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1.
The synthesis and crystal structure of a novel calix[8] arene ester are reported herein. The calix [8] arene ester derivative has been characterized by IR,NMR and X-ray crystal analysis. The X-ray structure analysis revealed that the 8 phenolic hydroxy groups of the calix [8] arene have been substituted by 4 diethyl dibromomalonate molecules with each two adjacent hydroxy oxygen atoms attached to a bridge diethyl malonate. 相似文献
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Furer VL Borisoglebskaya EI Kovalenko VI 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(1-2):355-359
The experimental IR and Far IR spectra of the calix[4]arene, p-tert-butylcalix[4]arene, thialcalix[4]arene and p-tert-butylthiacalix[4]arene were examined at different temperatures and interpreted. The band frequencies and intensities in the IR spectra of the calix[4]arene and thialcalix[4]arene were calculated. The absorption curves of the four possible calix[4]arene conformations: cone, partial cone, 1,2- and 1,3-alternate were computed. The bands characteristic for each conformation are defined and assigned. The obtained spectra-structure correlation can be used for the characteristic of calixarenes conformation. 相似文献
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杯芳烃与NO2硝化反应的研究 总被引:1,自引:0,他引:1
系统地研究了羟基杯[n]芳烃、甲氧基杯[n]芳烃和对特丁基杯[n]芳烃(n=4, 6, 8)与NO2气体的硝化反应, 发现可以成功地得到25,26,27,28-四羟基杯[4]芳烃、37,38,39,40,41,42-六羟基杯[6]芳烃以及25,26,27,28-四甲氧基杯[4]芳烃的对位全硝化产物, 产率分别为90%, 70%和40%; 尤其是25,26,27,28-四羟基杯[4]芳烃与NO2的反应20 min即可完成. 认为共振式酚氧负离子结构是影响该类硝化反应的关键, 并对反应机理进行了探讨. 相似文献
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Salmon L Thuéry P Ephritikhine M 《Dalton transactions (Cambridge, England : 2003)》2006,(30):3629-3637
Reactions of UCl4 with calix[n]arenes (n = 4, 6) in THF gave the mononuclear [UCl2(calix[4]arene - 2H)(THF)2].2THF (.2THF) and the bis-dinuclear [U2Cl2(calix[6]arene - 6H)(THF)3]2.6THF (.6THF) complexes, respectively, while the mono-, di- and trinuclear compounds [Hpy]2[UCl3(calix[4]arene - 3H)].py (.py), [Hpy](4)[U2Cl6(calix[6]arene - 6H)].3py (.3py), [Hpy]3[U2Cl5(calix[6]arene - 6H)(py)].py (.py) and [Hpy]6[U3Cl11(calix[8]arene - 7H)].3py (.3py) were obtained by treatment of UCl4 with calix[n]arenes (n = 4, 6, 8) in pyridine. The sodium salt of calix[8]arene reacted with UCl4 to give the pentanuclear complex [U{U2Cl3(calix[8]arene - 7H)(py)5}2].8py (.8py). Reaction of U(acac)4 (acac = MeCOCHCOMe) with calix[4]arene in pyridine afforded the mononuclear complex [U(acac)2(calix[4]arene - 2H)].4py (.4py) and its treatment with the sodium salt of calix[8]arene led to the formation of the 1D polymer [U2(acac)6(calix[8]arene - 6H)(py)4Na4]n. The sandwich complex [Hpy]2[U(calix[4]arene - 3H)2][OTf].4py (.4py) was obtained by treatment of U(OTf)4 (OTf = OSO2CF3) with calix[4]arene in pyridine. All the complexes have been characterized by X-ray diffraction analysis. 相似文献
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采用密度泛函理论B3LYP方法得到了M@t-Bu-calix[4]arene和(M@t-Bu-calix[4]arene)Li′(M=Li,Na,K)体系的几何结构.其中(M@t-Bu-calix[4]arene)Li′(M=Li,Na,K)三个体系各有5个稳定异构体,在前三个异构体中,碱金属与t-Bu-calix[4]arene分子间具有很强的相互作用能,说明了体系的稳定性.在部分(M@t-Bucalix[4]arene)Li异构体中Li′原子以阴离子形式存在,整个体系表现出碱金属化物的特性.此外,使用CAMB3LYP方法计算了t-Bu-calix[4]arene及碱金属掺杂后体系的非线性光学性质.结果表明,t-Bu-calix[4]arene内部掺杂一个碱金属原子M后,体系的一阶超极化率(β0)有较大提高,而在配体外部又掺杂一个Li原子后,体系具有更大的β0值.其中(M@t-Bu-calix[4]arene)Li′体系的MLi′-4异构体表现出最高的β0值(41827-114354 a.u.),并且随着M原子序数的增加而逐渐增大.可见,碱金属掺杂是提高t-Bu-calix[4]arene非线性光学响应的一种有效策略. 相似文献
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Arisa Jaiyu 《Tetrahedron letters》2007,48(10):1817-1821
