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1.
Oleg KasyanDariusz Swierczynski Andrew DrapailoKinga Suwinska Janusz LipkowskiVitaly Kalchenko 《Tetrahedron letters》2003,44(38):7167-7170
The synthesis and structure of new tetrahydroxythiacalix[4]arenes, existing in the cone conformation and possessing reactive bromide, chloromethyl or diorganylphosphoryl groups on the upper rim of the macrocycle are described. The molecular structure of tetrakis(diisopropoxyphosphorylmethyl)thiacalix[4]arene was examined by X-ray crystallography. 相似文献
2.
Organo VG Sgarlata V Firouzbakht F Rudkevich DM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(14):4014-4023
We report the synthesis and encapsulation properties of long (up to 5 nm) molecular nanotubes 1-4, which are based on calix[4]arenes and can be filled with multiple nitrosonium (NO(+)) ions upon reaction with NO(2)/N(2)O(4) gases. These are among the largest nanoscale molecular containers prepared to date and can entrap up to five guests. The structure and properties of tubular complexes 1(NO(+))(2)-4(NO(+))(5) were studied by UV/Vis, FTIR, and (1)H NMR spectroscopy in solution, and also by molecular modeling. Entrapment of NO(+) in 1(NO(+))(2)-4(NO(+))(5) is reversible, and addition of [18]crown-6 quickly recovers starting tubes 1-4. The FTIR and titration data revealed enhanced binding of NO(+) in longer tubes, which may be due to cooperativity. The described nanotubes may serve as materials for storing and converting NO(x) and also offer a promise to further develop supramolecular chemistry of molecular containers. These findings also open wider perspectives towards applications of synthetic nanotubes as alternatives to carbon nanotubes. 相似文献
3.
《Tetrahedron letters》2003,44(44):8093-8097
A novel thiacalix[4]arene derivative bearing four phenyl groups on the upper rim was prepared by the direct condensation of biphenyl-4-ol with elemental sulphur. As revealed by X-ray diffraction analysis, this compound adopts the cone conformation in the solid state, thus creating a cavity with an extended π-aromatic system potentially applicable for solid-state inclusion of suitable molecules. Subsequent alkylation (RI/K2CO3/acetone, R=Me, Et, Pr) yielded tetraalkylated derivatives, which were studied for their conformational preferences using 1H NMR spectroscopy. While the Me or Et derivatives are conformationally mobile and exhibit thermodynamic equilibria of several conformers in solution (CDCl3 or CD2Cl2), the corresponding propoxy derivative is infinitely stable at room temperature. 相似文献
4.
A family of novel calix[4]arene derivatives containing nucleoside bases were designed and synthesized. Coupling reaction between para mono- or bis-amino calix[4]arenes 5, 6 or 7 and thymin-1-ylacetic acid in the presence of DCC afforded mono- or bis-thymine-substituted calix[4]arenes 8, 9 or 10 in over 70% yield. Owing to the low solubility of adenine-N9-ylacetic acid in DMF and DMSO and the weak nucleophilicity of aminocalix[4]arene derivatives, alternatively, the substitution reaction of bromoacetylated aminocalix[4]arenes derivatives 11, 12, 13 with adenine in the presence of sodium hydride was carried out to synthesize mono- or bis-adenine-substituted calix[4]arenes. Two kinds of isomers 15 and 16 or 17 and 18 were obtained due to the non-regiospecific alkylation of adenine, and their structures have been confirmed by 13C NMR and 1H NMR spectra. 相似文献
5.
