Synthesis of novel 2,5-bis(5-aryl-1,3,4-oxadiazol-2-yl)furans from furan-2,5-dicarboxylic acid dihydrazide and trichloromethylarenes

2,5-Bis(5-aryl-1,3,4-oxadiazol-2-yl)furans are synthesized via the reaction of trichloromethylarenes with furan-2,5-dicarboxylic acid dihydrazide. The structures of the products are confirmed by IR and mass spectra.N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, Moscow 117913, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 993–996, July, 1999.     

Synthesis of novel imidazole-4,5-dicarboxylic acid derivatives

A convenient general method for the synthesis of unsymmetrical imidazole-4,5-dicarboxylic acid derivatives is described. The key intermediates are 5,10-dioxo-5H,10H-diimidazo[1,5-a:1′,5′-d[pyrazine-1,6-dicarboxylic acid, -1,6-dicarboxylic ester and -1,6-dicarboxamide.     

Novel organogelators based on pyrazine-2,5-dicarboxylic acid derivatives and their mesomorphic behaviors

A series of new low molecular organogelators (LMOGs) with thermotropic mesophase were synthesized via the reaction of 3,6-dimethyl-pyrazine-2,5-dicarboxylic acid with p-alkoxyl anilines. These compounds readily formed stable gels in a variety of organic solvents and their self-assembly behavior, structure–property relationship were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), ¹H nuclear magnetic resonance (¹H NMR), Fourier transform infrared spectroscopy (FTIR) and ultra-violet–visible spectroscopy (UV). The results showed a combination of intra-hydrogen bonding, π–π stacking and van der Waals interaction resulted in the aggregation of the organogelators to form three-dimension fibrous networks. The gels formed were multi-responsive to environmental stimuli, such as temperature, fluorinion, and shear stress. More importantly, all the organogelators exhibited thermotropic hexagonal column mesophase as revealed by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable temperature XRD studies. A control compound was synthesized and its gelling ability was also checked.     

Synthesis and characterization of metal-organic frameworks based on 4-hydroxypyridine-2,6-dicarboxylic acid and pyridine-2,6-dicarboxylic acid ligands

The self-assembly of 4-hydroxypyridine-2,6-dicarboxylic acid (H(3)CAM) and pyridine-2,6-dicarboxylic acid (H2PDA) with Zn(II) salts under hydrothermal conditions gave two novel coordination polymers {[Zn(HCAM)].H2O}n (1) and {[Zn(PDA)(H2O)(1.5)]}n (1a). 1 and 1a comprise of a 2D (4,4) net and a 1D zigzag chain, respectively, in which a new coordination mode of PDA is found. The reactions of H(3)CAM and H2PDA with Nd2O3 in the M/L ratio 2:3 gave {[Nd2(HCAM)3(H2O)4].2H2O}n (2) and {[Nd(2)(PDA)3(H2O)(3)].0.5H2O}n (2a). In 2, a square motif as a building block constructed by four Nd(III) ions was further assembled into a highly ordered 2D (4,4) grid. 2a is a 3D microporous coordination polymer. It is interesting to note that, when Ln(III) salts rather than oxides were employed, the reaction produced {[Ln(CAM)(H2O)3].H2O}n (Ln = Gd, 3; Dy, 4; Er, 5) for H(3)CAM and {[Gd2(PDA)3(H2O)3].H2O}n (3a) for H2PDA. 3-5 are 2D coordination polymers with a 3(3)4(2) uniform net, where hydroxyl groups of H3CAM coordinate with metal ions. The reaction of H3CAM and Er2O3 instead of Er(ClO4)3 produced {[Er2(HCAM)3(H2O)4].2H2O}n (6). The compounds 2a and 3a, 2 and 6 are isomorphous. The stereochemical and supramolecular effects of hydroxyl groups result in the dramatic structural changes from 1D (1a) to 2D (1) and from 2D (2) to 3D (2a). When Ln(III) salts instead of Ln2O3 were employed in the hydrothermal reactions with H(3)CAM, different self-assembly processes gave the products of different metal/ligand ratio with reactants (3-5).     

Synthesis, Structural Characterization and Luminescence of Lanthanide Coordination Polymers with Pyridine-2,5-dicarboxylic Acid

The complexes of formulas [Ln₂(pydc)₂(Hpydc)₂(H₂O)₄]·2H₂O [Ln=Ce ( 1 ), Pr ( 2 ), H₂pydc=pyridine‐2,5‐di‐carboxylic acid] have been hydrothermally synthesized and characterized by elemental analysis, IR, TG and single‐crystal X‐ray diffraction. The structure analyses for 1 and 2 indicate that one‐dimensional metal helical chains are linked through carboxylate groups, and the helical chains are connected with the bridging pydc^2? anion, forming two‐dimensional layered polymeric structures. The luminescent properties of complexes were also discussed.     

