Synthesis of new proton‐ionizable crown ether compounds containing substituted lh‐pyridin‐4‐one subcyclic units

Five novel pyridono‐18‐crown‐6 ( 10‐14 ) and two new benzyloxy‐substituted pyridino‐18‐crown‐6 ( 15 and 16 ) ligands have been prepared. By the catalytic hydrogenative removal of the benzyl group from the benzyloxy moiety at position 4 of the pyridine ring of 15 and 16 , pyridono‐18‐crown‐6 ethers 5 and 12 were obtained. These ligands were transformed to their 3,5‐dibromo ( 10 and 13 ) and 3,5‐dinitro derivatives ( 11 and 14 ) by treatment with bromine in methylene chloride and nitric acid in acetic anhydride, respectively. The latter proton‐ionizable crown ethers have pK_avalues of about 7.5 for 10 and 13 and 4.5 for 11 and 14 . Thus, they are good candidates for complexation and proton‐coupled transport of selected cations.     

Synthesis of novel benzo‐substituted macrocyclic schiff bases containing two triazole rings

A synthesis of a series of novel macrocyclic Schiff bases containing two triazole rings 10a,b, 11a,b, 34‐37 in good yields by heating the appropriate bis‐amines 1f, 6a,b, 31 with the corresponding bis‐aldehydes 2, 9a,b, 29 in refluxing acetic acid under high dilution conditions was described. Attempts to synthesize macrocyclic Schiff bases containing pyridine and two triazole rings were also described.     

New proton-ionizable macrocyclic compounds containing one and two triazole subcyclic units — synthesis and complexation properties

A series of new macrocyclic compounds containing one and two proton-ionizable triazole subcyclic units have been prepared and characterized. These triazolo-crowns containing benzo, tert-butylbenzo or cyclohexano lipophilic groups show varying solubilities in chloroform. The bistriazolo-crowns dissolved in chloroform are highly effective for extraction of lead, mercury, and gold from aqueous solutions.     

Synthesis of novel macrocyclic di‐ and tetralactams containing triazole subunits

The new macrocyclic di‐ and tetralactams 9 , 15 , and 16 were obtained in 16–24% yields by heating the appropriate bis‐amines 7 or 8 with the corresponding bisaldehyde 5 or 14 in refluxing acetic acid under high‐dilution conditions. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:551–559, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10191     

Synthesis of hyperbranched polymers via proton‐transfer polymerization of acrylate monomer containing two hydroxy groups

The hyperbranched polymer 2 was produced via triphenylphosphine initiated polymerization of the acrylate monomer 1 containing two hydroxy groups. The reaction resulting in 2 is based on a Michael‐type addition followed by a proton‐transfer process. The molecular weights evaluated by VPO measurements were vanging between 1 170–2 700 g/mol. The results of the methanolysis experiments of the polymers were used to determine the degrees of branching, that ranged between 0.45 and 0.60. In this polymerization, the hydroxy groups of the monomer and of the polymer are latent propagating species, which are converted into the corresponding anions, which are the actual propagating species active during the proton‐transfer reactions. The proton‐transfer occur frequently during this polymerization in order to afford the formation of hyperbranched polymers.     

Synthesis of new proton-ionizable and neutral macrocyclic,macrobicyclic and macrotricyclic crown compounds containing dibenzo-16-crown-5 units

Fifteen new macrocyclic, macrobicyclic and macrotricyclic crown ether compounds with sym-dibenzo-16-crown-5 units have been prepared. The series includes macrocyclic polyether and bis(crown ether) compounds with proton-ionizable carboxylic or phosphonic acid monoethyl ester groups and bis(crown ether) and macrotricyclic polyether compounds with two sym-dibenzo-16-crown-5 units linked by amide, diamide, or diester functions.     

Intramolecular interactions in acyclic and macrocyclic compounds containing nucleotide bases

Acyclic and cyclic counterparts containing thymine and two 3,6-dimethyluracil fragments bridged by methylene chains have been prepared and studied by UV and NMR spectroscopy; in water the uracil units of the acyclic counterpart form an intramolecular stack but arrange in a linear array in chloroform while the fragments of the uracilophane form an intramolecular stack both in chloroform and water; uracil units of bis(3,6-dimethyluracil-1-yl)butane and the macrocyclic counterpart form a stack in chloroform.     

