Two Zinc Complexes Supported by in situ Formed Etheric Ligands

Two zinc complexes, [Zn(MPIP)Cl2](1) and [Zn(EPIP)Cl2](2), where MPIP = 1-(methoxymethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridine and EPIP = 1-(ethoxymethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridine, were synthesized under solvothermal conditions. The etheric ligand MPIP was formed in situ via metal ligand reaction between(3-(pyridin-2-yl)imidazo[1,5-a]pyridin-1-yl)methanol(HPIPM) and methanol solvent. Similarly, the ligand EPIP was generated in situ from the reaction of HPIPM with ethanol solvent. The structures of 1 and 2 were characterized by X-ray single-crystal diffraction analysis. They are four-coordinated mononuclear complexes, and the ZnII ion of 1 and 2 displays distorted tetrahedral geometry. The photoluminescent properties of 1 and 2 were investigated. Strong emissions were observed for both 1 and 2, which were ascribed as the intraligand(π-π*) fluorescent transitions. This paper provides a simple and efficient method for the synthesis of etheric compounds.     

Enantiomeric Sesquiterpene Lactones from Senecio tsoongianus

From Senecio tsoongianus,two pairs of enantiomeric isomers,tsoongianolides A(1) and B(2),tsoongianolides C (3) and D(4) were isolated. Their structures were elucidated by 1D and 2D-NMR techniques and X-ray diffractions. The cytotoxicity to KB cell of 1 and 2 is also reported.     

POLAR SUBSTITUENT EFFECTS OF ORGANOPHOSPHORUS ESTERS IN STRUCTURE-REACTIVITY STUDIES

In order to study the polar substituent effect almost with no steric effect in organophosphoruschemistry,a series of 4-substituted-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxides(1)and p-substitutedphenylphosphonates(2)and corresponding mono hexyl esters(3)as model were synthesized.~(31)P-NMR chemicalshifts of compounds(1)in methanol and deuterioacetone were determined.The Δδ values reflect 4-sbstituent po-lar effect.The ~(31)P-NMR of compounds(2)and(3)and the pKa of compounds(3)were also measured.Theresults showed that the trend of polar effects of substituents in both carboxylic and organophosphates chemistryare similar,and the change of polar effects in variation with the alkyl groups is not significant.     

Synthesis,Crystal Structure and Spectroscopic Properties of 1,2-Benzothiazine Derivatives:An Experimental and DFT Study

1,2-Benzothiazine derivatives methyl 3-methoxy-4-oxo-3,4-dihydro-2H-benzo[e] [1,2]thiazine-3-carboxylate 1,1-dioxide(1) and methyl 2-ethyl-3-hydroxy-4-oxo-3,4-dihydro-2Hbenzo[e][1,2]thiazine-3-carboxylate 1,1-dioxide(2) were synthesized, and characterized by spectroscopic techniques; 1H-NMR and infrared(IR) spectroscopy. Crystals of 1 and 2 were grown by slow evaporation of methanol and ethyl acetate, respectively and their crystal structures were investigated by single-crystal X-ray diffraction analysis. Geometric properties were calculated by the B3 LYP method of density functional theory(DFT) at the 6-31G+(d) basis set to compare with the experimental data. Simulated properties were found in strong agreement with the experimental ones. Intermolecular forces have also been modeled in order to investigate the strength of packing and strong hydrogen bonding was observed in both compounds 1 and 2. Electronic properties such as Ionization Potential(IP), Electron Affinities(EA) and coefficients of the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO) of com- pounds 1 and 2 were simulated for the first time.     

Thermal Properties of K（Y1-xYbx）（WO4）2（x=0.098,0.196,0.294） Crystal

Thermal properties of pure KY(WO4)2 and K(Y1-xYbx)(WO4)2(x=0.098,0.196,0.294) crystals were investigated.The specific heat and thermal diffusivity of crystals were calculated at a range of 50～300 ℃.The calculated result shows that the specific heat and thermal diffusivity of K(Y1-xYbx)(WO4)2(x=0.098,0.196,0.294) crystals were slightly affected by the Yb3+ concentration.The thermal expansion coefficient of K(Y0.804Yb0.196)(WO4)2 crystals along x,y and z axes were determined to be 13.51,4.474 and 16.60×10-6 K-1,respectively.These results suggest the K(Y1-xYbx)(WO4)2(x=0.098,0.196,0.294) crystal as a laser crystal of low-middle power.     

Two New Monoterpene Diglycosides from Winchia calophylla A. DC

Two new monoterpene diglycosides, wincaloside A (1) and wincaloside B (2), along with loganin (3) were isolated from the stem barks of Winchia calophylla A. DC. The structures of 1 and 2 were established by spectroscopic and chemical methods.     

