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111.
Harry Biller Swantje Lerch Katharina Tölke Dr. Hans-Georg Stammler Prof. Dr. Berthold Hoge Prof. Dr. Thomas Strassner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(53):13325-13329
We synthesized new imidazolium-based tunable aryl alkyl ionic liquids (TAAILs) with the weakly coordinating tetrakis(pentafluoroethyl)gallate anion, [Ga(C2F5)4]−. Phenyl and phenyl derivatives (2-Me, 4-OMe, 2,4-F) were combined with varying alkyl chain lengths at the imidazolium core leading to TAAILs, which were investigated with regard to their viscosity, conductivity, and electrochemical window and compared to EMIM and BMIM standard cations. Remarkable low viscosities of 29 cP at 25 °C for [BMIM][Ga(C2F5)4] were achieved. However, the EMIM and BMIM gallates show electrochemical instability, releasing pentafluoroethane at a voltage of 1.5 V. The 2-Me-substituted gallate-TAAILs slowly decompose over several weeks, whereas all other gallate-TAAILs showed no decomposition at all. With electrochemical windows of up to 5.15 V and low viscosities in a range of 66–162 cP, the gallate-TAAILs are promising candidates as electrolytes in electrochemical applications. 相似文献
112.
Harry R. Hudson Rosalind J. Lee 《Phosphorus, sulfur, and silicon and the related elements》2014,189(7-8):1149-1155
AbstractReports on the anticancer activity of representative α-aminophosphonic acid derivatives are briefly reviewed, with comments where possible on modes of action. Preliminary in vitro screening results are also presented for selected dialkyl α-aryl (or heteroaryl)-α-(diphenylmethylamino)methanephosphonates against the National Cancer Institute (NCI) 60-cell line panel of human tumor cells, which showed average response parameters for active compounds of GI50 between 4.81 × 10?6 and 2.40 × 10?5 M, TGI between 1.88 and 6.28 × 10?5 M, and LC50 between 5.71 and 9.37 × 10?5 M. The highest activity was shown by the α-phenyl compound for which GI50 10?7 M was recorded against leukemia cell line MOLT-4. 相似文献
113.
Sylvestre P. J. T. Bachollet Dean C. Cocker Harry Adams Prof. Joseph P. A. Harrity 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(40):12889-12893
The aza‐Diels–Alder cycloaddition of 1,2,4‐triazines with alkynes offers a rapid and convenient method for the synthesis of highly substituted pyridines, but often requires harsh conditions and long reaction times. The present study offers a solution to these limitations by use of a temporary tether established by a Lewis acid–base complexation of in situ generated alkynylboranes and triazines bearing a Lewis basic donor. The cycloaddition reactions take place within 20 min at 40 °C and provide direct access to a broad range of pyridines with complete and predictable regiocontrol. The carbon?boron bond can be further functionalised by cross‐coupling allowing further functionality to be introduced after cycloaddition. 相似文献
114.
Pengpeng Liu Dr. Patrik Neuhaus Dr. Dmitry V. Kondratuk Prof. T. Silviu Balaban Prof. Harry L. Anderson 《Angewandte Chemie (International ed. in English)》2014,53(30):7770-7773
α‐ and β‐Cyclodextrins have been used as scaffolds for the synthesis of six‐ and seven‐legged templates by functionalizing every primary CH2OH with a 4‐pyridyl moiety. Although these templates are flexible, they are very effective for directing the synthesis of macrocyclic porphyrin oligomers consisting of six or seven porphyrin units. The transfer of chirality from the cyclodextrin templates to their nanoring hosts is evident from NMR and circular dichroism spectroscopy. Surprisingly, the mean effective molarity for binding the flexible α‐cyclodextrin‐based template within the six‐porphyrin nanoring (74 M ) is almost as high as for the previously studied rigid hexadentate template (180 M ). The discovery that flexible templates are effective in this system, and the availability of a template with a prime number of binding sites, open up many possibilities for the template‐directed synthesis of larger macrocycles. 相似文献
115.
Subhi A. Al-Jibori Rawaa A. Q. Al-Nassiry Ghassan H. H. Al-Jibori Kurt Merzweiler Christoph Wagner Harry Schmidt Sucharita Basak-Modi Graeme Hogarth 《Transition Metal Chemistry》2014,39(7):735-740
Reaction of Na2[PdCl4] with two equivalents of amino- or acetylamino-pyridines (LH) affords trans-[PdCl2-(LH)2] {LH = 2-amino-3-methylpyridine (2-ampyH), 3-aminopyridine (3-apyH), 2-acetylamino-3-methylpyridine (2-acmpyH), 3-acetylamino-pyridine (3-acpyH)}. An X-ray crystal structure of trans-[PdCl2(2-ampyH)2] shows that the 2-ampy-H ligands are coordinated in a monodentate fashion via the nitrogen atoms of the pyridine rings. Treatment of trans-[PdCl2(2-acmpyH)2] with NEt3 affords the cyclometalated complex, trans-[Pd(κ2-2-acmpy)2], the X-ray structure of which shows that the 2-acmpy ligand is coordinated to palladium in a bidentate fashion via the nitrogen atom of the pyridine ring and oxygen. Reaction of trans-[PdCl2(LH)2] with two equivalents of sodium saccharinate affords the bis(saccharinate) complexes, trans-[Pd(sac)2(LH)2], in which the saccharinate anions are coordinated via the amide nitrogen atom. 相似文献
116.
