49633-28-5

This paper describes the synthesis of a novel intrinsically conductive two-dimensional (2D) covalent organic framework (COF) through the aromatic annulation of 2,3,9,10,16,17,23,24-octa-aminophthalocyanine nickel(II) and pyrene-4,5,9,10-tetraone. The intr

Transformation of carbon dioxide to high value-added chemicals becomes a significant challenge for clean energy studies. Here a stable and conductive covalent organic framework was developed for electrocatalytic carbon dioxide reduction to carbon monoxide

Herein, we report the synthesis of oleylamine-capped CdS nanowires (NWs) and the dispersion of a small optimized amount of these NWs in the Colhphase of a recently synthesized phenazine-fused-triphenylene discotic liquid crystal (PFT DLC) to un

We report steady state and time resolved fluorescence measurements on acetonitrile (ACN) solutions of the model compounds, energy donor anisole (A) and a photoswitchable acceptor N,N′-1,2-phenylene di-p-tosylamide (B) and the multichromophore (M) where A

The poor electrical conductivity of two-dimensional (2D) crystalline frameworks greatly limits their utilization in optoelectronics and sensor technology. Herein, we describe a conductive metallophthalocyanine-based NiPc-CoTAA framework with cobalt(II) te

The first synthesis of spirocyclic tetrasulfonamidosilanes is described. According to the X-Ray structure analysis of the most stable tetratosylamidosilane obtained the Silicon is bonded to four Nitrogen atoms in a spirocycle and surrounded by four Oxygen

Large π-conjugated conductive two-dimensional (2D) metal-organic frameworks (MOFs) via the bottom-up approach have recently emerged as novel and interesting 2D materials. For the first time, herein we demonstrate the design and successful bottom-up fabric

Ligand-controlled regiodivergence has been developed for catalytic semireduction of allenamides with excellent chemo- and stereocontrol. This system also provides an example of catalytic regiodivergent semireduction of allenes for the first time. The divergence of the semireduction is enabled by ligand switch with the same palladium pre-catalyst under operationally simple and mild conditions. Monodentate ligand XPhos exclusively promotes selective 1,2-semireduction to afford allylic amides, while bidentate ligand BINAP completely switched the regioselectivity to 2,3-semireduction, producing (E)-enamide derivatives.

The invention provides a compound and a preparation method thereof, and application of the compound as an n-type dopant. The structural formula of the compound is shown as a formula (I) which is described in the specification. The compound can be used as

In transition-metal-mediated catalysis, designing new, well defined coordination architectures and subjecting them to catalysis testing under the same reaction conditions is a necessary tool for gaining an improved understanding of desirable active site geometries and characteristics. In this work, three ligands varying in chelation and charge characters (1= tridentate, dianionic N^N^N;2= bidentate, dianionic N^N;3= bidentate, neutral N^O) were synthesized and introduced as organic backbones around cobalt(ii) centres. Four multinuclear coordination assemblies incorporating various group I metal ions (i.e., (Na-Co1-i)2, (Na-Co1-e)2, (K-Co1-e)2and (Cs-Co1-e)2) and two mononuclear complexes (i.e.,Co2andCo3) were isolated, structurally characterized and studied as phenoxazinone synthase models. X-ray data and Continuous Shape Measure (CShM) calculations described unusual vacant trigonal bipyramidal geometries for (Na-Co1-i)2, (Na-Co1-e)2andCo3, trigonal bipyramids for (K-Co1-e)2and (Cs-Co1-e)2, and a tetrahedron forCo2. According to mass spectrometry data, the four multinuclear (MI-Co1-solvate)2complexes of ligand1easily dissociate in solution to yield the corresponding ions including a common mononuclearCo1unit. Testing as models in the oxidative coupling ofo-aminophenol revealed that an increasing chelate character of the organic ligand backbone produces an undesirable catalyst activity reduction. Furthermore, the similarity in coupling efficiencies observed among complexes (Na-Co1-i)2, (Na-Co1-e)2, (K-Co1-e)2and (Cs-Co1-e)2proves that the presence of varying group I metal ions contributed no catalytic effects to the coupling efficiencies and that theCo1species, which is generated by dissociation in solution, is the only active species responsible for the observed biomimetic behaviours. Therefore, the combination of anionic chelate ligands with easily detachable, neutral co-ligands (e.g., water or pyridine) around a cobalt(ii) centre could be recommended for the generation of a successful catalyst material, rather than the combination of a neutral chelate ligand with counter-anionic monodentate co-ligands like halides.

