四-(p-羟基苯基)杯[4]间苯二酚芳烃的烃基化和酰胺化反应

间苯二酚和对羟基苯甲醛在盐酸/乙醇中缩合生成四-(p-羟基苯基)杯[4]间苯二酚芳烃(1), 在K₂CO₃/丙酮体系中将1分别与溴乙酸乙酯、溴丙烯、N,N-二丙基氯乙酰胺反应可得到全氧烃基化产物2a～2c. 含有12个乙氧基羰基甲氧基支链的2a被苯乙胺、N,N-二甲基二丙胺或三乙烯四胺直接胺解生成杯[4]间苯二酚芳烃酰胺衍生物3a～3c. 2a经过碱性水解、酰氯化、胺化反应转化为含吡啶基的酰胺衍生物3d. 化合物结构都用¹H NMR, IR和元素分析等方法进行了表征.     

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.     

含噻二唑基的对叔丁基杯[4]芳烃衍生物的合成及表征

以对叔丁基杯[4]芳烃(1)为原料, 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选择性烷基化反应, 生成杯[4]芳烃衍生物2和3. 在氢氧化钠存在下, 化合物2和3与过量的含不同官能团的2-巯基噻二唑反应, 生成下缘含噻二唑基的杯芳烃衍生物4a～4c, 5a～5c, 其结构经¹H NMR, ¹³C NMR, IR, MS和元素分析确证.     

含酰胺和席夫碱单元的杯[4]芳烃衍生物的合成与配合性能

杯[4]-1,3-二乙酸乙酯衍生物1与水合肼反应生成杯[4]芳烃酰肼衍生物2, 然后进一步与相应的芳醛反应, 高产率地合成了三个新型的含酰胺和席夫碱单元的杯[4]芳烃衍生物3a～3c和一例新型杯[4]冠醚4. 阳离子萃取实验表明新型杯芳烃衍生物比只含有酰胺基或席夫碱基的杯芳烃衍生物有更强的软金属离子配合性能, 杯[4]冠醚4还对Ag^＋有较好的选择性萃取能力.     

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.     

杯芳烃多齿水杨醛亚胺衍生物的合成

以对叔丁基杯[n]芳烃1a～1b (n＝6, 8)为原料, 经过三步反应, 以较高产率合成了一系列含多个水杨醛亚胺端基的西佛碱衍生物5a～5f. 对叔丁基杯[n]芳烃用溴乙酸乙酯进行烃基化反应, 生成杯芳烃氧代乙酸乙酯2a～2b, 后者与过量脂肪族二胺NH₂(CH₂)_mNH₂ (m＝2, 4, 6)反应, 生成含有游离氨基的杯芳烃酰胺衍生物4a～4f, 再与水杨醛在乙醇中反应生成目标产物席夫碱衍生物.     

含卤素端基的单取代对-叔丁基杯[6]芳烃的合成与表征

用THF作为反应溶剂, K₂CO₃作碱, 对-叔丁基杯[6]芳烃与二溴丁烷、二溴己烷和1,4-二氯丁炔-2反应以中等产率选择性地合成了含有卤素端基的单取代对-叔丁基杯[6]芳烃2a～2c. 2a和2b可与对甲苯磺酸甲酯(MeOTs)反应高产率地得到全甲基化产物3a和3b. 通过核磁共振谱(¹H NMR)和质谱(FAB-MS)表征, 发现所有化合物都具有预期结构, 2a～2c和3b在室温下是锥式构象, 而3a没有固定构象.     

新型多重氮杂杯[4]芳烃衍生物的合成

对叔丁基杯[4]芳烃-1,3-二醛基衍生物1与水杨酰肼、烟酰肼、异烟酰肼反应, 合成了具有开链结构新型杯[4]多重氮杂衍生物2a～2c, 产率分别为88%, 85%和90%. 化合物1与乙二酰肼、丙二酰肼、己二酰肼反应, 得到具有桥联结构的新型杯[4]多重氮杂衍生物3a～3c, 产率分别为86%, 89%和90%. 新化合物的结构经元素分析、质谱、核磁共振谱等表征证实, 杯[4]芳烃单元均为1,3-取代且采取锥式构象.     

杯[4]芳烃黄原酸酯衍生物的合成与阳离子萃取性能

以二氧六环作溶剂, 杯[4]芳烃二甲氧基二羟乙氧基衍生物2与氢氧化钾、二硫化碳作用合成了杯芳烃黄原酸盐衍生物3, 并进一步与碘甲烷或氯化苄反应首次合成了含黄原酸酯基的杯芳烃衍生物4a和4b. 阳离子萃取试验表明该新型杯芳烃衍生物比单硫杂杯芳烃衍生物具有更好的过渡金属离子萃取性能.     

锥形构象含氟杯芳烃衍生物对铜离子的高选择性识别

合成了具有锥形构象的含氟功能基团的杯芳烃衍生物1~3,并用单晶X射线衍射和核磁共振证实了其锥形构象。在混合溶剂中,研究了杯芳烃衍生物1~3对多种金属离子的识别行为。测试了化合物1~3的紫外-可见吸收光谱和荧光发射光谱,结果显示铜离子对化合物1~3具有明显的荧光猝灭特性,而其它金属离子（如Na^',K^',Cs^',Mg^2',Ca^2',Ba^2',Fe^3',Cd^2',Mn^2',Co^2',Ni^2',Zn^2'）对化合物1~3的紫外-可见吸收光谱和荧光发射强度无显著的影响,表明化合物1~3对铜离子的识别具有高选择性。     