Synthesis of chiral fused heterocyclic compounds containing 1,2,4‐triazole ring

A series of new chiral (S)‐3‐ary1‐6‐pyrrolidin‐2‐yl‐[1,2,4]triazolo[3,4‐b]thiadiazole (II_1‐5), (S)‐1‐(3‐aryl‐[1,2,4]triazolo[3,4‐b][1,3,4]thiadiazol‐6‐yl)‐ethylamine (II_6‐8) and (S)‐1,2‐bis(3‐aryl‐[1,2,4]triazolo‐[3,4‐b][1,3,4]thiadiazol‐6‐yl)‐ethylamine (II_9‐11) were prepared by the condensation of 3‐aryl‐4‐amino‐5‐mercapto‐1,2,4‐triazoles with different L‐amino acids in the presence of phosphorus oxychloride and evaluated for their antibacterial activity.     

Intramolecular electrophilic aromatic substitution in gas-phase-protonated difunctional compounds containing one or two arylmethyl groups

A variety of dibenzyl esters and ethers undergo a rearrangement process upon isobutane chemical ionization and collision-induced dissociation of their MH(+) ions, whereby a new bond is formed between the two benzyl groups, giving rise to abundant [C(14)H(13)](+) (m/z 181) ions. This rearrangement has been explained as an intramolecular electrophilic substitution in the gas phase occurring in an ion-neutral complex formed by the cleavage of one of the benzyl-oxygen bonds. A similar highly efficient intramolecular electrophilic substitution takes place in di-alpha- and beta-naphthylmethyl adipates affording m/z 281 [C(22)H(17)](+) ions, but not in the sterically hindered di-9-anthracylmethyl adipate. An analogous efficient rearrangement occurs in benzyl alpha- and beta-naphthylmethylcyclohexane-1,4-dicarboxylates and in benzyl alpha- and beta-phenylethylcyclohexane-1,4-dimethanol ethers. The analogous rearrangement is much less efficient in benzylallyl, benzylpropargyl and benzyl-9-anthracylmethyl derivatives, even less in benzylisopropyl and benzylacetyl analogs, and it is absent in benzyltetrahydropyranyl derivatives. The distinctive behavior of the protonated difunctional benzyl derivatives is interpreted in terms of the energy requirements of the O-R bond heterolysis of the protonated functionalities, the ability of the neutral R' groups (non-dissociated from the oxygen atom) to play the role of the nucleophile in the intramolecular electrophilic substitution processes and the electrophilicity of the R(+) ions.     

Synthesis of novel isoindolone‐based medium‐sized macromolecules and triazole containing heterocyclic compounds

A series of novel isoindolone‐based macromolecules of medium‐sized heterocyclic rings, such as 7,8‐dihydro‐6H‐benzo[4,5][1,6,3]dioxazonino[2,3‐a]isoindol‐14(9aH)‐one derivatives ( 5a‐l ), were synthesized and its frame work incorporating with a triazole moiety on phenol, ie, 2‐(4‐((1‐(2‐methoxyphenyl)‐1H‐1,2,3‐triazol‐4‐yl)methoxy)phenyl)isoindoline‐1,3‐dione ( 9a‐f ) and also a triazole moiety on carboxylic acid, ie, (1‐(2‐methoxyphenyl)‐1H‐1,2,3‐triazol‐4‐yl)methyl 4‐(1,3‐dioxoisoindolin‐2‐yl)benzoate derivatives ( 13a‐e ) with various substitutions on aryl ring system have synthesized. All the synthesized compounds were characterized and confirmed with IR, ¹H NMR_, ¹³C NMR, and ESI mass spectral analysis.     

Synthesis of azo compounds containing triazole and tetrazole residues

Triazole- and tetrazolediazonium sulfates were coupled with aromatic azo components. The effect of the structure and medium on the chromaticity of the azo compounds was studied.     

Copolyfluorenes containing pendant bipolar carbazole and 1,2,4‐triazole groups: Synthesis,characterization, and optoelectronic applications

