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.     

Ring-ring tautomerism in 1,3-alkanoylhydrazonoximes of acetylacetone

The coexistence in solution of tautomeric isoxazoline and pyrazoline forms of 1,3-alkanoylhydrazonoximes of acetylacetone has been detected and investigated by¹H and¹³C NMR spectroscopic methods. The compounds indicated eliminate hydroxylamine under the action of acid catalysts, forming 1-acyl-3,5-dimethylpyrazoles.Institute of High Molecular Compounds, Russian Academy of Sciences, St. Petersburg 199004, RussiaTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 825–829, June, 2000.     

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.     

Synthesis and crystal structure of 4-acetoxy-5,6-dihydro-5,5-dinitro-2H-1,3-oxazineN-oxide

A novel heterocyclic compound, 4-acetoxy-5,6-dihydro-5,5-dinitro-2H-1,3-oxazineN-oxide, has been synthesized by the reaction of the dipotassium salt of 1,1,5,5-tetranitro-3-oxapentane with aqueous acetic acid. The synthesized compound has been studied by X-ray diffraction analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2207–2210, December, 1994.We would like to thank G. V. Lagodzinskaya (Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences) for recording and interpreting¹H NMR spectra, A. M. Korolev (Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences) for helpful discussion, and V. I. Fetisov (Institute of Physiologically Active Compounds, Russian Academy of Sciences) for performing quantum-chemical calculations by the AM1 SCF MO LCAO method.     

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.     

Salts of alkyl-substituted 3,4-dihydroiso-quinolines with 2-acetylcyclopentane-1,3-dione

Reactions of alkyl-substituted 3,4-dihydroisoquinolines, with 2-acetylcyclopentane-1,3-dione were used to prepare 3,4-dihydroisoquinolinium 2-acetylcyclopentane-1, 3-dionates, which could not be converted into ABCD-tetracyclic derivatives of the 8-azagonane series (benzo[a]cyclopentano[f]quinolizines). The salts obtained were studied and characterized by physicochemical methods. It was shown by combining the NMR and H/D-isotope exchange methods that for 1-alkyl-3,4-dihydroisoquinolines and their salts in solutions, an imine-enamine (iminium-enaminium), and for the 2-acetylcyclopentane-1,3-dione anion, a keto-enol tautomeric equilibrium takes place.Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus', Minsk 220141. Chemical Engineering Institute, Russian Academy of Sciences, Perm'614000. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 681–690, May, 1998.     

Simple synthesis of substituted 3-oxabicyclo[3.1.0]hexan-2-ones and their rearrangement in the presence of lithium iodide

2-Alkenylidenemalonic ester monoepoxides react with organolithium and organomagnesium compounds to give 1-ethoxycarbonyl-4-alkyl-6-alkenyl(alkyl, aryl, alkynyl)-3-oxabicyclo[3.1.0]hexan-2-ones in high yields. The latter, when an alkenyl fragment is present, undergo rearrangement in the presence of LiI to substituted 1-ethoxycarbonyl-3-oxabicyclo[3.3.0]-6-octen-2-ones or 3-(1,3-butadienyl)-4-butanolides.Institute of Chemistry, Bashkir Science Center, Ural Branch, Russian Academy of Sciences, Ufa 450054. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 946–954, April, 1992.     

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 of dodeca-8e, 10e-dien-1-ol — the sex pheromone ofLaspeyresia pomonella via the acetolysis of 4-propenyl-1,3-dioxane

A new scheme has been developed for the synthesis of dodeca-8E,10E-dien-1-ol (the sex pheromone of the codling moth) from sorbyl acetate, available from 4-propenyl-1,3-dioxane through the intermediate diacetate of 3 propenyl-2-oxapentane-1, 5-diol.Scientific Research Institite of Fine Organic Synthesis, Academy of Sciences of the Republic of Bashkortostan, Ufa. Institute of Organic Chemistry of the Scientific Center, Russian Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp 602–604, July–August, 1996. Original article submitted January 29, 1996.     