The present invention provides a borylimide catalyst and further relates to compositions comprising the borylimide catalysts and processes for the polymerisation of olefins (e.g. ethylene) using the borylimide catalysts or the compositions comprising the

The invention discloses a 5,6-dinitrobenzimidazole compound shown as a formula (I). The synthesis method of the compound comprises the following steps: firstly, performing amino protection, nitrification and deprotection on o-phenylenediamine to prepare a compound shown as a formula (V), and finally, reacting the compound shown as the formula (V) with a compound shown as a formula (VI) to obtain aproduct, namely the 5,6-dinitrobenzimidazole compound shown as the formula (I). The 5,6-dinitrobenzimidazole compound and the method have the main beneficial effects that: the preparation method hasthe advantages of short route, easily available raw materials, simple process, mild reaction conditions and the like, meanwhile, the application of the 5,6-dinitrobenzimidazole compound in third-ordernonlinear optics is developed, and the 5,6-dinitrobenzimidazole compound has relatively high implementation value and good social and economic benefits.

The molecular-level structuration of two full photosystems into conjugated porous organic polymers is reported. The strategy of heterogenization gives rise to photosystems which are still fully active after 4 days of continuous illumination. Those materials catalyze the carbon dioxide photoreduction driven by visible light to produce up to three grams of formate per gram of catalyst. The covalent tethering of the two active sites into a single framework is shown to play a key role in the visible light activation of the catalyst. The unprecedented long-term efficiency arises from an optimal photoinduced electron transfer from the light harvesting moiety to the catalytic site as anticipated by quantum mechanical calculations and evidenced by in situ ultrafast time-resolved spectroscopy.

We herein report a versatile, regio- and enantioselective palladium-catalyzed tandem allylic substitution powered by a chiral bisphosphorus ligand WingPhos with the palladium loading as low as 0.1 mol %, forming a series of chiral vinyl-substituted heterocycles, including tetrahydroquinoxalines, piperazines, dihydro-2H-benzo[b][1,4]-oxazines, and morpholines, in exellent ee's and yields. The protocol features readily available starting materials, mild reaction conditions, and a broad substrate scope. Mechanistic investigation supports a tandem allylic substitution process.

Palladium-catalyzed allylic substitution, or "Tsuji-Trost"reactions, can be run under micellar catalysis conditions featuring not only chemistry in water but also numerous combinations of reaction partners that require low levels of palladium, typically on the order of 1000 ppm (0.1 mol %). These couplings are further characterized by especially mild conditions, leading to a number of cases not previously reported in an aqueous micellar medium. Inclusion of diverse nucleophiles, such as N-H heterocycles, alcohols, dicarbonyl compounds, and sulfonamides is described. Intramolecular cyclizations further illustrate the broad utility of this process. In addition to recycling studies, a multigram scale example is reported, indicative of the prospects for scale up.

B-Phenyl BIII subporphyrin-α-diones prepared in a three-step reaction sequence from the parent subporphyrin were condensed with 1,2-diaminobenzenes to give the corresponding quinoxaline-fused subporphyrins in variable yields. Quinoxaline-fused B-phenyl-5,10,15-triphenyl BIII subporphyrin was transformed to the corresponding subporphyrin-α-dione in the same three-step reaction sequence, which was then condensed with 1,2-diaminobenzene to give doubly quinoxaline-fused subporphyrin. These quinoxaline-fused subporphyrins exhibit redshifted absorption and fluorescence spectra compared with the parent one. A singly quinoxaline-fused subporphyrin bearing three meso-bis(4-dimethylaminophenyl)aminophenyl substituents shows blueshifted fluorescence in less polar solvent, which has been ascribed to emission associated with charge recombination of intramolecular charge transfer (CT) state.

