硫杂杯芳烃冠醚的合成及其与氨基酸配合性能的研究

在普通杯芳烃骨架中引入硫原子可以改善普通杯芳烃的配合性能。文中首先合成了硫杂杯[4]芳烃四酰肼衍生物3,在弱酸的催化下继续与化合物4反应,高产率地合成了同时含酰胺和席夫碱单元的硫杂杯[4]芳烃冠醚衍生物5,新化合物的结构经1H NMR、元素分析、ESI-MS等表征证实。同时探讨了新型硫杂杯[4]芳烃衍生物5与系列-α氨基酸的配合性能。     

新型硫杂杯[4]芳烃衍生物的合成

在对叔丁基硫杂杯[4]芳烃(1)的下缘1,3-位引入芳醛基制得硫杂杯[4]二醛基衍生物(3);3在水合肼中肼解制得硫杂杯[4]二醛腙基衍生物(4);4与5,5'-亚甲基二水杨酰基二水杨酰氯经缩合反应合成了具有桥连结构的硫杂杯[4]芳烃桥联氮杂衍生物(6),3,4和6为新化合物。其结构经1H NMR,IR,ESI-MS和元素分析表征。     

一些新型含氮、硫杂官能团的杯[4]芳烃衍生物的合成

以杯[4]芳烃-1,3-二溴乙氧基衍生物1为合成平台,在K2CO3/MeCN体系中分别与乙醇胺、L-亮氨醇、2-巯基苯并咪唑、巯基乙酸乙酯反应,以49%～76%的产率合成了4种新型含氮、硫杂官能团的杯[4]芳烃衍生物2,4,5和6.化合物2进一步与异硫氰酸苯酯反应,以84%的产率得到了新型树枝状杯[4]芳烃氮、硫杂衍生物3.新化合物的结构与构象经元素分析、质谱、核磁共振谱等表征证实.     

系列新型硫杂杯[4]芳烃氮杂衍生物的合成

在对叔丁基硫杂杯[4]芳烃的下缘1,3位引入芳醛基, 合成了硫杂杯[4]二醛基衍生物2. 化合物2与苯胺、水杨酰肼、烟酰肼、异烟酰肼等通过席夫碱缩合反应得到新型硫杂杯[4]氮杂衍生物3a～3d, 产率分别为83%, 80%, 77%和79%. 化合物2与邻苯二胺、乙二酰肼、丙二酰肼、己二酰肼等通过“1＋1”分子间缩合得到新型1,3-桥联硫杂杯[4]氮杂衍生物4a～4d, 产率53%, 51%, 59%和66%. 新化合物的结构经IR, ¹H NMR, MS和元素分析等证实.     

苄连氮桥联双硫杂杯[4]芳烃的合成

硫杂杯[4]二醛基衍生物(1)在水合肼中肼解,合成了新化合物硫杂杯[4]二醛腙基衍生物(2);1和2在弱酸的催化下反应合成了新的具有对称结构的苄连氮双硫杂杯[4]芳烃(3);2和3的结构经1H NMR,IR,ESI-MS和元素分析表征.     

含酰胺和硫脲单元的杯[4]芳烃衍生物的合成

杯[4]芳烃．1,3-二乙酸乙酯衍生物与水合肼反应生成杯[4]芳烃酰肼衍生物(2),2与异硫氰酸苯酯反应得到新型含酰胺和硫脲单元的杯[4]芳烃衍生物,总产率85％。     

硫杂杯[4]芳烃衍生物的合成及萃取性能研究

通过两个不同的平台合成了一系列结构新颖的硫杂杯[4]芳烃衍生物,阳离子萃取试验表明该硫杂杯[4]芳烃衍生物比含有相似官能团的杯[4]芳烃衍生物具有更好的软金属离子萃取性能,新化合物的结构经IR, 1H NMR,MS和元素分析等证实.     

硫杂杯[4]芳烃化学修饰的研究进展

硫杂杯[4]芳烃是由S原子取代经典杯芳烃中的桥联亚甲基而成的大环化合物,在分子识别、多核金属配合物、化学传感器等方面有广泛的应用.对硫杂杯[4]芳烃的化学修饰进行综述,有助于新型功能化硫杂杯芳烃衍生物的研究.     

N-硫脲基套索杯[4]冠醚与四硫脲基杯[4]芳烃的合成

控制反应物的物质的量比, 杯式对叔丁基杯[4]-1,3-二乙酸乙酯衍生物1与5或50倍二乙烯三胺反应, 分别得到杯[4]氮杂冠醚2和开链的氮杂杯[4]芳烃衍生物3. 化合物2和3进一步与异硫氰酸苯酯反应得到首例侧链含硫脲基的套索杯[4]氮杂冠醚4和含4个硫脲基的杯[4]芳烃衍生物5, 产率为92%和87%. 新化合物的结构与构象经元素分析、红外、质谱、核磁共振谱等表征证实.     

新型杯[4]芳烃四胆固醇衍生物的合成

杯[4]芳烃和氯乙酸乙酯在碱性条件下反应制得杯[4]芳烃四乙酸乙酯（b）; b经肼解反应制得杯[4]芳烃四乙酰肼(c),再与胆固醇氯甲酸脂反应合成了以肼片段为连接臂的杯[4]芳烃四胆固醇衍生物（d）,其结构经¹H NMR, IR,MS和元素分析表征。     

Anion receptors based on ureido-substituted thiacalix[4]arenes and calix[4]arenes

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.     

