邻甲氧基羰基苄氧基取代杯[4]芳烃衍生物的合成及其性？…

杯芳烃是继冠醚、环糊精之后的第三代主体分子 [1] .据文献 [2 ,3]报道 ,在杯 [4]芳烃下沿酚氧原子上连接乙酸酯得到的四取代衍生物对 Na+ 有很高的选择性 ,核磁与晶体结构研究均证实这是由于羧酸酯的羰基和酚氧基参与了对 Na+ 的配位 ,而且配位基团所形成的包络空间大小与钠离子相匹配 .一般认为 ,随着包络空间改变 ,对金属离子的识别作用会有所变化[4] .但目前对这方面的工作并没有给予更多的重视 .我们发现 ,用 2 -溴甲基苯甲酸甲酯与杯 [4 ]芳烃反应 ,得到了一种新的四取代杯 [4]芳烃衍生物 2 ,萃取研究结果表明 ,该化合物对钾离子有较…     

邻甲氧基羰基苄氧基取代杯[4]芳烃衍生物的合成及其性能研究

杯芳烃是继冠醚、环糊精之后的第三代主体分子[1].据文献[2,3]报道,在杯[4]芳烃下沿酚氧原子上连接乙酸酯得到的四取代衍生物对Na+有很高的选择性,核磁与晶体结构研究均证实这是由于羧酸酯的羰基和酚氧基参与了对Na+的配位,而且配位基团所形成的包络空间大小与钠离子相匹配.一般认为,随着包络空间改变,对金属离子的识别作用会有所变化[4].但目前对这方面的工作并没有给予更多的重视.我们发现,用2-溴甲基苯甲酸甲酯与杯[4]芳烃反应,得到了一种新的四取代杯[4]芳烃衍生物[2]萃取研究结果表明,该化合物对钾离子有较好的选择性.此外,在合成该衍生物的过程中,还得到了另一新的二取代衍生物(3).     

二羟基二羟乙氧基杯[4]芳烃的合成与性质研究

通过杯[4]芳烃与碘乙醇的反应,制得了25,27-二羟基-26,28-二羟乙氧基杯[4]芳烃,经IR,UV,1HNMR,13CNMR和MS等分析证实了产物的结构.用荧光光谱法研究了产物与稀土(Ⅲ)硝酸盐在乙腈溶液中的配位作用,并根据扩展的Hilderbrand-Benesi公式计算了配合物的稳定常数和配位反应的Gibbs自由能变化,结果发现,25,27-二羟基-26,28-二羟乙氧基杯[4]芳烃与稀土(Ⅲ)硝酸盐在乙腈溶液中具有较强的配位能力.     

25,26,27,28-羟乙氧基-杯[4]芳烃的合成

以对叔丁基苯酚为原料,经4步反应合成了新的杯[4]芳烃衍生物--25,26,27,28-羟乙氧基-杯[4]芳烃,其结构经~1H NMR和MS表征.     

25-[(乙氧基羰基)甲氧基]-26,27,28-三丁氧基对叔丁基杯[4]芳烃的合成

以对叔丁基杯[4]芳烃为起始原料,合成了25-羟基-26,27,28-三丁氧基对叔丁基杯[4]芳烃(2)和25-[(乙氧基羰基)甲氧基]-26,27,28-三丁氧基对叔丁基杯[4]芳烃(3),2和3的结构经1HNMR和IR表征。通过正交实验[L16(45)和L9(33)]优化了实验条件,使3的总收率提高到60%。     

四乙氧羰基甲氧基杯[4]芳烃的合成与性质

配位作用;液膜传递;四乙氧羰基甲氧基杯[4]芳烃的合成与性质     

杯芳烃的研究 II: 四羟基杯[4]芳烃包合性能的研究

本文利用X射线衍射法研究了四羟基杯[4]芳烃与水、氯仿的包合物的晶体结构,它们属六方晶系, 为分子间包合物。通过这些研究发现: 在晶体中, 四羟基杯[4]芳烃是通过六重螺旋轴的作用形成一种管道型的空间来包合客体分子, 这种管道具有对客体分子选择性等特点。     

