冠醚化合物的合成 X: 双酰胺双-(3'正十五烷基-苯并-15-冠-5)的合成

本文设计并合成了3'-正十五烷基-5'-硝基-苯并-15-冠-5(1)、3-正十五烷基-5'-氨基-苯并-15-冠-5(2)和十种双酰胺双(3'-正十五烷基-苯并-15-冠-5)(3a-3j), 其合成路线如下.     

冠醚化合物的合成 X: 双酰胺双-(3'正十五烷基-苯并-15-冠-5)的合成

本文设计并合成了3'-正十五烷基-5'-硝基-苯并-15-冠-5(1)、3-正十五烷基-5'-氨基-苯并-15-冠-5(2)和十种双酰胺双(3'-正十五烷基-苯并-15-冠-5)(3a-3j), 其合成路线如下.     

双冠醚的研究——Ⅰ.三个新类型双(4′-并苯-15-冠-5)冠醚的合成

苯并-15-冠-5与四种脂肪族二元酸在多聚磷酸中反应,制备了酮型的二酰双(4＇-苯并-15-冠-5)(1a-d)。后者与Raney镍反应(或用Pd(OH)_2/C催化氢化)和用硼氢化钠还原,分別得到烃型的亚烷基双(4＇-苯并-15-冠-5)(2a-d)和醇型的α,α＇-二羟基亚烷基双(4＇-苯并-15-冠-5)(3a-d)。这是从苯并-15-冠-5制备双(4＇-苯并-15-冠-5)的最简便方法,也可能适用于其它双(4＇-苯并冠醚)的合成。     

2,3-苯并-10-氮杂-1,4,7,13-四氧杂环十五烷与轻稀土硝酸盐配合物的合成和表征

苯并-15-冠-5与轻稀土配合物的研究早有报道。标题化合物,氮杂苯并-15-冠-5(L)稀土配合物尚未见报道。由于NH取代了冠醚环上的一个氧,使冠醚本身具有一定的碱性,致使其稀土配合物合成比较困难。本文采用不同脱水剂合成了氮杂苯并-15-冠-5与硝酸镧(镨、钕)的配合物,并对其进行了表征。     

4'-磺酰腙苯并-15-冠-5的合成及阴离子识别研究

由苯并-15-冠-5经磺酰化、肼解两步合成了4’-磺酰肼苯并-15-冠-5(2).后者与芳香醛在室温下发生缩合制得了一系列未见文献报道的冠醚化磺酰腙类化合物3a～3h,产物经元素分析,IR,1H NMR,13C NMR,MS确证了其结构.利用紫外-可见吸收光谱考查了其对不同阴离子的识别作用,结果表明,化合物3d,3e,3h对碱性较强的阴离子有较强的选择性识别作用.     

铁系元素冠醚配合物的研究——Ⅸ.铁系氯化物与4′-溴-5′-硝基苯并-15-冠-5固体配合物的合成及性质

近年来,有关过渡金属离子冠醚配合物的研究虽有一些报道,但这些研究所涉及的配体大多数是单取代苯并冠醚,对双取代苯并冠醚配位的研究则很少。为了进一步弄清取代冠醚对过渡金属配位性能的影响,我们研究了混合双取代的苯并-15-冠-5,根据文献[2,3]合成了4′-溴-5′-硝基苯并-15-冠-5,并制得了一种新的配合物FeCl_3·L,经性质证明此配合物是1:1型非溶剂合、不含水的固体配合物,其三个Cl~-离子位丁配合物的外界。     

4'-取代苯并-15-冠-5-苦味酸分子络合物的核磁共振研究

研究了15种4'-取代苯并-15-冠-5-及其与苦味酸所形成的电荷转移络合物的~1HNMR,测定了其中12种络合物的络合常数.络合常数,参考线RFL-[D]的斜率以及络合物前后4'-取代苯并-15-冠-5-各类质子与苯并-15-冠-5-相应的质子化学位移之差△δ均与Hammett取代基常数[σ~p+σ~m]呈线性关系.根据取代基对各类质子化学位移变化的影响.讨论了有关化合物的结构与性能的关系.     

