杂氮三环类化合物的分子量测定

2,8,9-三氧杂-5-氮杂-1-M三环[3,3,3,0~(1,5)]十一碳烷,(?)(M=Si,B,Al,Ti),简称杂氮M三环。由于这类化合物具有特殊的分子结构及生物活性而受到人们的重视。作者报道过一系列杂氮三环类化合物的合成及结构测定,本文报道在非水介质中用酸碱滴定法     

Ti(OR)4类化合物与一些醇及其衍生物交换反应的规律

我们在探讨Sharpless不对称环氧化反应机理,提高水溶性环氧醇产率,以及改进杂氮钛三环化合物合成方法的工作中,遇到了Ti(OR)_4类化合物与一些醇及其衍生物的配体交换反应。找出这类反应的规律,将有助手以上问题的研究。     

杂氮钛三环的合成

本文报道了具有N→Ti配位键的2,8,9-三氧杂-5-氮杂-1-钛杂三环[3.3.3.0~(1,5)]十一碳烷的合成及其性质。共制得六个新的化合物。研究了制备它们的最佳条件及化学稳定性。     

手性钛锆化合物在不对称合成中的应用

本文综述了近年来手性钛锆化合物在不对称合成中的应用, 特别是手性柄型金属钛和锆化合物在不对称合成中的应用。对这类催化剂的特点和前景作了简要介绍。     

具有生物活性的有机硅化合物的研究VII.1-芳酰氧基-2,8,9-三氧杂-5-氮杂-1-硅杂三环[3,3,3,0[1.5]]十一碳烷的研究

用新的方法合成了九个1-芳酰氧基2,8,9-三氧杂-5-氮杂-1-硅杂三环[3.3.3.0[1,5]]十一碳烷(简称 1-芳酰氧基杂氮硅三环)。本方法具有产率高,后处理简便等优点。X-射线晶格衍射确定了该类化合物分子内N→Si键键长较短,说明配键强度较大。报道该类化合物的IR, 1H NMR及MS,并讨论了质谱断裂机理。     

双-杂氮硅三环化合物的合成

杂氮硅三环是一类分子内具有N→Si配位键的化合物，作者曾报道了一系列该类化合物的合成方法和化学结构。对于一个分子内带两个对称的硅三环结构的双一杂氮硅三环化合物的合成，文献报道还很少啪。我们用下     

具有生物活性的有机硅化合物的研究——Ⅶ.1-芳酰氧基-2,8,9-三氧杂-5-氮杂-1-硅杂三环[3.3.3.0~(1,5)]十一碳烷的研究

本文用新的方法合成了九个1-芳酰氧基-2,8,9-三氧杂-5-氮杂-1-硅杂三环[3.3.3.0~(1,5)]十一碳烷(简称1-芳酰氧基杂氮硅三环)。本方法具有产率高,后处理简便等优点。X-射线晶格衍射确定了该类化合物分子内 N→Si 键键长较短,说明配键强度较大。报道该类化合物的 IR,1~H NMR 及 MS,并讨论了质谱断裂机理。     

杂氮铝三环类化合物的合成

具有 N→M 配位键的杂氮三环(Atrane)类化合物近年来正日益引起人们的浓厚兴趣。作者曾经报道了杂氮硅(硼、钛)三环的合成及其分子结构和化学     

具有生物活性的有机硅化合物的研究IX:1-(N-芳基呋喃甲酰胺)亚甲基-2,8,9-三氧杂-5-氮杂-1-硅杂三环[3.3.3.O^1^.^5]十一烷的合成

本文合成了六个1-(N-芳基呋喃甲酰胺)亚甲基-2,8,9-三氧杂-5-氮杂-1-硅杂三环[3.3.3.O^1^.^5]十一烷的化合物。合成方法简便, 反应时间短。易于后处理。经元素分析, IR, ^1H NMR, MS确定了新化合物的结构, 并经化合物3的X射线晶格衍射分析确定了该类化合物的空间排布情况。     