杯芳烃的研究 II: 四羟基杯[4]芳烃包合性能的研究

本文利用X射线衍射法研究了四羟基杯[4]芳烃与水、氯仿的包合物的晶体结构,它们属六方晶系, 为分子间包合物。通过这些研究发现: 在晶体中, 四羟基杯[4]芳烃是通过六重螺旋轴的作用形成一种管道型的空间来包合客体分子, 这种管道具有对客体分子选择性等特点。     

25,27-二异丙氧基-26,28-二羟基杯[4]芳烃的合成

在乙腈中,25,26,27,28.四羟基杯[4]芳烃(1)与碘代异丙烷(i-PrI)在碳酸钾的催化下经双烷基化反应合成了25,27-二异丙氧基-26,28-二羟基杯[4]芳烃(2),其结构经<'1>H NMR和MS确证.最佳反应条件为:1 23mmol,n(1):n(K<,2>CO<,3>):n(i-PrI):n(Me...     

去叔丁基杯[8]芳烃乙酸钠对紫杉醇包合作用的研究

采用紫外分光光度法和荧光光谱法研究去叔丁基杯[8]芳烃乙酸钠对紫杉醇的包合和释放过程,考察了二者物质的量之比、温度等因素对包合作用的影响.结果显示去叔丁基杯[8]芳烃乙酸钠在一定条件下与紫杉醇可形成稳定的超分子包合物,包合后水溶性明显提高,且随着去叔丁基杯[8]芳烃乙酸钠/紫杉醇物质的量之比的增加,荧光强度明显增强.去叔丁基杯[8]芳烃乙酸钠今后有望成为紫杉醇类抗肿瘤药物的良好载体.     

The crystal structure of the syn-proximal-5,11,17,23-tetra-tert-butyl-25,26-bis[(2-pyridylmethyl)oxy]-27,28-dihydroxy-calix[4]arene ethanol 1 : 1 Inclusion Complex

The crystal structure of the title compound (1 · C₂H₅OH) has been determined by single-crystal X-ray analysis and refined to anR-value of 0.074 for 2732 observed reflections [I > 2.0(I)]. Crystals are triclinic, space group P , witha = 13.6150(18),b = 13.7195(11),c = 16.5497(16) Å, = 73.132(7), = 66.165(9), = 65.580(8)° andZ = 2. Calix[4]arene (1) adopts a relatively open distorted cone conformation in the solid state, with two pendantsyn-proximal O-CH₂-Py groups. The major conformation determining features in (1 · C₂H₅OH) are the presence of (a) an intramolecular O-H...O hydrogen bond between adjacent proximal phenolic oxygens, O...O 2.719(7) Å and (b) an intramolecular O-H...N hydrogen bond between a phenolic oxygen and a proximal pyridinyl nitrogen, O...N 2.810(8) Å. The intramolecular hydrogen bonding and the interplanar angles of 65.1(3) and 50.7(3)° between opposite aromatic rings facilitate the inclusion of an ethanol molecule within the calixarene cup.Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82141 (26 pages).     

Metallic macrocycle with a 1,3-alternate calix[4]arene salicylideneamine ligand

The calix[4]arene-based podand which incorporates two salicylideneamine units in 1,3-alternate positions of the lower rim has been prepared and subjected to complexation studies with transition metal ions. The nickel and copper complexes form a 2 : 2 stoichiometric metallic macrocyclic framework.     

Inclusion Complexation of Diphenylamine-4-diazonium Chloride and p-Sulfonatocalix[4]arene

Inclusion complexation of p-sulfonatocalix[4]arene (SC4A) and diphenylamine-4-diazonium chloride (DDC) in aqueous solution was investigated in this study. The inclusion of DDC in the cavity of SC4A leads to ¹H NMR chemical shifts of DDC moving towards higher magnetic field. The complexation of SC4A also results in a bathochromic shift and a decrease in optic intensity of the absorption spectrum of DDC. In the presence of SC4A, the thermal stability of DDC in aqueous solution increases significantly while its photosensitivity still remains high.     

