共查询到20条相似文献,搜索用时 31 毫秒
1.
Rudzevich Yu. I. Drapailo A. B. Rudzevich V. L. Miroshnichenko V. I. Kal'chenko V. I. Smirnov I. V. Babain V. A. Varnek A. A. Wipff G. 《Russian Journal of General Chemistry》2002,72(11):1736-1742
A series of calix[6]arenes substituted with phosphoryl functional groups were prepared by the Arbuzov reaction of hexakis(chloromethyl)calix[6]arene hexamethyl ether with isopropyl esters of trivalent phosphorus acids, followed by appropriate chemical transformations. Molecular modeling and NMR data show that phosphorylated calix[6]arenes exist in the stereochemically labile 1,2-alternate conformation. The extractive power of these compounds with respect to americium and europium was studied. Due to the cooperative binding of the metal cation with phosphoryl groups, the phosphorylated calixarenes are more effective extractants than their acylcic analogs and commercial organophosphorus extractants. 相似文献
2.
Xiaodong Liu 《Tetrahedron》2009,65(31):5893-1397
A series of di-ionizable calix[4]arene-1,3-crown-4 compounds has been synthesized. The ionizable groups are oxyacetic acid and N-(X)sulfonyl oxyacetamide groups with X=methyl, phenyl, 4-nitrophenyl and trifluoromethyl, which ‘tunes’ the acidity of the latter. The efficiency and selectivity of these novel ligands are assessed with competitive solvent extractions of alkaline earth metal cations from aqueous solutions into chloroform. The results are compared with those reported previously for calix[4]arene-crown analogues with crown-6 and crown-5 rings. 相似文献
3.
A tetra L-prolinylmethyl derivative of a tetra-sulfonated calix[4]resorcarene (1) is an effective chiral NMR solvating agent for water-soluble compounds with phenyl, pyridyl, bicyclic aromatic, or indole rings. These aromatic compounds form host-guest complexes with the calix[4]resorcarene in water. Complexation of substrates with the calix[4]resorcarene is likely promoted by hydrophobic effects, and bicyclic substrates have association constants with the calix[4]resorcarene larger than those of similar phenyl-containing compounds. Aromatic resonances of the substrates show substantial upfield shifts because of shielding from the aromatic rings of the calix[4]resorcarene, and several resonances in the 1H NMR spectra typically exhibit enantiomeric discrimination. The extent of enantiomeric discrimination depends in part on interactions of the substituent groups of the substrates with the prolinylmethyl groups of the calix[4]resorcarene. The effectiveness of a calix[4]resorcarene prepared from N-methyl-L-alanine (2) as a chiral NMR discriminating agent is compared to the L-prolinylmethyl derivative. 相似文献
4.
Jong Seung Kim Won Ku Lee Soo Heon Lee Jin-Gyu Kim Il-Hwan Suh Jong Yeol Kim Jong Wan Kim 《Journal of inclusion phenomena and macrocyclic chemistry》2001,40(3):183-187
An unsymmetrical calix[4]-bis-crown ether having both conventional crown-6 and dibenzocrown-6 rings in a fixed 1,3-alternate conformation was synthesized with good yield by the reaction of a monocyclic calix[4]crown-6 with dibenzodimesylate in the presence of cesium carbonate. The cesium ion selectivity among alkali metal ions increased compared to symmetrical calix[4]-bis-crown-6. The solid state structureof the ligand-cesium complex illustrates a 1:2 complex ratio. On the contrary, insolution, e.g., extraction equilibrium and 1H NMR experiment gave a 1:1 complex ratio. From the result of the chemical shift change upon metal ion complex, the cesium ion seems to prefer the dibenzocrown loop to the conventional crown-6 ring. 相似文献
5.
Novel proton di-ionizable p-tert-butylcalix[4]arene-crown-6 compounds in cone, partial-cone and 1,3-alternate conformations are synthesized to compare the efficiency and selectivity with which they extract alkaline earth metal ions. In these ligands, a crown-6 polyether unit links alternate aromatic rings of the calix[4]arene framework. To the remaining lower-rim positions are attached oxyacetic acid or N-(X)sulfonyl oxyacetamide groups. Changing the conformation varies the spatial relationship between a polyether-complexed divalent metal ion and the ionized side arms of the ligands. This is found to markedly affect the efficiency and selectivity in competitive solvent extraction of alkaline earth metal ions from aqueous solutions into chloroform by the di-ionizable calix[4]arene-crown-6 ligands. 相似文献
6.
