冠醚与碱金属苦味酸盐在氯仿中形成络合物的电导

测定了氯仿中碱金属苦味酸盐——冠醚络合物的电导率及络合比。确定了体系中电导率、冠醚浓度和络合比之间的关系。讨论了这些结果的某些应用。     

苦味酸锂与二苯并18-冠-6的缔合结构

培养了苦味酸锂与二苯并18-冠-6缔合物的单晶体[Li(pic)(H_2O)]_2·[C_(20)H_(24)O_6],化学式为C_(32)H_(32)Li_2N_6O_(22),用X射线法测定了缔合物的晶体结构,证明该晶体属单斜晶系,空间群为P2_1/m,晶胞参数:a=8.299(2),b=25.216(3),c=9.158(2)(?),β=100.34(2)°,V=1885.4(?)~3,Z=2。     

几种单基取代二苯并-18-冠-6的合成

在功能基取代二苯并-18-冠-6类化合物中,两个苯环上对称地引入两个功能基的合成报道较多,而不对称性引入单个功能基取代的     

含二苯并-18-冠-6和二苯并-14-冠-4的酰胺型液晶冠醚的合成

以4-[(4-正烷氧基联苯基)-4-碳酰氧基]苯甲酸、二氨基二苯并-18-冠-6和二氨基二苯并-14-冠-4为中间体, 通过溶液缩合反应, 合成了两个系列酰胺型液晶冠醚. 并用元素分析、核磁共振、红外光谱、基质辅助激光解析电离飞行时间质谱、示差扫描量热法和偏光显微镜对其进行了表征. 随分子末端烷氧基碳原子数增加, 化合物4I, 4II, 6I和6II的熔点(T_m)和液晶态的清亮点(T_i)逐渐降低, 近晶相范围递增.     

癸二酸-二苯并-18-冠-6共聚物的合成

脂肪族二元羧酸与二苯并 １８ 冠 ６在多聚磷酸中进行酰基化反应，可以制得酮型冠醚聚合物，二元酸的分子链长度会影响聚合反应的难易程度．对聚合反应条件进行优化控制，可以制得分子量高、成膜性能良好的癸二酸 二苯并 １８ 冠 ６共聚物．     

含二苯并-18-冠-6冠醚环的偶氮型液晶冠醚的合成

含二苯并-18-冠-6冠醚环的偶氮型液晶冠醚的合成;偶氮型;冠醚;热致性液晶;合成     

异硫氰酸铬(Ⅲ)二(18-冠-6)铵配合物的合成、特征和光化学

本文报道了标题中所指的配合物固体和单晶的制备,测定了IR,UV-Vis光谱以及该配合物在CH₃CN和DMF中的光化学性质。采用单晶X射线衍射测定了该配合物的结构,它属于单斜晶系,空间群P2₁/n,测定了固体配合物在CH₃CN和DMF中的量子产率Φ_NCS,并讨论了光反应机制。     

4'',4"-(二苯并-18-冠-6)二甲酸二芳酯的合成和液晶性质

本文为了探讨冠醚液晶化的途径及冠醚衍生物结构与液晶性能的关系, 参照二芳酯向列相液晶结构的特点, 用易得的二苯并-18-冠-6为起始原料, 合成了4',4"-(二苯并-18-冠-6)二甲酸二芳酯6, 6有顺式和反式两种异构体。层析分离得6A和6B, 本文考查了它们的液晶性质, 定性地检查了络合钾离子的性能, 用合成法确证了具有各向异性的6B为反式构型。     

含二苯并-18-冠-6席夫碱型液晶冠醚钾配合物的合成与表征

以顺(反)-4,4＇-双[4-(4＇-正烷氧基联苯基-4-羧基) 苯亚氨基] 二苯并-18-冠-6（I和II）为配体合成了2个系列席夫碱型液晶冠醚钾配合物,产率分别为85.5%~92.1%和88.7%~90.7%。配合物的结构通过元素分析、IR、UV-Vis和AAS等方法确证。液晶行为通过DSC、POM、XRD等方法表征。实验结果表明,所有配合物均具有热致液晶性,且随分子末端烷氧基碳原子数增加,其熔点和清亮点呈规律性变化。近晶相温度范围渐增,向列相温度范围递减。与配体相比,配合物液晶态温度范围变宽     

含二苯并-18-冠-6酰胺型液晶冠醚钾配合物的合成和性质

合成了2个系列酰胺型液晶冠醚钾配合物，配合物的结构通过元素分析、IR、UV-Vis和AAS等方法表征。液晶行为通过DSC、POM、XRD等方法表征。实验结果表明，所有配合物均具有热致液晶性，且随分子末端烷氧基碳原子数增加，其熔点和清亮点呈规律性变化。与配体相比，配合物液晶态温度范围变宽。液晶相态类型发生改变，配体只有近晶相，而配合物既有近晶相，又有向列相。     

