苯并-15-冠-5作为气相色谱固定液的研究

试用冠醚作为气相色谱固定液文献中曾有报道,但未述及有关极性常数的测定,也未见有与其他固定液进行比较,因而无法确认所试冠醚作为固定液存在的真正必要性。本文首次报道常用冠醚—苯并-15-冠-5作为气相色谱固定液的研究结果。测定了苯并-15-冠-5的极性常数和热重稳定性,并将测定结果与其他固定液进行比较。认为苯并-15-冠-5是一种比双(2-甲氧乙基)己二酸酯更好的固定液。     

4′-乙酰基苯并-15-冠-5缩氨基硫脲的微波合成及晶体结构

硫脲衍生物主要通过氢键与阴离子相互作用达到识别的目的，冠醚和硫脲两个主体分子亚单元之间的协同作用往往使冠醚和硫脲表现出对某些客体更加优越的络合识别能力，我们在以前工作的基础上，微波辐射下合成了标题化合物并用红外光谱、核磁共振氢谱、元素分析、X射线单晶衍射对其结构进行了表征，欲进一步研究其对阳离子和阴离子识别的双重功效。     

单苯并15-冠-5的超声作用合成

以邻苯二酚、一缩二乙二醇双氯乙醚为原料,氢氧化钠为模板剂,DMF为溶剂及适量抗氧化剂2,6-二-叔丁基对甲苯酚存在下,在超声辐射作用下60~70 ℃反应合成了B-15-C-5。 反应时间缩短为2 h,产率最高可达30.7%。     

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.     

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.     

锕系元素冠醚配合物研究(Ⅲ)——二水合硝酸铀酰苯并-15-冠-5配合物的晶体结构

锕系元素冠醚配合物中,研究得最多的是铀酰与冠醚形成的配合物,以往的工作主要集中在配合物的合成及性质研究方面,而对其结构很少研究。迄今为止,只测定过硝酸铀酰与18-冠-6配合物的晶体结构,铀酰与其它种类冠醚形成的配合物的结构文献中还未见报道。我们在乙腈溶液中培养出硝酸铀酰与苯并-15-冠-5的配合物[UO_2(NO_3)_2(H_2O)_2]·(B15C5)单晶,并研究该配合物的晶体及分子结构。     

钾（Ⅰ）（苯并－15－冠－5）新型配合物的合成及性质

在非水溶剂中合成了苯并－１５－冠－５与碘化钾、硫氰化钾及苦味酸钾形成的三种新型固体配合物，并进行了有关物理、化学性质表征．结果表明，钾（Ⅰ）离子不仅易与苯并－１５－冠－５形成常见的１：２夹心式配合物，而且还能生成稳定的１：１型固体配合物．     

The Novel Benzo-15-Crown-5 with Palladium(II) Complex:[Na(B15C5)]2[Pd(SCN)4]

A novel Pd(II) Benzo-15-crown-5 complex [Na(B15C5)]2[Pd(SCN)4] has been isolated and characterized by IR and X-ray diffraction analysis.The crystal structure belongs to monoclinic,space group P21/n with cell dimensions,a=1.0164(6),b=1.3743(3),c=1.4987(7) nm,b=95.248(6)o ,V=2.0847nm3,Z=2,F(000)=944,R=0.053,Rw=0.072.The compound consists of two [Na(B15C5)]+ complex cations and a [Pd(SCN)4]2- complex anion.Each sodium ion is coordinated by five crown ether oxygen atoms and one N atom from the SCN group of [Pd(SCN)4]2- to form stable neutral complex.     

The Novel Benzo-15-Crown-5 with Palladium(II) Complex: [Na(B15CS)]_2,[Pd(SCN)_4]

The extensive pioneering study of Pedersen I has led to a vialal explosion of solutionand solid-state investigation of crown ethers and metal ions which include alkali metal,alkali earth metal, other main-group and transition-metal ions. It is shown that singlecrystal X-ray diffraction analysis is a most powerful technique for the characterization ofthese complexes and numerous solid-state structUral stIJdies have appeared through theyears. The reported B15CS complexes strllcturally charact…     

网络骨架组装工程：5-硝基间苯二甲酸形成的配位聚合物网络多样性

Two novel coordination polymers, [Cu(nip)(phen)]_n (1) and [Co₂(nip)₂(phen)₂]_n (2), have been synthesized by hydrothermal synthesis using 5-nitroisophthalic acid (H₂nip), 1,10-phenanthroline (phen) and metal salts and structurally characterized by X-ray single-crystal structure analysis. The results indicated that the nip ligand in compound 1 has a μ₃ mono-atomic bridging-monodentate coordination mode and the structure is a two-dimensional network, while the nip ligand in compound 2 has a chelating-bridging coordination mode and the structure is a one-dimensional network. CCDC: 222202, 1; 222203, 2.     

