Synthesis and structure of new 3,7,10-substituted-phenothiazine derivatives

The synthesis of new 3,7-dibromophenothiazine derivatives bearing bromoalkyl, mercaptoalkyl and alkylthioacetate groups on the N atom at position 10 is reported. The Suzuki coupling reaction of one of these derivatives via the bromine atoms at positions 3 and 7 with bromothiophene derivatives is also discussed.      

Preparative synthesis of benzo[b]thio-(seleno,telluro)phene derivatives

A preparative synthesis of aminomethyl derivatives of benzo[b]thio(seleno,telluro)phenes and their hydrohalides by the reaction of sulfur, selenium, and tellurium halides with 1-phenylpropynamines was developed.Communication 12 from the series Electrophilic reactions of halides of group VI elements. See [1] for Communication 11.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1331–1334, October, 1990.     

Radiometric analysis based on redox substoichiometry I. Principles and application for the determination of tellurium

A radiometric method based on the redox substoichiometry has been developed for the determination of tellurium. The oxidation of tellurium(IV) to tellurium(VI) with potassium dichromate was employed as the substoichiometric reaction, followed by TBP (tributyl phosphate) extraction of the unreacted tellurium(IV) as the substoichiometric isolation. The oxidation of tellurium(IV) with dichromate under the substoichiometric conditions was incomplete. The chemical yield of tellurium(VI) produced by the oxidation of tellurium(IV) with dichromate was 83%. It was found that a tellurium content of 50 to 160 g could be determined with an accuracy of ±1.3% by means of the comparison method.     

Tellurium(II)‐Centered Dications from the Pseudohalide “Te(OTf)2”

Te for two : Supported by pyridine‐ or carbene‐based ligands, tellurium‐centered dications are prepared in high yield and include a dicationic tellurium analogue of the recently synthesized “carbodicarbene”. The key to accessing these compounds is the isolation of a base‐stabilized form of TeOTf₂ (see structure), a new highly electrophilic reagent for tellurium chemistry.

     

Reactions of N-substituted allylacetic acid amides with selenium and tellurium tetrahalides

The addition of selenium tetrabromide to the olefinic bond of N-substituted allylacetic acid amides (reagent molar ratio 21) proceeds counter to Markownikoff's rule with the formation of tetrahydrofuran derivatives. The addition of tellurium tetrahalides under the same conditions (reagent molar ratio 11) proceeds in accordance with Markownikoff's rule with the formation of tetrahydropyran derivatives.Communication 10 in the series Electrophilic reactions of halides of elements of the sixth group; see [1] for Communication 9.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 743–745, June, 1989.     

Syntheses and conversion of polyhedral compounds. 26. Synthesis of new heteropolyhedral compounds by heterocyclization of certain 3,7-disubstituted derivatives of 3,7-diaza-and 1,3,7-triazabicyclo-[3.3.1]nonanes

The following heterocyclization reactions have been carried out: heterocyclization of 3,7-diacryloyl-3,7-diazabicyclo[3.3.1]nonane by benzylamine, heterocyclization of 3,7-diacryloyl-, 3,7-bis(-bromopropionyl)-, and 3,7-bis(-chloroethyl)-3,7-diazabicyclo[3.3.1]nonanes by hydrogen sulfide, and heterocyclization of 3,7-bis(bromoacetyl)- and 3,7-diacryloyl-1,3,7-triazabicyclo[3.3.1]nonanes by benzylamine and hydrogen sulfide. New compounds were obtained, based on previously unknown thiadiaza-, triaza-, and tetraazatricyclic systems.For Communication 25, see [1].A. L. Mndzhoyan Institute of Fine Organic Chemistry, National Academy of Sciences of the Republic of Armenia, Erevan 375014. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1133–1136, August, 1998.     

Azobenzene-bridged calix[8]arenes

An azobenzene bridge was introduced into the lower (or smaller) rim of p-tert-butylcalix[8]arene (1) and 1,5-calix[8]crown-3 (2) to form 1,4-singly bridged (3) and 1,5:3,7-doubly bridged (4) calix[8]arene derivatives, respectively. Trans and cis isomers of conformationally rigid 4 were isolated. The quantum yields of the trans-cis photoisomerisation reactions have been measured.     

Synthesis of halo derivatives of 2-selenaadamantane

The corresponding halo derivatives of 2-selenaadamantane were obtained by reaction of bicyclonona-3,7-diene with selenium tetrahalides. The structures of the reaction products were confirmed by the results of analysis and PMR and IR spectral data.Communication III from the series Organic Compounds of Selenium and Tellurium; see [1] for communication II.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1633–1635, December, 1977.     

Design and synthesis of organochalcogen (Se or Te) based multifunctional derivatives: structural determination and dynamic behavior of 2-chloro-4,6-bis(phenylselenoethylamino)-1,3,5-triazines

A novel class of multifunctional and multinucleate chalcogen (selenium and tellurium) containing derivatives (1-10) has been developed based on sequential chloride substitution of 2,4,6-trichloro-1,3,5-triazine with chalcogen-bearing amines. The structure of compound 1 has been determined in the solid state by X-ray crystallography.     