Herein, we have reported the alkyl and alkoxy phenylacetylene containing phenazine fused triphenylene discotic liquid crystals (DLCs) which are obtained by the condensation reaction of triphenylene-1,2-diquinone with 1,2-diamino-4,5-dibromobenzene, followed by Sonogashira C–C coupling reaction with 4-alkyl-phenylacetylene or 4-alkoxy-phenylacetylene. Six novel derivatives were synthesized and evaluated for their thermal and optical properties. They show a broad range of hexagonal columnar phase and retain their mesophase up to room temperature upon cooling from the isotropic liquid. Thermotropic liquid crystalline properties of all the compounds were studied by polarised optical microscopy (POM), differential scanning calorimetry (DSC). The self-assembly of mesophase structure was investigated by X-ray diffraction (XRD) studies. Thermogravimetric analysis of all the mesogens shows good thermal stability over a broad temperature range. The photophysical properties of newly synthesized compounds were measured using UV–Vis absorption and photoluminescence emission spectroscopy in anhydrous chloroform solvent. The π-extended conjugation in these mesogens exhibit strong absorption bands falling around 270–487 nm and corresponding emission band at 657–663 nm respectively. The high delocalization of π– electrons in extended discotic mesogens show high nonlinear optical properties when measured under excitation by nanosecond laser pulses at 532 nm. These materials may find distinctive applications in the semiconducting devices.

A practical, concise and straightforward total synthesis of kealiiquinone 1, a naphtho[2,3-d]imidazole alkaloid obtained from the Micronesian marine sponge Leucetta sp. was accomplished. The squaric acid chemistry to construct the 1,4-quinoid ring and the regioselective N-methylation through a benzo[c][1,2,5]selenadiazolium heterocycle are the key features in this report. The full details of the representative approaches involving the different attempted synthetic strategies are also presented. Finally a successful total synthesis of this complex secondary metabolite is described.

Ring-closing metathesis (RCM) of ynamides, having alkene substituents of various lengths on the side chain, was demonstrated using the second-generation Grubbs catalyst. When the reaction of ene-ynamides was carried out in the presence of 5 mol% of the catalyst, RCM proceeded smoothly to give quinoline or isoquinoline derivatives having a dienamide unit in good yields. Furthermore, RCM of ene-ynamides, having one more carbon on the side chain, proceeded smoothly to provide seven-membered heterocycles having a dienamide component. Similarly, eight-membered heterocycles, diazocine and benzodiazocine, were also synthesized by RCM of ene-ynamides in good yields.

The post-cyclization strategy rather than the conventional ante-cyclotetramerization method was employed for the synthesis of multinuclear phthalocyanine-fused molecular nanoarrays. Reaction of 2,3,9,10,16,17-hexakis(2,6-dimethylphenoxy)-23,24-diaminophth

A Pd(II)-catalyzed aerobic intermolecular 1,2-diamination of conjugated dienes was developed for the regio- and chemoselective preparation of a variety of functionalized tetrahydroquinoxalines, using simple sulfonyl protected o-phenylendiamines as a nitrogen source. This methodology provides a direct and efficient synthesis of tetrahydroquinoxalines. O2 was used as the stoichiometric oxidant, and reaction conditions were applied to a series of o-phenylendiamines and conjugated dienes. 35 examples are described, and good yields and selectivities are obtained for the majority of the products.

Bis(sulfonamide) based synthetic carriers are reported for inversion of ion selectivity upon deviation of pH within a narrow window. A liposomal membrane potential is also generated when potassium ions are passively transported by these carriers.

