含芳基三氮唑结构的3-乙砜基吡啶类化合物的合成及杀虫活性研究

以3,6-二氯吡啶-2-羧酸为起始原料,依据活性亚结构拼接原理,设计合成了结构新颖的含芳基三氮唑结构的3-乙砜基吡啶类化合物,所有目标化合物均经1HNMR, 13CNMR和HRMS结构表征.初步杀虫活性测试结果表明,在500mg/L浓度下,目标化合物均对玉米粘虫(Mythimnaseparatawalker)表现出良好的致死活性,2-(3-(2,6-二氟苯基)-1-甲基-1H-1,2,4-三唑-5-基)-3-(乙基磺酰基)-6-(吡咯烷-1-基)吡啶(9c),N-(仲丁基)-6-(3-(2,6-二氟苯基)-1-甲基-1H-1,2,4-三唑-5-基)-5-(乙基磺酰基)吡啶-2-胺(9g),6-(3-(2,6-二氟苯基)-1-甲基-1H-1,2,4-三唑-5-基)-5-(乙基磺酰基)-N-异丁基吡啶-2-胺(9h)在100 mg/L时,致死率仍达到80%.     

铁、钴催化剂乙烯聚合原位紫外-可见光谱研究

利用乙烯常压聚合原位紫外 可见 (UV Vis)光谱技术 ,对 3个铁、钴络合物作为催化剂前体的催化剂体系进行了研究 .3个铁、钴络合物分别为 2 ,6 双 [1 (2 ,6 二甲基苯基亚胺 )乙基 ]吡啶二氯化铁 (a)、2 ,6 双 [1 (2 ,4,6 三甲基苯基亚胺 )乙基 ]吡啶二氯化铁 (b)和 2 ,6 双 [1 (2 ,6 二异丙基苯基亚胺 )乙基 ]吡啶二氯化钴(c) .实验结果表明 ,MAO对络合物催化剂前体的活化作用是一个快速过程 ;在聚合条件下分别观察到 5 6 0、6 30和 5 80nm的活性峰 ,考察了它们在聚合过程中的生长和在加入无水乙醇逐步使催化剂中毒时活性峰的消失规律 .对催化剂活性物种的结构和聚合机理进行了探讨     

丁酸氯维地平降解杂质的合成

以4-(2,3-二氯苯基)-1,4-二氢-2,6-二甲基-3,5-吡啶二羧酸(2-氰基乙基)（甲基）酯(5)为起始原料,合成了丁酸氯维地平的5种降解杂质：4-(2,3-二氯苯基)-1,4-二氢-2,6-二甲基-3,5-吡啶二羧酸单甲酯(A), 4-(2,3-二氯苯基)-1,4-二氢-2,6-二甲基-3-吡啶羧酸甲酯(B), 4-(2,3-二氯苯基)-2,6-二甲基-3,5-吡啶二羧酸单甲酯(C), 4-(2,3-二氯苯基)-2,6-二甲基-3,5-吡啶二羧酸（丁酰氧基甲基）（甲基）酯(D)和4-(2,3-二氯苯基)-2,6-二甲基-3-吡啶羧酸甲酯(E)。其中A由5水解制得;B由A脱羧制得;C由5氧化后再经水解制得;D由C和丁酸氯甲酯缩合制得;E由C脱羧制得,化合物结构经¹H NMR和MS（ESI）确证。     

新型吡啶双亚胺铁催化乙烯聚合反应

合成与表征了一种新型吡啶双亚胺铁烯烃聚合催化剂2,6-二[1-(4-羟基-2,6-二甲基苯胺)乙基]吡啶氯化铁（1a）。结果表明,在亚胺环的对位引入羟基,可同时提高催化剂的活性和聚合物的分子量。在改性甲基铝氧烷(MMAO)的活化下,该催化剂引发乙烯聚合的活性（以单位时间（h）mol Fe引发乙烯聚合的PE质量（g）来表征）可达到6.78×10⁶ g/（mol•h）,明显高于已知催化剂2,6-二[1-(2,6-二甲基苯胺)乙基]吡啶氯化铁（1b）,且能得到更高分子量的聚乙烯。     