8-O-4’ Neolignan glycosides from the aerial parts of Matteuccia struthiopteris

Two new 8-O-4’ neolignan glycosides, named matteustruthiosides A(1) and B(2) were isolated from the aerial parts of Matteuccia struthiopteris. Their chemical structures were characterized on the basis of various spectroscopic techniques. The absolute configurations of them were determined by experimental circular dichroism(CD) spectra. Compounds 1 and 2 were inactive against influenza A(H1N1) virus in vitro.     

Synthesis of （1H）—3,4—Dithydropyrrolo[2,1—c][1,4]oxazin—1—one Derivatives

In search of new anti-inflammatory and analgesic agents,(1H)-3,4-dihydro-pyrrolo [2,1-c][1,4]oxazin-1-one(3) and its acyl derivatives were designed and prepared .Compound 3 was prepared by treatment of methyl 1-(2-bromoethyl) pyrrole-2-carboxylate with silver oxide and its derivatives were obtained by Friedel-Carftes reaction.Nine of 6-acyl derivatives of compound 3 were prepared.     

Studies on synthesis and kinetics of thermodecomposition of the nickel(Ⅱ) compounds with Schiff base derived from amino acids

Monoaqua salicylaldehyde-o-aminobenzoic acid Ni(Ⅱ) monohydrate (cp1) and monoaqua o-vanillin-o-aminobenzoic acid Ni(Ⅱ) monohydrate (cp2) were synthesized. The composition and structures of these two compounds were analyzed. Their thermal stability and non-isothermal kinetics were also investigated by use of TG and DTG curves. The possible reaction mechanisms in their first steps of thermal decomposition reactions were deduced by means of integral and differential methods. Thermodecomposition kinetic equations of the compounds are as follows:Cp1: da/At = A . exp(-E/RT) . 3/2(1 - a)4/3 . [1/(1 - a)1/3 -1]-1 Cp2 : da/At = A . exp(-E/RT) . (1 - a)     

Crystal structure and single crystal EPR of (NH_4)_2(15-crown-5)_3[Cu(mnt)_2] and (NH_4)_2(benzo-15-crown-5)_4[Cu(mnt)_2]·0.5H_2O

The X-ray crystal structures of (NH4)2(15-crown-5)3[Cu(mnt)2] (1) and (NH4)2(benzo-15-crown-5)4- [Cu(mnt)2]·0.5H2O (2) were determined. Two single crystals are composed of distinct structures of ammonium-crown ether supramolecular cation and [Cu(mnt)2]2? anion. The triple-decker dication in complex 1 and a sandwich dimmer in complex 2 were observed. X-Band EPR studies on the single crystals of both complex 1 and complex 2 have been carried out at room temperature, which revealed that complex 2 showed a perfect hyperfine structure of Cu whereas that of complex 1 could not be observed. The principal values and direction cosines of the principal axes of the g and A tensors were computed by a least-squares fitting procedure. The spin density of Cu(II) was estimated according to the principal values of the A tensors and compared well with the results calculated based on DFT method.     

新型含1,2,4-三唑基的1,5-苯并硫氮杂的合成和表征

以α-溴代苯乙酮为原料,在三乙胺作用下制备α-(1,2,4-三唑-1-基)-芳基乙酮(1a～1c),再与芳香醛发生羟醛缩合反应制备相应的含三唑基的查尔酮2a～2l,将中间体2a～2l同邻氨基硫酚合成新型的2,4-二芳基-3-(1,2,4-三唑-1-基)-2,3-二氢-1,5-苯并硫氮杂(3a～3l).所得化合物的结构经元素分析,IR,MS和1HNMR确认,同时用X射线衍射法测定了化合物2a和3a的晶体结构.     

蝶形主体分子的设计、合成及其包结性能的研究

设计、合成了两种蝶形主体分子：2，5－二（三苯甲基）对苯二酚1，2，5－二（二苯甲基）对苯二酚2.1和2可与许多有机小分子形成配位包合物。用IR表征了主体分子1和2 的包结物， 用¹H NMR测定了主客体分子的摩尔比：1•DMF (1：2)，1•DMSO (1:2)，1 •吡啶 （1：2），1•环戊酮 （2：3）和2•DMF 1：2），2•DMSO （1：2），2 •THF （1：1），2•苯甲醛（1：2），2•苯乙酮 （1：2），2•2，5－己二酮 （1：1），2 •N－甲基－2－吡咯烷酮 （1：3）。单晶X-射线衍射分析了包结物2·苯甲醛的晶体结构，在分子间氢键的相互作用下晶体得以稳定。     

