Synthesis of 6′-carbamoylmethylthio-5′-cyano-1′,4′-dihydro-3,4′-bipyridine-3′-carboxylic and 6′-carbamoylmethylthio-5′-cyano-1′,4′-dihydro-4,4′-bipyridine-3′-carboxylic esters and investigation of their stability. 2. Esters of 6′-carbamoylmethyl-thio-5′-cyano-1′,4′-dihydro-4,4′-bipyridine-3-carboxylic acids

The stability of solutions of esters of 6′-carbamoylmethylthio-5′-cyano-2′-methyl-1′,4′-dihydro-4,4′-bipyridine-3′-carboxylic acids was investigated by HPLC. The corresponding esters of 6′-carbamoylmethylthio-5′-cyano-4,4′-bipyridine-3′-carboxylic acids,esters of 8-cyano-5-methyl-3-oxo-7-(4-pyridyl)-2,3-dihydro-7H-thiazolo-[3,2-a]pyridine-6-carboxylic acids, methyl 3-amino-2-carbamoyl-6-methyl-4-(4-pyridyl)-4,7-dihydrothieno[2,3-b]pyridine-5-carboxylate, and methyl 3-amino-2-carbamoyl-6-methyl-4-(4-pyridyl)-thieno[2,3-b]pyridine-5-carboxylate were synthesized as standard compounds (typical impurities). Analysis by HPLC was realized under the conditions of reverse-phase chromatography. It was established that solutions of the investigated compounds (with mixtures of acetonitrile with phosphate buffer, having pH values of not less than 3 and not more than 5, as solvents) are stable for one month when the solutions are stored in a place protected against light. It is also necessary to use chromatographic systems in which the aqueous components have pH 3–5 during determination of the purity of the esters of 6′-carbamoylmethylthio-5′-cyano-2′-methyl-1′,4′-dihydro-4, 4′-bipyridine-3′-carboxylic acid by HPLC in order to separate the analyzed sorbates and their typical impurities more completely. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 841–848, June, 2007.     

Film Composites of polyimide with polyaniline and poly(aniline-<Emphasis Type="Italic">co</Emphasis>-anthranilic acid)

New two-component composite polymer films are prepared and studied in terms of thermal stability and stress-strain properties. The matrix component of the composite is polyimide based on 3,3′,4,4′-(1,3-diphenoxybenzene)tetracarboxylic dianhydride and 4,4′-bis(4″-aminophenoxy)diphenyl sulfone. Another component is polyaniline or the copolymer poly(aniline-co-2-aminobenzoic acid). Composite films are cast from mixed solutions of individual polymers in N-methyl-2-pyrrolidone. Interpolymer interactions in polyimide composites with polyaniline or the copolymer of aniline and 2-aminobenzoic acid are investigated via viscometry and IR spectroscopy. The thermal treatment of composite films with poly(aniline-co-2-aminobenzoic acid) results in decarboxylation of the copolymer and formation of polyimide-polyaniline composite films. The morphology, microphase structure, and porosity of the composite films are different from those of the films cast from solutions of polyimide-polyaniline mixtures.     

Synthesis and studies of homopolyamides based on 2,4-bis(6-chlorocarbonyl-2-naphthyloxy)-6-(4-methyl-1-piperazinyl)-s-triazine

Abstract  

Ten homopolyamides have been synthesized by polycondensation of the monomer 2,4-bis(6-chlorocarbonyl-2-naphthyloxy)-6-(4-methyl-1-piperazinyl)-s-triazine and different diamines such as 4,4′-biphenyldiamine, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfonamide, 2,4-diaminotoluene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and ethylenediamine. All polyamides were characterized by solubility, density, viscosity measurements, IR, NMR spectroscopy, and thermogravimetric analysis. The products were found to possess high thermal stability.     

