含酰亚胺骨架的大环化合物合成、结构及其对阴离子的识别研究

在磷酸催化作用下,采用前体二胺N,N’-(2-胺基苯基)-2,6-二甲酰亚胺吡啶(1)和前体二醛1,4-二(2’-甲酰苯氧基)丁烷(2)进行缩合作用得到[1+1]Schiff碱大环化合物3,进一步将Schiff碱大环3还原得到饱和大环4.并采用1H NMR,IR,质谱和元素分析等技术对大环3和4的组成进行了表征.采用X射线单晶衍射技术测定了Schiff碱大环3的晶体结构,结果表明大环3具有扭曲的"8"字形结构.采用UV-vis光谱滴定技术对大环与系列阴离子的键合作用进行了考察,结果表明,Schiff碱大环3对F-离子有明显的选择性识别作用,并测定了该配位反应的配位比和平衡常数.     

取代苯基吡唑醛缩邻氨基苯酚Schiff碱的合成与表征

取代苯肼与乙酰丙酮经过缩合反应合成取代苯基吡唑．取代苯基吡唑在Vilsmeier—Haak反应条件下,得到取代苯基吡唑醛．取代苯基吡唑醛与邻氨基苯酚作用生成取代苯基吡唑醛缩邻氨基酚Schiff碱．这些化合物的结构经IR光谱、质谱和^1H NMR确认．     

新型大环席夫碱化合物的合成及其抗菌活性研究

利用Ca2＋, Ba2＋离子作为模板离子, 由2,4-二羟基-5-乙酰苯乙酮与烷基二胺[即1,3-丙二胺, 1,4-丁二胺, 1,6-己二胺]反应, 分别合成了系列新型席夫碱大环化合物Ln (n＝3, 4, 6). 对合成得到的新型大环席夫碱化合物采用元素分析, 1H NMR, IR, 紫外-可见光谱和MS等进行组成和结构表征, 体外抗菌活性也被试验.     

氮杂冠醚取代基对schiff碱锰(Ⅲ) 配合物催化苯乙烯环氧化反应的影响

合成并表征了苯并-10-氮杂-15-冠-5或吗啉基取代的单和双Schiff碱锰（Ⅲ）配合物MnL2^1Cl,MnL2^2Cl,Mnl^3Cl和MnL^4Cl．研究了它们作为仿P450模型化合物催化苯乙烯环氧化反应的性能,并考察了催化反应的动力学．结果表明,氮杂冠醚取代的Schifft碱锰（Ⅲ）配合物优于相应的吗啉基取代的Schiff碱锰（Ⅲ）配合物,且反应遵从Michaelis—Menten规律．这是由于具有特殊功能和空间构型的氮杂冠醚大环的引入。改善了催化中心周围的微环境,从而显著地提高了Schiff碱锰（Ⅲ）配合物的催化活性．     

不对称Schiff碱镍(Ⅱ)配合物的合成及其晶体结构

合成了3个具有不对称结构的Schiff碱配体H2Ln(n=1、2、3)。H2L1由乙酰丙酮、乙二胺和水杨醛缩合作用得到,H2L2由乙酰丙酮、(1R,2R)-环己二胺和水杨醛缩合作用得到,H2L3由苯甲酰丙酮、乙二胺和水杨醛缩合作用得到,每个反应中3个反应物的物质的量之比均为1∶1∶1。配体H2Ln分别与Ni(OAc)2.4H2O进行配位反应得到3个单核Ni(Ⅱ)配合物1,2和3。分别采用1H NMR、FTIR和元素分析对化合物进行了表征,并通过X-射线单晶衍射技术测定了3个配合物的晶体结构。     

含脲基Schiff碱大环合成、结构及其对阴离子的识别研究

采用前体二胺1,3-二(3-胺基苯基)脲(1)和二醛1,3-二(2-甲酰基苯氧基)-2-丙醇(2)进行缩合作用得到[1+1]Schiff碱大环3.用~1H NMR、FT-IR、FABMS和元素分析等对大环组成进行了表征,并通过X射线单晶衍射技术解析了大环3的晶体结构.采用UV-vis光谱滴定技术对大环与系列阴离子的键合作用进行了考察,结果表明,Schiff碱大环3对AcO~-离子有明显的选择性识别作用,并用紫外-可见吸收光谱、核磁和等温量热滴定等技术分别对大环3与AcO~-阴离子的识别反应进行了考察,获得了识别反应的配位比、平衡常数(K)及Δ_rH_m、Δ_rS_m、Δ_rG_m等热力学参数信息.     

3-氨基-二氢噻吩-2-酮类Schiff碱的合成和生物活性研究

通过3-氨基-二氢噻吩-2-酮(DL-高半胱氨酸硫内酯)盐酸盐与取代苯甲醛反应, 得到3-氨基-二氢噻吩-2-酮类Schiff碱. 合成了9个化合物, 其中7个为首次报道的新Schiff碱类化合物. 化合物结构经IR, ¹H NMR和元素分析证实, 并对这些化合物进行了室内毒力测试, 结果表明此类化合物具有很好的杀菌、抑菌活性.     