Three novel copolyfluorenes ( P1 ‐ P3 ) containing pendant bipolar groups (2.5–7.7 mol %), directly linked hole‐transporting carbazole and electron‐transporting aromatic 1,2,4‐triazole, were synthesized by the Suzuki coupling reaction and applied to enhance emission efficiency of polymer light‐emitting diodes based on conventional MEH‐PPV. The bipolar groups not only suppress undesirable green emission of polyfluorene under thermal annealing, but also promote electron‐ and hole‐affinity of the resulting copolyfluorenes. Blending the bipolar copolyfluorenes with MEH‐PPV results in significant enhancement of device performance [ITO/PEDOT:PSS/MEH‐PPV+ P1 , P2 or P3 /Ca(50 nm)/Al(100 nm)]. The maximum luminance and luminance efficiency were enhanced from 3230 cd/m² and 0.29 cd/A of MEH‐PPV‐only device to 15,690 cd/m² and 0.81 cd/A (blend device with MEH‐PPV/ P3 = 94/6 containing about 0.46 wt % of pendant bipolar residues), respectively. Our results demonstrate the efficacy of the bipolar copolyfluorenes in enhancing emission efficiency of MEH‐PPV. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis,crystal structures,and properties of two novel compounds containing triphosphonate groups

Two novel phosphonate compounds (H₂L)·Hphen (1) and [Ca(HL)(H₂O)]_n·3.5nH₂O (2) (L = N(CH₂PO₃H)₃^3?) were synthesized under hydrothermal conditions. Compound 1 features a chain structure in the ac plane, where HL^2? anions are interconnected through sharing hydrogen ions to form a 1D zigzag type. Compound 2 features a layered structure in the ab plane, which has inorganic calcium cores with the organic part of the phosphonate anions being encircling the cores through coordination actions. The free water molecules can form hydrogen bonds with the coordinated water molecules and phosphonate oxygen atoms, which are able to link the adjacent layers to generate a 3D network structure. In addition, the thermal stability and photoluminescence properties were also studied.     

Synthesis and properties of novel sulfonated polyimides containing binaphthyl groups as proton‐exchange membranes for fuel cells

A novel sulfonated diamine monomer, 2,2′‐bis(p‐aminophenoxy)‐1,1′‐binaphthyl‐6,6′‐disulfonic acid (BNDADS), was synthesized. A series of sulfonated polyimide copolymers containing 30–80 mol % BNDADS as a hydrophilic component were prepared. The copolymers showed excellent solubility and good film‐forming capability. Atomic force microscopy phase images clearly showed hydrophilic/hydrophobic microphase separation. The relationship between the proton conductivity and degree of sulfonation was examined. The sulfonated polyimide copolymer with 60 mol % BNDADS showed higher proton conductivity (0.0945–0.161 S/cm) at 20–80 °C in liquid water. The membranes exhibited methanol permeability from 9 × 10^?8 to 5 × 10^?7 cm²/s at 20 °C, which was much lower than that of Nafion (2 × 10^?6cm²/s). The copolymers were thermally stable up to 300 °C. The sulfonated polyimide copolymers with 30–60 mol % BNDADS showed reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 40 mol % BNDADS was 80.6 MPa under high moisture conditions. The optimum concentration of BNDADS was found to be 60 mol % from the viewpoint of proton conductivity, methanol permeability, and membrane stability. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 222–231, 2007     

Synthesis of macrocyclic compounds containing thiophene and thiazole nuclei

Macrocyclic ketones that contain a thiophene nucleus and have 14 or more carbon atoms in the ring can form systems with a condensed thiazole ring, in high yield.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 841–844, June, 1986.     

Syntheses and structures of one CuI‐containing coordination polymer and two macrocyclic supramolecular complexes based on flexible 1,3,4‐oxadiazole‐containing ligands

Three coordination complexes with Cu^I centres have been prepared using the symmetrical flexible organic ligands 1,3‐bis{[5‐(quinolin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl]sulfanyl}propane (L1) and 1,4‐bis{[5‐(quinolin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl]sulfanyl}butane (L2). Crystallization of L1 with Cu(SO₃CF₃)₂ and of L2 with Cu(BF₄)₂ and Cu(ClO₄)₂ in a CH₂Cl₂/CH₃OH mixed‐solvent system at room temperature afforded the coordination complexes catena‐poly[[copper(I)‐μ‐1,3‐bis{[5‐(quinolin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl]sulfanyl}propane] methanesulfonate dichloromethane 0.6‐solvate], {[Cu(C₂₅H₁₈N₆O₂S₂)](CF₃SO₃)·0.6CH₂Cl₂}_n, (I), bis(μ‐1,4‐bis{[5‐(quinolin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl]sulfanyl}butane)dicopper(I) bis(tetrafluoridoborate)–dichloromethane–methanol (1/1.5/1), [Cu₂(C₂₆H₂₀N₆O₂S₂)₂](BF₄)₂·1.5CH₂Cl₂·CH₃OH, (II), and bis(μ‐1,4‐bis{[5‐(quinolin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl]sulfanyl}butane)dicopper(I) bis(perchlorate)–dichloromethane–methanol (1/2/1), [Cu₂(C₂₆H₂₀N₆O₂S₂)₂](ClO₄)₂·2CH₂Cl₂·CH₃OH, (III). Under the control of the dumbbell‐shaped CF₃SO₃⁻ anion, complex (I) forms a one‐dimensional chain and neighbouring chains form a spiral double chain. Under the control of the regular tetrahedron‐shaped BF₄⁻ and ClO₄⁻ anions, complexes (II) and (III) have been obtained as bimetallic rings, which further interact viaπ–π interactions to form two‐dimensional networks. The anions play a decisive role in determining the arrangement of these discrete molecular complexes in the solid state.     