含二苯并-18-冠-6席夫碱型液晶冠醚钾配合物的液晶行为

以顺(反)-4,4′-双[4-(4′-正烷氧基联苯基-4-羧基)苯亚氨基]二苯并-18-冠-6(Ⅰ和Ⅱ)为配体合成了2种系列席夫碱型液晶冠醚钾配合物,产率分别为85.5%～92.1%和88.7%～90.7%。配合物的结构通过元素分析、IR、UV-Vis和AAS等测试技术确证。液晶行为通过DSC、POM、XRD等方法表征。实验结果表明,所有配合物均具有热致液晶性,且随分子末端烷氧基碳原子数增加,其熔点和清亮点呈规律性变化。近晶相温度范围渐增,向列相温度范围递减。与配体相比,配合物液晶态温度范围变宽。     

On the Mechanism of Action of Dibenzo-18-crown-6 Diacyl-Derivatives on Malignant Tumors

Ca²⁺ permeable channels have been registered in bilayer membranes formed from phospholipids of sarcoma-45 and sarcocarcinoma Walker-256. On the basis of data obtained, it is supposed that the channels are proteins located in the plasmalemmal membrane of tumor cells. Diacetyl-dibenzo-18-crown-6 was found to suppress Ca²⁺ currents through the channels. In in vivo experiments diacetyl-dibenzo-18-crown-6 inhibited the sarcoma-45 and carcinosarcoma Walker-256 tumors growth, whereas divaleril-dibenzo-18-crown-6, which is known to be a Ca²⁺ ionophore, acted as a growth-stimulating agent. The mechanism of the tumor growth inhibition by diacetyl-dibenzo-18-crown-6 is supposed to consist in cytostatic action of the compound, presumably, by blocking Ca²⁺ channels of tumor cells.     

Poly(Vinyl Chloride) Containing Dibenzo-18-crown-6 as an Ion-Selective Membrane for Hyamine 1622

Abstract

A poly(vinyl chloride) membrane ion-selective electrode for the Hyamine 1622 cation is proposed. The active substance of the electrode was the neutral carrier dibenzo-18-crown-6 and di-iso-octylphthalate was used as plasticizer. The electrode had a Nernstian behaviour between 6.0 × 10^?6 and 1.6 × 10^?3 mol/dm³, a pH working range of 2 – 12 and high selectivity towards inorganic cations. Among the organic cations tested, only those having surfactant properties did interface. The electrode was suitable for determining the critical micelle concentration and as end-point detector in the potentiometric titration of the cationic surfactants.     

18-crown-6 ether complexes with aralkylammonium perchlorates

Thermochemical properties of crown ether complexes have been studied by simultaneous TG-DTA (thermogravimetric analysis-differential thermal analysis) coupled with a mass spectrometer, DSC (differential scanning calorimetry) and hot stage microscopy (HSM). The examined complexes contain benzylammonium- [BA], (R)-(+)-a-phenylethylammonium- [(R)-PEA], (R)-(+)- and (S)-(-)-a-(1-naphthyl)ethylammonium perchlorate [(R)-NEA and (S)-NEA] salts as guests. In the cases of BA and (R)-PEA an achiral pyridono-18-crown-6 ligand [P18C6], and in the case of (R)-NEA and (S)-NEA a chiral (R,R)-dimethylphenazino-18-crown-6 ligand [(R,R)-DMPh18C6] was used as host molecule to obtain four different crown ether complexes. In all cases, the melting points of the complexes were higher than those of both the host and the guest compounds. The decomposition of the complexes begins immediately after their melting is completed, while the BA and (R)-PEA salts and the crown ether ligands are thermally stable by 50 to 100 K above their melting points. During the decomposition of the salts and the four complexes strongly exothermic processes can be observed which are due to oxidative reactions of the perchlorate anion. Ammonium perchlorate crystals were identified among the decomposition residues of the salts. P18C6 was observed to crystallize with two molecules of water. The studied complexes of P18C6 did not contain any solvate. BA was observed to exhibit a reversible solid-solid phase transition upon heating. The heterochiral complex consisting of (S)-NEA and (R,R)-DMPh18C6 shows a solid-solid phase transition followed by two melting points. HSM observations identified three crystal modifications, two of them simultaneously co-existing. This revised version was published online in July 2006 with corrections to the Cover Date.     

Crystal Structures of Dibenzo-13-crown-4 and sym-(2-Picolyloxy)dibenzo-13-crown-4

Solid-state structures are determined for two compounds which containdibenzo-13-crown-4 rings. These include the parent crown etherdibenzo-13-crown-4 and its lariat ether derivativesym-(2-picolyloxy)dibenzo-13-crown-4. The solid-state structure ofdibenzo-13-crown-4 is complicated by disorder of the carbon atoms in theethylene and propylene bridges. The asymmetric unit of the crystal for thelariat ether derivative consists of two chemically identical, butcrystallographically different, molecules.