Secondary bonding in functionalized organotellurium compounds: preparation and structural characterization of bis(acetamido)tellurium(IV) diiodide and bis(4-methylbenzoylmethyl)tellurium(II)

Elemental tellurium inserts, under mild conditions, between C-I bond of iodoacetamide to afford bis(acetamido)tellurium(IV) diiodide (NH₂COCH₂)₂TeI₂, 1. Heating of N-bromomethylphthalimide with activated tellurium powder however, resulted in the formation of bis(phthalimido)methane, 2, instead of the expected product bis(phthalimidomethyl)tellurium(IV) dibromide. The IR spectrum of 1 is indicative of intramolecular Te?OC interaction which is also substantiated by its single-crystal structure. The compound with planar small-bite chelating organic ligands acquires butterfly shape that imparts almost perfect C_2v molecular symmetry but unlike other organotellurium(IV) iodides, the solid state structure of 1 is devoid of any intermolecular Te?I or I?I secondary interactions owing to the presence of intramolecular Te?O secondary bonds as well as intermolecular N-H?O, N-H?I and C-H?I hydrogen bonds. Bis(4-methylbenzoylmethyl)telluride (4-MeC₆H₄COCH₂)₂Te, 3b, prepared by the reduction of the corresponding dibromide, is the first structurally characterized acyclic dialkyltelluride and interestingly, does not involve intramolecular Te?OC interaction invariably present in the parent dihalides (4-YC₆H₄COCH₂)₂TeX₂ (Y = H, X = I 4a; Y = H, X = Br 5a; Y = MeO, X = Br 5c). Weak intermolecular Te?Te and C-H?O hydrogen bonds appear to be the non covalent intermolecular associative forces that dominate its crystal packing in the solid state of this Te(II) derivative. The dialkyltellurides (4-YC₆H₄COCH₂)₂Te, (Y = H, 3a, Me, 3b) undergo oxidation in presence of (SCN)₂ to give the corresponding bis(isothiocyanato)tellurium(IV) derivatives and form 2:1 adducts with Pt(II) and Pd(II) chlorides.     

Synthesis of 3,7-disubstituted hexahydro- and tetrahydro-2<Emphasis Type="Italic">H</Emphasis>-indazoles from cross-conjugated dienones

The oxidation of 3,7-disubstituted hexahydroindazoles with potassium hexacyanoferrate(III) afforded previously unknown tetrahydro-2H-indazole derivatives. A novel ring contraction reaction leading to 2,3-diazaspiro[4.4]non-3-en-1-one derivatives was discovered. The product structure was proved by NMR spectroscopy, mass spectrometry, and X-ray analysis.     

Synthesis of new types of tetracyclo[4.3.0.02,4.03,7]nonane hydrocarbons by cyclocodimerization of norbornadiene and its derivatives with diacetylenes and vinylacetylenes,catalyzed by low-valence cobalt complexes

Conclusions Three-component complex cobalt-containing catalysts are proposed, which are activated by PPh₃ or by an excess of acetylenic hydrocarbons, with which cyclocodimerization of norbornadiene or spiro{bicyclo[2.2.1]hepta-2,5-diene-7,1-cyclopropane} with diacetylenes can be carried out leading to derivatives of the bitetracyclo[4.3.0.0^2,4.0^3,7]nonane series in high yields.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1061–1067, May, 1987.     

Synthesis and structure of 3,7-dihydro-2h-1,2,4-triazolo-[1′,5′-a′]tripyrimido[4,5-d]benzo[bpyrans

The condensation of 5-(2-hydroxyphenyl)-6, 7-dihydro-1, 2, 4-triazolo[l, 5-a]pyrimidines with aldehydes yields derivatives of a new heterocyclic system, namely, 3,7-dihydro-2H-1,2,4-triazolo[1,5-a]pyrimido[4,5-d]-benzo[b]pyran, including the 9-methyl-2,3-diphenyl derivative, whose structure was established by x-ray diffraction structural analysis.*Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2. pp. 240–246, February, 1996.     

Reactions of tellurium tetrahalides with 1,5- and 1,6-diolefins and their derivatives

1,4-Dihalo-substituted tellurolanes were obtained by reaction of tellurium tetrabromide and tetrachloride with 1,5-hexadiene, and the corresponding six-membered heterocyclic compounds with a tellurium atom in the ring were obtained with 1,6-diolefins.Communication IV from the series Organic Selenium and Tellurium Compounds. See [1] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1212–1214, September, 1978.     