Angelina Osipyan Dr. Shabnam Shaabani Robert Warmerdam Dr. Svitlana V. Shishkina Harry Boltz Prof. Dr. Alexander Dömling 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(30):12523-12527
Miniaturization and acceleration of synthetic chemistry is an emerging area in pharmaceutical, agrochemical, and materials research and development. Herein, we describe the synthesis of iminopyrrolidine-2-carboxylic acid derivatives using chiral glutamine, oxo components, and isocyanide building blocks in an unprecedented Ugi-3-component reaction. We used I-DOT, a positive-pressure-based low-volume and non-contact dispensing technology to prepare more than 1000 different derivatives in a fully automated fashion. In general, the reaction is stereoselective, proceeds in good yields, and tolerates a wide variety of functional groups. We exemplify a pipeline of fast and efficient nanomole-scale scouting to millimole-scale synthesis for the discovery of a useful novel reaction with great scope. 相似文献
117.
Dr. John A. Seed Dr. Helen R. Sharpe Harry J. Futcher Dr. Ashley J. Wooles Prof. Dr. Stephen T. Liddle 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16004-16008
Treatment of [Ph3EMe][I] with [Na{N(SiMe3)2}] affords the ylides [Ph3E=CH2] (E=As, 1As ; P, 1P ). For 1As this overcomes prior difficulties in the synthesis of this classical arsonium-ylide that have historically impeded its wider study. The structure of 1As has now been determined, 45 years after it was first convincingly isolated, and compared to 1P , confirming the long-proposed hypothesis of increasing pyramidalisation of the ylide-carbon, highlighting the increasing dominance of E+−C− dipolar resonance form (sp3-C) over the E=C ene π-bonded form (sp2-C), as group 15 is descended. The uranium(IV)–cyclometallate complex [U{N(CH2CH2NSiPri3)2(CH2CH2SiPri2CH(Me)CH2)}] reacts with 1As and 1P by α-proton abstraction to give [U(TrenTIPS)(CHEPh3)] (TrenTIPS=N(CH2CH2NSiPri3)3; E=As, 2As ; P, 2P ), where 2As is an unprecedented structurally characterised arsonium-carbene complex. The short U−C distances and obtuse U-C-E angles suggest significant U=C double bond character. A shorter U−C distance is found for 2As than 2P , consistent with increased uranium- and reduced pnictonium-stabilisation of the carbene as group 15 is descended, which is supported by quantum chemical calculations. 相似文献
118.
P. R. Srikanth Sharma Peiguang Zhou Harry L. Frisch 《Journal of polymer science. Part A, Polymer chemistry》1996,34(6):1049-1058
We report the synthesis and characterization of interpenetrating polymer networks (IPNs) exhibiting nonlinear optical (NLO) properties. The network consists of aliphatic polycarbonate urethane (PCU) and poly(methyl methacrylate-co-N,N-disubstituted urea), with a nonlinear optical (NLO) chromophore incorporated into N,N-disubstituted urea. The full IPNs have only one Tg, as determined by differential scanning calorimetry (DSC), together with scanning electron microscopy (SEM) observations, suggest a single phase morphology. The thin films of IPNs are transparent and the unpoled samples produced second harmonic generation (SHG) signals at room temperature. This result indicates that the NLO chromophore is oriented noncentrosymmetrically during the IPN formation process and is tightly held between the permanent entanglements of the two component networks of the IPN. © 1996 John Wiley & Sons, Inc. 相似文献
119.
Maren Lorenzen Peter Bsecke Christian Riekel Karen Reynders Harry Reynaers Noel Overbergh 《Macromolecular rapid communications》1996,17(3):189-192
Small-angle X-ray scattering using synchrotron radiation at pressures up to 700 MPa has been performed on triblock-copolymer gels, polystyrene-rubber-polystyrene with poly(ethylene/butylene) as the rubber mid-blocks. A 2-stage pressure behaviour could be verified by comparison of the experimental data with the Tait-equation and a model of pressure screening. 相似文献
120.
Saturation-transfer difference (STD)-NMR spectroscopy has been widely used to screen potential ligands for binding to large receptor molecules. The STD-NMR experiment is typically based on a proton NMR spectrum, which can suffer from spectral overlap, leading to missing information in STD-based epitope mapping. Two-dimensional STD-NMR experiments can alleviate spectral overlap, but are time consuming. Here, we examine the feasibility of saturating protons in a receptor molecule and observing the STD effect on nearby carbon nuclei after transferring polarization from protons to carbons using the insensitive nuclei enhanced by polarization transfer (INEPT) pulse sequence. We show that under favorable conditions, a 1H→13C STD-INEPT experiment can give information similar to that obtained from a two-dimensional heteronuclear experiment, but in significantly less time. The STD-INEPT experiment could be especially useful when studying mixtures of ligands in which the peak positions in the proton and HSQC spectrum change significantly, and in particular, when using high-throughput, automated methods to analyze the data. 相似文献