Functional modification,self-assembly and application of calix[4]resorcinarenes

As a special subset of calix[4]arene, calix[4]resorcinarene is an excellent molecular platform which could be modified by introducing functional groups to multiple sites at the upper and lower rims. There are mainly three ways to build functionalized calix[4]resorcinarene derivatives: (1) modification on the C-2 sites of calix[4]resorcinarenes; (2) modification on the phenolic hydroxyl groups of calix[4]resorcinarenes; (3) modification on the bridging methylenes at lower rim of calix[4]resorcinarenes. Functionalized calix[4]resorcinarene derivatives play an important role in the development of self-assembly chemistry, among which hydrogen bonding and metal coordination are the two most common interactions to obtain multicomponent structures. Moreover, due to the excellent topological structures and various active substituents of functionalized calix[4]resorcinarene derivatives, their applications in various fields, such as nanoparticles, catalysts, fluorescent materials, and sensors, have been briefly presented in this paper.

     

无溶剂法合成杯[4]芳烯星形化合物

以对苯二甲醛、乙酸酐为原料合成对苯二甲醛单缩醛, 接着与间苯二酚反应, 制备了含醛基杯[4]芳烯. 利用季戊四醇与含醛基杯[4]芳烯反应, 进而再与3-[4-(2,5-二氧杂环戊基)苯基]-9-[4-二(甲羰氧基)甲基苯基]-2,4,8,10-四氧杂螺环[5.5]十一烷反应, 合成了杯[4]芳烯星形化合物, 收率为65.2%. 产品结构经 IR, ¹H NMR, MS 和元素分析进行了表征.     

Syntheses of novel calix[4]arene hydrazone-based receptors and their cooperative complexation with soft and hard metal ions

Four novel calix[4]arene hydrazone-based receptors 3a?Cd were prepared in yields of 69?C87% by condensating formylated calix[4]arene ester (2) with salicylyl hydrazine, 2,4-dinitrophenyl hydrazine, nicotinyl hydrazine or phenyl thiosemicarhazide, respectively. New compounds were characterized through elemental analysis, IR, ESI?CMS, ¹H NMR studies. Compounds 3a?Cd containing two binding sites had the complexation abilities for hard and soft cations concurrently. The noncompetitive extracting experiments showed compounds 3a?Cd were excellent receptors for hard and soft metal cations. The competitive extracting experiments exhibited the cooperative complexation in binding hard and soft metal cations and compound 3a possessed outstanding selectivity for Na⁺ and Hg²⁺. The IR spectra of compound 3a before and after complexation revealed that the soft metal cation was binded in the cavity composed of hydrazone groups and azo groups at the upper rims of calix[4]arene units and hard metal cations was binded in cavity composed of ester groups and phenolic hydroxyl groups at the lower rims of calix[4]arene units.     

A sulfonated calix[4]resorcinarene with α-methyl-l-prolinylmethyl groups as a water-soluble chiral NMR solvating agent

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.     

Design and Syntheses of Novel Calix[4](aza)crowns: Neutral Receptors for α‐Amino Acids

A series of novel calix[4](aza)crowns 2a–2d containing acylhydrazone groups was designed and synthesized via 1+1 condensation of calix[4]‐1,3‐substituted benzaldehyde derivative 1 with bis‐hydrazides in 85–90% yields. They showed good complexation abilities toward α‐amino acids and exhibited complexation selectivity toward tryptophane.     

Synthesis and mesomorphic properties of calix[4]resorcinarene–triphenylene oligomers

By controlling the mol ratios of reactants, novel calix[4]resorcinarene–triphenylene monomer, dimer and tetramer were designed and synthesised in yields of 50–60% via Click chemistry. Their structures were characterised by NMR and MS. Their liquid crystalline behaviours were studied by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction analysis. The more triphenylene units on calix[4]resorcinarene resulted in the wider temperature scopes of mesophase and higher phase transition temperatures. The monomer 6 and dimer 7 showed the mixed columnar mesophase with hexagonal columnar structure and disordered lamellar columnar structure, and compound 8 possessed only disordered lamellar columnar mesophase. These research results suggest that calix[4]resorcinarene was a good platform to construct columnar liquid crystal and the mesomorphic properties were greatly influenced by the substituted numbers of mesogen units on calix skeleton.     

Synthesis and Complexation Abilities of Novel Multiple-Sites Calix[4]arene Receptors: Calix[4]arene Derivatives with Anthraquinone Groups on Lower Rims and Hydrazone Groups on Upper Rims

By formylation of 1,3-bisubstituted calix[4]arene anthraquinone derivative 1 in hexamethylenetetramine/trifluoroacetic acid system, the corresponding formylated gecalix[4]arene anthraquinone derivative 2 was synthesized in yield of 63%. By further reacting compound 2 with salicylic hydrazide, 2,4-dinitrophenyl hydrazine, nicotinyl hydrazine or phenyl thiosemicarhazide, novel calix[4]arene derivatives with anthraquinone and hydrazone groups 3a–3d were obtained in yields of 74–83%. The extracting experiments for series of metallic cations showed that compounds 3a–3d possessed high extracting abilities and extracting selectivity for tested cations. The complexation UV-Vis spectra for a series of anions indicated compounds 3a–3d exhibited the strong complexation abilities for tested anions. The ¹H-NMR titration study showed that compound 3d possessed excellent complexation abilities for ion-pair of NaH₂PO₄ in 1:1 host-guest complex with the association constant of 4.6 × 10⁴ M^?1.     

Synthesis,extraction and chromogenic properties of Amidoazocalix[4]arenes and their telomer derivatives

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.