硫杂杯[4]芳烃酰胺型氮杂冠醚的合成

硫杂杯[4]芳烃与N,N'-亚乙基双(2-氯乙酰胺)发生分子内"1+1"缩合反应,合成了新型硫杂杯[4]芳烃酰胺型氮杂冠醚--25,27-二羟基-26,28-(1',10'-二氧杂-4',7'-二氮杂-3',8'-二氧代亚癸基)-硫杯[4]芳烃(叔丁基硫杯[4]-1,3-酰胺冠醚)(3),产率68%.1H NMR,ESI-MS和元素分析确证3为1,3-桥联模式且为杯式构象.     

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.     

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.     

新型水溶性杯[4]-1,3-氮杂冠醚衍生物的合成及其催化性能

杯[4]芳烃与N,N′-亚乙基双(2-氯乙酰胺)反应得杯[4]-1,3-氮杂冠醚衍生物(2);2经浓硫酸磺化合成了新型水溶性杯[4]-1,3-氮杂冠醚衍生物(3),其结构经1H NMR,ESI-MS和元素分析表征。探讨了3作为反相转移催化剂对氯化苄和硫氰酸钾的亲核取代反应的催化性能,结果表明,3具有一定的催化活性。     

新型杯[4]冠醚衍生物聚合单体的合成

从对叔丁基杯[4]芳烃出发,对其下沿的酚羟基进行修饰,先后在1,3-和2-酚羟基位点引入冠醚环和乙基;最后在NaH/THF中与3-溴丙烯酸丙酯反应制得聚合单体——新型杯[4]冠醚衍生物,其结构经1H NMR和MS表征。     

多重氮杂杯[4]芳烃和双杯[4]芳烃的合成与阳离子萃取性能

多重氮杂杯[4]芳烃和双杯[4]芳烃的合成与阳离子萃取性能;杯[4]芳烃;双杯[4]芳烃;多重氮杂;萃取     

新型席夫碱基杯[4]冠醚衍生物的合成

杯[4]-1,3-二酯衍生物与水合肼反应后再与二水杨醛二甘醚发生"1 1"分子间缩合,高产率合成了新型席夫碱基杯[4]冠醚衍生物,其结构经1HNMR,IR,MS和元素分析表征。     

新型手性杯[4]氮杂冠醚衍生物的简便合成及其对甲醇分子的包结行为

本文报道新型手性杯[4]氮杂冠醚衍生物的简便合成.即在路易斯酸（ZnCl2）催化下,二氰基取代杯[4]芳烃与各种光学活性的1,2-氨基醇反应,高产率得到了手性杯[4]氮杂冠醚衍生物.该方法具有反应条件温和、操作简便、产率高等特点.产物的晶体X-衍射及ESI-MS数据表明,通过主客体之间的O–H…π作用,杯芳烃上沿的空腔对甲醇分子具有较强的包结作用.     

香豆素冠醚双功能化杯[4]芳烃的合成

以对叔丁基杯[4]芳烃为原料,经碱催化合成了26,28-双(4,7-双甲氧基香豆素)-5,11,17,23-四叔丁基杯[4]-冠-6(2)。其结构经1H NMR,IR和元素分析表征,2为锥形结构。     

氮杂冠醚的研究 Ⅲ.酰胺型氮杂冠醚的合成

2,3-苯并-10-氮杂-1,4,7,13-四氧杂环十五-2-烯分别与酰氯、苯磺酰氯和对甲苯磺酰氯反应,合成了15种酰胺型氮杂冠醚,其中14种为新化合物。产物易纯化,产率高。它们的结构经元素分析、IR、~1HNMR 和 MS 所证实。     

一类新型四酰胺杯[4]氮杂冠醚的合成及阴离子识别研究

合成了一类新型四酰胺杯[4]氮杂冠醚（4a，4b），其结构经~1H NMR、质谱及 元素分析证实。用紫外可见光谱研究了主体与阴离子之间的相互作用，并计算出其 配合常数。结果表明，四酰胺杯[4]氮杂冠醚（4a，4b）对四面体型阴离子（p - O_2GC_6OPO_3~2_4）没有识别性能，而对平面型阴离子（p - O_2NC_6H_4O）有较 好地选择性识别性能，且主客体间形成1：1配合物。     

Unprecedented synthesis of chiral calix[4](aza)crowns and its potent encapsulating methanol

Unprecedented synthesis of chiral (aza)crown ethers of calix[4]arene derivatives bearing a carboxyl amide bridge was described. The synthesis proceeds through condensation of the corresponding dinitriles with optically active 1,2-aminoalcohols,and is catalyzed by the ZnCl2 Lewis acid at elevated temperature in a very efficient one-pot process. The cavity of calix[4](aza)crowns can encapsulate methanol molecules by O—H...π interaction,which has been confirmed by X-ray crystal structures and ESI-MS.     