Structure and conformational equilibrium of thiacalix[4]arene by density functional theory

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.     

A Rare and Exclusive Endoperoxide Photoproduct Derived from a Thiacalix[4]arene Crown‐Shaped Derivative Bearing a 9,10‐Substituted Anthracene Moiety

A rare and exclusive endoperoxide photoproduct was quantitatively obtained from a thiacalix[4]arene crown‐shaped derivative upon irradiation at λ=365 nm; the structure was unambiguously confirmed by ¹H/¹³C NMR spectroscopy and X‐ray crystallography. The prerequisites for the formation of the endoperoxide photoproduct have also been discussed. Furthermore, the photochemical reaction rate could be greatly enhanced in the presence of the thiacalix[4]arene platform because it served as a host to capture oxygen.     

Thiacalix[4]arene derivatives as radium ionophores: a study on the requirements for Ra2+ extraction

The synthesis and NOE-based structural characterization is described of thiacalix[4]arene tricarboxylic acid (7), thiacalix[4]crown-5 and -6 monocarboxylic acids (2 and 5), and the bis(N-methylsulfonyl)thiacalix[4]crowns-5 and -6 (4a,b). The 226Ra2+ selectivity coefficients, log(K(Ra)ex/K(M)ex), of the new thiacalix[4]arene derivatives are compared directly with those of thiacalix[4]crown-5 and -6 (1a,b), thiacalix[4]crown-5 and -6 dicarboxylic acids (3a,b), and thiacalix[4]arene di- and tetracarboxylic acids (6 and 8). Thiacalix[4]arene dicarboxylic acid (6) already exhibits a high 226Ra2+ selectivity, but this is significantly improved in the case of 3b, having an additional crown-(6-)ether bridge. The covalent combination of a crown ether and carboxylic acid substituents as in the thiacalix[4]arenes 2,3a,b,4a,b, and 5 gives a better 226Ra2+ selectivity in the presence of Sr2+ or Ba2+ than mixtures of dibenzo-21-crown-7 and thiacalix[4]arene dicarboxylic acid (6) or of pentadecanoic acid and thiacalix[4]crown-6 (1b).     

含噻二唑官能基的对叔丁基硫桥杯[4]芳烃衍生物的合成及结构

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.     

Conformational behaviour of tetramethoxythiacalix[4]arenes: solution versus solid-state study

The conformational behaviour of simple thiacalix[4]arene derivatives was studied using a combination of NMR spectroscopy and X-ray diffraction analysis. The 25,26,27,28-tetramethoxythiacalix[4]arene was found to adopt an unprecedented solid-state structure, where the cone and 1,3-alternate conformers co-exist in the crystal lattice in the 3:1 ratio. This phenomenon reflects the basically distinct conformational behaviour of thiacalix[4]arene skeleton as compared with classical calixarenes.     

单取代罗丹明-硫杂杯[4]芳烃衍生物的合成及对Fe~(3+)离子的荧光探针性质研究

以1,3-交替-二羧基甲氧基硫杂杯[4]芳烃为原料,通过与罗丹明乙二胺衍生物的酰化反应得到罗丹明基团单取代的硫杂杯[4]芳烃衍生物。目标化合物结构经IR,NMR,MS及元素分析等技术表征。荧光及可见吸收光谱法研究表明化合物对Fe3+具有探针性质,在乙醇-水(1/1,V/V)Tris-HCl(pH=6.0)缓冲溶液中,对Fe3+呈现光关-开响应,并观察到显著的荧光增强和颜色变红现象。测定了Fe3+-配合物的组成、稳定常数及荧光量子产率。     

Synthesis and conformational evaluation of p-tert-butylthiacalix[4]arene-crowns

Bridging of p-tert-butylthiacalix[4]arene afforded 1,3-dihydroxythiacalix[4]arene-monocrown-5 (3b), 1,2-alternate thiacalix[4]arene-biscrown-4 and -5 (4a,b), and 1,3-alternate thiacalix[4]arene-biscrown-5 and -6 (5a,b), depending on the metal carbonates and oligoethylene glycol ditosylates used. Starting from 1,3-dialkylated thiacalix[4]arenes, the corresponding bridging reaction gave 1,3-alternate, partial-cone, and cone conformers 10-19, depending on the substituents present. Temperature-dependent studies revealed that the conformationally flexible 1,3-dimethoxythiacalix[4]arene-crowns 10a-c exclusively occupy the 1,3-alternate conformation. Demethylation exclusively gave the cone 1,3-dihydroxythiacalix[4]arene-crowns (3a,c), which could not be obtained by direct bridging of thiacalix[4]arene. The different structures were assigned on the basis of several X-ray crystal structures and extensive 2-D (1)H NMR studies.     

Supramolecular assembly based on π-π stacking and π-cation interactions between thiacalix[6]arene and DMF

The molecular assembly of thiacalix[6]arene was formed by π-π stacking and π-DMF interactions between thiacalix[6]arene and adjoining thiacalix[6]arene and between thiacalix[6]arene and DMF, respectively. The X-ray crystal analysis also revealed that hydroxyl groups of thiacalix[6]arene adopted novel two sets of hydrogen bond with two DMF and intramolecular hydrogen bond between phenolic units, which cause to make 1,2,3-alternate configuration structure of thiacalix[6]arene.