Novel soluble aromatic poly(amideimide)s containing 9,9-diphenylfluorene moieties: characterization and optical properties

A series of aromatic poly(amideimide)s containing 9,9-diphenylfluorene moieties and the amide units in the main chain have been synthesized by solution polycondensation reaction of newly prepared diamidedianhydride with several aromatic diamines: 1,3-phenylenediamine, 3,3′-dimethoxy-biphenyl-4,4′-diamine, 4,4′-oxydianiline, 4,4′-(1,3-phenylenedioxy)dianiline, 4,4′-(9-fluorenylidene)dianiline and 1,5-diaminonaphthalene. Molecular structures of the polymers obtained have been characterized using ¹³C NMR, ¹H NMR and FTIR spectroscopies. The polymers prepared are readily soluble in aprotic polar solvents, and form optically transparent films by solution casting. The resultant poly(amideimide)s have been analyzed by differential scanning calorimetry (DSC), thermogravimetry (TG) and wide-angle X-ray diffraction measurements. They exhibited high levels of thermal stability, with decomposition temperatures in the range 452–494 °C, and high glass transition temperatures (181–278 °C). The optical behavior of these polymers has been investigated in NMP solution as well as in the films. The photoluminescence (PL) spectra of the free-standing films prepared from the poly(amideimide)s exhibited maximum emission bands around 506–525 nm in the green region.     

Features of photolytic transformation of [4-(2-methyl-5-t-butyl-cyclohexadiene-1,5-dion-3,4-yl)-3-methyl-6-<Emphasis Type="Italic">tert</Emphasis>-butyl-catecholato]triphenylantimony(V)

Photolysis of [4-(2-methyl-5-tert-butyl-cyclohexadiene-1,5-dion-3,4-yl)-3-methyl-6-t-butyl-catecholato] triphenylantimony(V) in toluene by irradiation with the light of wavelength 546 nm leads to excitation of the molecule of parent compound which reacts with a molecule of Ph3SbCatQ affording 4,4′-di-(3-methyl-6-tert-butyl-o-benzoquinone) and 4,4′-di[(3-methyl-6-tert-butyl-catecholato)triphenylantimony(V)]. The formed compounds react with each other returning the system into the initial state. Action of light of wavelength 313 and 405 nm on the initial reaction mixture leads to the formation of carbon monoxide, Ph3SbCatCatSbPh3 and the products of photolytic transformation of 4,4′-di(3-methyl-6-tert-butyl-o-benzoquinone).     

Investigations on 2,3′-Biquinolyl. 16. The Regioselectivity of Reduction of 1-Alkyl-3-(2-quinolyl)quinolinium and 1,1′-Dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-biquinolyl Iodides Using Metallic Zinc,Lithium and Potassium

The reaction of 1-alkyl-3-(2-quinolyl)quinolinium iodides with excess zinc in THF gives a diastereomeric mixture of 1,1′-dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-tetrahydro-4,4′-biquinolyls. An excess of lithium in THF gives a mixture of 1′,2′-dihydro-2,3′-biquinolyl and 1′-alkyl-1′, 4′-dihydro-2,3′-biquinolyl with the former predominating. The reduction by lithium in THF of 1,1′-dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-tetrahydro-4,4′-biquinolyls leads to analogous products. Reduction of 1-alkyl-3-(2-quinolyl)quinolinium iodides by metallic potassium gives 1-alkyl-1′,4′-dihydro-2,3′-biquinolyls. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1208–1212, August, 2005.     

Electroactive films of interpolymer complexes of polyaniline with polyamidosulfonic acids: advantageous features in some possible applications

With the purpose of determining prospects of possible applications of interpolymer complexes of polyaniline (PANI) with poly(amidosulfonic acid)s, we have performed a comparative study of polyaniline films prepared by electrochemical polymerization of aniline in the presence of the polyacids distinguished by different rigidities of the polymer backbone: (1) poly(2-acrylamido-2-methyl-1-propanosulfonic acid) (flexible backbone); (2) poly-p,p′-(2,2′-disulfoacid)-diphenylen-iso-phthalamid (semi-rigid backbone); (3) poly-p,p′-(2,2′-disulfoacid)-diphelylen-tere-phthalamid (rigid backbone); and (4) a copolymer of the latter two acids with monomer feed ratio 1:1 (co-PASA). Spectroelectrochemical studies in the UV–vis–NIR range showed that PANI complexes with rigid-chain polyacids far more effectively modulate absorbance in the Vis–NIR range and can be considered as promising candidates for “smart windows” development. Due to the presence of bulky unmovable polyacid anion, PANI interpolymer complexes (particularly those with the semi-rigid-chain polyacids) possess much wider pH range of electroactivity than common PANI, which is of great importance for biosensor applications. The interpolymer complexes with flexible-chain and semi-rigid-chain polyacids exhibit good optical response to ammonia vapors at conditions of high humidity, which make them promising materials for the development of ammonia optical sensors.     