The present invention relates to cyanated naphthalenebenzimidazole compounds of the formula (I) and mixtures thereof, in which R1, R 2, R 3, R 4, R5, R6, R7, R8, R9 and R10 are each independently hydrogen, cyano or aryl which is unsubstituted or has one o

2-Methylerythritol 2,4-cyclodiphosphate synthase (IspF) is an essential enzyme for the biosynthesis of isoprenoid precursors in plants and many human pathogens. The protein is an attractive target for the development of anti-infectives and herbicides. Using a photometric assay, a screen of 40 000 compounds on IspF from Arabidopsis thaliana afforded symmetrical aryl bis-sulfonamides that inhibit IspF from A. thaliana (AtIspF) and Plasmodium falciparum (PfIspF) with IC50 values in the micromolar range. The ortho-bis-sulfonamide structural motif is essential for inhibitory activity. The best derivatives obtained by parallel synthesis showed IC50 values of 1.4 μm against PfIspF and 240 nm against AtIspF. Substantial herbicidal activity was observed at a dose of 2 kg ha-1. Molecular modeling studies served as the basis for an in silico search targeted at the discovery of novel, non-symmetrical sulfonamide IspF inhibitors. The designed compounds were found to exhibit inhibitory activities in the double-digit micromolar IC50 range.

A simple and convenient method is reported for the synthesis of a series of sulphonamides in PEG-400 using potassium carbonate as the base. The reaction is carried out in a heterogeneous medium and consequently product recovery is simple. The desired products with a variety of aromatic amines could be synthesized in a short reaction time in good yield. The PEG could be recovered for reuse.

Four derivatives of the laminate acceptor ligand dipyrido-[3,2-a:2′,3′-c]phenazine (dppz) and their corresponding ruthenium complexes, [Ru(phen)2(dppzX2)]2+, were prepared and characterized by NMR spectroscopy, ESI-MS, and elemental analysis. The new ligands, generically denoted dppzX2, were symmetrically disubstituted on the distal benzene ring to give 10,13-dibromodppz (dppz-p-Br), 11,12-dibromodppz (dppz-o-Br), 10,13-dicyanodppz (dppz-p-CN), 11,12-dicyanodppz (dppz-o-CN). Solvated ground state MO calculations of the ruthenium complexes reveal that these electron-withdrawing substituents not only lower the LUMO of the dppz ligand (dppz(CN)22dppz), but that the para disubstitution results in a lower LUMO than the ortho disubstitution (dppz-p-CN(dppz-o-CN), and dppz-p-Brdppz-o-Br). The validity of the calculations was confirmed experimentally using cyclic voltammetry. Of the complexes evaluated in this study, only the dicyanodppz complexes showed multiple dppz-based reductions prior to reduction of the phen ligands. The capacity to form singly and doubly reduced dppz-based anions at modest reduction potentials was confirmed using a combination of spectroelectrochemical and chemical titration methods. When subjected to photolysis with visible light in the presence of a sacrificial donor, such as triethylamine, both cyano complexes showed multi-electron reduction. The other complexes only show a single reduction.

In search of supramolecular antenna systems for light-harvesting applications, we report on a short and effective synthesis of a fused NDI-zinc-salphen-based chromophore (salphen = bis-salicylimide phenylene) and its photophysical properties. A supramolec

A series of quinoxaline-fused [7]carbohelicenes (HeQu derivatives) was designed and synthesized to evaluate their structural and photophysical properties in the crystal state. The quinoxaline units were expected to enhance the light-emitting properties an

A photoreaction between benzoyl compounds, such as benzoylformate derivatives, and 2-(p-anisyl)-1,3-dimethylbenzimidazoline in the presence of allyl bromide was found to give various allylated alcohols. In the reaction of benzoylformates, α-hydroxy ester enolates, for which the negative charge occurs on the carbonyl carbon of benzoyl (umpolung reactivity), are proposed to be generated as intermediates by electron-transfer from benzimidazolines to the photoexcited benzoylformates; these species react with allyl bromide to produce α-allyl-α-hydroxy esters.