2-取代-3,4-二氢-1-异喹啉酮的合成和舒张血管活性

以3-羟基-4-甲氧基苯甲酸甲酯等为原料, 通过烯丙基醚化、Claisen重排、氧化、与伯胺反应(生成Schiff碱)、还原、分子内酯的胺解六步反应合成了一系列2-取代-3,4-二氢-1-异喹啉酮类化合物. Schiff碱的制备、还原、酯的胺解三步在“一锅”内完成. 采用1H NMR, MS和元素分析对目标化合物的结构进行了表征. 离体动脉环张力实验证明此类化合物具有明显舒张血管的作用.     

新型[1+1]Schiff碱大环化合物的合成与表征

在硫酸催化作用下,采用前体二醛1,7-二(2’-甲酰苯基)-4-氮-1,7-二氧-4-(4’-对甲苯磺酸基)庚烷(1)和1,7-二(2’-甲酰苯基)-1,4,7三氧庚烷(2)与二胺化合物N,N’-(2-胺基苯基)-2,6-二甲酰亚胺吡啶(3)分别进行缩合,得到[1+1]Schiff碱大环化合物4和5,并用元素分析、1H NMR、IR和质谱等对大环化合物4和5进行表征.同时用X射线衍射方法测定了2个前体和2个Schiff碱大环的晶体结构.单晶X射线衍射结果表明,2个大环化合物分子中,分子内氢键作用导致整个分子呈现为一扭曲"8"字形构型,分子内一对苯环之间的π-π相互作用进一步稳定其分子的扭曲结构.其紫外研究结果显示,大环化合物4和5对镧(III)离子具有选择性识别作用.     

[Ln（TOv）（phen）（NO3）]·2H2O的合成表征与热分解动力学

合成了三种稀土元素与牛磺酸缩邻香草醛Schiff碱的配合物[Ln（TOv）（phen）（NO3）]·2H2O（TOv：牛磺酸缩邻香草醛Schiff碱配体;phen：1,10-邻菲哕啉;Ln：Er,Tm,Yb）,并对其进行了结构表征．采用Achar微分法和Coats．Redfem积分法拟合得到了配合物的热分解动力学方程．     

新型含席夫碱大环化合物的合成

以乙二胺、1,2-丙二胺、乙酰丙酮和2,5-二巯基-1,3,4-噻二唑为原料, 经缩合、溴代和成环作用得到了两个新型席夫碱大环化合物6a和6b. 用元素分析, 1H NMR, IR和质谱进行表征, 同时用X射线衍射方法测定了两个中间体的晶体结构.     

Novel chiral "calixsalen" macrocycle and chiral robson-type macrocyclic complexes

A family of novel chiral "calixsalen" Schiff base macrocycles R,R-H(3)L4, R,R-H(3)L5, containing three chiral diamino moieties were synthesized by an efficient self-assembly and characterized by (1)H and (13)C NMR, mass spectrometry, and X-ray diffraction. The systematic synthesis, structure, and coordination properties of the [2 + 2] and [3 + 3] Robson-type Schiff base macrocyclic mono-, di-, tri-, and tetranuclear metal complexes were explored.     

Synthesis, spectral, antimicrobial and antitumor assessment of Schiff base derived from 2-aminobenzothiazole and its transition metal complexes

N-(thiophen-2-ylmethylene)benzo[d]thiazol-2-amine Schiff base (L) derived from 2-aminobenzothiazole and 2-thiophenecarboxaldehyde was synthesized and characterized using elemental analysis, IR, mass spectra, (1)H NMR and UV-vis spectra. Its complexes with Cu(II), Fe(III), Ni(II) and Zn(II) were prepared and isolated as solid products and characterized by elemental and thermal analyses, spectral techniques as well as magnetic susceptibility. The IR spectra showed that the Schiff base under investigation behaves as bidentate ligand. The UV-vis spectra and magnetic moment data suggested octahedral geometry around Cu(II) and Fe(III) and tetrahedral geometry around Ni(II) and Zn(II). In view of the biological activity of the Schiff base and its complexes, it has been observed that the antimicrobial activity of the Schiff base increased on complexation with the metal ion. In vitro antitumor activity assayed against five human tumor cell lines furnished the significant toxicities of the Schiff base and its complexes.     