Thiophene-based glass-forming hole-transporting hydrazones

The synthesis, optical, thermal, and photoelectrical properties of new thiophene-based hydrazones are reported. The ionization potentials of the films of thiophene-based hydrazones, measured by the electron photoemission technique, range from 4.99 to 5.58 eV. Hole-drift mobilities in the solid solutions in bisphenol-Z polycarbonate (PC-Z) of the synthesized hydrazones were studied by time of flight technique. Room temperature charge mobilities in the solid solution of 5,2″-diformyl-2,2′:5′,5″-terthiophene di(N,N-diphenylhydrazone) in PC-Z exceeded 10⁻⁵ cm²/Vs at high applied electric fields. Correspondence: Juozas Vidas Grazulevicius, Department of Organic Technology, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas, Lithuania.     

Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one with phenanthrenequinone and dibenzoyl

Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one with 9,10-phenanthrenequinone and dibenzoyl gave hydrolytically unstable spirophosphoranes with five- and seven-membered rings, 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydrospiro[[1,3,2]benzodioxaphosphepine-2,2′-phenanthro[9,10-d][1,3,2]dioxaphosphol]-5-one and 2,4′,5′-triphenyl-4,4-bis(trifluoromethyl)-4,5-dihydrospiro[[1,3,2]benzodioxaphosphepine-2,2′-[1,3,2]dioxaphosphol]-5-one. The structure of the first of these was proved by X-ray analysis.     

Dynamic mechanical properties and thermal degradation process of the compositions obtainedfrom unsaturated poly(ester urethanes) cross-linked with styrene

Dynamic mechanical and thermal properties of poly(ester urethanes) (PEU) cross-linked with styrene have been studied. The investigated polyurethanes were obtained from 4,4′-diphenylmethane diisocyanate and unsaturated oligo(alkyleneester)diol based on cis-2-butene-1,4-diol. The conducted analyses dealt with the correlation between the chemical structure of poly(ester urethanes) and their ability to phase separate as well as their thermal stability. The products of PEU thermal degradation were characterized using infrared spectroscopy.     

Influence of acceptor functionality on charge transfer interactions in mixtures of poly(9-vinylcarbazole) with nitroaromatic compounds

Charge transfer interactions in mixtures of poly(9-vinylcarbazole) with three nitro compounds (4,4′dinitrodibenzyl, ethyl 3,5-dinitrobenzoate and 2,2′,4,4′-tetranitrodibenzyl) were examined.     

Reactions of 3-nitro-1,2,4-triazole derivatives with alkylating agents. 8*. Alkylation of 3-nitro-5-R-1,2,4-triazoles with derivatives of diethylene glycol in the presence of alkali

The interaction of 3-nitro-1,2,4-triazole and 5-methyl-3-nitro-1,2,4-triazole with bifunctional agents ‒ β,β′-dichloro- and β,β′-(dinitroxy)diethyl ethers ‒ in the presence of alkali proceeds with the formation of a mixture of products substituted at the N(1) and N(2) atoms of the heterocycle, consisting of three reaction products, the N(1),N′(1)-, N(1),N′(2)-, and N(2),N′(2) isomeric derivatives of nitrotriazoles. Replacement of the Cl leaving group in the alkylating agent by a NO₂ group does not lead to a substantial change in the degree of conversion and overall yield of alkylation products. The ratio of N(1),N′(1):N(1),N′(2):N(2),N′(2) isomeric reaction products from 3-nitro-1,2,4-triazole was (82.0-85.7): (7.7-9.9):(6.6-8.1), and from 5-methyl-3-nitro-1,2,4-triazole was (76.9-79.8):(10.1:11.4):(10.1-11.7) respectively.     

