- Synthesis, Crystal Structure, and Photophysical Properties of Nickel Complex from Triphenylamine Schiff Base Ligand
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A novel Schiff base ligand L and its mononuclear nickel complex Ni(L)2(SCN)2 were designed, synthesized and characterized by elemental analysis, IR spectra, MS, 1H-NMR spectroscopy, and single-crystal X-ray diffraction analysis. The crystals of L and Ni(L)2(SCN)2 belong to orthorhombic crystal system with the space group of P212121 for L and Pbcn for Ni(L)2(SCN)2, respectively. The center atom Ni(II) is coordinated with six nitrogen atoms in a distorted octahedron coordination environment. The four N atoms of them are from the two independent ligands and the other two nitrogen atoms from two SCN-. Their photophysical properties of the ligand and its Ni(II) complex were investigated and interpreted on the basis of theoretical calculations (TD-DFT).
- Chen, Jiang,Wang, Hui,Jin, Zhepeng,Gao, Bingfei,Wu, Jieying,Tian, Yupeng
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- Divergent synthesis and biological evaluation of 2-(trifluoromethyl)pyridines as virulence-attenuating inverse agonists targeting PqsR
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A short and divergent route towards new derivatives of 2-(trifluoromethyl)pyridines as potent inverse agonists of the bacterial target PqsR against Pseudomonas aeruginosa (PA) infections is described. This Gram-negative pathogen causes severe nosocomial infections and common antibiotic treatment options are rendered ineffective due to resistance issues. Based on an earlier identified optimized hit, we conducted derivatization and rigidification attempts employing two central building blocks. The western part of the molecule is built up via a 2-(trifluoromethyl)pyridine head group equipped with a terminal alkyne. The eastern section is then introduced through aryliode motifs exploiting Sonogashira as well as Suzuki-type chemistry. Subsequent modification provided quick access to an array of compounds, allowed for deep SAR insights, and enabled to optimize the hit scaffold into a lead structure of nanomolar potency combined with favorable in vitro ADME/T features.
- Abdelsamie, Ahmed S.,Bauer, Maximilian,Blankenfeldt, Wulf,Empting, Martin,Hamed, Mostafa,Hodzic, Amir,Kany, Andreas M.,Schmelz, Stefan,Scrima, Andrea,R?hrig, Teresa,Schütz, Christian
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- Organic hole transport material and preparation method and application thereof
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The invention provides an organic hole transport material and a preparation method and application thereof. The structural general formula of the organic hole transport material is shown in the specification, and in the formula, R is ethyl, propyl, isopropyl or butyl. The preparation method is simple and easy to implement, the structure is definite, and the prepared organic hole transport materialhas high photoelectric conversion efficiency and can be applied to perovskite solar cells.
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Paragraph 0033-0035
(2019/07/01)
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- Carbon Dioxide as a Directing Group for C-H Functionalization Reactions Involving Lewis Basic Amines, Alcohols, Thiols, and Phosphines for the Synthesis of Compounds
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Methods of synthesizing compounds using CO2 as a directing group for C—H functionalization, and compounds made thereby, are described.
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Paragraph 0132
(2019/07/03)
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- Photocatalytic Oxidative Iodination of Electron-Rich Arenes
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A visible-light-mediated oxidative iodination of electron-rich arenes has been developed. 2.5 mol% of unsubstituted anthraquinone as photocatalyst were used in combination with elementary iodine, trifluoroacetic acid and oxygen as the terminal oxidant. The iodination proceeds upon irradiation in non- or weakly-electron donating solvents (DCM, DCE and benzene) wherein a spectral window in strongly coloured iodine solutions can be observed at around 400 nm. The method provides good to excellent yields (up to 98%) and shows excellent regioselectivity and good functional group tolerance (triple bonds, ketone, ester, amide). Moreover, the photo-iodination was also upscaled to a 5 mmol scale (1.1 g). Mechanistic investigations by intermediate trapping and competition experiments indicate a photocatalytic arene oxidation and the subsequent reaction with iodine as a likely mechanistic pathway. (Figure presented.).