Fenglei Zhang Kenji Kumamaru Hideto Yamamoto 《Journal of inclusion phenomena and macrocyclic chemistry》2002,42(1-2):51-60
An attempted O-alkylation of the flexible macrocycle 1with 2-(chloromethyl)pyridine in the presence of Cs2CO3 under THF reflux afforded a mixture of twoconformers of tetra-O-alkylated product 4a in a ratio of 91:9 (cone-4a:1,2-alternate-4a)in 70% yield, while other possible isomers were not observed. In the case of Na2CO3, there was no reaction product,only the starting compound 1, whereasonly monoalkylated compound 3 was obtained when usingK2CO3 as the base. The distribution of cone conformer decreased in the case of O-alkylation of tetraol 1with 4-(chloromethyl)pyridine or benzyl bromide in the presence of Cs2CO3 in comparison with that ofO-alkylation with 2-(chloromethyl)pyridine, while the 1,2-alternate conformer increased in the same sequence. The larger Cs+might increase the contribution of the metal template effect, which can hold the 2-pyridylmethyl group(s) and theoxide group(s) on the same side of the tetrathiacalix[4]arene 1 through the cation-O- and -N-interaction in the caseof O-alkylation of tetraol 1 with 2-(chloromethyl)pyridine.Only when the template metal can hold the 2-pyridyl group(s) andthe oxide group(s) on the same side of the tetrathiacalix[4]arene is the conformation immobilized to thecone. The template effect of the cesium cation plays an important role in this alkylation reaction. The structuralcharacterization of these products is also discussed.The two-phase solvent extraction data indicated thattetrakis[(2-pyridylmethyl)oxy]thiacalix[4]arenes 4a show strong Ag+ affinity and a high Ag+ selectivity wasobserved for cone-4a. A good Job plot proves 1:1 coordination of cone-4a with Ag+ cation.1H-NMR titration of cone-4a with AgSO3CF3 also clearly demonstrates that a 1:1complex is formed with retention of the original symmetry. In contrast, the 1,2-alternate-4a can form a 2:1 metal/thiacalix[4]arene complex and the two metal-binding sites display positive allostericity. The conformational changes ofpyridine moiety from the original outward orientation of the ring nitrogen to the inside orientation toward thethiacalixarene cavity were observed in the processof Ag+ complexation. 相似文献
6.
The synthesis, extraction and chromogenic properties of calix[4]arenes, carrying phenylazo and amido groups on their upper and lower rims, respectively, are described. Novel azocalix[4]arene amides (1a–d, 2a–d, 3a–d) and some of their telomers (T1a–T1d) have been synthesised and characterised by spectroscopic methods as well as elemental analysis techniques. Compounds 1c and 2b were additionally characterised by two-dimensional nuclear magnetic resonance spectroscopic methods. Some of the compounds were examined by absorption spectra using different solvents. The colour changes of the resulting solutions can be observed by the ‘naked eye’. Metal extraction abilities of compounds have been investigated comparatively. Telomer structures of azocalix[n]arenes exhibited higher extraction rates compared to those of their monomers. Products obtained under this study, especially telomers, can be used in the field of ion-selective electrodes. 相似文献
7.
Thomas J Van Hecke K Robeyns K Van Rossom W Sonawane MP Van Meervelt L Smet M Maes W Dehaen W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(37):10339-10349
Homothiacalix[n]arenes have been largely underexposed compared with related (homo)heteracalixarenes, although their inherent structural features are particularly attractive for supramolecular host-guest chemistry. In this contribution, the synthetic macrocyclization protocols that afford homothiacalix[n]arenes have been reinvestigated and optimized, providing straightforward access to the parent homothiacalix[4]arene skeleton. Moreover, inner-rim (bis and tetrakis) ester functionalization and dimethylenethia bridge oxidation were successfully performed as well. Solution-phase (variable-temperature) NMR spectroscopy studies and solid-state X-ray structures provided complementary information on the conformational features of the novel macrocycles. 相似文献
8.
MEIER Herbert 《中国科学:化学(英文版)》2012,55(2):223-228
A facile method for the synthesis of pillar[6]arenes was developed.A series of pillar[6]arenes were prepared with FeCl 3 as catalyst and chloroform as solvent at room temperature in moderate yields(30%-40%).Their host-guest properties with n-cetyltrimethyl ammonium bromide were investigated by 1 HNMR.The results showed that high selectivity in the host-guest relationship became apparent between pillar[6]arenes and pillar[5]arenes based on the different size of the inner cavity. 相似文献
9.