A novel protection/deprotection method leading to the regioselective ipso-substitution of calix[4]arenes is described. The introduction of nosyl (p-nitrobenzenesulfonyl) groups into the lower rim of partly alkylated tert-butylcalix[4]arenes leads subsequently to the exclusive ipso-nitration of the alkylated phenol rings, while the protecting groups can be easily removed in the next step. This method gives dialkoxy- or trialkoxy-substituted calix[4]arenes with nitro groups on the alkylated rings and tert-butyl groups on the remaining ones. The above substitution pattern is complementary to the isomers so far known in the chemistry of calix[4]arenes and could be used in the design of novel type of calixarene-based receptors. 相似文献
7.
《Tetrahedron: Asymmetry》1999,10(3):429-437
The synthesis of chiral calix[4]arenes with tartaric acid ester moieties has been achieved by the reactions of tartaric ester chloroacetates with calix[4]arenes in moderate yields. All the chiral calix[4]arene derivatives are in a cone conformation according to the 1H NMR doublet–doublet pattern of the protons of the methylene groups between the phenol rings. The results of NMR and specific rotations indicate that the molecules have C2 symmetry with asymmetric features. 相似文献
8.
Hasalettin Deligöz 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(3-4):285-289
In this study, seven new compounds p-(4-butyl-phenylazo)calix[6]arene(1), p-(4-(phenylazo)phenylazo)calix[6]arene (2),p-(4-hydroxyphenylazo)calix[6]arene (3),p-{4-[N-(thiazol-2-yl)sulfamoyl]phenylazo\}calix[6]arene(4), p-(4-acetamidophenylazo)calix[6]arene (5),p-(thiazol-2-ylazo)calix[6]arene (6) andp-(2-sulfanylphenylazo)calix[6]arene (7) have been synthesizedfrom calix[6]arene by diazo coupling with the corresponding aromaticamines. UV-Vis, IR, 1H and 13C NMR spectral data have been used to elucidate the structures of the compounds elemental analyses 相似文献
9.
Ngoc H. PhamThomas J. Wenzel 《Tetrahedron: Asymmetry》2011,22(6):641-647
A water-soluble calix[4]resorcinarene containing α-methyl-l-prolinylmethyl groups was investigated as a chiral NMR solvating agent. Substrates form complexes by insertion of the aromatic ring into the cavity of the calix[4]resorcinarene. Amino acid derivatives with phenyl or indole rings, ammonium substrates with pyridyl, indane or dihydroindole rings, and phenyl-containing substrates with carboxylic acid and/or hydroxyl groups were studied. The effectiveness of the α-methyl-l-prolinylmethyl calix[4]resorcinarene is compared to similar reagents with proline and hydroxyproline moieties that have previously been reported. The α-methyl-l-prolinylmethyl derivative causes larger enantiomeric discrimination of one or more 1H resonances than the previous systems for most of the substrates. 相似文献
10.
Xavier Delaigue C. David Gutsche Jack M. Harrowfield Mark I. Ogden Brian W. Skelton Donald F. Stewart 《Supramolecular chemistry》2013,25(8):603-609
The syntheses and structures of uranyl complexes of p-t-Bu-calix[6]arene (calix[6]H6) and p-t-Bu-calix[9]arene (calix[9]H9) are reported, further developing the role of calixarenes as 'cluster keepers'. The calix[6]arene complex, formulated as [(HO){UO2(calix[6]H4)(dmso)}3H], is trinuclear and linked symmetrically by the hydroxyl O atom. The calix[9]arene complex is binuclear, with a carbonate atom bridging between the two uranyl cations to give the complex, (HNEt3)3[(OCO2)(UO2)3(calix[9]H4)]. 相似文献
11.
Abstract The synthesis and full characterization of eight new calix[n]arene sulfonate esters including their conformational analysis were carried out. While p-tBucalix[6]arene and p-tBu-calix[8]arene esters are conformationally labile in the temperature interval of 25–100°C, p-tBu-calix[4]arene mono-and diesters were isolated as stable conformers at ambient temperature. Two 1,3-functionalised compounds of these derivatives, p-tert-butylcalix[4]arene ditriflate (5) and dimesylate (6) were shown unexpectedly high conformational stability up to 100°C by dynamic NMR measurements. The NMR measurements confirm the pinched-cone conformation for both derivatives. For the dealkylated calix[4]arene derivatives the partial cone conformer of the triesters have been obtained as major products in all cases. 相似文献
12.