吡啶-2,6-二甲酰胺衍生物Tb(Ⅲ)、Eu(Ⅲ)配合物的制备及荧光性能测试

从吡啶-2,6-二甲酸(L1)出发,合成了2种含有多个共轭体系和多齿的N2,N6-二(3-甲基吡啶)-2-取代吡啶-2,6-二甲酰胺(L2)配体和N2,N6-二对甲苯基吡啶-2,6-二甲酰胺 (L3) 配体;制备了化合物N2,N6-二(3-甲基吡啶)-2-取代吡啶-2,6-二甲酰胺(L2)与Tb(Ⅲ)和Eu(Ⅲ)的配合物,培养出了单晶.通过红外光谱、元素分析和X射线单晶衍射仪确定配合物的组成和结构.结果表明:在Tb(Ⅲ)配合物的稀溶液中,当溶液pH值为7时荧光强度最强,pH值大于或小于7荧光强度都逐渐减弱;当溶液pH为7时,N2,N6-二(3-甲基吡啶)-2-取代吡啶-2,6-二甲酰胺对Tb(Ⅲ)的荧光强度敏化远大于吡啶-2,6-二甲酸;N2,N6-二(3-甲基吡啶)-2-取代吡啶-2,6-二甲酰胺和吡啶-2,6-二甲酸与Eu(Ⅲ)形成稀的配合物溶液的荧光强度随pH值的增加而增大(pH 3～11).     

新型桥连双卟啉化合物的合成及结构表征

通过将4,4′-二羧基-2,2′-联吡啶、2,6-二溴甲基吡啶、2,6-二羟甲基吡啶和1,8-二氨基萘分别与5-(4-羟基苯基)-10,15,20-三苯基卟啉(1a)、5-(4-甲酰苯基)-10,15,20-三苯基卟啉(1b)和5-[4-(4′-溴代丁氧基)苯基]-10,15,20-三苯基卟啉(1c)反应,合成了3类新型的双卟啉化合物2a-2e,经IR,¹HNMR,MS,UV-Vis光谱及元素分析对中间体和目标化合物的结构进行了表征.     

吡啶二亚胺Ni(Ⅱ)配合物的合成、晶体结构及其催化乙烯聚合的研究

由三齿配体2,6-二[1-(2-甲基苯基亚胺)乙基]吡啶(L₁)和2,6-二[(1-苯基亚胺)乙基]吡啶(L₂)分别与NiCl₂.6H₂O在乙腈中反应,合成了两个吡啶二亚胺基氯化镍配合物L₁Ni(Ⅱ)Cl₂.CH₃CN(1)和L₂Ni(Ⅱ)Cl₂(2).通过元素分析、IR和¹HNMR对配体和配合物进行了结构表征,并测定了配合物1和2的晶体结构.X射线衍射分析结果表明,两个配合物均为五配位扭曲三角双锥构型,属单斜晶系,C_c空间群.配合物1的晶胞参数a=2.5783(5)nm,b=1.4843(3)nm,c=1.5866(3)nm;β=122.82(3),°V=5.1024(18)nm³,Z=4,R₁=0.0708,配合物2的晶胞参数a=1.5772(1)nm,b=0.8594(1)nm,c=1.5459(1)nm;β=103.27(1),°V=2.039(2)nm³,Z=4,R₁=0.0375.配合物1和2经MAO活化后对乙烯聚合表现出较低的催化活性.     

双核铕(Ⅲ)配合物的合成及选择性激发

成功地合成一种新的四齿配体2,5-二(4-((2-吡啶-1氢-苯并[d]嘧唑)甲基)苯基)-1,3,4-噁二唑(L),并且将该配体作为第二配体合成出双核Eu3+配合物[Eu(TTA)3]2L(TTA二2-噻吩三氟甲基乙酰丙酮),配合物[Eu(TTA)3]2L的结构用红外光谱,吸外-可见吸收光谱进行了充分表征.为了讨论配...     

