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.     

一锅法合成含两种桥联链的杯[4]双冠醚和双杯[4]冠醚

报道了"一锅法"合成含两种桥联链的新型杯[4]双冠醚和双杯[4]冠醚.杯[4]芳烃先与N,N’-乙撑基-二(2-氯乙酰胺)发生"1+1"缩合反应,然后直接加入三甘醇双对甲苯磺酸酯继续进行"2+2"缩合反应,合成了含两种桥联链的新型双杯[4]冠醚4.按照相似程序,杯[4]芳烃先后与N,N’-乙撑基-二(2-氯乙酰胺)、溴乙酸乙酯和二乙烯三胺反应,得到含两种桥联链的新型杯[4]双冠醚5.化合物5进一步与异硫氰酸苯酯反应合成带硫脲支链的杯[4]双冠醚6.所有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.     

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]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。     

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。     

环氧丙基杯[6]-1,4-冠-4聚合物的合成与吸附性能

通过具有稳定锥式构象的杯[6]-1,4-冠-4与环氧氯丙烷反应,再与多乙烯多胺开环聚合,合成了一系列具有稳定构象的新型含氮杯[6]芳烃冠醚聚合物(3a-3c)。并研究了它们对阳离子的吸附性能,结果表明,其吸附选择性较没有稳定构象的类似杯[6]芳烃聚合物好,聚合物3b和3c对Cu^2 表现较好的选择性吸附能力。     

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.     

简便合成新型四桥联双杯[4]管道和1,2-3,4-双桥联杯[4]芳烃

报道了一种间接缩合法高产率简便合成新型四桥联双杯[4]管道和1,2-3,4-双桥联杯[4]芳烃.杯[4]二酰肼衍生物2与丁二酸酐发生开环反应,以95%的产率得到杯[4]羧酸衍生物4.化合物4在DCC/DMAP/CH2Cl2体系中发生分子间自缩合反应,以90%产率得到新型四桥联双杯[4]管道6.改用高度稀释的条件则以26%的产率得到新型1,2-3,4-双桥联杯[4]芳烃5.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.     

含酰胺基和酯基的新型杯[4]冠醚的合成及其对金属离子的识别能力

利用杯[4]芳烃与含酰胺基和酯基的丙二酸酯衍生物的"1+1"分子间缩合合成了一例新型结构的杯[4]-1,3-冠醚;利用核磁共振、红外光谱、质谱及元素分析表征了其结构,并测定了其对金属离子的识别能力.结果表明,合成的新型杯[4]冠醚对金属阳离子和阴离子均有较好的识别能力.     

二氧化硅固载苯并冠醚的合成与性能

3-烯丙基邻苯二酚与氯乙醇反应,得到3-烯丙基-1,2-双羟乙氧基苯,它与二缩三乙二醇双对甲苯磺酸酯反应,得到3-丙烯基苯并18-冠-6。从4-烯丙基邻苯二酚类似地制得4-烯丙基1,2-双羟乙氧基苯。它与1,2-双羟乙氧基苯双对甲苯磺酸酯反应,合成了4-丙烯基二苯并-18-冠-6。二种丙烯基取代冠醚与三氯硅烷反应,以二氧化硅固载化,得到二氧化硅固载苯并冠醚,它们皆可与铂形成配合物,是一类新型烯烃硅氢化催化剂。     

Novel Cesium‐Selective Electrodes Based on Lipophilic 1,3‐Bisbridged Cofacial‐calix[6]crowns

Five bisbridged calix[6]crowns have been investigated as Cs⁺ ionophore in PVC membrane electrodes. As ionophores, three 1,3‐bisbridged calix[6]crown‐4‐ethers( I–III ), 1,3‐bisbridged calix[6]crown‐5‐ether( IV ), and 1,3‐bisbridged calix[6]crown‐6‐ether( V ) have been evaluated. The membranes all give good Nernstian response in the concentration range from 1×10^?7 to 1×10^?1 M of cesium ion. The best detection limits (?log aequation/tex2gif-inf-1.gif=7.08–7.36) are obtained for electrode membranes containing 1,3‐bisbridged cofacial‐calix[6]crown‐4‐ethers( I‐III ), and the values are the lowest compared with those reported previously. The highest selectivity coefficients [ 3.74(Cs/K), 2.63(Cs/Rb)] are obtained for the membrane of 1,3‐bisbridged calix[6]crown‐4‐ether( II ), and these values are also the highest compared with previous reports for Cs⁺‐ISEs. The highest selectivity towards cesium ion is attributed to the geometrically cofacial positions of two crown‐ethers in calix[6]crowns in order to provide the complex of cesium ion and eight oxygens of cofacial crowns.     

