【作者】 丁从文；

【导师】 张明杰；

【作者基本信息】 天津大学 ， 有机化学， 2011， 博士

【摘要】 基于硫脲类化合物的合成方法研究背景和大环超分子（磺酰）硫脲受体的应用进展以及磺酰胺类化合物作为亲核试剂参与的有机反应研究现状,提出了本文标题化合物大环超分子磺酰硫脲类受体的绿色合成方法,合成了26个新型中间体以及未见文献报道的标题化合物78个,探索了一些典型的硫脲受体对阴离子（包括氨基酸和路易斯酸）的络合性能。具体包括以下三部分内容:在无机碱NaOH或KOH存在的条件下,在水介质中合成了四亚乙基双对甲苯磺酸二醇酯、三对甲苯磺酰基二乙烯三胺、N-对甲苯磺酰基-氮杂环丙烷。用甲醛、氢氧化钠和对叔丁基苯酚混合加热制备了对叔丁基杯[4]芳烃,以此为合成平台进行了脱叔丁基化、酚羟基（冠）醚化、苯环硝化、氨基化、氯磺酰化、氨基磺酰化以及叔丁基本位氯磺酰化,制备了杯[4]芳烃、对叔丁基杯[6]芳烃、甲氧基乙氧基和N,N’-二甲基羰基亚甲基醚化的杯[4]芳烃、1,3-二氨基杯[4]芳烃、对叔丁基杯[4]（双）冠-5、1,3-交替式二氨基杯[4]冠-5等中间体。从对叔丁基杯[4]冠-5出发,经过本位氯磺酰化、胺解,然后与二硫化碳反应,在氯乙酸盐活化下,于水介质中合成了杯[4]冠-5-磺酰四氢咪唑-2-硫酮和杯[4]冠-5-磺酰六氢嘧啶-2-硫酮。同法合成了杯[6]咪唑磺酰四氢咪唑-2-硫酮和杯[6]咪唑磺酰六氢嘧啶-2-硫酮、N-杯[4]芳烃-N’-芳基或烷基磺酰基硫脲和N-杯[4]芳烃磺酰基- N’-芳基或烷基硫脲。在镁和甲醇作用下,合成了脱磺酰化产物1,3交替式杯[4]冠-5-四氢咪唑-2-硫酮、硫脲环番受体。在双氧水作用下,制备了氧化产物1,3交替式杯[4]冠-5-四氢咪唑-2-酮和脲类环番受体。在所测试的一系列阴离子H₂PO₄^-、HSO₄^-、C1^-、NO₃^-、ClO₄^-中,杯芳烃磺酰硫脲78a对H₂PO₄^-表现出更强的选择性络合能力。大环硫脲受体81c对一系列阴离子F^-、CH₃COO^-、Cl^-、Br^-、I^-、NO₃^-的络合中,发现Cl^-可被选择性络合。硫脲环番受体（92b）对一系列氨基酸均能有效地萃取,特别是对异亮氨酸呈现出较强的选择性络合能力。在大环配体杯冠醚磺酰咪唑-2-硫酮（62）与路易斯酸（MCl₂）的配合物（[M（62）]Cl₂ ）的氢谱中, ArCH₂Ar’分裂为1:1的1对双峰,说明受体（62）与MCl₂配位后仍然保持杯式构象。从配体（62）与氯化锌配位后的红外和氢谱表征变化量分析,结果足以说明具有杯式构像的更多还原

【Abstract】 The synthetic method of macrocyclic supramolecular sulfonyl thiourea receptors was developed, based on the research progress of the synthetic method of thiourea derivatives, the utilization of macrocyclic receptors and of sulfonamide-mediated reactions as nucleophilic reagent. Twenty-six new key intermediates and seven ty-eight undocumented topic compounds were synthesized conveniently. Complex action of these macrocyclic receptors with anions containing amino acid and Lewis acid was roughly explored. Including three parts are as follows:Tetraethylene glycol ditosylates, N,N’,N’’-tri-tosyl-diethylenetriamine and N-tosyl aziridines were synthesized in the presence of inorganic base NaOH or KOH in aqueous media. p-tert-butyl-calix[4]arene was synthesized taking HCHO and NaOH as meterial. Detertbutyl, hydroxybenzene （crown） etherification, aromatic nitration, aromatic amination and aromatic chlorosulfonylation, aminosulfonylation and ipso-chlorosulfonylation were performed on the platform of calixarene. Such intermediates as calix[4]arene, p-tert-butyl-calix[6]arene and methoxyethoxy- etherification calix[4]arene, N,N’-dimethylcarbonylmethy-etherification calix[4]arene, 1,3-diaminocalix[4]arene and p-tert-butyl-calix[4]-bis（crown-5） and 1,3-alternative diaminocalix[4]-crown-5 were designed and synthesized according to the improved procedures of literature.Calix[4]-crown-5-sulfonyl tetrahydroimidazo thione-2 and hexahydropyrimidine thione-2 were synthesized from calix[4]-crown-5-sulfonylethylenediamine and carbon disulfide through nucleophilic addition and subsequent cyclization of intramolecule promoted by ClCH₂COOK at room temperature in aqueous solution. In this paper, as a part of our program towards green synthesis, a series of calix[6] -sulfonyl tetrahydroimidazo thione-2 and hexahydropyrimidine thione-2 and N-calix[4]arene-N’-aryl or alkylsulfonyl-thioureas and N-calix[4]arenesulfonyl- N’-aryl or alkyl-thioureas were also synthesized. Their desulfonylation products were obtained in the presence of Mg and MeOH, subsequent oxidation products were given promoted by H₂O₂ through grinding. Macrocyclic cyclophane-based thiourea derivatives were synthesized that the nucleophilic reaction of diamines and carbon disulfide in aqueous NaOH afforded a series of bis-dithiocarbamate salts. Activation of these with aqueous ClCH₂COOK and subsequent nucleophilic substitution reaction with trisulfonamide aqueous KOH at room temperature provided N-tosyl-macrocycles containing two thiourea units, whose desulfonylation and subsequent oxidation were also carried out. This strategy has the advantages of simple operation, mild reaction condition, easy product-isolation and environmental friendliness.A series of anions such as H₂PO₄^-, HSO₄^-, C1-, NO₃^-, ClO₄^- was studied , which was found that calix[4]-bissulfonylthiourea receptor 78a showed higher selective complexation capability with H₂PO₄^- . The binding properties of calix[4]-tetrasulfonylthiourea receptor 81c with anions such as F^-, CH3COO^-, Cl^-, Br^-, I^-, NO₃^- were examined by UV-Vis and 1H NMR spectroscopy methods. The results showed that the receptor 81c had a better selectivity to Cl-over other anions. The extraction experiments for amino acids showed that compound 92b exhibited good selective extraction ability for isoleucine. From the IR and 1H NMR of complex [M（62）]Cl₂ , it was well concluded that macrocyclic receptor 62 had a better binding action with MCl₂ than reference compound. From the 1H NMR spectra, one pair of doublets for the ArCH2Ar protons can be split as 1:1, as a result, a flattened cone structure was kept after inclusion.更多还原