非洛地平原药中相关杂质的合成

根据杂质产生的机理,模拟杂质产生的条件,合成了欧盟药典7.8所载非洛地平的3种杂质———2,6-二甲基-4-(2,3-二氯苯基)-3,5-吡啶二甲酸甲乙酯(1),2,6-二甲基-4-(2,3-二氯苯基)-1,4-二氢-3,5-吡啶二甲酸二甲酯(2)和2,6-二甲基-4-(2,3-二氯苯基)-1,4-二氢-3,5-吡啶二甲酸二乙酯(3),其结构经1H NMR和MS确证。1~3的合成,为非洛地平生产、检验、贮存过程中对杂质的控制提供了依据。     

吡啶桥联的聚酰亚胺的合成与性能研究

以3,4-二甲基苯乙酮与3,5-双(三氟甲基)苯甲醛为原料,通过Chichibabin反应制备了吡啶桥联的四甲基化合物,该化合物再经氧化、脱水反应制备了主链含有吡啶环、侧链带有双三氟甲基取代苯侧基的新型含氟芳香族二酐单体,2,6双(3′,4′-二羧基苯基)-4-(3″-,5″-双三氟甲基苯基)吡啶二酐(6FDAPA).FT IR、NMR、质谱以及元素分析等测试结果表明,6FDAPA的结构与预期的相符.利用6FDAPA与另外一种不含氟的二酐单体2,6双(3′,4′二羧基苯基)4苯基吡啶二酐(DAPA)分别与含氟二胺单体,1,4双(2三氟甲基4氨基苯氧基)苯(6FAPB)通过两步热亚胺化法制备了两种聚酰亚胺(PI)薄膜.测试结果表明,6FDAPA6FAPB(PI2)与DAPA6FAPB(PI1)相比具有相近的耐热性能,玻璃化转变温度为280℃,起始热分解温度为580℃、700℃时的重量保持率64.5%.同时PI2具有更为优良的透光性,紫外可见光谱(UV Vis)测试表明,PI2与PI1薄膜在450nm处的透光率分别为85.7%与69.4%.     

A luminescent platinum(II) 2,6-bis(N-pyrazolyl)pyridine complex

Four platinum(II) cationic complexes were prepared with the mer-coordinating tridentate ligands 2,6-bis(N-pyrazolyl)pyridine (bpp) and 2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine (bdmpp): [Pt(bpp)Cl]Cl.H(2)O; [Pt(bdmpp)Cl]Cl.H(2)O; [Pt(bpp)(Ph)](PF(6)); [Pt(bdmpp)(Ph)](PF(6)). The complexes were characterized by (1)H NMR spectroscopy, elemental analysis, and mass spectrometry, and the structures of the bpp derivatives were determined by X-ray crystallography. [Pt(bpp)Cl]Cl.2H(2)O: monoclinic, P2(1)/n, a = 11.3218(5) A, b = 6.7716(3) A, c = 20.6501(6) A, beta = 105.883(2) degrees, V = 1522.73(11) A(3), Z = 4. The square planar cations stack in a head-to-tail fashion to form a linear chain structure with alternating Pt...Pt distances of 3.39 and 3.41 A. [Pt(bpp)(Ph)](PF(6)).CH(3)CN: triclinic, P, a = 8.3620(3) A, b = 10.7185(4) A, c = 13.4273(5) A, alpha = 96.057(1) degrees, beta = 104.175(1) degrees, gamma = 110.046(1) degrees, V = 1072.16(7) A(3), Z = 2. Cyclic voltammograms indicate all four complexes undergo irreversible reductions between -1.0 and -1.3 V vs Ag/AgCl (0.1 M TBAPF(6)/CH(3)CN), attributable to ligand- and/or metal-centered processes. By comparison to related 2,2':6',2' '-terpyridine complexes, the electrochemical and UV-visible absorption data are consistent with bpp being both a weaker sigma-donor and pi-acceptor than terpyridine. Solid samples of [Pt(bpp)(Ph)](PF(6)) at 77 K exhibit a remarkably intense, narrow emission centered at 655 nm, whereas the other three complexes exhibit only very weak emission.     