Copoly(p‐phenylene)s containing bipolar triphenylamine and 1,2,4‐triazole groups: Synthesis,optoelectronic properties,and applications

Two novel copoly(p‐phenylene)s ( P1 – P2 ) containing bipolar groups (12.8 and 6.8 mol %, respectively), directly linked hole transporting triphenylamine and electron transporting aromatic 1,2,4‐triazole, were synthesized to enhance electroluminescence (EL) of poly(p‐phenylene vinylene) (PPV) derivatives. The bipolar groups not only enhance thermal stability but also promote electron affinity and hole affinity of the resulting copoly(p‐phenylene)s. Blending the bipolar copoly‐(p‐phenylene)s ( P1 – P2 ) with PPV derivatives ( d6‐PPV ) as an emitting layer effectively improve the emission efficiency of its electroluminescent devices [indium tin oxide (ITO)/poly(3,4‐ethylenedioxythiophene) (PEDOT):poly(styrenesulfonate) (PSS)/polymer blend/Ca (50 nm)/Al (100 nm)]. The maximum luminance and maximum luminance efficiency were significantly enhanced from 310 cd m^?2 and 0.03 cd A^?1 ( d6‐PPV ‐based device) to 1450 cd m^?2 and 0.20 cd A^?1 (blend device with d6‐PPV / P1 = 96/4 containing ～0.5 wt % of bipolar groups), respectively. Our results demonstrate the efficacy of the copoly(p‐phenylene)s with bipolar groups in enhancing EL of PPV derivatives. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and characterization of proton‐conducting copolyimides bearing pendant sulfonic acid groups

A series of sulfonated copolyimides (co‐SPIs) bearing pendant sulfonic acid groups were synthesized from 1,4,5,8‐naphthalenetetracarboxylic dianhydride (NTDA), bis(3‐sulfopropoxy) benzidines (BSPBs), and common nonsulfonated diamines via statistical or sequenced polycondensation reactions. Membranes were prepared by casting their m‐cresol solutions. The co‐SPI membrane had a microphase‐separated structure composed of hydrophilic and hydrophobic domains, but the connecting behavior of hydrophilic domains was different from that of the homo‐SPIs. The co‐SPI membranes displayed clear anisotropic membrane swelling in water with negligibly small dimensional changes in the plane direction of the membrane. With water uptake values of 39–94 wt %, they showed dimensional changes in membrane thickness of about 0.11–0.58, which were much lower than those of homo‐SPIs. The proton conductivity σ values of co‐SPI membranes with ion exchange capacity values ranging from 1.95–2.32 meq/g increased sigmoidally with increasing relative humidity. They displayed σ values of 0.05–0.16 S/cm at 50 °C in liquid water. Increasing temperature up to 120 °C resulted in further increase in proton conductivity. The co‐SPI membranes showed relatively good conductivity stability during the aging treatment in water at 100 °C for 300 h. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1545–1553, 2005     

含呋喃环Schiff碱型大环化合物的合成及其与Ba^2+,Sr^2+配合行为

利用Mn^2+，Ba^2+及Sr^2+作为模板离子，合成了一类新型的含呋喃环系 Schiff碱型大环化合物，如L^1和配合物L^2Ba(ClO4)2，L^3Ba(ClO4)2和L^4Ba (ClO4)2.L^2-L^4的Ba^2+配合物经与NaSO4水溶液反应解络，得到自由配体L^2， L^3和L^4，配体L^2和L^3分别与Sr^2+作用，得到配合物L^2Sr(ClO4)2和L^3Sr (ClO4)2。上述大环配体和各种配合物均经元素分析，IR，^1H NMR，MS等证实了它 们的结构和组成。