Quinoxalino[2′,3′:9,10]phenanthro[4,5-abc]phenazine (QPP) dyes have been studied as electron acceptor materials, fluorophores, and building blocks for self-organizing organic semiconductors. Condensation of tetraketopyrene with electron-rich diamino-terphenylene and -triphenylene derivatives generates new donor-acceptor QPP derivatives that display columnar mesomorphism over wide ranges of temperature; are fluorescent in solution, liquid crystal, and solid phases; and have electron acceptor properties. Also reported are the synthesis and properties of the first diamino-(tetraalkoxy) triphenylene as a valuable new synthon.

A bisoxamate ligand containing three different types of coordination sites was designed and synthesized. The developed synthetic strategy was adopted to prepare a related 1,2-bis(2-hydroxybenzamido)benzene-derived ligand. Nickel(ii) complexes of both the

RuII complexes incorporating both amide-linked bithiophene donor ancillary ligands and laminate acceptor ligands; dipyrido[3,2-a:2′, 3′-c]phenazine (dppz), tetrapyrido[3,2-a:2′,3′-c: 3′′,2′′-h:2′′′,3′′′- j]phenazine (tpphz), and 9,11,20,22-tetr

The invention relates to bimetallic complexes in which the ligand contains a salophen unit which complexes copper, manganese or cobalt and a phenanthroline unit which complexes palladium and the two systems are linked by a continuous conjugated system. The invention further relates to the use of these bimetallic complexes as catalysts for the oxidative carbonylation of aromatic hydroxy compounds to form diaryl carbonates, a process for preparing diaryl carbonates using the bimetallic complex as catalyst and also diaryl carbonates prepared by oxidative carbonylation of aromatic hydroxy compounds using the bimetallic complexes of the invention as catalysts.

A series of linear and star-shaped pyrazine-containing acene molecules 1a-b, 2a-b and 3 substituted by dicarboximide groups are synthesized via condensation reactions between o-diamine and dione. High electron affinity (up to 4.01 eV) is achieved due to t

A novel asymmetric ligand 2-(pyridine-2-yl)-1-H-imidazo[4,5-i]dibenzo[2,3- a:2′,3′-c]phenazine (pidbp) and its ruthenium complexes [Ru(L) 2(pidbp)]2+ (L = bpy (2, 2′- bipyridine), phen (1, 10 - phenanthroline)), have been synthesized

In ongoing studies on the role of the individual bromine atoms of 4,5,6,7-tetrabromobenzotriazole (TBBt) in its relatively selective inhibition of protein kinase CK2α, we have prepared all the possible two mono-, four di-, and two tri-bromobenzotriazoles and determined their physicochemical properties in aqueous medium. They exhibited a general trend of a decrease in solubility with an increase in the number of bromines on the benzene ring, significantly modulated by the pattern of substitution. For a given number of attached bromines, this was directly related to the electronic effects resulting from different sites of substitution, leading to marked variations of pK a values for dissociation of the triazole proton. Experimental data (pKa, solubility) and ab initio calculations demonstrated that hydration of halogenated benzotriazoles is driven by a subtle balance of hydrophobic and polar interactions. The combination of QM-derived free energies for solvation and proton dissociations was found to be a reasonably good predictor of inhibitory activity of halogenated benzotriazoles vs CK2α. Since the pattern of halogenation of the benzene ring of benzotriazole has also been shown to be one of the determinants of inhibitory potency vs some viruses and viral enzymes, the present comprehensive description of their physicochemical properties should prove helpful in efforts to elucidate reaction mechanisms, including possible halogen bonding, and the search for more selective and potent inhibitors.

The design and synthesis of two novel quinoxalinophenanthrophenazine-based anion sensors are reported. Binding studies of these sensors with an array of mono- and polyatomic anions using UV-vis, fluorescence, and NMR titrations have shown 1:1 and 1:2 sens

"Chemical Equation Presented" The synthesis and characterization of a highly fluorescent core-substituted naphthalene diimide sensor (φ = 0.34) bearing a bis-sulfonamide group is described. The compound shows a unique selectivity and reactivity for the fl

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(Chemical Equation Presented) A series of 47 novel N1-alkylated- 2-aryl-5(6)-substituted-1H-benzimidazoles and their three novel indole analogues were synthesized and evaluated for in vitro antifungal activities against Candida species by the tube dilution method. The results showed that compounds 79 and 80, having pyridine at the position C-2, of benzimidazoles exhibited the greatest activity with MIC values of 6.25-3.12 μg/mL. Indole analogues 108-110 have no inhibitory activity.

