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.     

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.     

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.     

Synthesis of n2-guanylcarboxylic acids

A novel method has been developed for synthesizing N²-guanylcarboxylic acids by reaction of 2-chloro-7-benzyl-hypoxanthine with amino acids and debenzylation of the 7-benzyl-N²-guanylcarboxylic add products by means of palladium catalyzed hydrogenation.Center 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, Zaporozh'e 330074. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 395–398, March, 1996. Original article submitted January 17, 1996.     

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.     

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.     

Oxidative reactions of azines. 2.* Synthesis and molecular structure of 3,4-dihydroxy-1-methyl-2-oxo-4-(γ-pyridyl)piperidine

The oxidative ketodihydroxylation of a 1,2,3,6-tetrahydropyridine is reported. Using PMR and x-ray structured analysis, the product was shown to be 3,4-dihydroxy-1-methyl-2-oxo-4-(-pyridyl)piperidine.For communications 1, see [1].Russian University of National Friendship, Moscow 117198. L. Ya. Karpov Physicochemical Science Research Institute, Moscow 103603. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1372–1375, October, 1996. Original article submitted June 20, 1996.     

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.     

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.     

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 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.     

Synthesis of some alkaloids using the allyl derivatives of boron (review)

Data on the application of the allylic derivatives of boron for the synthesis of piperidine, indolizine, pyrrolizidine, and indole alkaloids are reviewed.A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1015–1027, August, 1999.     

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.     

Insect pheromones and their analogues. XLVI. Synthesis of 13RS-hydrooxytetradec-5Z-enoic acid — The acyclic precursor of the macrolide component of the pheromone of Cryptolestes pusillus

New routes for the synthesis of 13RS-hydroxytetradec-5Z-enoic acid — the acyclic precursor of the macrolide component of the pheromone ofCryptolestes pusillus have been developed on the basis of the readily accessible 1-methylcycloocta-1Z, 5Z-diene or isopropyl nona-3E,8-dienoate.Institute of Biological Plant Protection, Moldovian Academy of Sciences, Kishinev. Scientific-Research Institute of Forestry and Forestry Mechanization, Pushkino. Moscow Institute of Wood Technology; and Georgia Institute of Mountain Forestry, Tbilisi. Translated from Khimiya Prirodnykh Soedeninii, No. 1, pp. 150–155, January–February, 1993.     

Indolopyridines with a bridging heteroatom. 9. Synthesis,structure, and thermolysis of 5-hydroxy-5-(2-pyridyl)-fluorene and 4-azafluorene

Treatment of fluorenone or 4-azafluoren-9-one with 2-pyridyllithium gives 45-hydroxy-5-(2-pyridyl)fluorene and its aza analog. The structure of the former has been studied by x-ray crystallography. It was found that, in contrast to the non-condensed diaryl-2-pyridylcarbinols, these alcohols do not undergo acid catalyzed dehydration and heterocyclization. Under pyrolytic conditions. 5-pyridylfluorenol undergoes fission to form fluorenone.Russian University of National Friendship, Moscow 117198 and A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow 117813. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 955–959, July, 1996. Original article submitted March 18, 1996.     

Synthesis of halogenopyridines (review)

Published data on the synthesis of derivatives of pyridines containing halogen atoms directly at the carbon atoms of the pyridine ring are reviewed.Moscow State Textile Academy, Moscow 117918. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1155–1187, September, 1996. Original article submitted July 6, 1994.     

Synthesis of heterocyclic compounds by the cyclization of isatin and its derivatives (review)

Published data on the synthesis of heterocyclic compounds formed as the result of the recyclization of isatin and its derivatives are classified and summarized.Academician A. N. Kosygin Moscow State Textile Academy, Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 291–323, March, 1996. Original article submitted September 14, 1995.     

Synthesis of shikalkin and certain related compounds

A successful total synthesis of a biologically active pigment from plants of the Boraginaceae family was carried out with naphthazarine as the starting material, and using the 1,4,5,8-tetramethoxynaphthalene, the corresponding 2-vinyl derivative and its epoxide or a cyclopropane adduct with diazoacetic ester at the key stages. In the course of developing the scheme of the synthesis of shikalkin, its three analogs were obtained, differing in the nature of the monoterpenoid side chain.For preliminary report, see [1].Pacific Ocean Institute of Bioorganic Chemistry, Far East Branch of the Russian Academy of Sciences, 690022 Vladivostok. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1901–1910, August, 1992.     

Solid-phase synthesis of peptides on the polymeric support TRILAR®

The solid-phase synthesis of peptides has been achieved using the polymeric support TRILAR^® proposed by the Biolar Scientific-Production Association (Olaine).M. V. Lomonosov Moscow Institute of Fine Chemical Technology. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 261–266, March–April, 1992.     

Synthesis of the N-terminal tripeptide of the oxytocin sequence

Two schemes for the synthesis of the hydrazide of the N-terminal tripeptide of the oxytocin sequence are considered. It is shown that the most rational is a 1 + 2 scheme.All-Union Scientific-Research Institute of the Technology of Blood Substitutes and Hormone Preparations, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 116–122, January–February, 1989.