Kuzovkina Elena V. Lavrinovich Elena A. Novikov Alexander P. Stepanova Ekaterina S. Karavan Maria D. Smirnov Igor V. 《Journal of Radioanalytical and Nuclear Chemistry》2017,311(3):1983-1989
Kinetics of 152Eu and 241Am extraction by nitrogen-bearing alkyl amino phenol oligomer YaRB and tert-butylthiacalix[4]arene TCA from carbonate-alkaline media was studied. Both extractants efficiently extract americium and europium in pH interval 12–14. The maximum of americium extraction is located at the lower values of pH, compared with europium. YaRB extracts americium and europium faster than TCA, and at the same time, americium is extracted faster than europium by both extractants. In general, thiacalixarene TCA is regarded as more efficient extractant than alkyl amino phenol oligomer YaRB.
相似文献10.
11.
The regioselective nitration of 25,27-dipropoxythiacalix[4]arene was carried out as a key step in the synthesis of thiacalix[4]arene derivative bearing two arylureido functions on the upper rim. The preorganisation of ureido units using the thiacalix[4]arene/calix[4]arene moieties as a molecular scaffold gave novel anion receptors. These compounds, albeit based on hydrogen bonding interactions, show good complexation ability even in highly HB-competitive solvent, such as DMSO. Direct comparison of otherwise identical structures 6a and 7a revealed remarkable dominance of the thiacalix[4]arene derivative over its classical analogue in anion binding. 相似文献
12.
Noriyoshi Kon Nobuhiko Iki Yusuke Yamane Shin Shirasaki Sotaro Miyano 《Tetrahedron letters》2004,45(1):207-211
2,14-Dithiacalix[4]arene 34 was conveniently prepared in 16% yield by acid-catalyzed cyclocondensation of 2,2′-thiobis[4-tert-butylphenol] with formaldehyde. The present method also afforded the first isolation of the analogues with six and eight phenol units, 36 (10%) and 38 (5%), respectively. Solvent extraction showed that 34 had high selectivity toward Cu2+ ion at pH 5.5 by coordination of the bridging sulfur with cooperative donation of the adjacent phenolate oxygens. 相似文献
13.
Reza Eivazzadeh-Keihan Ehsan Bahojb Noruzi Fateme Radinekiyan Milad Salimi Bani Prof. Ali Maleki Dr. Behrouz Shaabani Prof. Mohammad Haghpanahi 《ChemistryOpen》2020,9(7):735-742
One of the most common phenol-formaldehyde cyclic oligomers from hydroxyalkylation reactions that exhibit supramolecular chemistry are calixarenes. These macrocyclic compounds are qualified to act as synthetic catalysts due to their specific features including being able to form host-guest complexes, having unique structural scaffolds and their relative ease of chemical modifications with a variety of functions on their upper rim and lower rim. Here, a functional magnetic nanocatalyst was designed and synthesized by using a synthetic amino-functionalized calix[4]arene. Its catalytic activity was evaluated in a one-pot synthesis of 2-amino-4H-chromene derivatives. Besides, this novel magnetic nanocatalyst was characterized by spectroscopic and analytical techniques such as FT-IR, EDX, FE-SEM, TEM VSM, XRD analysis. 相似文献
14.
The linear and nonlinear optical polarizabilities of donor-acceptor (D-pi-A) chromophores in confined geometries of calix[4]arenes are investigated through a model for interacting polar-polarizable molecules. Both the linear polarizability (alpha) and the first hyperpolarizability (beta) decrease with increasing the interdipolar angle, as expected in the oriented-gas picture. However, within the polar-polarizable model we predict deviations from the additive result, irrespective of the interdipolar angle. Depending on the nature of the chromophore, electrostatic intermolecular interactions between polar and polarizable chromophores lead to cooperative damping or enhancement of the optical responses. Specifically, for chromophores whose ground state is dominated by the neutral D-pi-A structure both alpha and beta are suppressed with respect to the prediction of the oriented-gas model, whereas the opposite holds true for chromophores whose ground state is dominated by the zwitterionic D(+)-pi-A(-). These results explain recent experimental data on a calix[4]arene functionalized with a donor-acceptor dye for nonlinear optical applications. Density functional theory calculations on the relevant crystal structure further support our interpretation. 相似文献
15.