OCS+经由A2П←X2П激发的光解离光谱

在超声分子束条件下,由423、420、412.2和408.4nm的电离激光使OCS分子通过[3+1]共振增强多光子电离(REMPI)制备出OCS+(X2Π)离子后,在260-325nm范围内扫描解离激光获得了OCS+离子经由A2Π3/2←X2Π3/2(000)和A2Π1/2←X2Π1/2(000,001)跃迁的分质量光解离谱(母体离子OCS+的凹陷谱和碎片离子S+的增强谱).其中A2Π1/2←X2Π1/2(001)跃迁的光解离谱是首次观察到.由A2Π3/2←X2Π3/2(000)光解离谱得到了A2Π3/2电子态的光谱常数T0=31411.3cm-1,ν1=814.3cm-1;由A2Π1/2←X2Π1/2(000)光解离谱得到了A2Π1/2电子态的光谱常数ν1=816cm-1,ν2=(380.4±2.8)cm-1,ν3=(2052.7±5.1)cm-1,而从A2Π1/2←X2Π1/2(001)光解离谱拟合出的A2Π1/2电子态的ν1(786.4cm-1)稍有不同,表明在A2Π1/2←X2Π1/2(001)跃迁中X2П1/2电子态的C-O键振动(ν3)激发影响了A2Π1/2电子态C-S键的振动(ν1).实验结果表明:在A2Π1/2←X2Π1/2(000,001)跃迁的光解离谱中能够显著观察到属于A2Π电子态的ν2弯曲振动模激发的谱峰,例如A2Π1/2(020,120,021,…),而在A2П3/2(υ1υ2υ3)←X2Π3/2(000)跃迁的光解离谱中几乎没有观察到属于ν2弯曲振动模激发的谱峰.这种弯曲振动激发和A2П电子态的旋轨分裂分量(Ω)的相关性可以通过A2Π电子态的Fermi共振和Renner-Teller效应来解释.     

Sub-Doppler rotationally resolved spectroscopy of lower vibronic bands of benzene with Zeeman effects

Sub-Doppler high-resolution excitation spectra and the Zeeman effects of the 6(0)(1), 1(0)(1)6(0)(1), and 1(0)(2)6(0)(1) bands of the S1(1)B2u<--S(0)(1)A1g transition of benzene were measured by crossing laser beam perpendicular to a collimated molecular beam. 1593 rotational lines of the 1(0) (1)6(0) (1) band and 928 lines of the 1(0)(2)6(0)(1) band were assigned, and the molecular constants of the excited states were determined. Energy shifts were observed for the S1(1)B2u(v1=1,v6=1,J,Kl=-11) levels, and those were identified as originating from a perpendicular Coriolis interaction. Many energy shifts were observed for the S1(1)B2u(v1=2,v6=1,J,Kl) levels. The Zeeman splitting of a given J level was observed to increase with K and reach the maximum at K=J, which demonstrates that the magnetic moment lies perpendicular to the molecular plane. The Zeeman splittings of the K=J levels were observed to increase linearly with J. From the analysis, the magnetic moment is shown to be originating mostly from mixing of the S1(1)B2u and S2(1)B1u states by the J-L coupling (electronic Coriolis interaction). The number of perturbations was observed to increase as the excess energy increases, and all the perturbing levels were found to be a singlet state from the Zeeman spectra.     

Relative Contributions of Diabatic and Adiabatic Channels to Photoisomerization and Photocyclization of Diarylethylenes

Relative contributions of diabatic and adiabatic channels to photoisomerization and photocyclization processes were measured for stilbene, 1-phenyl-2-(2-naphthyl)ethylene (Ph-2N), 1,2-di-(1-naphthyl)ethylene (1N-1N), 1-(1-naphthyl)-2-(2-naphthyl)ethylene (1N-2N), and 1,2-di-(2-naphthyl)ethylene (2N-2N) by the steady-state spectrophotometric method in solutions at room temperature. The effects of solvent nature and atmospheric oxygen on the quantum yields of these processes in 1N-1N and 2N-2N were studied.     

[Z]-1-[2-(三芳基锡基)乙烯基]环辛醇的合成和性质

本文用三苯基氢化锡、三对甲苯基氢化锡作为锡氢化试剂与1-乙炔基环辛醇进行反应, 合成了两个有机锡化合物: [Z]-1-[2-(三苯基锡基)乙烯基]环辛醇(1)和[Z]-1-[2-(三对甲苯基锡基)乙烯基]环辛醇(2), 并测定了1的晶体结构。1和2分别与ICl, Br2, I~2反应, 得到六个有机锡一卤化物和三个有机锡二卤化物(3-11)。有机锡二卤化物6和一卤化物5与KOH乙醇溶液反应, 分别得到相应的锡氧化物和锡氢氧化物(12, 13)。有机锡二卤化物8分别与含氮双齿配体[2,2'-联吡啶(Bipy),5-硝基-1,10-邻菲罗啉(Nphen),8-羟基喹啉(Oxin)]反应, 得到三个相应的配合物(14-16)。十六个新化合物通过元素分析、锡含量测定、IR、^1H NMR测定对其结构进行了表征, 同时提出了1和2的生成反应历程。     

