【作者】 蔡亚华；

【导师】 颜朝国；

【作者基本信息】 扬州大学 ， 物理化学， 2005， 硕士

【摘要】 作为第三代超分子化学主体的杯芳烃的分子设计和应用的研究是超分子化学的热点研究课题,在过去的几十年里,空腔较小的杯[4]芳烃作为主客体化学研究的平台,在液膜传输、络合萃取、分子器件、传感器、液晶、非线性光学材料等领域,发挥了巨大的作用。空腔较大的杯[6]芳烃和杯[8]芳烃的研究近年来受到更多的重视。为探索在超分子化学中功能化杯芳烃的分子结构对客体分子选择性识别的作用规律,本文深入开展了以对叔丁基杯[n]芳烃(n=4,6,8)为母体的一系列杯芳烃酰胺衍生物的分子设计、合成、性质和配合物的研究,取得了一系列有意义的实验结果: 1、合成数十个对叔丁基杯芳烃(n=4,6,8)的醚酯类、酰胺类、Schiff碱类、硫脲类衍生物及其金属配合物。用核磁共振、红外光谱、紫外光谱、元素分析等方法表征了化合物的结构,并测定了两个代表性化合物的单晶分子结构。 2、通过对叔丁基杯芳烃乙酸酯类衍生物与脂肪族二胺、二乙烯三胺、三乙烯四胺、盐酸羟胺、肼等化合物反应合成了一系列多官能化的杯芳烃酰胺类衍生物。再通过末端游离氨基与水杨醛、吡啶醛、二茂铁甲醛等反应,合成了Schiff碱类衍生物;与葡萄糖异硫氰酸酯反应合成了硫脲衍生物。 3、通过对叔丁基杯芳烃乙酸酯类衍生物与乙醇胺、二乙醇胺、三羟甲基甲胺反应,合成了以杯芳烃为核心,外围为多个羟基的树枝醇化合物。通过重复利用脂肪族二胺的单酰胺化,丙烯酸甲酯的共轭加成和水杨醛的缩合反应合成了外围为多个水杨醛亚胺端基的二代树枝状酰胺化合物。 4、通过将对叔丁基杯芳烃乙酸酯类衍生物的碱性水解,合成杯芳烃全氧代乙酸衍生物;通过三氟乙酸的催化水解合成了对叔丁基杯芳烃单酸类衍生物。并以单酸为原料,通过胺、醛缩合反应合成了双杯芳烃。 5、用多齿杯芳烃水杨醛Schiff碱为配体与过渡金属醋酸盐反应,合成了一系列杯芳烃金属配合物。更多还原

【Abstract】 Calix[n]arene like crown ethers and cyclodextrms represent an important class of host in supraraolecular chemistry, which has two intrinsic feature including molecular recognition and self-assembly. During the past two decades, calix[n]arenes have become an very important framework in host-guest chemistry, which have versatile applications in crystal engineering as well as many other fields. We initiated the studies concerning the molecular design, syntheses of P-tert-butylcalix[n]dendrimers, making a series of significant and creative results and developments. The main interesting results are as follows:1. We totally synthesized several new p-tert-Buty\ca\ix[n]arene derivatives, including esters, allyl ethers, amides, Schiff bases,thiourea derivatives and calixarene organometallic compounds. Besides characterizing their structers by NMR and IR, Uv-vis. Two single crystal structure were determined by X-raydiffraction method.2. We synthesized a series p-tert-Butylcalix[n]arene amide derivatives, which are directly amidination of p-tert-Butylcalix[n]arene esters with amines including diamines, triethylene tetramine, hydroxylamine hydrochloride, trihydroxymethyl amine and so on.3. A series of polydentate Schiff base ligands ofp-fer/-Butylcalix[n]arene were prepared from the amides which containing terminal amino groups with aldehyde such as salicylaldehyde, pyridinecaldehyde, From the reactions of this kind of amides with glycosyl isothiocyanate to give thiourea derivatives.4. From the successfully amidination reaction of diamine, Michael addition of methyl acrylate and condensation with saliclylaldehyde, the arbrol and polyamidoamine types of p-terM3utylcalix[n]arene core dendrimers were prepared. The two generation of dendrimers contains mostly 16 terminal long chain salicylideneimine groups.5. Basic hydrolysis of the /7-tert-Butylcalix[n]arene esters gave quantitatively the /?-tert-Butylcalix[n]arene carboxylic acids. Besides the /?-ter￡-Butylcalix[n]arene esters can be selectively hydrolyzed by trifluoroaceticacid in chloroform to give the monoacid.6. A series of calixarene metal complexes were prepared from the />tert-Butylcalix[n]arene Schiff base or acylhydrone with metal acetates.更多还原