A series of stilbene-bridged calix[4]arenes was synthesized through an intramolecular reductive McMurry coupling of bisbenzaldehyde calix[4]arene in high yields. Tetra- and pentaethylene glycol chains were tethered to the phenolic groups of calix[4]arene to form stilbene-bridged calix[4]arene crown-5 and crown-6, respectively. The presence of stilbene bridge over the calix[4]arene rim effectively prevented the connection of the polyether chains in the cone conformation resulting in the exclusive formation of 1,3-alternate stilbene-bridged calix[4]arene crown product. Compared to the cone analogues, the 1,3-alternate calix[4]arene crown ethers showed a greater extraction ability and selectivity toward Cs+. 相似文献
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A selective nitration of calix[4]arene at the upper rim in one pot process was described by monitoring the time dependence of the distribution of products by high‐performance liquid chromatography (HPLC). The discrimination of five nitrated products was accomplished by molecular symmetry considerations and 1H NMR analysis. As a result, unusual 5,11,17‐trinitrocalix[4]arene ( 2d ) was obtained in 57% isolated yield. 5,11‐Dinitro‐calix[4]arene ( 2b ) and 5,11,17‐trinitrocalix[4]arene ( 2d ) with tetranitrocalix[4]arene 2e were further characterized by crystal X‐ray diffraction analysis. Furthermore, as an example of potential application, trinitrocalix[4]arene 2d could be converted to triaminocalix[4]arene 3d conveniently. 相似文献
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以对叔丁基硫桥杯[4]芳烃(1)为原料, 在碳酸钾存在下与碘甲烷反应, 生成1,3-二取代桥杯[4]芳烃(2), 其分别与1,2-二溴乙烷, 1,3-二溴丙烷在碳酸钾的存在下进行烷基化反应, 生成硫桥杯[4]芳烃衍生物3和4. 在氢氧化钠存在下,其与过量的含不同官能团的2-巯基-1,3,4-噻二唑反应, 生成下缘含1,3,4-噻二唑基的硫桥杯[4]芳烃衍生物5a, 5b, 6a和6b, 并通过了1H NMR, 13C NMR, IR, MS和元素分析的确证. 同时, X射线分析确定了硫桥杯[4]芳烃3和5a的晶体结构. 相似文献
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采用密度泛函理论B3LYP方法得到了M@t-Bu-calix[4]arene和(M@t-Bu-calix[4]arene)Li'(M=Li,Na,K)体系的几何结构. 其中(M@t-Bu-calix[4]arene)Li'(M=Li,Na,K)三个体系各有5个稳定异构体,在前三个异构体中,碱金属与t-Bu-calix[4]arene分子间具有很强的相互作用能,说明了体系的稳定性. 在部分(M@t-Bucalix[4]arene)Li异构体中Li'原子以阴离子形式存在,整个体系表现出碱金属化物的特性. 此外,使用CAMB3LYP方法计算了t-Bu-calix[4]arene及碱金属掺杂后体系的非线性光学性质. 结果表明,t-Bu-calix[4]arene内部掺杂一个碱金属原子M后,体系的一阶超极化率(β0)有较大提高,而在配体外部又掺杂一个Li原子后,体系具有更大的β0值. 其中(M@t-Bu-calix[4]arene)Li'体系的MLi'-4异构体表现出最高的β0值(41827-114354 a.u.),并且随着M原子序数的增加而逐渐增大. 可见,碱金属掺杂是提高t-Bu-calix[4]arene非线性光学响应的一种有效策略. 相似文献
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Structure and conformational equilibrium of thiacalix[4]arene by density functional theory 总被引:2,自引:0,他引:2
Density functional theory calculations for the structure and conformational equilibrium of thiacalix[4]arene are reported. The conformational equilibrium of thiacalix[4]arene, a heterocalixarene in which the phenol groups are bridged by sulphur atoms is compared to the conformational equilibrium of calix[4]arene. Thiacalix[4]arene conformational energies relative to the cone conformer (ΔE's) are reduced in comparison with calix[4]arene. This conformational change is in qualitative agreement with recent NMR spectroscopy measurements of the conformational equilibrium for a tetraethylether of thiacalix[4]arene in a CDCl3 solution which indicates an enhanced chemical exchange of thiacalixarene conformers in comparison with similar methylene bridged structures. Density functional theory results for the structure of thiacalix[4]arene are in good agreement with recent X-ray diffraction measurements. The electrostatic potentials in the cone conformers of thiacalix[4]arene and calix[4]arene suggest that their complexation or recognition abilities can be significantly different. Dipole moments of the four thiacalix[4]arene conformers are in the order: cone>1,2-alternate>partial-cone>1,3-alternate. 相似文献
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Si-Zhe Li Ke Yang Hong-Bing Liu Yu-Xiang Xia Rong-Xiu Zhu Jun Luo Qian Wan 《Tetrahedron letters》2013