新型间苯二酚杯芳烃硫脲衍生物对阴离子的识别

通过间苯二酚杯芳烃连续三步反应, 以较高产率合成了分子中连有8个和12个硫脲端基的间苯二酚杯芳烃的酰胺衍生物. 用紫外可见光谱法研究了两个代表性化合物4,6,10,12,16,18,22,24-八[6-(苯基硫脲基)-己氨甲酰基甲氧基]-2,8,14,20-四苯基杯[4]间苯二酚芳烃(THBC)和4,6,10,12,16,18,22,24-八[2-(苯基硫脲基)-1-甲基乙基-1-氨甲酰基甲氧基]-2,8,14,20-四苯基杯[4]间苯二酚芳烃(TPBC), 对各种阴离子(AcO^－, H₂PO₄^－, HSO₄^－, H₂PO₄^2－, C₁₂H₂₅-C₆H₄-SO₃^－, Cr₂O₇^2－, B₄O₇^2－, Cl^－, Br^－)的识别性能, 结果表明它们对AcO^－, H₂PO₄^－, HSO₄^－等阴离子有较好的配位作用, 能形成1∶3的配合物.     

Synthesis and nitration of calix[4] (aza)crowns

Calix[4] (aza) crowns containing amide groups 3a-d were synthesized by the reactions of calix[4]arene (1a) or p-tert-butylcalix[4]arene (1b) with N, N'-ethylenebis(2-chloroac-etamide) (2a) or N, N'-1,2-phenylenebis(2-chloroacetamide) (2b) by one step procedure in yields of 85-90% . Calix[4]-(aza) crowns 4a-b could be obtained by the reduction of 3a-b with LiAlH4 in yields of 51 and 67% , respectively. The nitration of 3a or 3c afforded new chromogenic calix[4]arenes 5a bearing two nitrophenol moieties and 5c bearing one nitro-phenol and one quinone moiety, respectively. The ipso-nitrations of 3b and 3d were also studied. Both gave the products containing one nitrophenol and one quinone moiety. Moreover, a very interesting calix[4]arene derivative 5d containing one cyclohexadienone moiety was also separated as the main product when 3d was ipso -nitrated.     

新型生色杯[4]芳烃衍生物的合成及其对CU2+的识别

设计并合成了含偶氮基、酰胺基和席夫碱基的新型生色杯[4]芳烃衍生物(1),其结构经1H NMR,IR,MS和元素分析表征.荧光光谱研究表明,1在λex/λem=370 nm/422 nm处有最大峰;1与Cu2+配合时荧光显著猝灭.     

毛细管电泳研究杯[4]吡咯和二吡咯化合物对无机阴离子的识别作用

Capillary electrophoresis （CE） can separate charged and neutral substances with high speed and efficiency. In this paper, utilizing meso-octamethylcalix[4]pyrrole, meso-tetraspirocyclohexylcalJx[4]pyrrole, bimethyl bi（2-pyrryl）- methane and 1,1-bi（2-pyrryl）cyclohexane as additives in capillary zone electrophoresis （CZE） electrolyte, their recognition ability to inorganic anions was discussed. The dipyrrylmethanes have better recognition ability than others. Their effects on separation of seven normal inorganic anions by CZE were studied.     

New Tetrafunctionalized Cone Calix[4]arenes as Neutral Hosts for Anion Recognition

Abstract

The synthesis and anion binding properties of several new cone calix[4]arenes having different flexibility and tetrafunctionalized at the upper rim with various type of hydrogen bonding donor groups such as thioureas (1–3), trifluoroacetamides (4, 5) and perfluorinated alcohols (6) are reported. The results obtained show that thiourea receptors are the most effective in the complexation of all anions and that the rigid cone compound 2 is more efficient than the mobile cone analog 1 in the binding of spherical anions, whereas the reverse is true for the complexation of tetrahedral H₂PO₄ ^? anion.     

Syntheses of Novel Chiral Calix[4]crown: Lariat Calix[4]-1,3-aza-crowns with Chiral Amino Acid Groups as Branched Chains

The first examples of lariat calix[4]-1,3-aza-crowns with chiral amino acid groups as branched chains (5a and 5b) were designed and synthesized via a 1 + 1 addition reaction of calix[4]-1,3-substituted benzaldehyde derivative (4) and amino acid hydrazide derivatives (3a and 3b) in yields of 70% and 75%, respectively. The preliminary extraction experiments suggested that hosts 5a and 5b possessed good complexation abilities for α-amino acids.