Investigation of furan compounds L. Synthesis of N-alkyl- and N-aryl-substituted diureides of tetrahydrofuran-2,5- and tetrahydrothiophene-2,5-dicarboxylic acids

The corresponding diureides of tetrahydrofuran-2,5- and tetrahydrothiophene-2,5-dicarboxylic acids and the dithioureide of tetrahydrothiophene-2,5-dicarboxylic acid were obtained by the acylation of thiourea, urea, and its N-methyl-, N-tert-butyl- and N-phenyl derivatives with the acid dichlorides of tetrahydrofuran-2,5- and tetrahydrothiophene-2,5-dicarboxylic acids.See [1] for communication XLIX.DeceasedTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1587–1589, December, 1971.     

以吡啶-2,5-二羧酸或噻吩-2,5-二羧酸为配体的过渡金属配合物的合成、晶体结构及性质

以吡啶-2,5-二羧酸(2,5-pyridinedicarboxylic acid,H_2L_1)、噻吩-2,5-二羧酸(Thiophene 2,5-dicarboxylic acid,H_2L_2)为主要配体,4,4′-联吡啶(4,4′-bipy)、菲咯啉(phen)为辅助配体,采用溶剂热法成功合成了3个过渡金属配合物:[Co_2(L_1)_2(bipy)(H_2O)_6]·bipy·H_2O (1)、[Cu(L_2)_2(bipy)_2]n(2)、[Ni_2(L_2)(phen)_2(H_2O)_4](3),并利用X射线单晶衍射法、红外光谱(IR)、荧光光谱(FL)和热重分析(TG/DTG)等测试手段对其进行了表征。单晶结构分析表明:配合物1、配合物2为P1空间群,配合物3为P2/n空间群;配合物1和配合物3为零维双核小分子结构,配合物2为二维层状结构。     

A new method for the isolation and estimation of Furan-2,5-dicarboxylic acid in human urine

Summary A new, concise and efficient method of isolation and estimation of F. D. A. avoiding heating with acids, has been devised.Inositol and calcium gluconate when added to urine and subjected to the old method of isolation of F. D. A. result in no increase in the amount of F. D. A. This indicates that the increase in the output of this acid obtained before⁴ was a process within the body itself.Metabolic experiments with inositol and calcium gluconate adopting the new method gave a 3–4 fold increase in the F. D. A. output confirming that this increase is anin vivo process.

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Zusammenfassung Eine neue, genaue Methode zur Isolierung und Bestimmung von Furandicarbonsäure (F. D. C.) ohne Erhitzen des angesäuerten Untersuchungs-materials wurde ausgearbeitet. Werden Inosit und Calciumgluconat dem Harn vor Aufarbeitung nach der alten Methode zugesetzt, so führt dies zu keiner Erhöhung der F. D. C.-Menge. Die früher beobachtete Vermehrung der F. D. C.-Menge ist also die Folge von Vorgängen innerhalb des Organismus. Stoffwechselexperimente mit Inosit und Calciumgluconat mit der neuen Methode zeigen eine drei bis vierfach gesteigerte F. D. C.-Ausscheidung und bestätigen damit deren vermehrte Bildung in vivo.

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Résumé On a imaginé une nouvelle méthode rapide et efficace pour isoler et doser le F. D. A. en évitant le chauffage avec les acides. L'inositol et le gluconate de calcium, ajoutés à l'urine et soumis à la vieille méthode d'isolement du F. D. A. ne produisent pas de surcharge sur la quantité de F. D. A. Ce fait indique que l'augmentation du rendement de cet acide, obtenue auparavant, était un processus dans le corps humain lui-même.Des expériences sur le métabolisme avec l'inositol et le gluconate de calcium, en adoptant la nouvelle méthode, ont donné une augmentation de trois à quatre fois le rendement en F. D. A., ce qui confirme que cette augmentation se produitin vivo.

     

Structures and magnetic properties of several novel lanthanide coordination polymers based on thiophene-2,5-dicarboxylic acid

Eight novel lanthanide complexes: {Ln(TDA)1.5(H2O)2}n (Ln = Pr(1a), Nd(2a)) and {Ln(TDA)(Ac)(H2O)}n (Ln = Pr(1), Nd(2), Eu(3), Gd(4), Tb(5), Dy(6); TDA = Thiophene-2,5-dicarboxylic acid anion) have been constructed by hydrothermal reaction. Structural analyses reveal that complexes 1a and 2a belong to the space group C2/c, exhibiting three-dimensional (3D) frameworks. Complexes 1-6 with P21/c space group were prepared in the presence of excessive ammonium acetate, giving rise to interesting 3D frameworks different from those of 1a and 2a. Magnetic property studies of 4-6 reveal the weak antiferromagnetic interaction exists between adjacent Gd3+ in 4. The complex 6 displays rather rare slow magnetization relaxation behavior in 3D frameworks.     

