477-75-8Relevant academic research and scientific papers
Soluble Tetraaminotriptycene Precursors
White, Nicholas G.,MacLachlan, Mark J.
, p. 8390 - 8397 (2015)
An efficient route to soluble triptycene tetraamines, shape-persistent molecules containing two ortho-phenylenediamine motifs, is reported. These tetraamines are stable, prepared in good yields, easily purified by column chromatography, and can be readily condensed to give a range of imidazole and pyrazine derivatives.
Synthesis, Structure, and Complexation Properties of a C3-Symmetrical Triptycene-Based Anion Receptor: Selectivity for Dihydrogen Phosphate
Granda, Jaroslaw M.,Grabowski, Jakub,Jurczak, Janusz
, p. 5882 - 5885 (2015)
A new anion binding motif based on triptycene core has been synthesized from 2,7,14-trinitrotriptycene. Its well-defined binding pocket allowed for the selective recognition and sensing of dihydrogen phosphate in DMSO-d6 + 0.5% H2O.
THE ELECTRON SPIN RESONANCE OF THE RADICAL CATIONS OF P-TERPHENYL, TRIPHENYLENE AND TRIPTYCENE
Courtneidge, John L.,Davies, Alwyn G.,McGuchan, Deborah C.
, p. 190 - 196 (1988)
The ESR spectra of the radical cation of p-terphenyl (1), triphenylene (2), and triptycene (3) have been investigated in fluid solution. .The hyperfine coupling constants of 1+. are in line with those predicted on the simple Hueckel-McLachlan-McConnel model, and suggested that it is a simple near planar monomeric species.The radical cation from 2 formed an adduct with 2 and only the spectrum of the dimeric species 22+. could be detected.The ESR spectrum of 3+. is in accord with that predicted for the form of the SOMO, the bridgehesd protons showing only a very small hyperfine coupling.When 3+. is generated photolytically the presence of Hg(OCOCF3)2 or Tl(OCOCF3)3, the ESR spectra indicate that subsequent mercuration or thallation of 3+. occurs in the β-position.When AlCl3 is used as the reagent, 3+. can appereantly undergo a retro-Diels-Alder reaction, and the spectrum of 3+. becomes replaced by that of the anthracene radical cation.
Microwave-induced covalent functionalization of few-layer graphene with arynes under solvent-free conditions
Sulleiro,Quiroga,Pe?a,Pérez,Guitián,Criado,Prato
supporting information, p. 2086 - 2089 (2018/03/06)
A non-conventional modification of exfoliated few-layer graphene (FLG) with different arynes under microwave (MW) irradiation and solvent-free conditions is reported. The described approach allows reaching fast, efficient and mild covalent functionalization of FLG.
Anhydrous proton conduction in porous organic networks
Klumpen,Winterstein,Papastavrou,Senker
supporting information, p. 21542 - 21549 (2018/11/20)
Solid electrolyte separators within fuel cells enable efficient charge transport and prevent a mass bypass between the two half cells. Hydrated systems, like Nafion, reach unprecedented proton conductivities at ambient temperatures, but the demanding humidity management prevents their use beyond 80 °C, hence limiting the efficiency of current polymer-based systems. As such, water free and chemically inert, solid materials with excellent conductivities between 100 °C and 200 °C, are of high interest. A promising approach is the incorporation of heavier amphoteric molecules into micro- and mesoporous frameworks. Stronger host-guest interactions allow for higher temperatures, while still maintaining sufficient mobility and efficient transport pathways. Here, we present a systematic study investigating the influence of porosity, framework topology and dimensionality as well as framework functionality and charge carrier uptake on the proton conductivity for six porous organic networks (PONs) loaded with imidazole via gas phase adsorption. The resulting materials were thoroughly characterized by multinuclear NMR and IR spectroscopy and physisorption as well as powder X-ray diffraction and DSC experiments, revealing homogeneous distribution of the amphoteric guests within the pore structure. Electrochemical impedance spectroscopy up to 130 °C revealed remarkable conductivities of up to 10?3 S cm?1 under anhydrous conditions. We found 3D networks to favour high imidazole loading leading to high proton conductivities based on the Grotthuss mechanism. In contrast, 2D networks showed a lower guest molecule uptake and thus lower proton conductivities, which were governed by vehicle transport. Additional acid/base functionalities within the frameworks seem to have a negative effect on the proton conduction.