3-芳基戊二酰基双(4′-苯并-15-冠-5)的合成

苯甲醛和对氯苯甲醛在碱存在下分别与4′-乙酰基苯并-15-冠-5缩合,生成冠醚化查尔酮1a和1b。此二化合物作为中间体进一步与4′-乙酰基苯并-15-冠-5发生Michael反应,生成两种酮型双冠醚2a和2b。     

4′-取代苯并-15-冠-5-苦味酸分子络合物的核磁共振研究

研究了15种4＇-取代苯并-15-冠-5及其与苦味酸所形成的电荷转移络合物的~1H NMR,测定了其中12种络合物的络合常数。络合常数、参考线REL～[D]的斜率以及络合前后4＇-取代苯并-15-冠-5各类质子与笨并-15-冠-5相应的质子化学位移之差△σ均与Hammett取代基常数[σ_p σ_m]呈线性关系。根据取代基对各类质子化学位移变化的影响,讨论了有关化合物的结构与性能的关系。     

芳香桥式双(苯并氮杂-15-冠-5)的合成及其对碱金属和重金属离子的选择键合

通过11,12-苯并-1,7,10,13-四氧杂-4-氮杂环十五烷-11-烯(苯并氮杂-15-冠-5)分别与间二苄溴, 间苯二甲酰氯和对苯二甲酰氯反应, 合成了N,N'-间二苄基双(苯并氮杂-15-冠-5) (1)、N,N'-间苯二甲酰基双(苯并氮杂-15-冠-5) (2)和N, N'-对苯二甲酰基双(苯并氮杂-15-冠-5) (3) 等三个芳香桥式双(苯并氮杂-15-冠-5)衍生物, 并解析了化合物3的晶体结构. 进而采用溶剂萃取的方法研究了它们与一价金属阳离子的键合行为. 结果表明, 双冠醚2对碱金属钠离子和重金属铊离子表现出较高的选择萃取能力, 而双冠醚1对重金属银离子表现出较高的选择萃取能力.     

Synthesis and Cation Recognition Study of Novel Benzo Crown Ether Functionalized Enamine Derivatives

A novel series of benzo crown ether (dibenzo 18-crown-6 ether, benzo 18-crown-6 ether, and benzo 15-crown-5 ether) functionalized enamines derivatives from amino benzo crown ether (4-amino dibenzo 18-crown-6 ether, 4-amino benzo 18-crown-6 ether, 4-amino benzo 15-crown-5 ether) and substituted 3-(dimethylamino)-1-phenylprop-2-en-1-one compounds have been synthesized. All the synthesized compounds were characterized by infrared, ¹H NMR, ¹³C NMR, distortionless enhancement polarization transfer, and mass and elemental analysis techniques. The cation recognition property for benzo crown ether enamine 8a was studied by absorption and fluorescence spectroscopy.     

含嘧啶环的双冠醚 V.双冠醚为载体的碱金属离子选择性电极的研究

本文报道由５－硝基－６－三氟甲基嘧啶环桥联苯并－１２－冠－４、苯并－１５－冠－５和苯并－１８－冠－６的三种新的双冠醚的合成。用它们作为载体分别制成钠、钾和铯离子选择性电极，测定了电极的响应功能、选择性系数和适用的ｐＨ范围。结果表明三种电极都有较好的性能。     

5-(2’-羧乙基)-6-烷基-3,4-二氢吡喃酮的合成

吡喃酮是许多天然产物的结构单元,我们曾由4-异丁酰基庚二酸在过量醋酸酐及乙酰氯存在下回流得到7-氧代-8,8-二甲基-△~9-六氢香豆素.本文由二氰乙基-β-二酮进行酮解水解反应得到4-酰基庚二酸1_(a-c)。 在过量醋酸酐、乙酰氯存在下由1_a、1_c为底物进行反应没有得到双环的香豆素衍生物.其产物和单纯以乙酐为缩合剂时的产物2_a、2_c相同,产率分别为68％、63％。2_c可在硫酸铁催化     

Synthesis and characterisation of helical beta-peptide architectures that contain (S)-beta3-HDOPA(Crown Ether) derivatives