Synthese et caracterisation de fluorotellurates IV alcalins et d'ammonium partie I. Etude du pentafluorotellurate IV de lithium LiTeF5

Lithium pentafluorotellurate (IV) LiTeF₅ has been prepared by different methods:

• •slow evaporation of a 1/1 mixture of lithium fluoride and tellurium dioxide or tellurium tetrachloride in anhydrous hydrogen fluoride,
• •heating a 1/1 mixture of lithium fluoride and tellurium tetrafluoride. LiTeF₅ is orthorhombic

(a = 9,52 Å b = 9,12 Å c = 11, 60 Å)     

Synthesis and conversions of polyhedral compounds 17. Conversion of 1,3-diaza- and 1,3,5-triazaadamantanes to nitrogen-containing pentacyclic compounds

It has been shown that derivatives of 1,3-diaza- and 1,3,5-triazzaadaniantanes, and also derivatives of 3,7-diazabicyclo[3.3.1]nonane, interact with 3,7-bis(bromoacetyl)-3,7-diaza- and 3,7-bis(bronwacetyl)-1,3,7-triazabicyclo[3. 3. 1]nonanes in the presence of bases to form previously unknown types of heteropolyhedral structures — nitrogen-containing pentacyclic compounds.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 106–110, January, 1994. Original article submitted October 20, 1993.     

7-Substituted 8-vinyl-1,3-dimethyl-3,7-dihydro-1H-purine-2,6-diones and their broncholytic activity

Summary Alkylation of 8-vinyl-1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione (1) with alkyl halides inDMF in the presence of potassium carbonate, or alternatively, alkylation of its sodium salt (2) with alkyl iodide or hydroxyalkyl iodide afforded the 7-alkyl- or 7-(-hydroxyalkyl)-8-vinyl-1,3-dimethyl-3,7-dihydro-1H-purine-2,6-diones3. 2-Substituted oxiranes reacted with1 catalyzed by2 or Triton B to yield 7-(2-hydroxyalkyl)-8-vinyl-1,3-dimethyl-3,7-dihydro-1H-purine-2,6-diones4. Compounds3 and4 were tested for broncholytic activity. The most effective derivatives were3c and4b.

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7-Substituierte 8-Vinyl-1,3-dimethyl-3,7-dihydro-1H-purin-2,6-dione und ihre broncholytische Wirkung

Zusammenfassung Alkylierung von 8-Vinyl-1,3-dimethyl-3,7-dihydro-1H-purin-2,6-dion (1) mit Halogenalkanen in Gegenwart von Kaliumkarbonat inDMF oder Alkylierung seines Natrium-Salzes (2) mit Iodalkanen beziehungsweise Iodalkanolen führte zu den 7-Alkyl- bzw. 7-(-Hydroxyalkyl)-8-vinyl-1,3-dimethyl-3,7-dihydro-1H-purin-2,6-dionen3. 2-Substituierte Oxirane reagierten mit Verbindung1 unter Katalyse durch2 oder Triton B zu den entsprechenden 7-(2-Hydroxyalkyl)-derivaten4. Die Substanzen3 und4 wurden auf ihre broncholytische Wirkung geprüft. Die höchste Aktivität wurde bei den Derivaten3c und4b festgestellt.

     

Tellurium‐Based Polymeric Surfactants as a Novel Seleno‐Enzyme Model with High Activity

Summary: A tellurium‐based polymeric sufactant as a seleno‐enzyme model has been constructed by employing 11‐acryloyloxyundecyltriethylammonium bromide (AUTEAB, 4 ) and a tellurium‐containing compound ( 1 ). It demonstrates strong substrate binding ability for thiols and high glutathione peroxidase (GPx) activity about 6 orders of magnitude more efficient than the well‐known GPx mimic PhSeSePh in an ArSH assay system. More importantly, a series of tellurium‐based polymeric micelle catalysts with the catalytic tellurium center located at various positions in the micelle have been constructed, and the dramatic difference in activity indicates that the exact match of the catalytic center and binding site plays a key role in enzyme catalytic efficiency.

Schematic representation of the proposed mode of the telluro‐micelle catalysts.     

Cooligomerization of 1,2-dienes with norbornadienes catalyzed by cobalt complexes

Conclusions Under the action of low-valency cobalt complexes [2 + 2 + 2] cycloaddition of allene, cyclopropylallene, phenylallene, and 1,2-cyclononadiene to norbornadiene and spirocyclo-[2.2.l]hepta-2,5-diene-7,1-cyclopropane takes place with the formation of derivatives of tetracyclo[4.3.0.0^2,4. 1.0^3,7] nonane in high yields.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1346–1356, June, 1988.     

Mechanism of the fragmentation of the methyl ester of α-bromo-α-(3-bromoadamantyl-1) acetic acid

The mechanism and stereochemical peculiarities of the fragmentation of -dibromo-derivatives of adamantane by zinc in DMFA were investigated on the example of chiral dibromides. It was shown that the reaction proceeds with the formation of intermediate carbanions; moreover, the formation of a carbanion at the chiral center is accompanied by racemization, and at the bridge carbon atom by transformation of the central chirality of the initial dibromide into the planar chirality of derivatives of 3,7-dimethylenebicyclo[3. 3.1]nonane. This transformation, which obeys definite stereoelectronic requirements, provides for the genetic interrelationship of the configurations of the fragmentable dibromides and fragmentation products.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 620–623, September–October, 1985.