- Narobe, Rok,Düsel, Simon J. S.,Iskra, Jernej,K?nig, Burkhard
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supporting information
p. 3998 - 4004
(2019/07/17)
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- Effect of alkyl chain length on the properties of triphenylamine-based hole transport materials and their performance in perovskite solar cells
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A new series of diacetylide-triphenylamine (DATPA) derivatives with five different alkyl chains in the para position, MeO, EtO, nPrO, iPrO and BuO, were synthesised, fully characterised and their function as hole-transport materials in perovskite solar cells (PSC) studied. Their thermal, optical and electrochemical properties were investigated along with their molecular packing and charge transport properties to analyse the influence of different alkyl chains in the solar cell parameters. The shorter alkyl chain facilitates more compact packing structures which enhanced the hole mobilities and reduced recombination. This work suggests that the molecule with the methoxy substituent (MeO) exhibits the best semiconductive properties with a power conversion efficiency of up to 5.63%, an open circuit voltage (Voc) of 0.83 V, a photocurrent density (Jsc) of 10.84 mA cm-2 and a fill factor of 62.3% in perovskite solar cells. Upon replacing the methoxy group with longer alkyl chain substituents without changing the energy levels, there is a decrease in the charge mobility as well as PCE (e.g. 3.29% for BuO-DATPA). The alkyl chain length of semiconductive molecules plays an important role in achieving high performance perovskite solar cells.
- Fuentes Pineda, Rosinda,Troughton, Joel,Planells, Miquel,Sanchez-Molina Santos, Irene,Muhith, Farmin,Nichol, Gary S.,Haque, Saif,Watson, Trystan,Robertson, Neil
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p. 1252 - 1260
(2018/01/17)
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- Carbon Dioxide-Mediated C(sp3)-H Arylation of Amine Substrates
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Elaborating amines via C-H functionalization has been an important area of research over the past decade but has generally relied on an added directing group or sterically hindered amine approach. Since free-amine-directed C(sp3)-H activation is still primarily limited to cyclization reactions and to improve the sustainability and reaction scope of amine-based C-H activation, we present a strategy using CO2 in the form of dry ice that facilitates intermolecular C-H arylation. This methodology has been used to enable an operationally simple procedure whereby 1° and 2° aliphatic amines can be arylated selectively at their γ-C-H positions. In addition to potentially serving as a directing group, CO2 has also been demonstrated to curtail the oxidation of sensitive amine substrates.
- Kapoor, Mohit,Liu, Daniel,Young, Michael C.
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supporting information
p. 6818 - 6822
(2018/05/31)
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- A method of preparing alkoxyl monoiodo-benzene
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The invention relates to a method for preparing alkoxy iodobenzene. The method comprises the following steps: adding alkoxy benzene, I2, the catalyst nitrosonium tetrafluoroborate and an organic solvent into a reaction vessel, sealing the reaction vessel, performing a magnetic stirring reaction at the temperature of 20-60 DEG C under an airy condition, cooling to the room temperature after reaction, and performing purification on the mixture after reaction through column chromatography, so as to obtain the alkoxy iodobenzene. According to the method for preparing the alkoxy iodobenzene, any other auxiliary reagent is not added expect the catalyst and the solvent, used auxiliary material is less, the utilization rate of the iodine material under the optimum condition is high, the product purity is good, the reaction can be effectively performed at the room temperature, the production cost is remarkably reduced, and as acid is not added in the reaction system, the cost of production equipment can be lowered.
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Paragraph 0043; 0044
(2016/10/31)
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- Synthesis, crystal structures, and two-photon absorption of a series of cyanoacetic acid triphenylamine derivatives
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A specific series of chromophores (CN1, CN2, CN3, and CN4) have been synthesized, in which contained a triphenylamine moiety as the electron donor (D), a cyanoacetic acid moiety as the electron acceptor (A), vinylene or phenylethyne as the π-bridge, and ethyoxyl groups as auxiliary electron donor (D′) to construct the D-π-A or D′-D-π-A molecular configuration. Photophysical properties of them were systematically investigated. These results show that the chromophores display a solvatochromism (blue shift) and large Stokes shifts for their absorption bands with increasing polarity of the solvent. Furthermore, the chromophore CN4 shows the strongest intensity of two-photon excited fluorescence and largest two-photon absorption cross section (2783 GM) in the near infrared region. Finally, the connections between the structures and properties are systematically investigated relying on the information from linear and nonlinear optical properties, crytsal structures and quantum chemical calculation.
- Hao, Fuying,Li, Dandan,Zhang, Qiong,Li, Shengli,Zhang, Shengyi,Zhou, Hongping,Wu, Jieying,Tian, Yupeng
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supporting information
p. 867 - 878
(2015/07/02)
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- A series of triphenylamine-based two-photon absorbing materials with AIE property for biological imaging
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A specific series of D-π-A (1A-3A) and D-π-A (1B-3B) structural chromophores with various electron donors and π-conjugated bridges were designed, synthesized, and fully characterized. Their crystal structures were determined by single crystal X-ray diffraction analysis. The one/two-photon absorption properties of the chromophores have been successfully tuned by using different electron donors and π-bridges. Interestingly, it was found that chromophore 3B shows quite weak fluorescence in pure DMSO, while a significant AIE (aggregation-induced emission) effect is observed in water-DMSO (v/v 90%) mixtures with a sharp increase in fluorescence intensity of about 11 times. Furthermore, chromophore 3B shows strong two-photon excited fluorescence (TPEF) and has a large 2PA action cross-section (394 GM). The results of live-cell imaging experiments show that 3B can be effectively used as a bio-imaging probe in two-photon fluorescence microscopy towards HepG2 cells in vitro. The TPEF images of 3B not only exhibit cellular cytosol uptake but also exhibit actin regulatory protein uptake which are different from OPEF images.