High optical transparency and low dielectric constant of novel organosoluble poly(ether ketone amide)s derived from an unsymmetrical diamine containing trifluoromethyl and methyl pendant groups

A series of novel fluorinated poly(ether ketone amide)s (PEKAs) were prepared from an unsymmetrical aromatic diamine, (4′-(4″-amino-2″-trifluoromethylphenoxy)-3′,5′-dimethylphenyl)(4-aminophenyl)-methanone (1), with various aromatic dicarboxylic acids using the phosphorylation polycondensation technique. The PEKAs had inherent viscosities ranging from 0.43 to 0.65 dl/g. All the fluorinated PEKAs could be soluble in many polar organic solvents such as N-methyl-2-pyrrolidinone (NMP), N,N′-dimethylacetamide (DMAc), N,N′-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF). Flexible and tough polymer films could be prepared by casting from DMAc solvent. The PEKA films exhibited high optical transparency with a cutoff wavelength of 354–365 nm and good mechanical properties with tensile strengths of 78–98 MPa and elongations at break of 11.5–18.5%. They showed glass-transition temperatures in the range of 288−323 °C and the onset decomposition temperatures in the range of 450−461 °C in nitrogen atmosphere. Meanwhile, the PEKA films possessed low dielectric constants of 1.98–2.71 at 1 MHz and low moisture absorption (<2%). Due to their properties, the fluorinated PEKAs could be considered as photoelectric and microelectronic materials.     

Syntheses based on 8-substituted 3-bromoacetyl-3,8-dimethyl-2,7-dioxaspiro[4,4]nonane-1,6-diones

By reaction of 8-substituted 3-bromoacetyl-3,8-dimethyl-2,7-dioxaspiro[4,4]nonane-1,6-diones with thiourea and substituted thioureas under Hansch reaction conditions, we have obtained the novel heterocycles 3-[2′-amino(arylamino)thiazol-4-yl]-3,8-dimethyl-2,7-dioxaspiro[4,4]nonane-1,6-diones. By reacting the above-indicated bromoacetyl spirodilactones with 5-aryl-3-mercapto-1,2,4-triazoles, we obtained 8-substituted 3-(aryl-3,8-dimethyl-1′,2′,4′-triazol-3′-yl)thioacetyl-2,7-dioxaspiro[4,4]nonane-1,6-diones. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 123–129, January, 2006.     

Anion-dependent binding of zinc calix[4]pyrrole-bisporphyrinate triethylenediamine

The complexation properties of zinc 10,20-bis[5-(2,3,7,8,12,13,17,18-octaethylporphyrinate)ethynylphenyl]-5,5′,10′,15,15′,20′-hexamethylcalix[4]pyrrole toward halide ions, triethylenediamine, and 4,4′-bipyridyl were studied by spectrophotometric titration and ¹H NMR spectroscopy. The influence of binding of anions (F⁻ and Cl⁻) by the calix[4]pyrrole fragment of zinc calixpyrrole-bisporphyrinate on the complexation properties of its interporphyrin cavity toward the bidentate organic ligand triethylenediamine.     

4,4-dimethyl-4,5-dihydro-1,2-dithiolo-[3,4-c]quinoline-1-thiones in 1,3-dipolar cycloaddition reactions with acetylenic dipolarophiles

The behavior of 4,4-dimethyl-4,5-dihydro-1,2-dithiolo[3,4-c]quinoline-1-thiones in the 1,3-dipolar cycloaddition reaction with acetylenic dipolarophiles has been studied. The rate of cycloaddition is reduced along with the decrease of electron-deficiency of the triple bond. Substituted 4-(1′,3′-dithiol-2′-ylidene)-1,2-dihydroquinoline-3-thiones were shown to be the reaction products. On using a twofold excess of acetylenedicarboxylic acid dimethyl ester, adducts of composition 1∶2 were formed which occured to be substituted 1′, 3′-dithiole-2′-spiro-1-(5,6-dihydrothiino[2,3-c]quinolines). Voronezh State University, Voronezh 394693, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 656–660, May, 1999.     