Novel crystal engineering in the crown ether nickel maleonitriledithiolate complexes,synthesis and crystal structures of [Na(N15C5)2]2[Ni(mnt)2] and [Na(N15C5)]2[Ni(mnt)2]

Reactions of N15C5 (2,3-naphtho-15-crown-5) with nickel maleonitriledithiolate sodium complex, Na₂[Ni(mnt)₂] (mnt?=?maleonitriledithiolate) using different molar ratios (2?:?1 and 4?:?1) afforded two structurally different complexes [Na(N15C5)₂]₂[Ni(mnt)₂] (1) and [Na(N15C5)]₂[Ni(mnt)₂] (2). The sandwich [Na(N15C5)₂]⁺ and mono-capped [Na(N15C5)]⁺ organic cations are observed in the crystals of 1 and 2, respectively, with the same [Ni(mnt)₂]^2? inorganic conteranions. It is these structurally different organic cations that lead to the dissimilar structures. Complex 1 exhibits a one-dimensional (1D) chain-like structure assembled by intercantionic {[Na(N15C5)₂]⁺}_∞ π–π stacking interactions and electrostatic interactions, while 2 displays a novel two-dimensional (2D) corrugated sheet-like structure constructed by Na–N interactions which occur between the [Na(N15C5)]⁺ inorganic cations and [Ni(mnt)₂]^2? inorganic anions.     

Total synthesis based modification of benzoquinone ansamycin antibiotics: C8 diversification of C5-C15 fragments

Benzoquinone ansamycins are known to be potent Heat shock protein (Hsp90) inhibitors, and total-synthesis-based structure modification of this natural product family may lead to the discovery of novel cancer chemotherapeutics. Described in this paper is a unified synthetic route that gives access to both natural and C-8-modified C5-C15 fragments of this natural product family.     

Synthesis under Micromave Irradition and Crystal Structure of 4''-Acetylbenzo-15 -crown-5thiosemicarbazone

The title compound is a bifunctional receptors including a thiourea group and a crown ether ring. Due to many possible potentials as a new class of reagents for membrane transports,ion-selective electrodes as well as reaction catalysts, the design and synthesis of bifunctional receptors for simultaneous binding of cations and anions is of ongoning interest in srprarnolecular chemistry1-5. In bifunctional receptors, the binding sites for anions and cations are covalently linked so as to exhibit allosteric or cooperative complexation where the binding affinity for anions(cations)is modified as a result of the cation(anion) complexation.Literature[6] reported that the ability of the thiourea group to bind anions is significantly enhanced when Na+ is bound to the crown moiety. To date, however only a few receptors of this class have been reported.6-8In this paper, we report an improved procedure under microwave irradiation that gives higher yields of title compound and needs fewer reaction times than traditional method.The structure of this compound was determined by IR ,element analysis and X-ray analysis.Scheme 1 The reaction equationThe crystal belongs to triclinic crystal system, P-1 space group, a=0.9547(0)nm, b=1.3637(3)nm,c=1.6029(3)nm, α =75.33(3) , β =83.62(3) , γ =70.99(3) ,Z=4,Dc=1.335g/cm3,F(000)=816,R1= 0.0557 ,wR2=0.1281. It is assembled into a three-dimensionalsupramolecule by intermolecular hydrogen bonds.     

苯基氮杂—15—冠—5对钼同多酸以及钨钼杂多酸阴离子的选择

合成了两种氮杂大环八聚多酸超分子配合物［Na（N-Ph）aza-15C5（Et2O）］2Na2MO8O26（Ⅰ）和［Na（N－Ph）aza－15C5（Et2O）］2Na2Wo25Mo7.75O26（Ⅱ），用元素分析、IR、1HNMR和H，H－COSY谱进行了表征，并用X射线测定了配合物（Ⅱ）的晶体结构．配合物（Ⅱ）属单斜晶系，空间群为P21/c，晶胞参数为：a=1.7644（4）nm，b=1．3702（3）nm，c=1．4507（3）nm，β=114．02（3）°，Z=2．该类晶体由大环金属销配位阳离子和二维阴离子网络［Na2WxMo8-xO26」2-组成，阴、阳离子分层堆积．研究了苯基氮杂-15-冠-5和与之键合的多酸阴离子的结构及相互关系．发现在苯基氮杂-15-冠-5分别与八错多酸和六聚钨错杂多酸反应所得的产物中，多酸阴离子的聚合度均为8．表明大环化合物的结构与阴离子的结构有一定的对应关系．     