Tuning redox potentials of bis(imino)pyridine cobalt complexes: an experimental and theoretical study involving solvent and ligand effects

The structure and electrochemical properties of a series of bis(imino)pyridine Co(II) complexes (NNN)CoX(2) and [(NNN)(2)Co][PF(6)](2) (NNN = 2,6-bis[1-(4-R-phenylimino)ethyl]pyridine, with R = CN, CF(3), H, CH(3), OCH(3), N(CH(3))(2); NNN = 2,6-bis[1-(2,6-(iPr)(2)-phenylimino)ethyl]pyridine and X = Cl, Br) were studied using a combination of electrochemical and theoretical methods. Cyclic voltammetry measurements and DFT/B3LYP calculations suggest that in solution (NNN)CoCl(2) complexes exist in equilibrium with disproportionation products [(NNN)(2)Co](2+) [CoCl(4)](2-) with the position of the equilibrium heavily influenced by both the solvent polarity and the steric and electronic properties of the bis(imino)pyridine ligands. In strong polar solvents (e.g., CH(3)CN or H(2)O) or with electron donating substituents (R = OCH(3) or N(CH(3))(2)) the equilibrium is shifted and only oxidation of the charged products [(NNN)(2)Co](2+) and [CoCl(4)](2-) is observed. Conversely, in nonpolar organic solvents such as CH(2)Cl(2) or with electron withdrawing substituents (R = CN or CF(3)), disproportionation is suppressed and oxidation of the (NNN)CoCl(2) complexes leads to 18e(-) Co(III) complexes stabilized by coordination of a solvent moiety. In addition, the [(NNN)(2)Co][PF(6)](2) complexes exhibit reversible Co(II/III) oxidation potentials that are strongly dependent on the electron withdrawing/donating nature of the N-aryl substituents, spanning nearly 750 mV in acetonitrile. The resulting insight on the regulation of redox properties of a series of bis(imino)pyridine cobalt(II) complexes should be particularly valuable to tune suitable conditions for reactivity.     

含氮配体Co、Fe配合物的合成、结构及性质

报导了四个单核Co（Ⅱ）和Fe（Ⅱ）的配合物[Co（L1）2]（ClO4)2·（CH3CN）（1）,[Fe（L1）2]（ClO4）2·（H2O）（2）,[Co（L2）]（ClO4）2（3）,以及[Fe（L2）]（ClO4）2·2H2O（4）,（其中L1＝4’-苯基-2,2’：6’,2”-三联吡啶,L2＝N,N,N-三-（2-（2-吡啶甲叉氨基）乙基）胺）的合成和性质,以及配合物1、3的晶体结构．配合物1和3的晶体都属于单斜晶系．它们的晶胞参数分别为：1a＝1．0855（4）nm,b＝1．6201（5）nm,c=2.5236（5）nm,β＝92．63（2）°,V＝4．433（1）nm3;3a=2.8351（8）nm,b＝1．0670（3）nm,c＝1．9255（5）m,β＝101．03（4）°,V＝5717（2）nm3．2和4的氧化还原电位分别为E＝0．78V和0．63V‘它们的d-d跃迁吸收最大值分别位于565和521nm处．     

Synthesis,Crystal Structure,and Catalytic Performance of 2,6-Bis[1-(2,4,6-trimethylphenylimino)ethyl]pyridine Nickel(Ⅱ)Complex

A novel nickel(Ⅱ) complex Ni[L]Cl2·CH3CN(1) containing the tridentate ligand 2,6-bis[1-(2,4,6-trimethylphenylimino)ethyl]pyridine(L) has been synthesized. The crystal structure of complex 1 was determined by single crystal X-ray diffraction analysis. The catalytic activity of complex 1 for the polymerization of ethylene was studied under activation with methylaluminoxane(MAO).     

