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。     

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。     

1,3-交替构象杯[4]芳烃-香豆素衍生物的合成

以对叔丁基杯[4]芳烃为原料,通过醚化、原位硝化、还原、缩合四步反应合成了三个新型的具有1,3-交替构象的杯芳烃-香豆素衍生物,其结构经1H NMR,13C NMR,IR和MS表征.     

杯[4]芳烃单取代1,3-二酮衍生物的合成及生物活性研究

以杯[4]芳烃为原料经醚化和克莱森缩合两步反应首次合成杯[4]芳烃单取代1,3-二酮衍生物,其结构经1H NMR、13C NMR及MS表征。初步的HIV-1整合酶链转移反应活性测试结果表明,该杯[4]芳烃单取代1,3-二酮衍生物在测试浓度为25μM时其抑制率为12.67%。     

杯[4]芳烃硫脲基席夫碱衍生物的合成

对叔丁基杯[4]芳烃-1,3-二醛基衍生物与苯基氨基硫脲反应,高产率地合成了含硫脲基席夫碱单元的新型杯[4]芳烃衍生物,其结构经1H NMR,IR和ESI-MS表征。     

新型对叔丁基杯[4]芳烃1,3-二酮衍生物的合成

以对叔丁基苯酚为起始原料,经聚合反应得对叔丁基杯[4]芳烃(2);2经醚化和缩合反应合成了一个新型的对叔丁基杯[4]芳烃1,3-二酮衍生物,其结构经1H NMR,13C NMR和MS表征。     

NMR和XAFS方法研究溶液中杯芳冠醚与碱金属离子配位化学

给出了1,3-二辛氧基杯[4]芳烃冠醚-6(25,27-bis-octyloxy-calix[4]arene-26,28-crown-6, BOC6)和杯[4]芳烃双冠醚-6(1,3-alternate biscrown-6, BisC6)晶体结构参数, 用NMR(CDCl₃作溶剂)和XAFS(X-ray absorption fine structure)方法研究了邻硝基苯甲醚(o-nitro-phenyl methyl ether, NPME)和正辛醇(n-octyl alcohol, OA)溶液中BOC6和BisC6与碱金属离子的配位行为. 结果表明: 铯离子的嵌入使得杯芳冠醚分子中冠醚链的对称性明显提高; 在溶液中,配合物分子中铯离子的配位数为7, 7个氧的配位是一种稳定结构.     

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.     

四硫脲基杯[4]芳烃衍生物的合成

对叔丁基杯[4]-1,3-二乙酸乙酯与过量的二乙基三胺反应,生成含有游离氨基的杯芳烃酰胺衍物(2),2再与异硫氰酸苯酯反应合成了含4个硫脲基的杯[4]芳烃衍生物,其结构经1H NMR,IR,MS和元素分析表征。     

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。     

Investigation of Light-harvest Material： Synthesis and Characterization of Nanometer Porphyrin Trimer

ω-Bromopropylporphyrin ether synthesized from the raction of 1,3-dibromopropane as the bridge-linkedreagent and 5- (4-hydroxyphenyl)-10,15,20-triphenylporphyrin (H2MHTPP) as the matrix reacts with 5, 15-di(4- hydroxyphenyl)-10, 20-diphenyl porphyrin(trans-H2DHDPP) to give the title nanometer porphyrintrimer. The characterization was carried out by means of elemental analyses, UV-Vis, IR, ^1H NMR andXRD.     

Synthesis and Structure Characterization of Novel Triazole Compounds Containing 1,3-Dioxolane

Five novel triazole compounds containing group 1,3-dioxolane were designed and synthesized by taking difenoconazole as the start compound and changing diphenyl ether for benzyl phenyl ether. Their structure swere confirmed by elemental analyses, ^1H NMR and IR spectra. The single crystal structure of 2-[-4-(2,4-dichlorophenylmethoxy] phenyl-2-(1,2,4-triazol-l-yl ) methane-I, 3-dioxolane was determined by means of X-ray diffraction. The preliminary bioassays showed that the synthesized compounds exhibited some activities of fungicides and plant growth regulators.     

Guest exchange in dimeric capsules formed by tetra-urea calix[4]arenes

Ten tetra-urea calix[4]arene derivatives with different ether residues (methyl, pentyl, benzyl, all combinations of methyl and pentyl, 1,3-dibenzyl-2,4-dipentyl), including also the tetrahydroxy compound and the 1,3-dipentyl ether, were synthesised. Their urea groups were substituted with a lipophilic residue to ensure sufficient solubility in cyclohexane. Thus, kinetics for the exchange of the included guest (benzene) against the solvent (cyclohexane) could be followed by 1H NMR spectroscopy. The apparent first order rate constants decrease with increasing size of the ether residues from methyl to benzyl by more than three orders of magnitude. This can be understood by a decreasing flexibility/mobility of the calixarene skeleton. In line with this explanation is the rather slow exchange for the tetrahydroxy compound, where the cone conformation is stabilised by a cyclic array of intramolecular OH...OH hydrogen bonds.     