三种2-羟基-1-萘醛酰腙的晶体结构、热分解及其与CT-DNA的相互作用

Three acyl hydrazones N'-((2-hydroxynaphthalen-1-yl)methylene)-2-phenylacetohydrazide (1), N'-((2-hydroxynaphthalen-1-yl) methylene)-2-(4-hydroxyphenyl)acetohydrazide hydrate (2), and N'-((2-hydroxynaphthalen-1-yl) methylene)-2-(2-methoxyphenyl) acetohydrazide hydrate (3) were synthesized and then characterized by elemental analysis and single-crystal X-ray diffraction. The crystallographic data indicated that both compounds 2 and 3 crystallized in the monoclinic crystal lattice, space group C2/c, while compound 1 crystallized in the orthorhombic space group Pbca. The thermal decomposition processes of the three hydrazones were studied by thermogravimetry. The thermal decomposition temperatures of compounds 1, 2, and 3 were 318.23, 319.04, and 323.01℃, respectively. Meanwhile, the apparent activation energies for thermal decomposition for compounds 1, 2, and 3 were 115.90, 145.18, and 129.38 kJ·mol^-1, respectively, calculated according to the Kissinger and Ozawa equations. The interactions of compounds 1-3 with calf thymus (CT)-DNA were evaluated by microcalorimetry. The results indicated these interactions were homogenous endothermic processes with non-identical interaction time (1.00-50.0 min) and interaction enthalpies (0.47-15.50 kJ·mol^-1). The interaction enthalpies of compounds 1 and 2 were higher than those of their precursors, while the interaction enthalpy of compound 3 was lower than that of its precursor.     

The liquid‐phase oxidation of isomeric methoxy‐(1‐methylethyl)benzenes with oxygen to the hydroperoxides

The kinetics of liquid‐phase oxidation of 1‐methoxy‐2‐(1‐methylethyl)benzene ( 1a ), 1‐methoxy‐3‐(1‐methylethyl)benzene ( 1b ), and 1‐methoxy‐4‐(1‐methylethyl)benzene ( 1c ) with oxygen as oxidant to yield the corresponding 1‐methyl‐1‐(2‐methoxyphenyl)ethyl ( 2a ), 1‐methyl‐1‐(3‐methoxyphenyl)ethyl ( 2b ), and 1‐methyl‐1‐(4‐methoxyphenyl)ethyl ( 2c ) hydroperoxides was studied. The oxidizabilities of 1a , 1b , and 1c were established over the temperature range 50–120°C. The overall activation energies of oxidation were determined for 1b and 1c over the temperature range 50–120°C. Thermal stability of 2a and 2b and the initiating properties of hydroperoxides 2a , 2b , and 2c were studied. Long‐term noncatalytic oxidations of 1b and 1c to respective hydroperoxides were carried out. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 37: 10–16, 2005     

Synthesis of 1-alkoxy-3-(2-hydroxyethyl)-1-triazene 2-oxides

Synthetic procedure to access the first representatives of a new series of 3-monosubstitued functional derivatives of 1-alkoxy-1-triazene 2-oxides, i.e., 1-alkoxy-3-(2-hydroxyethyl)- and 1-alkoxy-3-(2-acetoxyethyl)-1-triazene 2-oxides, were elaborated. 1-Alkoxy-3,3-bis(2-hydroxyethyl)-1-triazene 2-oxides were used to derive 3-(2-acetoxyethyl)-, 3-(2-bromoethyl)- and 3-(2-cyanoethyl)substituted 1-alkoxy-3-(2-acetoxyethyl)-1-triazene 2-oxides.     

两个新型三核镍(Ⅱ)配合物的合成及其晶体结构

5-溴水杨醛和5-氯水杨醛分别与N-环己基-1,2-丙二胺经缩合反应制得Schiff碱配体(L1和L2); L1和L2分别与Ni(Ac)₂·4H₂O经配位反应合成两个新型的三核Schiff碱配合物(1和2),其结构经X-射线单晶衍射表征。1(CCDC: 1 008 203)和2(CCDC: 1 008 204)属单斜晶系,空间群P2₁/c,晶胞参数1：a=9.111(4) , b=12.089(6) , c=18.724(8) , β=92.117(7)°; 2： a=9.346 8(12) , b=11.507 3(15) , c=18.539(2) , β=93.774(2)°。