Family of mixed-valence oxovanadium(IV/V) dinuclear entities incorporating N4O3-coordinating heptadentate ligands: synthesis, structure, and EPR spectra

Dinuclear (V(IV)V(V)) oxophenoxovanadates of general formula [V2O3L] have been synthesized in excellent yields by reacting bis(acetylacetonato)oxovanadium(IV) with H3L in a 2:1 ratio in acetone under an N2 atmosphere. Here L3- is the deprotonated form of 2,6-bis[{{(2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L1), 2,6-bis[{{(5-methyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L2), 2,6-bis[{{(5-tert-butyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L3), 2,6-bis[{{(5-chloro-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol(H3L4), 2,6-bis[{{(5-bromo-2-hydroxybenzyl)(N'N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L5), or 2,6-bis[{{(5-methoxy-2-hydroxybenzyl)(N'N'-(dimethylamino)ethyl)}methyl]-4-methylphenol (H3L6). In [V2O3L1], both the metal atoms have distorted octahedral geometry. The relative disposition of two terminal V=O groups in the complex is essentially cis. The O=V...V=O torsion angle is 24.6(2) degrees . The V-O(oxo)-V and V-O(phenoxo)-V angles are 117.5(4) and 93.4(3) degrees , respectively. The V...V bond distance is 3.173(5) A. X-ray crystallography, IR, UV-vis, and 1H and 51V NMR measurements show that the mixed-valence complexes contain two indistinguishable vanadium atoms (type III). The thermal ellipsoids of O2, O4, C10, C14, and C15 also suggests a type III complex in the solid state. EPR spectra of solid complexes at 77 K display a single line indicating the localization of the odd electron (3d(xy)1). Valence localization at 77 K is also consistent with the 51V hyperfine structure of the axial EPR spectra (3d(xy)1 ground state) of the complexes in frozen (77 K) dichloromethane solution: S = 1/2, g(parallel) approximately 1.94, g(perpendicular) approximately 1.98, A(parallel) approximately 166 x 10(-4) cm(-1), and A(perpendicular) approximately 68 x 10(-4) cm(-1). In contrast isotropic room-temperature solution spectra of the family have 15 hyperfine lines (g(iso) approximately 1.974 and A(iso) approximately 50 x 10(-4) cm(-1)) revealing that the unpaired electron is delocalized between the metal centers. Crystal data for the [V2O3L1].CH2Cl2 complex are as follows: chemical formula, C32H43O6N4Cl2V2; crystal system, monoclinic; space group, C2/c; a = 18.461(4), b = 17.230(3), c = 13.700(3) A; beta = 117.88(3) degrees ; Z = 8.     

Synthesis,crystal structure and catalytic performance of bis (imino)pyridyl nickel complexes

Two new Ni(II) complexes of 2,6-bis[1-(2,6-diethylphenylimino)ethyl]pyridine (L¹), 2,6-bis[1-(4-methylphenylimino)ethyl]pyridine (L² ) have been synthesized and structurally characterized. Complex Ni(L¹)Cl₂?·?CH₃CN (1), exhibits a distorted trigonal bipyramidal geometry, whereas complex Ni(L¹)(CH₃CN)Cl₂ (2), is six-coordinate with a geometry that can best be described as distorted octahedral. The catalytic activities of complexes 1, 2, Ni{2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine} Cl₂?·?CH₃CN (3), and Ni{2,6-bis[1-(2,6-dimethylphenylimino) ethyl]pyridine}Cl₂?·?CH₃CN (4), for ethylene polymerization were studied under activation with MAO.     

有机锡配合物{[(o-MeC6H4CH2)2Sn(O)]2(o-MeC6H4CH2NHO)}2的合成、结构和性质研究

二(o-甲基苄基)二氯化锡与N-(o-甲基苄基)羟胺在碱性条件下反应,合成了有机锡配合物{[(o-MeC6H4CH2)2Sn(O)]2(o-MeC6H4CH2NHO)}2。经X-射线衍射方法测定了化合物的晶体结构。该化合物晶体属三斜晶系,空间群P-1,晶体学参数 a =1.0604(5) nm,b =1.3078(7) nm,c = 1.3742(47 nm,α=105.174(12)?,β = 90.229(7)?,γ=101.028(6)?,Z = 1,V =1.8025(15) nm3,Dc=1.522Mg•m-3,?(MoKa)= 1.423 mm-1,F(000)= 834,R1=0.0455,wR2=0.1017。化合物是三个以Sn2O2构成的平面四元环组成的梯状结构,锡原子均为五配位的畸变三角双锥构型。测定了配合物的体外抗癌活性,结果表明配合物对WiDr和MCF-7等癌细胞有一定的抑制能力。     