Synthesis and some properties of cyclic acetals of malonaldehyde

The Lewis acid-catalyzed addition of cyclic orthoformates to vinyl ethyl ether, which leads to the formation of malonaldehyde acetals, was studied. It is shown that of the linear-cyclic malonaldehyde acetals, 2-(2,2-diethoxyethyl)- and 5,5-dimethyl-2-(2,2-diethoxyethyl)-1,3-dioxanes are stable. The transacetalization of 1,1,3,3-tetraethoxypropane with 1,2- and 1,3-diols, which leads to the formation of cyclic malonaldehyde acetals, was studied. The physicochemical constants of the acetals were determined, and their ¹H and ¹³C NMR spectra are described.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 459–463, April, 1983.     

Synthesis and alkaline earth metal cation extraction by proton di-ionizable p-tert-butylcalix[4]arene-crown-5 compounds in cone, partial-cone and 1,3-alternate conformations

Synthetic strategies for novel, proton di-ionizable p-tert-butylcalix[4]arene-crown-5 compounds in cone, partial-cone and 1,3-alternate conformations are reported. Selective linkage of the two diametrical phenolic oxygens in p-tert-butylcalix[4]arene with tetraethylene glycol ditosylate gave 1,3-bridged p-tert-butylcalix[4]arene-crown-5. The two remaining phenolic units were alkylated using NaH and KH as the bases to give the cone and partial-cone conformers, respectively. Preparation of the 1,3-alternate conformers utilized a different sequence in which O-alkylation was followed by crown ether ring formation. Structures of these new ligands were elucidated by (1)H and (13)C NMR spectroscopy. These proton-ionizable ligands were tested for their solvent extraction properties toward alkaline earth metal cations. Surprising differences in their extraction behaviors are noted compared to those reported previously for di-ionizable p-tert-butylcalix[4]arenecrown-6 analogues.     

1,1,3,3-四甲基胍基衍生物的合成及其与二酸的分子识别性能研究

四甲基胍分别与间苯二甲酰氯和间苯二磺酰氯反应合成了间苯二甲酰四甲基胍和间苯二磺酰四甲基胍,其结构经元素分析,IR,1H NMR和EI-MS表征.核磁滴定研究表明,上述化合物可与二酸形成1 ∶1化学计量络合物,其络合常数在5.33×105～3.68×105.     

Poly(imino imino ether ether ketone ketone) as novel soluble heat-resistant polymer

In this paper, we introduce a novel high-performance polymer, poly(imino imino ether ether ketone ketone), which has been synthesized by the palladium-catalyzed C-N cross coupling reaction of 1,4-bis-(4-bromobenzoyl) benzene and 1,3-bis-(4-aminophenoxy) benzene. The structure of the polymer is characterized by means of ¹H NMR spectroscopy and elemental analysis, and the results show a good agreement with the proposed structure. Compared with traditional poly(ether ether ketone)s, the solubility of the synthesized polymer in common organic solvents was higher; it also exhibited high glass transition temperature (T _g = 176°C) and good thermal stability with high decomposition temperature (T ₅ = 400°C).     

一步法合成N-1,3-二羟基丙烷-2-基烷基乙酰胺

以5-氨基烷基-2,2-二甲基-1,3-二噁烷为起始原料, 乙酸酐为酰化剂, 一步法选择性地合成氨基二醇类氨基乙酰化产物N-1,3-二羟基丙烷-2-基烷基乙酰胺. 该方法操作简便, 收率高. 所合成的4个新化合物的结构均经FTIR, ¹H NMR, ¹³C NMR及HRMS确证. N-3-(1,3-二羟基丙烷-2-基)丙基乙酰胺(1a)作为关键的中间体, 可以用于HIV-1 Tat/ PCAF BRD抑制剂4的合成.     

Allosteric bindings of thiacalix[4]arene-based receptors with 1,3-alternate conformation having two different side arms

A novel ditopic receptor possessing two complexation sites such as crown ether and 2-pyridylmethyl groups bearing 1,3-alternate conformation based on thiacalix[4]arene was prepared. The binding behaviors with Li⁺ and Ag⁺ have been examined by ¹H NMR titration experiment. The exclusive formation of mononuclear complexes of 1,3-alternate-5 with Li⁺ and Ag⁺ was observed even though the formation of the heterogeneous dinuclear complexes was expected. The decomplexation of Li⁺ from the crown moiety of 1:1 complex 1,3-alternate-5?Li⁺ to form the Ag⁺?1,3-alternate-5 complex by addition of AgSO₃CF₃ clearly shows that pyridyl moiety works as an efficient switch-off of the recognition ability of the crown moiety. We have also developed the construction of hydrogen-bonding self-assembly heterodimeric systems based on bis(4-pyridyl) and dicarboxylic acid thiacalix[4]arene derivatives in 1,3-alternate conformation. Their supramolecular behaviors are studied by ¹H NMR titration experiments with K⁺ and Ag⁺ ions. Although the values of the dimerization constants are relatively small, the stability of the dimers is strong enough to overcome only small conformational changes upon complex formation.