Reaction of 2-aminobenzimidazole with acetylene

The reaction of 2-aminobenzimidazole (1) with acetylene under pressure proceeds with the formation of vinyl monomers, corresponding to amine and imine forms, 1-vinyl-2-amino- and 1,3-divinyl-2-iminobenzimidazoles, depending on the reaction conditions. 1,3-Divinyl-2-benzimidazolone was also isolated in aqueous dioxane in addition to the monovinyl derivative of1. Cyclization of the divinyl derivative of1 with acetylene proceeds to give 9-vinyl-1,2-dimethylimidazo[1,2-a]-benzimidazole.Irkutsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 664033 Irkutsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 749–751, March, 1992.     

New approach to the synthesis of 2,6-difluorobenzoyl isocyanate and its use in the preparation of N-(2,6-difluorobenzoyl)-N′-(polyfluoroaryl)ureas

The treatment of 2,6-difluorobenzoyl chloride with trimethylsilyl isocyanate gave 2,6-difluorobenzoyl isocyanate. This product reacts with polyfluoroaromatic amines to give the corresponding N-(2,6-difluorobenzoyl)-N-(polyfluoroaryl)urea, which hold potential as inhibitors for the biosynthesis of insect chitin.Institute of Chemistry, Bashkir Science Center, Urals Branch, Russian Academy of Sciences, 450054 Ufa. Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 468–470, February, 1992.     

Synthesis and alkylation of 3-cyano-4-isobutyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-2-thiol

By reaction of isovaleric aldehyde with cyanothioacetamide and cyclohexane-1,3-dione, 3-cyano-4-isobutyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-1-thiol has been obtained, and subsequently used in synthesis of the corresponding substituted 2-alkylthiohexahydroquinolines.Lugansk T. G. Shevchenko State Pedagogical Institute, Lugansk 348011, Ukraine. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 230–231, February, 1999.     

Magnetic resonance parameters and structure of substituted stannyloxyphenoxyl radicals: Investigation by means of ESR in the 2-mm band

Institute of Chemical Physics, Russian Academy of Sciences. Institute of Heteroorganic Compounds, Russian Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 33, No. 5, pp. 69–77, September–October, 1992.     

Electrochemical oxidation of 1,3-diketones in the presence of hydrohalic acid salts

In the presence of a mediator (sodium iodide) acetylacetone dimerizes with the formation of 3,4-diacetylhexane-2,5-dione, with a yield up to 90%. Salts of 2-halosubstituted 1,3-diketones form more highly enolized cyclic 1,3-diketones — 1,3-cyclohexanedione and dimedone under analogous conditions, with a yield up to 90%.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 154–158, January, 1992.     

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 some 5-aryl(hetaryl)tetrazoles by ultrasonication

The influence of ultrasound on the 1,3-dipolar cycloadditio of azides to organic nitriles to form of 1H-5-aryl(hetary)tetrazoles was studied. It was shown that ultrasound decreases the reaction time, and increases the yield of the desired compounds.Institute of Organic Synthesis, Ural Region Russian Academy of Sciences, Ekaterinburg, 620219. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1375–1377. Original article submitted November 1, 1994.     

Synthesis of heterocycles from the products of the addition of polyhaloalkanes to unsaturated systems

4-Methyl-5-(2,2,2-trichloroethyl) derivatives of 2-thiazolethione and 2-amino-3-hydroxythiazolium chloride were synthesized from 3-thiocyanato-5,5,5-trichloro-2-pentanone. The structures of these derivatives were determined using spectral data and x-ray diffraction structural analysis.For Communication 7, see [1]N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117813. A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences Moscow 117813. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 832–838, June, 1998.     

Crystal structure investigation of ternary molybdates Li3Ba2Ln3(MoO4)3 (Ln=Gd,Tm)

Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Institute of Physics, Siberian Branch, Russian Academy of Sciences. Buryat Institute of Natural Sciences, Siberian Branch, Russian Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 33, No. 3, pp. 126–130, May–June, 1992.     

Production of (+)-norsolanadione

Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Russian Academy of Sciences, Ufa. Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 735–736, September–October, 1991.     

Cycloaddition of bis(trifluoromethyl)diazomethane to activated alkenes and alkynes

Bis(Trifluoromethyl)diazomethane undergoes [3+2] cycloaddition with activated alkenes and alkynes regiospecifically to give substituted pyrazolines and pyrazoles.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 452–455, February, 1992.