Design and Syntheses of Novel Calix[4]crown: Calix[4]‐Dixanthates‐Crowns

Abstract

A series of novel calix[4]‐dixanthates‐crowns were designed and synthesized by the “1 + 1 condensation” of reacting calix[4]‐1,3‐dixanthate salts derivative (4) with polyethylene glycol ditosylates in 40–60% yields. It was found that the new calixcrowns showed outstanding complexation abilities towards soft cations. Calix[4]‐dixanthate‐crown‐4 (5b) exhibited high complexation selectivity towards Ni²⁺.     

Synthesis of p‐tert‐Butyl‐calix[6] ‐biscrown‐3 via Intramolecular Ring‐closure of 1,4‐Bis (2‐(2‐chloroethoxy) ethoxy) ‐p‐tert‐butyl‐calix[6]arene

With a variation in reaction conditions, 1, 4‐bis (2‐(2‐chloroethoxy)ethoxy)‐calix[6]arene (3) and l,3,5‐tris(2‐(2‐chloroethoxy) ethoxy)‐calix [6] arene (4) or 4 and 4‐chloroethoxyethoxy‐calix[6]crown‐3 (5) were selectively synthesized from p‐tert‐butyl‐calix [6] arene and 2‐(2‐chloroethoxy)ethyltosylate. l,3–4,6‐p‐tert‐butylcalix[6]‐bis‐crown‐3 (6) with (u,u,u,d,d,d) conformation and 1,3–4,5‐p‐tert‐butylcalix[6]‐biscrown‐3 (7) with self‐anchored (u,u, u, u, u, d) conformation were synthesized through an intramolecularly ring‐closing condensation of 1, 4‐bis (2‐(2‐chloroethoxy)ethoxy)‐p‐tert‐butyl‐calix[6]arene (3) in 25% and 15% yield, respectively. Using 5 instead of 3, only 7 was obtained in 65% high yield. 6 and 7 show different complexation properties toward alkali metal and ammonium ions.     

Synthesis of two 1,3‐2,4‐calix[4]bis‐crown ethers containing two 1,2‐phenylene and one pyridine or anisole units in each crown ether moiety

Syntheses of 1,3–2,4‐calix[4]bis‐crown ethers ( 1 and 2 ) fixed in the 1,3‐alternate conformation by 1,3‐ and 2,4‐bridges made of two modified polyether chains each containing two 1,2‐phenylene residues and one pyridine or anisyl unit are reported. The structures of compounds 1 and 2 were established by ¹H nmr, ¹³C nmr, hrms and elemental analyses.     

Regioselective intramolecular bridging of p-tert-butylcalix[10]arene

The synthesis and characterization of a series of regioselective intramolecular bridging of calix[10]arene are described for the first time. Reacting p-tert-butylcalix[10]arene with tri-ethylene glycol ditosylate using K₂CO₃ as a base in toluene, 1,2-calix[10]crown-4 2a, 1,4-calix[10]crown-4 2b and 1,6-calix[10]crown-4 2c were obtained in yields of 9%, 14% and 7%, respectively. While using Cs₂CO₃/acetone instead of K₂CO₃/toluene, the 1,4-calix[10]crown-4 2b was obtained selectively in good yield up to 50%.     

A New Four‐Component Reaction for the Synthesis of Spiro[4H‐indeno[1,2‐b]pyridine‐4,3′‐[3H]indoles]

A new four‐component synthesis of spiro[4H‐indeno[1,2‐b]pyridine‐4,3′‐[3H]indoles] and spiro[acenaphthylene‐1(2H),4′‐[4H‐indeno[1,2‐b]pyridines] by the reaction of indane‐1,3‐dione, 1,3‐dicarbonyl compounds, isatins (=1H‐indole‐2,3‐diones) or acenaphthylene‐1,2‐dione, and AcONH₄ in refluxing toluene in the presence of a catalytic amount of pyridine is reported.     