Synthesis of fluorine-containing esters of 2,5-furandicarboxylic acid

Fluorinated esters of 2,5-furandicarboxylic acid have been synthesized starting from 2,5-furan dicarboxylic acid dichloride and fluorine-containing diols. The reaction control was performed by means of ¹H, ¹⁹F NMR, and IR-spectroscopy. Thermal stability, as well as glass transition temperature, and intrinsic viscosity parameters of the obtained oligomers have been determined.     

Synthesis and new rearrangements of 4-isoxazolin-4,5-dicarboxylic acid derivatives

Acyclic nitrones react with dimethyl acetylenedicarboxylate (DMAD) to give stable isoxazolines, from which the ones that contain electron-donating aromatic rings at the C3 position (R¹) were shown to undergo unprecedented fragmentation at room temperature, giving the R¹-aldehyde and inseparable product mixtures, probably due to the formation of highly reactive species such as iminocarbenes. Attempts to convert the isoxazolines to the corresponding stable azomethine ylides, by refluxing in toluene, again led to the same product mixtures as above (e.g., the room temperature decomposition). Isoxazolines when reacted with methoxide at room temperature afforded highly functionalised diastereomeric mixtures. Also, isoxazolines, when reacted with propylamine, gave the corresponding amides regioselectively, all of which were more stable than the parent isoxazolines.     

Synthesis,characterization and crystal structure of a novel three-dimensional supramolecular architecture formed by manganese(II) and pyridine-2,5-dicarboxylic acid

A novel three-dimensional supramolecular compound formed by Mn(II) and pyridine-2,5-dicarboxylic acid of formula [Mn(Pydc)₂(H₂O)₂] (Pydc?=?pyridine-2,5-dicarboxylic acid) has been synthesized and characterized by elemental analyses, IR, electronic spectra, thermogravimetric analysis and X-ray diffraction techniques. The X-ray structure shows that the central Mn(II) ion is coordinated by two water molecules and two chelated Pydc ligands. Water molecules coordinate with Mn(II) ions in the cis mode. Intermolecular hydrogen bonds play an important role in stabilization of the lattice and construction of the supramolecular network.     

Synthesis and characterization of polymers derived from 2,5-dimethoxy-terephthaldehyde and 2,5-dimethoxy-terephthalic acid

Polyamides were synthesized from 2,5-dimethoxyterephthaloyl dichloride and diamines. Also, polyimines and polyaldoles were prepared from 2,5-dimethoxy-terephthaldehyde with diamines and ketones. The polymers were characterized by elemental analysis and infrared and NMR spectroscopy. Their intrinsic viscosity, glass transition temperature, and thermaldecomposition temperatures were determined.     

Solvothermal synthesis, crystal structure, and properties of lanthanide-organic frameworks based on thiophene-2,5-dicarboxylic acid

A series of lanthanide-organic framework coordination polymers, {[La(2)(TDC)(2)(NO(3))(H(2)O)(4)](OH)·5H(2)O}(n) (1) and [Ln(TDC)(NO(3))(H(2)O)](n) (TDC = thiophene- 2, 5- dicarboxylic acid; Ln = Nd(2), Sm(3), Eu(4), Gd(5), Tb(6), Dy(7), Ho(8), Er(9), Yb(10)) have been synthesized by solvothermal reaction and characterized by elemental analysis, FT-IR, TG analysis, single-crystal X-ray diffraction and power X-ray diffraction. The single-crystal X-ray diffraction analysis results show that 1 displays a 3-D porous framework with (3,7)-connected {4(10).6(11)}{4(3)} topology. The compounds 2-10 crystallized in the same P2(1)/c space group and exhibits a (3,6)-connected {4.6(2)}(2){4(2).6(10).8(3)} topology, Right-handed and left-handed helical chains coexist in the 2-D layer structure. The luminescence properties of 2-10 and the magnetic properties of 5,7,8,9 were investigated.     

Synthesis of monosubstituted amides of 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid

Monosubstituted amides of 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid were obtained when acetoacetic acid anilide and 2-pyridylamide were used in place of acetoacetic ester in the Hantzsch synthesis.     

Synthesis and N-Alkylation of 2-Alkyl-and 2-Arylimidazole-4,5-dicarboxylic acid esters

Nitration of d-tartaric acid, followed by treatment of the resulting dinitrotartaric acid with ammonia and aldehydes gave 2-phenyl-, 2-(2-pyridyl)-, 2-isopropyl-, and 2-isobutylimidazole-4,5-dicarboxylic acids. Some factors affecting the yield of the final products were revealed, and optimal conditions for their esterification were found. N-Alkylation of 2-substituted imidazole-4,5-dicarboxylates thus obtained involves considerable steric hindrances; therefore, the corresponding N-alkyl derivatives can be obtained in a poor yield only in the presence of such a strong base as 1,8-diazabicyclo[5.4.0]undec-7-ene. Original Russian Text A.V. Lebedev, A.B. Lebedeva, V.D. Sheludyakov, E.A. Kovaleva, O.L. Ustinova, V.V. Shatunov, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 5, pp. 855–859.