具有生物活性的有机硅化合物的研究IX:1-(N-芳基呋喃甲酰胺)亚甲基-2,8,9-三氧杂-5-氮杂-1-硅杂三环[3.3.3.O^1^.^5]十一烷的合成

本文合成了六个1-(N-芳基呋喃甲酰胺)亚甲基-2,8,9-三氧杂-5-氮杂-1-硅杂三环[3.3.3.O^1^.^5]十一烷的化合物。合成方法简便, 反应时间短。易于后处理。经元素分析, IR, ^1H NMR, MS确定了新化合物的结构, 并经化合物3的X射线晶格衍射分析确定了该类化合物的空间排布情况。     

Synthesis, characterization and antitumor activity of some arylantimony triphenylgermanylpropionates and crystal structures of Ph3GeCH(Ph)CH2CO2SbPh4 and [Ph3GeCH2CH(CH3)CO2]2Sb(4-ClC6H4)3

A series of novel arylantimony(V) triphenylgermanylpropionates with the formula (Ph₃GeCHR¹CHR²CO₂)_nSbAr_(5−n) (R¹=H, Ph; R²=H, CH₃; n=1, 2) were synthesized and characterized by elemental analysis, IR, ¹H-NMR, ¹³C-NMR and mass spectroscopy. The crystal structures of Ph₃GeCH(Ph)CH₂CO₂SbPh₄ and [Ph₃GeCH₂CH(CH₃)CO₂]₂Sb(4-ClC₆H₄)₃ were determined by X-ray diffraction. The in vitro antitumor activities of some selected compounds against five cancer cells are reported.     

Electrochemistry and spectroelectrochemistry of tert-butylcalix[4]arene bridged bis double-decker lutetium(III) phthalocyanine, Lu2Pc4 and dimeric lutetium(III) phthalocyanine, Lu2Pc2(OAc)2

In this study, electrochemical, electrochromic and spectroelectrochemical properties of a tert-butylcalix[4]arene bridged bis double-decker lutetium(III) phthalocyanine (Lu₂Pc₄ 2) were investigated explicitly as compared with a tert-butylcalix[4]arene bridged dimeric lutetium(III) phthalocyanine [Lu₂Pc₂(OAc)₂ 1]. Distinctive differences between electrochemical and electrochromic properties of 1 and 2 were detected. Moreover, the properties of 1 and 2 were compared with previously reported S₄(CH₂)₄ bridged Lu₂Pc₂(OAc)₂ and Lu₂Pc₄. The calixarene bridged phthalocyanine (Pc) compounds, 1 and 2 showed well-defined electrochromic behaviour with green-blue and blue-purple colour transitions. The enhanced electrochromic properties of 2, as compared to 1, were attributed to its double-decker structure, probably allowing the formation of suitable ion channels for the counter ion movement in the solid film.     

Low-temperature heat capacity and thermodynamic properties of crystalline [Re2(Ala)4(H2O)8](ClO4)6 (Re = Eu, Er; Ala = alanine)

[Re₂(Ala)₄(H₂O)₈](ClO₄)₆ (Re=Eu, Er; Ala=alanine) were synthesized, and the low-temperature heat capacities of the two complexes were measured with a high-precision adiabatic calorimeter over the temperature range from 80 to 370 K. For [Eu₂(Ala)₄(H₂O)₈](ClO₄)₆, two solid–solid phase transitions were found, one in the temperature range from 234.403 to 249.960 K, with peak temperature 243.050 K, the other in the range from 249.960 to 278.881 K, with peak temperature 270.155 K. For [Er₂(Ala)₄(H₂O)₈](ClO₄)₆, one solid–solid phase transition was observed in the range from 270.696 to 282.156 K, with peak temperature 278.970 K. The molar enthalpy increments, ΔH_m, and entropy increments,ΔS_m, of these phase transitions, were determined to be 455.6 J mol⁻¹, 1.87 J K⁻¹ mol⁻¹ at 243.050 K; 2277 J mol⁻¹, 8.43 J K⁻¹ mol⁻¹ at 270.155 K for [Eu₂(Ala)₄(H₂O)₈](ClO₄)₆; and 4442 J mol⁻¹, 15.92 J K⁻¹ mol⁻¹ at 278.970 K for [Er₂(Ala)₄(H₂O)₈](ClO₄)₆. Thermal decompositions of the two complexes were investigated by use of the thermogravimetric (TG) analysis. A possible mechanism for the thermal decomposition is suggested.     