Pseudocyclic Arylbenziodoxaboroles: Efficient Benzyne Precursors Triggered by Water at Room Temperature
Yoshimura, Akira,Fuchs, Jonathan M.,Middleton, Kyle R.,Maskaev, Andrey V.,Rohde, Gregory T.,Saito, Akio,Postnikov, Pavel S.,Yusubov, Mekhman S.,Nemykin, Victor N.,Zhdankin, Viktor V.
supporting information, p. 16738 - 16742 (2017/12/02)
New organohypervalent iodine compounds, arylbenziodoxaborole triflates, were prepared from 1-acetoxybenziodoxaboroles and arenes by treatment with trifluoromethanesulfonic acid under mild conditions. Single crystal X-ray crystallography of these compounds revealed a pseudocyclic structure with a short intramolecular interaction of 2.698 to 2.717 ? between oxygen and iodine in the benziodoxaborole ring. These new pseudocyclic aryliodonium salts readily generate aryne intermediates upon treatment with water at room temperature. The generated aryne intermediates react with various substrates to give the corresponding aryne adducts in moderate to good yields. Furthermore, the new benzyne precursors can also work as arylating reagents towards aromatic rings. The aryne intermediates generated from arylbenziodoxaborole triflates selectively react with tert-butyl phenol forming products of ortho arylation in moderate yields.
1,4-Selective Diels - Alder reaction of 9,10-diethynylanthracene with 3,6-difluorobenzyne
Tsuchido, Yoshitaka,Ide, Tomohito,Suzaki, Yuji,Osakada, Kohtaro
supporting information, p. 821 - 823 (2015/06/25)
Diels - Alder reaction of 9,10-bis(3-hydroxy-3-methyl-1-butynyl)anthracene with 3,6-difluorobenzyne yields the naphthobarrelene derivative via 1,4-addition of difluorobenzyne in a higher yield than the 9,10-adduct having a triptycene core. The DFT calculations revealed that the intermediate for the former reaction is stabilized more significantly by attractive interaction between a fluorine atom at the benzyne ring and a hydrogen atom at the anthracene ring.
Integrating reaction and analysis: Investigation of higher-order reactions by cryogenic trapping
Stockinger, Skrollan,Trapp, Oliver
, p. 1837 - 1842 (2013/10/22)
A new approach for the investigation of a higher-order reaction by on-column reaction gas chromatography is presented. The reaction and the analytical separation are combined in a single experiment to investigate the Diels-Alder reaction of benzenediazonium-2-carboxylate as a benzyne precursor with various anthracene derivatives, i.e. anthracene, 9-bromoanthracene, 9-anthracenecarbox-aldehyde and 9-anthracenemethanol. To overcome limitations of short reaction contact times at elevated temperatures a novel experimental setup was developed involving a cooling trap to achieve focusing and mixing of the reactants at a defined spot in a fused-silica capillary. This trap functions as a reactor within the separation column in the oven of a gas chromatograph. The reac-tants are sequentially injected to avoid undefined mixing in the injection port. An experimental protocol was developed with optimized injection intervals and cooling times to achieve sufficient conversions at short reaction times. Reaction products were rapidly identified by mass spectrometric detection. This new approach represents a practical procedure to investigate higher-order reactions at an analytical level and it simultaneously provides valuable information for the optimization of the reaction conditions.
Auto-tandem catalysis: Synthesis of acridines by Pd-catalyzed C=C bond formation and C(sp2)-N cross-coupling
Huang, Zhongxing,Yang, Yang,Xiao, Qing,Zhang, Yan,Wang, Jianbo
supporting information, p. 6586 - 6593 (2013/01/15)
A facile palladium-catalyzed synthesis of acridines has been realized by consecutive C=C double bond formation and C-N cross-coupling. A variety of functionalized acridines can be accessed from easily available o-dihalobenzenes and N-tosylhydrazones in a single operation. This one-pot protocol has a wide scope with respect to both coupling partners, and provides an efficient route to functionalized acridine derivatives, which are generally difficult to synthesize by previously known methods.
Microwave flash pyrolysis
Hee, Yeon Cho,Ajaz, Aida,Himali, Dibya,Waske, Prashant A.,Johnson, Richard P.
scheme or table, p. 4137 - 4142 (2009/09/25)
(Chemical Equation Presented) In a microwave reactor, graphite heats rapidly to high surface temperatures; applications of graphite thermal "sensitization" have been described previously. We report here that microwave thermal sensitization with graphite, carbon nanotubes, or silicon carbide can be used to carry out reactions more typically accomplished by flash vacuum pyrolysis (FVP) and which usually require temperatures much higher than the nominal limit of a microwave reactor. The graphite-sensitized microwave reaction of azulene in the solid phase at temperatures of 100 to 300°C affords rapid rearrangement to naphthalene, a reaction typically observed by FVP at 700-900°C. Multiwall carbon nanotubes give similar results when used as a thermal sensitizer. Other graphite-sensitized reactions that we have observed include the following: conversion of 2-ethynylbiphenyl to phenanthrene, fragmentation of phthalic anhydride to benzyne, cleavage of iodobenzene to phenyl radical, aryl-aryl bond cleavage, and a variety of cycloaromatizations. An advantage is seen for less volatile substrates. Rearrangement of azulene and generation of benzyne from phthalic anhydride have also been observed on powdered silicon carbide. Because of the high temperature, rapid heating, and frequent ejection of material from the irradiation zone, we refer to this general method as microwave flash pyrolysis (MFP).