Figur Presented Allylic allenic amides have been synthesized via a copper-catalyzed cross-coupling between allylic sulfonamides and bromoallenes in moderate to good yields. Copper(I) thiophene-2-carboxylate (CuTC) was used a source of copper with DMEDA as the ligand. The allenylated products obtained are potential substrates for palladium-catalyzed carbocyclizations.

Selective reduction of carbonyl amides from key tetraamido intermediate 12 afforded an unprecedented N-substituted 1,2-diamino-4,5-diamidobenzene (13) and/or the first member (14) of a new family of unsymmetrical 12π-electron quinonediimines. Wiley-VCH Ve

A process for producing an amine which is characterized by reacting an imine with a nucleophilic compound (except a trialkylsilyl vinyl ether) in the presence of a phosphoric acid derivative represented by the formula (1): wherein A1 represents a spacer; X1 and X2 represent each independently a divalent nonmetal atom or a divalent nonmetal atomic group; and Y1 is oxygen or sulfur. The invention provides a process by which amines (particularly optically active amines) useful as intermediates of medicines, agricultural chemicals, or the like can be produced without special post-treatment in high yield at high optical purity; and phosphoric acid derivatives (particularly optically active phosphoric acid derivatives) useful in the production of the amines.

Two artificial receptors, 1,2-bis-p-substituted phenyl-sulfonamido-4,5-bis-nitrobenzene, have been designed and synthesized. The interactions of these receptors with halide anions are determined by UV-vis and 1H NMR titration experiments. Resul

The crystal structures of 1,2-bis(N-benzenesulfonylamino)benzenes with secondary and/or tertiary sulfonamide groups were determined by X-ray crystallographic analysis. Every Ar-sulfonamide group existed in synclinal conformation in the crystals even thoug

In the photoreaction of benzophenones with 1,3-dimethyl-2- phenylbenzimidazoline (DMPBI), benzhydrols were major products. Addition of H2O accelerated the reaction with no change in the product distribution, while AcOH, PhOH, and metal salts such as LiClO4 and Mg(ClO4)2 were effective additives to produce benzpinacols. In contrast, benzpinacols were exclusively formed regardless of the solvent and the additive in the reactions with 2-(o-hydroxyphenyl)-1,3- dimethylbenzimidazoline (o-HPDMBI). These observations are consistent with the hypothesis that DMPBI.+ donates a proton at the C2 position to the benzophenone ketyl radicals while o-HPDMBI.+ donates a phenol proton.

An isomerization-ring-closing metathesis (RCM) strategy afforded N-substituted 4H-1,4-benzoxazines from the protected N-allyl-2-(allyloxy) anilines. In addition, RCM was used to synthesize the N-substituted, 8-membered benzo-fused heterocycles from the re

(Matrix presented) 1,2-Bis(N-benzenesulfonyl-N-methylamino)benzene (2), which has no fixed asymmetric element, was crystallized from ethyl acetate as chiral crystals belonging to space group P41212 (No. 92) or P4321/

Condensation of o-phenylenediamine 1 with benzoyl chloride in pyridine results in the formation of dibenzoyl derivative 2 irrespective of the molar ratios employed. However, the reaction of 1 with arylsulphonyl chlorides gives a mono 3 and diarylsulphonyl

3-Arylsulfonylamido-N-arylsulfonyl-1,4-benzoquinonimines are produced by oxidation of 1,2-diarylsulfonylbenzenes with phenyliodosodiacetate in the presence of boron(III) fluoride etherate. Addition of hydrogen chloride and oxidation with lead tetraacetate