base of glycine with (S)-2-N-(N¹-benzylprolyl)-o-aminobenzophenone with diethyl-3-bromo-2-hydroxypropyl phosphonate yields the corresponding complex from which (2R, 3S)-2-amino-3-hydroxy-5-phosphonovaleric acid is separated with HCl.See [1] for Communication 6.Institute of Bioorganic Chemistry and Petrochemistry, Ukrainian Academy of Sciences, 252660 Kiev; N. A. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1172–1175, May, 1992.     

Adamantylazoles. Acid-catalyzed adamantylation of 1,2,4-triazoles

The reaction of 1-adamantanol with 1,2,4-triazole in sulfuric acid forms 1-adamantyl derivatives. In boiling chloroform containing traces of sulfuric acid, a mixture of isomeric N-adamantyl-1, 2, 4-triazoles is obtained. It is shown that 1-adamantyl carbocation is formed at a sulfuric acid concentration above 70%.St. Petersburg State Technological Institute, St. Petersburg 198013. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsklicheskii Soedinenii, No. 8, pp. 1078–1087, August, 1996. Original article submitted June 7, 1996.     

2-Bromo-i-phenylethylidenemalononitrile in the synthesis of thieno[3,2-b]pyridines and thiazolo[4,5-b]pyridines

A novel regioselective synthesis of thieno[3, 2-blpyridines and thiazolo[4,5-blpyridines from 2-bromo-I-phenyl ethylidenemalononitrile is proposed. In the case of the thiazolo[4, 5-b]pyridines, the intermediate 5-(2, 2-dicyano-l-phenylvinyl)thiazoles were separated. Formation of the thiazolo(4,5-b]pyridines was confirmed by x-ray analysis.A. D. Zelinski Institute of Organic Synthesis, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 413–419, March, 1996. Original article submitted December 22, 1995.