Exploring the structural landscape of 2‐(thiophen‐2‐yl)‐1,3‐benzothiazole: high‐Z′ packing polymorphism and cocrystallization with calix[4]tube

We report here for the first time a cocrystal of the so‐called neutral calix[4]tube, which is two tail‐to‐tail‐arranged and partially deprotonated tetrakis(carboxymethoxy)calix[4]arenes, including three sodium ions, with 2‐(thiophen‐2‐yl)‐1,3‐benzothiazole, namely trisodium bis(carboxymethoxy)bis(carboxylatomethoxy)calix[4]arene tris(carboxymethoxy)(carboxylatomethoxy)calix[4]arene–2‐(thiophen‐2‐yl)‐1,3‐benzothiazole–dimethyl sulfoxide–water (1/1/2/2), 3Na⁺·C₃₆H₃₀O₁₂^2?·C₃₆H₃₁O₁₂^?·C₁₁H₇NS₂·2C₂H₆OS·2H₂O, which provides a new approach into the host–guest chemistry of inclusion complexes. Three packing polymorphs of the same benzothiazole with high Z′ (one with Z′ = 8 and two with Z′ = 4) were also discovered in the course of our desired cocrystallization. The inspection of these polymorphs and a previously known polymorph with Z′ = 2 revealed that Z′ increases as the strength of intermolecular contacts decreases. Also, these results expand the frontier of invoking calixarenes as a host for nonsolvent small molecules, besides providing knowledge on the rare formation of high‐Z′ packing polymorphs of simple molecules, such as the target benzothiazole.     

25,27‐(6‐Tosyl‐3,9‐dioxa‐6‐aza­un­decane‐1,11‐diyldioxy)‐26,28‐(3,6,9‐trioxaun­decane‐1,11‐diyldioxy)­calix­[4]­arene

A new calix­[4]‐­crowned aza­crown ether, C₅₁H₅₉NO₁₁S, consisting of four phenyl rings in a 1,3‐alternate conformation was synthesized from the reaction of 25,27‐bis(5‐chloro‐3‐oxa­pentyl­oxy)­calix­[4]­crown‐5 and p‐toluene­sulfon­amide in the presence of Cs₂CO₃. A crown‐5 loop was attached on the two facing lower rims of the calix­[4]­arene and the N‐tosyl aza­crown group was attached on the other set of lower rims of the calix­[4]­arene backbone. This mol­ecule seems to offer an inside cavity for the formation of a host–guest complex.     

Unusual conformations of 1,3‐dialk­oxy­thia­calix[4]arenes in the solid state

The structures of three syn‐1,3‐dialkoxy­thia­calix[4]arenes with unusual conformations in the solid state are reported. The pinched cone conformation of syn‐2²,4²‐dihydroxy‐1²,3²‐bis­(prop‐2‐enyl­oxy)thia­calix[4]arene, C₃₀H₂₄O₄S₄, (3a), is stabilized by two intra­molecular hydrogen bonds, remarkably formed from both OH groups to the same ether O atom. In syn‐2²,4²‐dihydroxy‐1⁵,2⁵,3⁵,4⁵‐tetra­nitro‐1²,3²‐bis­(prop‐2‐enyl­oxy)thia­calix[4]arene acetone disolvate, C₃₀H₂₀N₄O₁₂S₄·2C₃H₆O, (3b1), the mol­ecule is found in the 1,3‐alternate conformation. The crystallographic C2 symmetry is due to a twofold rotation axis running through the centre of the calixarene ring. The hydroxy groups cannot form intra­molecular hydrogen bonds as in (3a) and both are bonded to an acetone solvent mol­ecule. The mol­ecule of the pseudo‐polymorph of (3b1) in which the same compound crystallized without any solvent, viz. (3b2), is located on a crystallographic mirror plane. Only one of the two hydroxy groups forms a hydrogen bond, and this is with a nitro group of a neighbouring mol­ecule as acceptor. Mol­ecular mechanics calculations for syn‐1,3‐diethers suggest a preference of the 1,3‐alternate over the usual cone conformation for thia­calix[4]arene versus calix[4]arene and for para‐nitro versus para‐H derivatives.     

Synthesis of a calix[4]crown modified with germanium‐containing side chains

A germacalix‐crown, 25,27‐bis[1‐(3‐trimethylgermylpropyl)oxy]calix[4]arene‐crown‐6, 1,3‐alternate ( 1a ), and its carbon analog, 25,27‐bis‐[1‐(4,4‐dimethylpentyl)oxy]calix[4]arene‐crown‐6, 1,3‐alternate ( 1b ), were prepared and their structures were confirmed by elemental analysis and ¹H and ¹³C NMR spectroscopy. A cation transport test indicated that both compounds exhibited much the same cation transport ability, so that the role of the germanium moiety in capturing and transporting counteranions is not yet clear. Copyright © 2005 John Wiley & Sons, Ltd.