Sergey N. Podyachev Viktor V. Syakaev Svetlana N. Sudakova Roald R. Shagidullin Darya V. Osyanina Ludmila V. Avvakumova Boris I. Buzykin Shamil K. Latypov Ingmar Bauer Wolf D. Habicher Alexander I. Konovalov 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(1-2):55-61
A series of new calix[4]phenols, calix[4]resorcinols and calix[4]pyrogallols with acetylhydrazide substitutes has been␣synthesized
with high yields by hydrazinolysis of ester group containing calix[4]arenes. The synthesized calix[4]phenols adopt the cone
conformation while the calix[4]resorcinol and calix[4]pyrogallol derivatives prefer the boat conformation. The amide fragment
of the hydrazide groups predominantly exists in the trans-conformation. The binding ability of synthesized calix[4]arenes toward transition and alkali metals by solvent extraction
has been investigated. 相似文献
13.
[structure: see text] The water-soluble tetra l-prolinylmethyl derivative of a tetrasulfonated calix[4]resorcarene is an effective chiral NMR solvating agent for compounds with bicyclic aromatic or indole rings. Complexation of bicyclic substrates with the calix[4]resorcarene is likely promoted by hydrophobic effects. The bicyclic substrates have larger association constants with the calix[4]resorcarene than similar phenyl-containing compounds. Substantial enantiomeric discrimination is observed for several resonances in the (1)H NMR spectra of these substrates. 相似文献
14.
Chloride‐Selective Electrodes Based on “Two‐Wall” Aryl‐Extended Calix[4]Pyrroles: Combining Hydrogen Bonds and Anion–π Interactions to Achieve Optimum Performance
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Jad Sabek Dr. Louis Adriaenssens Tomàs Guinovart Dr. Enrique J. Parra Prof. F. Xavier Rius Prof. Pablo Ballester Dr. Pascal Blondeau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):448-454
The performance of chloride‐selective electrodes based on “two‐wall” aryl‐extended calix[4]pyrroles and multiwall carbon nanotubes is presented. The calix[4]pyrrole receptors bear two phenyl groups at opposite meso‐positions. When the meso‐phenyl groups are decorated with strong electron‐withdrawing substituents, attractive anion–π interactions may exist between the receptor’s aromatic walls and the sandwiched anion. These anion–π interactions are shown to significantly affect the selectivity of the electrodes. Calix[4]pyrrole, bearing a p‐nitro withdrawing group on each of the meso‐phenyl rings, afforded sensors that display anti‐Hofmeister behavior against the lipophilic salicylate and nitrate anions. Based on the experimental data, a series of principles that help in predicting the suitability of synthetic receptors for use as anion‐specific ionophores is discussed. Finally, the sensors deliver excellent results in the direct detection of chloride in bodily fluids. 相似文献
15.
Francine F. Nachtigall Eduardo Ernesto Castellano Faruk Nome 《Supramolecular chemistry》2013,25(6):453-458
The interactions of calix[6]arene and p-tert-butylcalix[6]arene with aliphatic amines in acetonitrile solution were studied by spectrophotometric titrations in the UV region and 1H NMR spectrometry. Calix[6]arenes can undergo two deprotonations by aliphatic amines and the extent of the second proton transfer is mainly governed by the size of the α-substituent of the amine. 1H NMR spectra show that the macrocycle adopts a 1,2,3-alternate conformation and that the α-hydrogens of the ammonium ions are shielded by the π-clouds of the aromatic rings. The X-ray crystal structure of the dihexylammonium complex of the p-tert-butylcalix[6]arene dianion, reported here, confirms the 1,2,3-alternate conformation and shows one of the two ammonium moieties encapsulated in the inner cavity of the macrocycle. 相似文献
16.