- Liu, Yanqiu,Kong, Ming,Zhang, Qiong,Zhang, Zhiwen,Zhou, Hongping,Zhang, Shengyi,Li, Shengli,Wu, Jieying,Tian, Yupeng
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supporting information
p. 5430 - 5440
(2014/08/18)
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- Aggregation-induced and crystallization-enhanced emissions with time-dependence of a new Schiff-base family based on benzimidazole
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A new Schiff-base family containing [4-(1H-benzimidazole-2-yl)-phenyl]-bis- (4-ethoxy-phenyl)-amine has been synthesized through a condensation reaction. All the derivatives possess properties of aggregation-induced and crystallization-enhanced emission (AIE and CEE), which show time-dependent characteristics at a concentration of 10 μM and are studied in detail by scanning electron microscope (SEM) and transmission electron microscope (TEM). Different aggregation forms and the growth of crystals of the compounds, could be responsible for the notably different degrees of fluorescence enhancement.
- Cao, Yuanle,Yang, Mingdi,Wang, Yang,Zhou, Hongping,Zheng, Jun,Zhang, Xiuzhen,Wu, Jieying,Tian, Yupeng,Wu, Zongquan
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p. 3686 - 3694
(2014/05/06)
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- An in situ acidic carbon dioxide/glycol system for aerobic oxidative iodination of electron-rich aromatics catalyzed by Fe(NO3)3·9H2O
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An environmentally benign CO2/glycol reversible acidic system was developed for the iron(iii)-catalyzed aerobic oxidative iodination of electron-rich aromatics without the need for any conventional acid additive or organic solvent. Notably, moderate to high isolated yields (up to 97%) of the aryl iodides were attained with comparable regioselectivity when ferric nitrate nonahydrate was used as the catalyst with molecular iodine under 1 MPa of CO2.
- Ma, Ran,Huang, Cheng-Bin,Liu, An-Hua,Li, Xue-Dong,He, Liang-Nian
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p. 4308 - 4312
(2015/01/08)
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- Nitrogen dioxide-catalyzed electrophilic iodination of arenes
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Nitrogen dioxide is demonstrated to be an effective catalyst precursor for the iodination of alkoxy-substituted benzenes and naphthalenes. Different from the transition metal catalysts, nitrogen dioxide can be easily separated from the final products, and is free of heavy metal waste. Although the present catalyst precursor is toxic, it does not stain the final products due to its low-boiling character. No other reagents apart from 0.5 equiv. of iodine (I 2), 6.5 mol% nitrogen dioxide and acetonitrile solvent were used in the iodination, and basically all the iodine atoms in the iodine source were transferred to the iodination products, showing that the presented protocol is highly atom-economic and practical. Copyright
- Ren, Yun-Lai,Shang, Huantao,Wang, Jianji,Tian, Xinzhe,Zhao, Shuang,Wang, Qian,Li, Fuwei
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supporting information
p. 3437 - 3442
(2013/12/04)
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- Synthesis of diphenyl-diacetylene-based nematic liquid crystals and their high birefringence properties
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We synthesized two series of diphenyl-diacetylene (DPDA)-based materials with alkoxy and alkyl tails of length m (DPDA-OCm and DPDA-Cm, respectively), and measured their nematic-phase birefringence (Δn) as a function of wavelength and temperature. We found that Δn decreases with an increase in m, possibly by a dilution effect of the low-Δn alkyl tail. Further, of the two series, Δn was found to be relatively higher in the DPDA-OCm materials, with the highest value of 0.4 obtained for DPDA-OC1 at 550 nm at 10 °C below the isotropic-to-nematic transition temperature. Further, we observed the temperature dependence for Δn, which is proportional to the order parameter (s). From extrapolation to s = 1 (the perfect orientation state), it is speculated that the DPDA-O moiety has the potential to afford a very large Δn of 0.9. The Royal Society of Chemistry 2012.