Electron diffraction study of the space group of Bi5Ti3FeO15 multiferroic ceramic

Bi₅Ti₃FeO₁₅ (pentabismuth trititanium iron pentadecaoxide), which is a multiferroic four‐layer Aurivillius phase compound, has received much attention in recent years. However, three mutually inconsistent orthorhombic space groups, i.e. A2₁am, Fmm2 and Pnn2, have been reported for the room‐temperature phase of Bi₅Ti₃FeO₁₅ by X‐ray and neutron diffraction investigations. Here, electron diffraction results are presented and discussed for the first time to unambiguously clarify the room‐temperature space group of ceramic Bi₅Ti₃FeO₁₅. It has been found that all the observed reflections from the ceramic agree with those expected in A2₁am, while the observed reflections 011, 013 and 015 should be forbidden in the case of Fmm2, and no 107 and 109 reflections were observed although allowed for Pnn2. The present study has demonstrated that the space group of Bi₅Ti₃FeO₁₅ ceramic is A2₁am rather than Fmm2 or Pnn2, an identification that proved to be a challenge for X‐ray diffraction. On the basis of the space group A2₁am, the lattice parameters of the Bi₅Ti₃FeO₁₅ ceramic were calculated from its X‐ray diffraction data.     

Hydrothermal Synthesis and Crystal Structure of a New Supramolecular Channel Framework Based on Cu Complexes and Polyoxovanadate:[Cu(I)(phen)_2]_5[HV_(15)O_(36)(Cl)]_(0.65)[H_3V_(16)O_(38)(Cl)]_(0.35)·2H_2O

1 INTRODUCTION In the past years, polyoxovanadates have attracted extensive interest in solid-state material chemistry owing to the formation of mixed-valence com- pounds that exhibit rich electronic and magnetic properties relevant to catalysis, medicine and ma- terials science[1～4]. The following polyoxovanadates have been found and structurally characterized: [V5O14]3-, [V6O19]8-, [V10O28]6-, [V12O32]4-, [V13- O34]3-, [V15O36]5-, [V15O42]9-, [V17O42]4-, [V18- O42]12-, [V16O38]7…     

f-Element/crown ether complexes: 21. Conformational changes in metal complexed versus hydrogen bonded benzo-15-crown-5 in the structure of [Y(OH2)3(NCMe)-(benzo-15-crown-5)][ClO4]3·benzo-15-crown-5·CH3CN

Crystalline [Y(OH₂)₃(NCMe)(benzo-15-crown-5)][ClO₄]₃·benzo-15-crown-5-CH₃CN can be obtained by slowly cooling a reaction mixture of Y(ClO₄)₃·n H₂O with benzo-15-crown-5 in a solution of acetonitrile and methanol (3 : 1) from 60°C to room temperature. The crystal structure of this complex has been determined at –150 and 20°C. The complex is triclinic,P . At –150°C the cell parameters area = 11.986(4),b = 12.071(7),c = 16.364(5) Å, = 93.56(3), = 98.68(3), = 109.68(4)°, vol = 2187 ų, andD _calc = 1.61 g cm^–3 forZ = 2 formula units. 3633 independently observed [F _o 5(F _o)] reflections were used in the final least-squares refinement leading to an agreement index ofR = 0.048. The Y(III) ion coordination geometry approximates a tricapped trigonal prism with three water molecules and three benzo-15-crown-5 oxygen atoms forming the prism, with the two remaining benzo-15-crown-5 oxygen atoms and the acetonitrile molecule completing the coordination as capping atoms. The three water molecules hydrogen bond a second crown ether molecule and two of the perchlorate anions. The two acetonitrile molecules have contacts with perchlorate oxygen atoms close enough for some weak interaction. One perchlorate is ordered, one is partially disordered as is the coordinated solvent molecule, and the third anion is totally disordered. The two unique crown ether molecules have distinctively different conformations.For Part 20, see reference [1].