Heat capacities of NaNO3 and KNO3 from 350 to 800 K

The heat capacities of NaNO₃ and KNO₃ were determined from 350 to 800 K by differential scanning calorimetry. Solid-solid transitions and melting were observed at 550 and 583 K for NaNO₃ and 406 and 612 K for KNO₃, respectively. The entropies associated with the solid-solid transitions were measured to be (8.43± 0.25) J K⁻¹ mole⁻¹ for NaNO₃ and (13.8±0.4) J K⁻¹ mole⁻¹ for KNO₃. At 298.15 K the values of C⁰_P S⁰_P, {H⁰(T)-H⁰(0)}/T and -{G⁰(T)-H⁰(0)}/T, respectively, are 91.94, 116.3, 57.73, and 58.55 J K⁻¹ mole⁻¹ for NaNO₃ and 95.39, 133.0, 62.93, and 70.02 J K⁻¹ mole⁻¹ for KNO₃. Values for S⁰_T, {H⁰(T)-H⁰(0)}/T, and -{G⁰(T)-H⁰(0)}/T were calculated and tabulated from 15 to 800 K for NaNO₃ and KNO₃.     

Coordination-driven self-assembly of palladium(Ⅱ)-based metallacalixarenes as anion receptors using flexible pyridine-bridged diimidazole ligands

Two types of palladiu m(Ⅱ)-based metallacalixarenes[ML]²⁺and[ML₂]²⁺have been synthesized through coordination-driven self-assembly from a series of flexible pyridine-bridged diimidazole ligands[2,6-bis((1 H-imidazol-1-yl)methyl)pyridine(L¹),2,6-bis((1 H-benzo[d]imidazol-1-yl)methyl)pyridine(L²),2,6-bis((1 H-naphtho[2,3-d]imidazol-1-yl)methyl)pyridine(L³)],with palladium(II)-based building blocks[Pd(BF₄)₂(M¹-BF_4)and(tmeda)Pd(NO₃)₂(M²-NO₃)(tmeda=N,N,N',N'-tetramethyl-ethylenediamine)].All complexes were characterized by NMR spectroscopy(¹H NMR and¹³C NMR),mass spectrometry(CSIMS,ESI-HRMS)and elemental analysis.The single crystal X-ray diffraction analysis of[M¹L²_2](NO₃)₂,[M¹L³_2](NO₃)₂,[M¹L³_2](PF_6)_2 and[M~2 L³](NO₃)₂further confirmed the uniquely single bowl-shape and double bowl-shape structures.The anion binding properties within the metallacalixarenes as receptors were also investigated by NMR titration experiments in DMSO.     

Flow injection analysis methods for determination of diffusion coefficients

Two flow injection analyses (FIA) methods for the determination of diffusion coefficients in a straight single tube FIA system were developed. Based on the analytical solution of the convection-diffusion equation, linear relationships of the logarithmic values of the dispersion coefficient (D) and the half-peak width (W_1/2) with the diffusion coefficient (D_m) were obtained. Experiments were designed to verify these methods. For example, for potassium hexacyanoferrate (III) a D_m value of 0.72 × 10⁵ cm² s⁻¹ was found versus a literature value of 0.76 × 10⁵ cm² s⁻¹ (error, 5%). For potassium hexacyanoferrate (II) a D_m value of 0.67 × 10⁵ cm² s⁻¹ was obtained versus a literature value of 0.63 × 10⁵ cm² s⁻¹ (error, 6%). The diffusion coefficients of some important biomedical compounds, such as dopamine, epinephrine, norepinephrine and ascorbic acid, were then determined. The values of 10⁵ D_m/cm² s⁻¹ are 0.60 ± 0.03, 0.44 ± 0.02, 0.60 ± 0.01 and 0.68 ± 0.06, respectively.     

Two Zinc(Ⅱ) Complexes Based on 7rany-(1R,2R)-cyclohexanediamine: Molecular Structure Analyses and Preparation of Composite Membrane