- Arakawa, Yuki,Nakajima, Shunpei,Ishige, Ryohei,Uchimura, Makoto,Kang, Sungmin,Konishi, Gen-Ichi,Watanabe, Junji
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scheme or table
p. 8394 - 8398
(2012/07/28)
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- Solid-phase combinatorial synthesis of ester-type banana-shaped molecules by sequential palladium-catalyzed carbonylation
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16 five-ring ester-type Br-substituted banana-shaped molecules were synthesized in a combinatorial manner using palladium-catalyzed carbonylative esterification on a polymer-support and their mesophase behavior was investigated. The Royal Society of Chemistry 2009.
- Yoshida, Masahito,Doi, Takayuki,Kang, Sungmin,Watanabe, Junji,Takahashi, Takashi
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supporting information; experimental part
p. 2756 - 2758
(2009/12/03)
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- An improved Cu-based catalyst system for the reactions of alcohols with aryl halides
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(Chemical Equation Presented) The use of 3,4,7,8-tetramethyl-1,10- phenanthroline (Me4Phen) as a ligand improves the Cu-catalyzed cross-coupling reactions of aryl iodides and bromides with primary and secondary aliphatic, benzylic, allylic, and propargylic alcohols. Most importantly, by employing this catalyst system, the need to use an excessive quantity of the alcohol coupling partner is alleviated. The relatively mild conditions, short reaction times, and moderately low catalyst loading allow for a wide array of functional groups to be tolerated on both the electrophilic and nucleophilic coupling partners.
- Altman, Ryan A.,Shafir, Alexandr,Choi, Alice,Lichtor, Phillip A.,Buchwald, Stephen L.
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p. 284 - 286
(2008/09/17)
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- Regioselective iodination of activated arenes using phenyl trimethylammonium dichloroiodate in ionic liquid under microwave irradiation
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The regioselective iodination of activated arenes has been achieved in the presence of phenyltrimethylammonium dichloroiodate and ionic liquid. The reaction has been carried out by both conventional heating as well as by microwave irradiation. Copyright Taylor & Francis, Inc.
- Tilve, Rutuja D.,Kanetkar, Vinod R.
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p. 1313 - 1318
(2007/10/03)
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- A comparison of microwave-accelerated and conventionally heated iodination reactions of some arenes and heteroarenes, using ortho-periodic acid as the oxidant
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A fast and simple method for the oxidative iodination of some activated arenes and heteroarenes, either under microwave irradiation or by conventional heating, is reported, using diiodine and ortho-periodic acid as the oxidant. The reactions were carried out in hot 95% ethanol under a reflux condenser. For the microwave assisted reactions, the reaction times were always notably shortened, but the yields were nearly the same as those afforded by the conventional method.
- Sosnowski, Maciej,Skulski, Lech
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p. 401 - 406
(2007/10/03)
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- Solvent-Free Iodination of Arenes at Room Temperature
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Silica supported bismuth(III)nitrate pentahydrate [BNP-SiO2] was prepared under simple co-grinding condition. The iodination of aromatic compounds using BNP-SiO2 and molecular iodine under solvent-free conditions is described. The reaction occurred in the solid state at room temperature, yielding the corresponding mono-iodo derivative in good yields. However, less activated aromatics required longer reaction time with comparatively less yield.
- Alexander, Varughese M.,Khandekar, Amit C.,Samant, Shriniwas D.
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p. 1895 - 1897
(2007/10/03)
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- Iodination of activated arenes using silfen: An improved protocol
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A simple and direct method for the iodination of activated arenes, using molecular iodine and silfen (silica supported ferric nitrate nonahydrate) as an oxidant, is presented. The reactions are performed at 20°C in dichloromethane. The method provides an easy access to the corresponding iodinated products in good yields. The observed orientation effects are in agreement with those based on general aromatic electrophilic substitution theory.
- Tilve, Rutuja D.,Alexander, Varughese M.,Khadilkar, Bhushan M.
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p. 9457 - 9459
(2007/10/03)
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- Piperazine compounds as inhibitors of MMP or TNF
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A compound of formula (I) wherein A is a sulfonyl or a carbonyl; R1is an optionally substituted aryl, an optionally substituted heterocyclic group, an optionally substituted lower alkyl or an optionally substituted lower alkenyl; R2is a hydrogen, an optionally substituted lower alkyl, an optionally substituted aryl or an optionally substituted heterocyclic group; R3is an optionally substituted lower alkyl, an optionally substituted lower alkoxy, an optionally substituted aryloxy, an optionally substitued lower alkenyl, an optionally substituted aryl, an optionally substituted heterocyclic group or an optionally substitued amino; R4is a hydrogen, an optionally substituted lower alkyl, an optionally substituted aryl or an optionally substituted heterocyclic group; R5is a hydrogen, an optionally substituted lower alkyl, an optionally substituted aryl or an optionally substituted heterocyclic group; and R10is a hydroxy or a protected hydroxy, and a pharmaceutically acceptable salt thereof. The compound of the present invention is useful as a medicament for prophylactic and therapeutic treatment of MMP- or TNFα-mediated diseases.