异烟酰肼缩水杨醛Schiff碱配合物的合成与表征

采用直接合成法用异烟酰肼、水杨醛合成了异烟酰肼缩水杨醛Schiff碱,并以此为配体合成了Zn（Ⅱ）、Co（Ⅲ）、Ni（Ⅱ）的配合物．对配合物进行了元素分析,红外光谱,紫外光谱,差热-热重分析及摩尔电导的测试等表征,推测配合物的组成分别为[Zn（H2O）L],[Co（H2O）2（HL）2]NO3-H2O,[Ni（H2O）2HL]NO3,其中L=C13 H9O2N3．     

Interaction of water-soluble amino acid Schiff base complexes with bovine serum albumin: fluorescence and circular dichroism studies

Fluorescence spectroscopy in combination with circular dichroism (CD) spectroscopy were used to investigate the interaction of water-soluble amino acid Schiff base complexes, [Zn(L1,2)(phen)] where phen is 1,10-phenanthroline and H2L1,2 is amino acid Schiff base ligands, with bovine serum albumin (BSA) under the physiological conditions in phosphate buffer solution adjusted to pH 7.0. The quenching mechanism of fluorescence was suggested as static quenching according to the Stern-Volmer equation. Quenching constants were determined using the Stern-Volmer equation to provide a measure of the binding affinity between amino acid Schiff base complexes and BSA. The thermodynamic parameters DeltaG, DeltaH and DeltaS at different temperatures (298, 310 and 318K) were calculated. The results indicate that the hydrophobic and hydrogen bonding interactions play a major role in [Zn(L1)(phen)]-BSA association, whereas hydrophobic and electrostatic interactions participate a main role in [Zn(L2)(phen)]-BSA binding process. Binding studies concerning the number of binding sites and apparent binding constant Kb were performed by fluorescence quenching method. The distance R between the donor (BSA) and acceptor (amino acid Schiff base complexes) has been obtained utilizing fluorescence resonant energy transfer (FRET). Furthermore, CD spectra were used to investigate the structural changes of the BSA molecule with the addition of amino acid Schiff base complexes. The results indicate that the interaction of amino acid Schiff base complexes with BSA leads to changes in the secondary structure of the protein. Fractional contents of the secondary structure of BSA (f(alpha), f(beta), f(turn) and f(random)) were calculated with and without amino acid Schiff base complexes utilizing circular dichroism spectroscopy. Our results clarified that amino acid Schiff base complexes could bind to BSA and be effectively transported and eliminated in the body, which could be a useful guideline for further drug design.     

Studies on Mononuclear Chelates Derived from Substituted Schiff Base Ligands: Synthesis and Characterization of a New 5-Methoxysalicyliden-<Emphasis Type="Italic">p</Emphasis>-Aminoacetophenoneoxime and Its Complexes with Co(II), Ni(II), Cu(II), and Zn(II)

New complexes of Co(II), Ni(II), Cu(II), and Zn(II) with new Schiff bases derived by the condensation of p-aminoacetophenoneoxime with 5-methoxysalicylaldehyde are synthesized. The compounds are characterized by elemental analyses, magnetic susceptibility measurements, IR, ¹H and ¹³C NMR spectra, electronic spectral data, and molar conductivity. The thermal stabilities of the compounds are also reported. The Schiff base acts as bidentate O,N-donor atoms, and their metal complexes are supposed to possess a tetrahedral geometry with respect to the central metal ion. The general formula of the 5-methoxysalicyliden-p-aminoacetophenoneoxime Co(II), Ni(II), Cu(II), and Zn(II) complexes is Co(L)₂, Ni(L)₂, Cu(L)₂, and Zn(L)₂.     

Synthese und Koordinationsverhalten neuer Schiffscher Basen aus 3‐Formylacetylaceton und natürlichen L‐Aminosäuren

Three novel chiral Schiff Base ligands (H₂L) were prepared from the condensation reaction of 3‐formyl acetylacetone with the amino acids L ‐alanine, L ‐phenylalanine, and L ‐threonine. X‐ray single crystal analyses revealed that the Schiff Base compounds exist as enamine tautomers in the solid state. The molecular structure of the compounds is stabilized by an intramolecular hydrogen bridge between the enamine NH function and a carbonyl oxygen atom of the pentandione residue. Treatment of the ligands H₂L with copper(II) actetate in the presence of pyridine led to the formation of copper complexes [CuL(py)]. In each of the complexes the copper atoms adopt a distorted square‐pyramidal coordination. Three of the basal coordination sites are occupied by the doubly deprotonated Schiff Bases L^2– which act as tridentate chelating O, N, O‐ligands. The remaining coordination sites are occupied by a pyridine ligand at the base and a carboxyl oxygen atom of a neighboring complex at the apical position. The latter coordination is responsible for a catenation of the complexes in the solid state.     

西佛碱型大环多胺过渡金属配合物的合成与表征

西佛碱型大环多胺过渡金属配合物的合成与表征     

希夫碱过渡金属配合物的合成及其荧光性能

合成了3,5-二氯水杨醛缩邻苯二胺配体(H2L);H2L与M(NO3)2(M=Cu,Ni,Zn)反应,合成了3种希夫碱过渡金属配合物ML。UV,1HNMR,IR和元素分析研究表明ML为四配位。用荧光激发光谱和发射光谱研究了H2L和ML的光物理性能,结果表明,H2L具有较强的荧光;ZnL具有较强的荧光和良好的热稳定性(分解温度达424.2℃)。