Investigations on 2,3′-biquinoline series. 19. Regioselectivity of the reaction of 1,1′-dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-tetrahydro-4,4′-biquinolines with organomagnesium and organolithium compounds

1,1′-Dialkyl-3,3′-di(2-quinolyl)-1,1′,4,4′-tetrahydro-4,4′-biquinolines react with organolithium and organo-magnesium compounds to form 1′-alkyl-2′-R-1′,2′-dihydro-2,3′-biquinolines. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, 224–226, February, 2006.     

Polyfused nitrogen-containing heterocycles 18. 2′-Amino-5-methyl-1,2,3,4,4′,5′-hexahydrospiro[quinoxaline-2,4′-thiazol]-3-ones. Synthesis,structure, and recyclization

Bis-3-(α-bromoethyl)quinoxalin-2-ones with 3-oxapentane or 3,6-dioxaoctane spacer binding two heterocyclic fragments react with thiourea to give the corresponding bis-spirothiazoloquinoxalines, which upon treatment with acetic anhydride can be converted to podands with terminal thiazoloannulated quinoxaline fragments. X-Ray data for 2′-amino-4-ethyl-5-methyl-1,2,3,4,4′,5′-hexahydrospiro[quinoxaline-2,4′-thiazol]-3-one indicate for this compound a potentiality to form clathrate structures with various solvate molecules. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2386–2393, December, 2007.     

Spirocyclohexadienones: XII. Dienone-phenol rearrangement of 1-substituted 2-azaspiro[4.5]undeca-1,6,9-trienes and their analogs

Hydrolytic cleavage of 1-substituted 2-azaspiro[4.5]undeca-1,6,9-trienes in acid medium is accompanied by dienone-phenole rearrangement with formation of substituted N-[2-(p-hydroxyphenyl)ethyl] carboxylic acid amides. 1,2-Dimethoxy-3-oxo-15-phenyl-14-azadispiro[5.1.5.2]pentadeca-1,4,14-triene and 2′-R-7a′-methyl-3a′,4′,5′,6′,7′,7a′-hexahydrospiro[cyclohexa[2,5]diene-1,3′-indol]-4-ones undergo analogous cleavage.     

Synthesis, FT-Raman, FT-IR, NMR spectroscopic characterization and antimicrobial activity of new mixed aza-oxo-thia macrocyclic compounds

Series of new mixed aza-oxo-thia macrocyclic ligands {2,6,12,16-tetraaza-1,7,11,17-tetraoxo-9,19-dithia-[(4′-methyl-5′,4,3′)(14′-methyl-15′,14,13′)]ditriazine}cyclocosane (L ₁ ); {2,6,13,17-teraaza-1,7,12,18-tetraoxo-9,10,20,21-tetrathia-[(4′-methyl-5′,4,3′)(15′-methyl-14′,16′,15)]di-triazine}cyclodocosane (L ₂ ); {2,6,14,18-tetraaza-1,7,13,19-tetraoxo-10,22-dithia-[(4′-methyl-5′,3′,4)(16′-methyl-15′,17′,16)]ditriazine}cyclotetracosane (L ₃ ) and {2,6,15,19-tetraaza-1,7,14,12-tetraoxo-10,11,23,24-tetrathia-[(4′-methyl-5′,4,3′)(17′-methyl-8′,17,16′)]ditriazine}cyclohexa-cosane (L ₄ ) were synthesized. The structural features of the compounds have been studied by elemental analyses, Mass, FT-Raman, FT-IR, ¹H and ¹³C NMR spectroscopy. The antimicrobial activities of the ligands were evaluated using disk diffusion method in dimethyl sulfoxide as well as the minimal inhibitory concentration (MIC) dilution method, against 9 bacteria. The obtained results from disk diffusion method were assessed in side-by-side comparison with those of Penicillin-g, Ampicillin, Cefotaxime, Vancomycin, Oflaxacin, and Tetracyclin, well-known antibacterial agents. The results from dilution procedure were compared with Gentamycin as antibacterial and Nystatin as antifungal. The antifungal activities are reported on five yeast cultures namely Candida albicans, Kluyveromyces fragilis, Rhodotorula rubra, Debaryomyces hansenii, and Hanseniaspora guilliermondii, and the results are referenced with Nystatin, Ketaconazole, and Clotrimazole, commercial antifungal agents. In most cases, the compounds show strong antifungal activity in the comparison tests.