A new set of beta-amino acids that carry various crown ether receptors on their side chains of the general formula (S)-beta(3)-HDOPA(crown ether) (HDOPA: homo-3,4-dihydroxyphenylalanine; (crown ether): [15]crown-5 ([15-C-5]), [18]crown-6 ([18-C-6]), [21]crown-7 ([21-C-7]), 1,2-Benzo-[24]crown-8 ([Benzo-24-C-8]) and (R)-Binol-[20]crown-6 ([(R)-Binol-20-C-6])) was prepared. Peptides that are based on these new crowned beta-amino acids combined with (1S,2S)-ACHC (2-aminocyclohexanecarboxylic acid), which is known to be a potent 3(14)-helix inducer, to the hexamer level, with two crowned residues at the i and i+3 positions of the main-chain, were synthesized in solution by stepwise coupling using Boc-N(alpha)-protection (Boc: tert-butoxycarbonyl) and the EDC/HOAt C-activation method. Their conformational analysis was performed by using FTIR absorption, NMR and CD spectroscopy techniques. Our results are in full agreement with a 3(14)-helix conformation.     

一种新型低带隙共轭聚合物的合成及其光学性质

在钯催化剂作用下, 通过4,7-二(5-溴-2-噻吩基)[2,1,3]苯并噻二唑与2,5-二乙炔基-3-辛基噻吩的偶联反应, 合成了一种新的共轭高分子聚4,7-二(2-噻吩基)苯并噻二唑-3-辛基噻吩二炔(PTE-DTBT). 通过紫外可见吸收光谱及荧光光谱对其光学性质进行了研究. 紫外-可见吸收谱结果表明, PTE-DTBT的固体膜光学带隙为1.71 eV; 电化学测试其带隙为1.88 eV. TiO₂/PTE-DTBT共混固体膜的荧光发射谱结果表明电子供体PTE-DTBT分子与电子受体TiO₂分子间存在有效的电子转移.     

Study on the syntheses of new 1-o-chlorobenzoyl-3-(5''''-substituted phenylamino-6''''-phenyl)-1'''',2'''',4''''-triazinyl ureas

Eight new 1-o-chlorobenzoyl-3-(5'-substituted phenylamino-6'-phenyl)-1',2',4'-triazinyl ureas (5a-h) have been synthesized and their bioactivities were detected.     

A Facile Method for the Synthesis of 4- Acetylaminobenzo[15]crown-5

The 4-acetylaminobenzo[15]crown-5 is an important intermediate in the synthesis of crown ether cyanine dyes1, in addition, the acetylamino can easily be hydrolyzed to be amine2, to our knowledge which also is an usful intermediate3,4, The classical procedure for the synthesis of 4-acetylaminobenzo[15]crown-5 involves several steps2,5: typically nitration of the benzo[15]crown-5, followed by reduction of the introduced nitro group to form amine, and finally, acylation of the amine to give the am…     

4'-磺酰腙苯并-15-冠-5的合成及阴离子识别研究

由苯并-15-冠-5经磺酰化、肼解两步合成了4'-磺酰肼苯并-15-冠-5 (2). 后者与芳香醛在室温下发生缩合制得了一系列未见文献报道的冠醚化磺酰腙类化合物3a～3h, 产物经元素分析, IR, ¹H NMR, ¹³C NMR, MS确证了其结构. 利用紫外－可见吸收光谱考查了其对不同阴离子的识别作用, 结果表明, 化合物3d, 3e, 3h对碱性较强的阴离子有较强的选择性识别作用.     

Design and Synthesis of Calixarene‐Based Bis‐alkynyl‐Bridged Dinuclear AuI Isonitrile Complexes as Luminescent Ion Probes by the Modulation of Au⋅⋅⋅Au Interactions

Two calixarene‐based bis‐alkynyl‐bridged Au^I isonitrile complexes with two different crown ether pendants, [{calix[4]arene‐(OCH₂CONH‐C₆H₄C≡C)₂}{Au(CNR)}₂] (R=benzo[15]crown‐5 ( 1 ); R=benzo[18]crown‐6 ( 2 )), together with their related crown‐free analogue 3 (R=C₆H₃(OMe)₂‐3,4) and a mononuclear gold(I) complex 4 with benzo[15]crown‐5 pendant, have been designed and synthesized, and their photophysical properties have been studied. The X‐ray structure of the ligand, calix[4]arene‐(OCH₂CONH‐C₆H₄C?CH)₂ has been determined. The cation‐binding properties of these complexes with various metal ions have been studied using UV/Vis, emission, ¹H NMR, and ESI‐MS techniques, and DFT calculations. A new low‐energy emission band associated with Au???Au interaction could be switched on upon formation of the metal ion‐bound adduct in a sandwich fashion.