Synthesis and Crystal Structure of a One-dimensional Mn（Ⅱ） Coordination Polymer with 1,3-bis（4-pyridyl）propane

A new 1D zigzag chain coordination polymer, { [Mn（bpp）（bac）2]·（CHaCN）}n 1 （bpp = 1,3-bis（4-pyridyl）propane, Hbac = benzoylacetone）, has been synthesized and characterized by FT-IR spectroscopy, thermal analysis and X-ray single-crystal diffraction. In the molecular structure, all Mn atoms locate in an octahedral geometry. The guest CH3CN molecules are included in the 1D channels of the 3D packing structure of 1. Crystal data： C35H35MnNaO4, Mr = 616.60, monoclinic, space group P211c, a = 17.691（4）, b = 18,955（4）, c = 9.712（6） A, β = 93.91（3）°, V = 3249.31（1） A^3, Z = 4, Dc = 1.260 g/cm^3, F（000） = 1292, 20max = 54.9°, μ = 0.447 mm^-1, the final S = 1.020, R = 0.0693 and wR = 0.1497.     

Tuning the electronic structure of octahedral iron complexes [FeL(X)] (L = 1-alkyl-4,7-bis(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane,X = Cl,CH(3)O,CN, NO). The S = 1/2 <==>3/2 Spin equilibrium of [FeL(Pr)(NO)

Two new pentadentate, pendent arm macrocyclic ligands of the type 1-alkyl-4,7-bis(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane where alkyl represents an isopropyl, (L(Pr))(2-), or an ethyl group, (L(Et))(2-), have been synthesized. It is shown that they bind strongly to ferric ions generating six-coordinate species of the type [Fe(L(alk))X]. The ground state of these complexes is governed by the nature of the sixth ligand, X: [Fe(III)(L(Et))Cl] (2) possesses an S = 5/2 ground state as do [Fe(III)(L(Et))(OCH(3))] (3) and [Fe(III)(L(Pr))(OCH(3))] (4). In contrast, the cyano complexes [Fe(III)(L(Et))(CN)] (5) and [Fe(III)(L(Pr))(CN)] (6) are low spin ferric species (S = 1/2). The octahedral [FeNO](7) nitrosyl complex [Fe(L(Pr))(NO)] (7) displays spin equilibrium behavior S = 1/2<==>S = (3)/(2) in the solid state. Complexes [Zn(L(Pr))] (1), 4.CH(3)OH, 5.0.5toluene.CH(2)Cl(2), and 7.2.5CH(2)Cl(2) have been structurally characterized by low-temperature (100 K) X-ray crystallography. All iron complexes have been carefully studied by zero- and applied-field M?ssbauer spectroscopy. In addition, Sellmann's complexes [Fe(pyS(4))(NO)](0/1+) and [Fe(pyS(4))X] (X = PR(3), CO, SR(2)) have been studied by EPR and M?ssbauer spectroscopies and DFT calculations (pyS(4) = 2,6-bis(2-mercaptophenylthiomethyl)pyridine(2-)). It is concluded that the electronic structure of 7 with an S = 1/2 ground state is low spin ferrous (S(Fe) = 0) with a coordinated neutral NO radical (Fe(II)-NO) whereas the S = 3/2 state corresponds to a high spin ferric (S(Fe) = 5/2) antiferromagnetically coupled to an NO(-) anion (S = 1). The S = 1/2<==>S = 3/2 equilibrium is then that of valence tautomers rather than that of a simple high spin<==>low spin crossover.