Inherently chiral biscalixarenes with hetero-cavities were synthesized by a covalent assembly of p-tert-butylcalix[5]arene with a 1,3-substituted calix[4]arene via 1,3-alkylation reaction and subsequent desymmetrization. The racemates were resolved by chiral HPLC method. 1H NMR spectra, VT-NMR spectra, and theoretical calculations support that the calix[5]arene subunit of the inherently chiral calix[4][5]arene ester adopts a cone-in conformation, with the aromatic ring bearing the CH2CO2Et group tilting inward the calix[5]arene cavity. By contrast, such a cone-in structural feature of the calix[5]arene subunit disappears for the corresponding inherently chiral calix[4][5]arene carboxylic acid, due to the intramolecular hydrogen bonding between the carboxyl group and an ethereal oxygen of the glycolic chain. 相似文献
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Jooyeon Hong 《Tetrahedron letters》2008,49(15):2393-2396
The first comparative theoretical study of three parent calix[4]arene analogues (calix[4]arene, thiacalix[4]arene, and homooxacalix[4]arene) has been performed using molecular dynamic simulations and density functional theory (MPWB1K/6-311G∗∗//B3LYP/6-311G∗∗) methods. The theoretical observations herein including optimized geometry, polarity, and atomic charge data provide that homooxacalix[4]arene would offer more efficient platform for metal ion recognition compared to thiacalix[4]arene or calix[4]arene. 相似文献
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Z Zhong A Ikeda M Ayabe S Shinkai S Sakamoto K Yamaguchi 《The Journal of organic chemistry》2001,66(3):1002-1008
To construct calixarene-based molecular capsules utilizing the pyridyl-Pd(II) interaction, reactions of cone-pyridylcalix[4]arene 3, cone-pyridylcalix[5]arene 13, and cone-pyridylcalix[4]arene bis-crown 16 with square-planar Pd(II) complex 7 were investigated. Because of the coexistence of intermolecular binding and chelate-forming intramolecular binding, the reactions of cone-pyridylcalix[4]arene 3 or cone-pyridylcalix[5]arene 13 with cis-Pd(II) complex 7 yield complicated, structure-unknown oligomers. The short dioxyethylene bridges on the lower rim of pyridylcalix[4]arene bis-crown 16 rigidify the cone conformation and thus prohibit 16 from the intramolecular binding with a metal component. Thus, two cone-tetrapyridylcalix[4]arene bis-crown 16 and four cis-Pd(II) complex molecules self-assemble into molecular capsules that exist as a parallel/antiparallel conformer mixture in a nearly 1:1 ratio. The results demonstrated that to prevent entropically favorable intramolecular binding is essential is constructing higher capsule-like structures with calixarene building blocks by self-assembling. 相似文献
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Ryan T. Chester Roland de Marco Mauro Mocerino Brian W. Skelton Allan H. White 《Supramolecular chemistry》2013,25(6):479-485
The tetra-isopropyl ethers of calix[4]arene and p-t-butylcalix[4]arene have been isolated in the cone conformation, and structurally characterised as chloroform solvates. Thermogravimetric analysis demonstrated that the parent isopropylcalix[4]arene solvate is significantly more stable than the p-t-butylcalix[4]arene analogue, retaining the solvent up to a temperature of 125°C. It was found that the calix[4]arene ether sublimes at atmospheric pressure, and solvent-free crystals appropriate for structure determination were produced at reduced pressure. The p-t-butylcalix[4]arene ether was also isolated without solvent in the lattice, but in this case the calixarene was crystallised from acetone, as sublimation did not produce crystals of sufficient quality. 相似文献