Two novel complexes Zn2(chda)2(TPA)Cl2(1) and [Zn(chda)2(H2O)2](TPAXH2O)2(2)[chda is a chiral ligand of trans-(1R,2R)-cyclohexanediamine, H2TPA is terephthalic acid] were synthesized at room temperature. The molecular structures of complexes 1 and 2 were identified by single-crystal X-ray diffraction measurement. The results showed that complex 1 had a binuclear structure, each Zn(Ⅱ) ion was four coordinated by two N atoms of chda, one O atom of TPA and one Cl atom, to construct a distorted tetrahedral geometry. For complex 2, the Zn(Ⅱ) ion was six coordinated by two chda molecules and two water molecules to form a ZnN4O2 octahedral geometry. Complexes 1 and 2 further extended into three-dimensional supramolecular frameworks by hydrogen-bonding interactions. Hirshfeld surface analysis and fingerprint plots were used to further analyze the contribution of diflerent intermolecular interactions. Further, a composite membrane [Zn(chda)2(H2O)2](TPA)(H2O)2/CA was prepared by adding 10%(mass fraction) of complex 2 into cellulose acetate using acetone/chloroform( V:V-1:1) as solvent.     

Synthesis and Structure of N-(E)-Enoyl(-)-bornane-10,2-sultams

Ｃｈｉｒａｌｉｔｙｄｕｅｔｏａｌｋｙｌｂｒａｎｃｈｉｎｇｉｓａｂｕｎｄａｎｔａｍｏｎｇｓｅｖｅｒａｌｎａｔｕｒａｌｌｙｏｃｃｕｒｒｉｎｇｓｅｃｏｎｄａｒｙｍｅｔａｂｏｌｉｔｅｓ .Ｔｈｉｓｓｔｒｕｃｔｕｒｅｆｅａｔｕｒｅｉｓｐａｒｔｉｃｕｌａｒｌｙｐｒｅｄｏｍｉｎａｎｔａｍｏｎｇｉｎｓｅｃｔｐｈｅｒｏｍｏｎｅｓ[1] ,ｍａｎｙｏｆｗｈｉｃｈａｒｅｏｆｅｃｏｎｏｍｉｃｓｉｇｎｉｆｉｃａｎｃｅ .Ａｓａｒｅｓｕｌｔ,ａｃｏｎｓｉｄｅｒａｂｌｅｅｆｆｏｒｔｈａｓｂｅｅｎｍａｄｅｔｏｓｙｎｔｈｅｓｉｚｅｔｈｅｍ…     

New Half-sandwich Zirconium（IV） Complexes Containing Salicylaldimine Ligands： Synthesis,Characterizations and Catalytic Properties

Two new half-sandwich zirconium（IV） complexes bearing salicylaldimine ligands of the type Cp＊Zr[2-tBu-4-R-6-（CH=NiPr）C6H2O]C12[R=H（1）, tBu（2）] were prepared by the reaction of Cp＊ZrC13 with the corresponding lithium of salicylaldimine ligands 2-tBu-4-R-6-（CH=NiPr）C6H2OLi[R=H（LiLa）, tBu（LiLb）]. Com- plexes 1 and 2 were characterized by 1H NMR, BC NMR spectroscopy and elemental analysis. When activated with AliBu3 and Ph3CB（C6F5）4, both complexes 1 and 2 exhibited reasonable catalytic activities for ethylene polymeriza- tion, producing polyethylenes with moderate molecular weight. Complexes 1 and 2 also exhibited reasonable catalyt- ic activities for ethylene copolymerization with 1-hexene, producing poly（ethylene-co-l-hexene）s with moderate molecular weight and reasonable 1-hexene content.     

相变贮热材料四氯合钴酸铵共析物的制备和热性能

在温度353 K的乙醇溶液中, 采用热回流法合成了热致相变化合物四氯合钴酸铵(1-C_nH_2n+1NH₃)₂CoCl₄(n=10, 18)(分别简写为C₁₀Co、C₁₈Co)及其二元混合物. 利用差示扫描量热和X射线法对二元体系进行了表征.根据测定实验数据构筑二元相图, 所得相图结果表明, 在w_C10Co=52.51% (质量分数)处存在中间化合物(1-C₁₀H₂₁NH₃)(1-C₁₈H₃₇NH₃)CoCl₄. 相图还包括两个三相线, 相对应的两个共析温度分别为(347±1)和(343±1) K, 共析点分别在w_C10Co=38.50%和w_C10Co=69.86%处. 并且, 在相图的左右边界存在端际固溶体(α、β)及中间区域存在非化学计量相(γ). 四氯合钴酸铵及其二元混合体系作为相变材料贮热时, 相变温度范围为340-370 K, 相变焓大小范围在2.13到141.12 J·g^-1之间.