Bilayer structure of tetrasodium thiacalix[4]arene tetrasulfonate

The title calixarene, tetrasodium thiacalix[4]arene tetrasulfonate, was prepared and its crystal structure was determined. Na₄[thiacalix[4]arene sulfonate]·9H₂O·CH₃CH₂OH, belongs to triclinic system, space group P , a=10.820(5), b=14.109(6), and c=14.514(6)Å, =99.702(7), β=93.445(8), and γ=93.445(8)°, V=2174.2(16)ų, Z=2. The title calixarene exists in the solid state as bi-layer of anionic calixarene in the cone configuration. These layers alternate with inorganic regions which contain the sodium cations and the water molecules.     

Crystal Structures of Uranyl Ion Complexes of Tetrahydroxy[3.1.3.1]metacyclophane (Homocalix[4]arene)

The first crystal structures of complexes of tetrahydroxy-[3.1.3.1]metacyclophanes, also termed homocalix[4]arenes, are reported. In the two uranyl ion complexes obtained, with different para-substituents, the complex core is analogous to that in tetrahomodioxacalix[4]arene complexes, with the cation in a tetra-phenoxide, distorted square-planar environment. The packing in one of these complexes comprises two different arrangements, one of them being a columnar stacking of complex molecules with sandwiched triethylammonium counter-ions hydrogen bonded to one complex and held by cation–π and CH–π interactions within the cavity of the other neighbouring one.     

以两种杯[4]芳烃衍生物为载体的PVC膜季铵盐正离子选择电极的研究

研究了两种新型杯[4]芳烃衍生物5，ll，17，23-四叔丁基-25，26，27，28-四-[3．(甲氧基羰基)苄氧基]杯[4]芳烃(I)和5，ll，17，23-四叔丁基-25，26，27，28-四-[3-(乙氧基羰基)苄氧基]杯[4]芳烃(Ⅱ)为载体的PVC膜电极的响应行为；实验结果表明，两电极对季铵盐正离子均具有优良的能斯特电位响应性能，以(I)为载体的电极对Bu4N^ 、Et4N^ 和Me4N^ 的线性响应范围分别为10^-6～10^-1mol／L、10^-6～10^-1mol／L和10^-4～10^-1mol／L，相应的斜率为59．2、55．0和55．9mV／pc；以(Ⅱ)为载体的电极对Bu4N^ 、Et4N^ 和Me4N^ 的线性响应范围分别为10^-6～10^-1mol/L，10^-5～10^-1mol/L和10^-4～10^-1mol／L，相应的斜率为59．8、56．6和56．0mV／pc；电极具有读数稳定，重复性好，可在pH值较宽范围内测定等优点；将该电极用于药品溴丙胺太林中丙胺太林含量的测定，所得结果与药典法基本一致。     

Synthesis and structural characterization of a binuclear zirconium complex of tetraanionic p-tert-butylthiacalix[4]arene bridged by methanol

A zirconium complex with the p-tert-butylthiacalix[4]arene anion was synthesized and its crystal structure was determined by single-crystal X-ray analysis. The complex [Zr(μ₂-CH₃OH)(p-tert-butylthiacalix[4]arene)]₂·9H₂O (1) belongs to the orthorhombic system, space group Pnnm, with a?=?20.436(16), b?=?12.160(8), c?=?20.305(12)?Å, V?=?6774(7)?ų and Z?=?2. In Complex 1 zirconium coordinates to four phenolic anions of the deprotonated p-tert-butylthiacalix[4]arene and is bridged by two methanol molecules; the p-tert-butylthiacalix[4]arene adopts a cone conformation.     

Catalytic investigations of calix[4]arene scaffold based phase transfer catalyst

Calix[4]arene scaffold based quaternary ammonium salts as multi-site phase transfer catalysts were prepared and their catalytic activities were investigated for Darzens condensation, O/N-alkylation reactions and ethyl benzene oxidation. These calix[4]arene based multi-site phase transfer catalysts showed significant high catalytic activity as compared to single-site phase transfer catalysts.