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- Zinc(II) promoted conversion of aryltriazenes to aryl iodides and aryl nitriles
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Aryltriazenes react with zinc perchlorate/zinc cyanide to produces arylnitriles and react with zinc iodide to produce aryliodides. The reaction mechanism involves aryl radicals that have been trapped by addition to propenenitriles in a good preparative Meerwein arylation process.
- Patrick, Timothy B.,Juehne, Thomas,Reeb, Elmer,Hennessy, Daniel
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p. 3553 - 3554
(2007/10/03)
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- The reactivity of organothallium compounds. Kinetics and mechanism of iodination of diarylthallium salts by molecular iodine in dioxane
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The kinetics and mechanism of the reactions of diarylthallium trifluoroacetates with molecular iodine in dioxane solutions have been studied. The reaction has the overall second order with the first order with respect to each reagent. The effect of substi
- Gun'kin,Butin
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p. 448 - 452
(2007/10/03)
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- The direct iodination of arenes with chromium(VI) oxide as the oxidant
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An easy and cheap laboratory method is presented for the direct mono- and diiodination of a number of activated and deactivated arenes. The main iodination reactions occurred at the temperatures not exceeding 65°C for 0.5-12 h in the anhydrous, strongly acidic liquid system, I2/AcOH/Ac2O/H2SO4, in the presence of prior dissolved CrO3 used as the oxidant. The yields of the pure iodinated products varied from 31% (for 3,5- diiodobenzoic acid) up to 90% (for 4-iodoanisole). So far, benzonitrile and some oxidizable aromatics, e.g. naphthalene, fluorene, xanthene, and thiophene, have been found to be unsuitable for the effective iodination. Nevertheless, this novel, simple method of direct iodination is worthy to be extended to other appropriate aromatics.
- Lulinski, Piotr,Skulski, Lech
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p. 1665 - 1669
(2007/10/03)
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- Aromatic iodination of activated arenes and heterocycles with lead tetraacetate as the oxidant
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An easy, cheap and fairly quick laboratory method is presented for aromatic iodination of some highly activated arenes and heterocycles with molecular iodine in the presence of either pure lead tetraacetate dissolved in glacial acetic acid, or with the same oxidant but prepared in situ from Pb3O4 dissolved in hot AcOH/Ac2O prior to the iodination. 4-Bromo- and 2,4-dibromoanisoles are obtained from anisole by the respective oxidative bromination.
- Krassowska-Swiebocka,Lulinski,Skulski
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p. 926 - 928
(2007/10/02)
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- On the regioselectivity of palladium catalyzed cross-coupling reactions of alkenylsilanes: participation of β-cationic organosilicate-palladium species during the transmetallation
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The cross-coupling reaction promoted by a palladium catalyst and fluoride salt of 1--1-phenylethene (1) with substituted aryl iodides gave the unexpected cine-substitution products (E)-1-aryl-2-phenylethenes (3) along with the normal ipso-substitution product 1-aryl-1-phenylethene (2).The product ratios were strongly dependent on the electronic nature of the substituent on aryl iodides: ipso-substitution products (2) were favoured by an electron-withdrawing substituent, and cine-substitution products (3) by an electron-donating substituent.On the basis of these observations, the following mechanism of transmetallation of alkenyl(fluoro)silicates with arylpalladium is proposed: electrophilic attack of an arylpalladium complex on the olefinic α-carbon of an alkenyl(fluoro)silicate produces a β-cationic organosilicate-palladium species which then transfers the alkenyl group from silicon to the palladium complex. Key words: Silane; Palladium; Transmetallation; Regioselectivity
- Hatanaka, Yasuo,Goda, Ken-ichi,Hiyama, Tamejiro
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- Iodination of Aromatic Ethers by Use of Benzyltrimethylammonium Dichloroiodate and Zinc Chloride
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The reaction of aromatic ethers with benzyltrimethylammonium dichloroiodate(1-) in acetic acid in the presence of zinc chloride at room temperature gave iodo-substituted aromatic ethers in good yields.
- Kajigaeshi, Shoji,Kakinami, Takaaki,Moriwaki, Masayuki,Watanabe, Masakazu,Fujisaki, Shizuo,Okamoto, Tsuyoshi
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p. 795 - 798
(2007/10/02)
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