Alessandro Casnati Francesco Sansone Jean-François Dozol Héléne Rouquette Fran¸oise Arnaud-Neu Declan Byrne Saowarux Fuangswasdi Marie-José Schwing-Weill Rocco Ungaro 《Journal of inclusion phenomena and macrocyclic chemistry》2001,41(1-4):193-200
Cesium possesses two long lived isotopes 135Cs and 137Cs and the first one has a very long (2.3 × 106 y) half life and is one of the most mobile nuclides in a repository.Calix[4]arene-crowns-6 in the 1,3-alternate conformation areemerging as a new class of ionophores exhibiting a very high efficiency and selectivity in the complexation of cesium ion and itsremoval from highly acidic ([HNO3] = 3–4 M) radioactive waste having also high sodium nitrate concentration ([NaNO3] = 2–4 M). In order to improve both efficiency and cesium selectivity we have synthesised the novel calix[4]arene dibenzo-crowns-6 1 and 2 and thecalix[4]arene-monobenzocrown-6 3 in 1,3-alternate conformationand evaluated their complexation properties towards alkali metal cations in homogeneous solution and in two phase systems, togetherwith their performance in radioactive waste treatment. All data confirm the higher Cs/Na selectivity of the 1,3-alternate calix[4]crown-6 1–3 containing aromatic rings in the polyether loop, in comparison to previously synthesised compounds of the same series. 相似文献
17.
O'Farrell CM Chudomel JM Collins JM Dignam CF Wenzel TJ 《The Journal of organic chemistry》2008,73(7):2843-2851
Water-soluble calix[4]resorcinarenes containing 3- and 4-hydroxyproline, d-nipecotic acid, (S)-2-(methoxymethyl)pyrrolidine, (S)-2-pyrrolidine methanol, and (S,S)-(+)-2,4-bis(methoxymethyl)pyrrolidine substituents are synthesized and evaluated as chiral NMR solvating agents. The derivatives with the hydroxyproline groups are especially effective at causing enantiomeric discrimination in the spectra of water-soluble cationic and anionic compounds with pyridyl, phenyl, and bicyclic aromatic rings. Binding studies show that mono- and ortho-substituted phenyl rings associate within the cavity of the calix[4]resorcinarenes, as do naphthyl rings with mono-, 2,3-, and 1,8-substitution patterns. Anthracene derivatives with an amino or sulfonyl group at the 1-position bind within the cavity, as well. Aromatic resonances of the substrates exhibit substantial upfield shifts because of shielding from the aromatic rings of the calix[4]resorcinarene. The effectiveness of the reagents at producing chiral recognition in 1H NMR spectra is demonstrated with sodium mandelate, the sodium salt of tryptophan, and doxylamine succinate. While no one reagent is consistently the most effective, the calix[4]resorcinarenes with trans-4-hydroxyproline and trans-3-hydroxyproline moieties generally produce the largest nonequivalence in the 1H NMR spectra of the substrates. 相似文献
18.
19.
Tadatomi Nishikubo Atsushi Kameyama Hiroto Kudo Kousuke Tsutsui 《Journal of polymer science. Part A, Polymer chemistry》2002,40(9):1293-1302
New photoreactive calixarene derivatives containing spiro ortho ester groups (calixarenes 3a–3c ) were synthesized by the reaction of 2‐bromomethyl‐1,4,6‐trioxaspiro[4.4]nonane with 2,8,14,20‐tetramethyl‐4,6,10,12,16,18,22,24‐octakis(carboxymethoxy)calix[4]resorcinarene, 5,11,17,23,29,35‐hexamethyl‐37,38,39,40,41,42‐hexakis(carboxymethoxy)calix[6]arene, and 5,11,17,23,29,35,41,47‐octa‐tert‐butyl‐49,50,51,52, 53,54,55,56‐octakis‐(carboxymethoxy)calix[8]arene, which were prepared by the reaction of C‐methylcalix[4]resorcinarene, p‐methylcalix[6]arene, and p‐tert‐butylcalix[8]arene, respectively. The thermal stability of the obtained calixarene derivatives containing spiro ortho ester groups was examined with thermogravimetric analysis, and it was found that these calixarene derivatives had good thermal stability. The photoinitiated cationic polymerization of spiro ortho ester groups in calixarene derivatives 3a–3c was examined with certain photoacid generators in the film state. Interestingly enough, the reaction of calixarene derivatives did not proceed with only photoirradiation; however, the reaction proceeded smoothly when the photoirradiation was followed by heating. Furthermore, calixarene 3a , composed of a C‐methylcalix[4]resorcinarene structure, showed the highest photochemical reactivity in this reaction system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1293–1302, 2002 相似文献
20.
The Wolff‐Kishner reduction of the half‐protected ketal calix[4]monoquinone 3 and its basic hydrolysis product 4 produced a partially reducing product 5 . When the same reduction conditions were applied to the calix[4]quinone benzoates 1 and 2 , the corresponding title compounds, p‐hydroxycalix[4]arenes ( 6 and 7 ), were afforded in one step. 相似文献