Oleg Kasyan Elisabeth R. Healey Andriy Drapailo Mike Zaworotko Sebastien Cecillon Anthony W. Coleman Vitaly Kalchenko 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(1-2):127-132
The synthesis and X-ray structure investigation of the cone shaped monodecyloxythiacalix[4]arene, as well as the introduction of the reactive bromide or chloromethyl groups on it’s
upper rim are described. Preparation of the amphiphilic derivative of thiacalixarene bearing three hydrophilic diethoxyphosphoryl
groups at the upper rim and lipophilic decyloxy group at the lower rim is presented. 相似文献
16.
Kwanghyun No Jong Seung Kim Seyoung Kim Duong Tuan Quang In-Chul Hwang Jacques Vicens 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(3-4):353-360
A series of tetrahomodiazacalix[4]arenes (1–8) with different substituents (or substituted) at the upper rim and/or N-side arm has been synthesized with acceptable yields. The compounds were characterized by elemental analysis, IR, MS and
NMR methods. In particular, 5 was shown by X-ray crystallography to adopt the cone conformation in the solid state. Two-phase picrate extraction showed
that 2 and 6, bearing N-2-picolyl arms, are the best extractants. Of the cations tested, Ag(I) is the best extracted by almost all ligands and the
extraction efficiency follows the order 2-picolyl > 3-picolyl > 4-picolyl. 相似文献
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19.
O. A. Plyusnina V. A. Emel’yanov I. A. Baidina I. V. Korol’kov S. A. Gromilov 《Journal of Structural Chemistry》2007,48(1):114-121
Double complex [RuNO(NH3)4OH][PtCl4] (I) and [RuNO(NH3)4OH][PdCl4] (II) salts have been prepared and explored with TGA, IR spectroscopy, powder and single crystals X-ray diffraction. Crystal phases
of I and II are isostructural (space group Cmc21) and have the following crystal chemical characteristics: a = 8.106 Å, b = 18.190(3) Å, c = 8.097 Å, V = 1194.0 Å3, Z = 4, ρcalc = 3.077 g/cm3 (I), and a = 8.116 Å, b = 18.135 Å, c = 8.062 Å, V = 1186.5 Å3, Z = 4, ρcalc = 2.600 g/cm3 (II). The product of thermal decomposition of I in inert and hydrogen atmospheres is a substitution solid solution Pt0.5Ru0.5 with the parameter of the FCC unit cell a = 3.856(3) Å. Thermolysis of II affords two-phase mixtures of limited solid solutions of the metals featuring Ru-based HCP and Pd-based FCC cells.
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Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No.1, pp.114–121, January–February, 2007. 相似文献
20.
Rahul S. Patil Dr. Chen Zhang Prof. Jerry L. Atwood 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(43):15202-15207
Macrocyclic compounds, such as resorcin[4]arenes and pyrogallol[4]arenes, have proven to be useful building blocks in the construction of supramolecular organic frameworks (SOFs) because of their unique bowl‐like shape and ability to interact through variety of intermolecular interactions. Herein, we report the synthesis and crystal structures of two functionalized resorcin[4]arenes and pyroagllol[4]arenes, 4‐hydroxyphenylresorcin[4]arenes, and 4‐hydroxyphenylpyrogallol[4]arenes. These phenyl‐functionalized macrocycles usually have different conformers, such as cone, boat, chair, saddle, and diamond. The successful separation of predominant conformers from the crude product was carried out with solvent‐extraction technique. The shape and molecular arrangement of these conformers in the individual crystal structure was verified with single‐crystal X‐ray diffraction studies. 相似文献