Synthesis and QSAR studies of novel triazole compounds containing thioamide as potential antifungal agents

Eighteen novel triazole compounds containing thioamide were designed and synthesized. Their structures were confirmed by elemental analysis, H-1 NMR, IR, and MS. The title compounds exhibited certain antifungal activity. And the geometry structures of the title compounds were optimized by means of the density functional theory (DFT) method at B3LYP/6-31G* level. The quantitative structure-activity relationship (QSAR) of the title compounds was systematically investigated. A correlative equation between FA and DELH, V was well established by using the multiple linear regression (MLR). (c) 2006 Elsevier Ltd. All rights reserved.

Synthesis and structural characterization of (pyrazolyl)alkenyl Fischer carbene complexes of chromium and tungsten

Michael addition of substituted pyrazoles 2 to 1-alkynyl Fischer carbene complexes (CO)(5)M=C(OEt)(CdropCPh) (1) (a, M = Cr and b M = W) afforded (pyrazolyl)alkenyl Fischer carbene complexes (CO)(5)M=C(OEt)(CH=C(R(1)R(2)R(3)pz)Ph) (R(1)R(2)R(3)pz = pyrazolyl) 3 (M = Cr) and 4 (M = W), respectively, with an exclusive (E)-configuration in mild to excellent yields. The reaction of la and 3,5-dimethylpyrazole (2b) was monitored to demonstrate the formation and decomposition of complex 3b by H-1 NMR measurements in CDCl3 at 23degreesC. Complexes 3 and 4 were characterized with H-1, C-13{H-1} NMR, IR spectroscopies and elemental analysis. When the substituted pyrazoles were 3-methylpyrazole (2a) and 3,5-di-tert-butylpyrazole (2d), molecular structures of the corresponding (pyrazolyl)alkenyl Fischer carbene complexes 3a and 4d were characterized by X-ray crystallographic study. (C) 2004 Elsevier Ltd. All rights reserved.

聚丁二烯的序列结构Ⅰ. ~(13)C-NMR研究聚丁二烯的序列结构 Ⅱ. 1,2-聚丁二烯的构象分析

本文详细分析了聚丁二烯分子链的序列结构，以聚丁二烯的(13)C-NMR波谱测试为依据，划分聚丁二烯分子链为三种序列、十七类脂碳碳核。在此基础上发现并论证了T_4碳核的存在，同时在聚丁二烯的~(13)C-NMR谱图上确认了与之对应的共振吸收峰－T_4峰。通过处理谱峰化学位移数据，得到一组计算聚丁二烯~(13)C-NMR谱图脂碳部分各谱峰化学位移的经验参数。应用这一组参数于聚丁二烯的~(13)C-NMR谱图（脂碳部分），各谱峰化学位移的计算值和实验值有良好的一致性。但是，与聚丁二烯分子链的1,2－序列两端的四类碳核：C_4、T_4、V_2和V_8相对应之谱峰的化学位移，其实验值一致地大于计算值而趋向低场方面，为深入研究聚丁二烯的链结构提供了有价值的情报。本文还讨论了对于4'峰和8'峰的归属，并对定量表征聚丁二烯分子链的序列结构进行了初步尝试。

全同1，2－聚丁二烯的合成及用~(13)C-NMR方法研究1，2－聚丁二烯的序列结构

采用Cr／Al催化体系，成功地合成了全同1，2－聚丁二烯（PBD），并用DSC方法、X－射线衍射、红外光谱及~(13)C－NMR的方法进行结构与物性测定，得如下结果：全同1，2－PBD的熔点为124.3℃；三角晶系中，分子链成了螺旋，晶胞参数为a＝17.3A，c＝ 6.5A；在红外光谱中，其特征谱带出现在694.4 cm~(-1)处；在~(13)C－NMR谱中仅出现四条谱峰，其化学位移分别为142.51、111.56、39.26、37.43 ppm。全同1，2－PBD的~(13)C－NMR谱提供的实验数据表明，在~(13)C－NMR谱中1，2－PBD－CH二碳十个五元组谱峰的归属是有别于Elgert、Kumar已有的归属。它属于一种新的归属，与半经验方法所推演的结果相符。它恰巧同聚丙烯侧甲基五元组谱峰的归属一致。采用半经验方法研究了1，2－PBD的~(13)C－NMR增中CH二碳五元组、CH_2－碳四元组及六元组共振谱峰，同时讨论了模型链的链长、温度以及立构序列的排列对各立构序列键概率的影响，求得了相应的r值。同时采用经验方法对1，2－PBD的~(13)C－NMR谱中CH_2=碳、CH－碳五元组及CH_2－碳四元组谱峰做了归属。两种方法对CH_2－碳谱峰的归属得到了一致的结果。

C-13 NMR study of ethylene/propylene/octene-1 terpolymers synthesized with TiCl4/MgCl2/i-Bu3Al as the catalyst

The theory of chemical shift effect of substituent was applied to the assignment of the C-13 NMR spectra of the ethylene/propylene and ethylene/octene-1 copolymers. Using the parameters derived above and the DEFT technique, we then entirely assigned the C-13 NMR spectra of the ethylene/propylene/octene(-1) terpolymers synthesized in the presence of the same heterogeneous supported Ziegler-Natta catalyst, TiCl4/MgCl2/i-Bu3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene-1 terpolymers.

The NMR-spectroscopic and X-ray crystal-structural characterization of two Cp*Ir halfsandwich complexes containing the 1,2-dicarba-closo-dodecaborane-1,2-diselenolato ligand

The reaction of [Cp*IrCl2](2) with dilithium 1,2-orthocarborane-1,2-diselenolate 3 leads to the green 16-electron diselenolene complex [Cp*Ir{Se2C2(B10H10)}] (4) which takes up two-electron ligands such as trimethylphosphane to give the 18-electron diselenolate derivative [Cp*Ir(PMe3)-{Se2C2(B10H10)}] (5). The molecular structures of 4 and 5 were determined by X-ray crystal structure analysis. The Se-77-nuclear shielding in 4 is lower by almost 500 ppm relative to that in 5.

NMR investigation of phenolphthalein polyether ether ketone .1. The chain structure and assignments of H-1, C-13 NMR lines of PEK-C

Amorphous samples of polyether ketone with cardo(PEK-C) have been studied in the solution state by C-13, H-1 high-resolution NMR, The H-1 and C-13 1D NMR spectra were assigned using two dimensional chemical shift correlated spectroscopy, 2D homonuclear correlated(COSY) and heteronuclear correlated (HETCOR) spectroscopy present important information. In this work, the structural units of PEK-C was determined by NMR. For some peaks, these assignments are confirmed by two dimensional long-range heteronuclear correlation experiments, A little modification is made on the original C-13 peak assignments for the main chain, The symmetry and the isotacticity of the chain structure for PEK-C are obvious on NMR data.

H-1 and C-13 NMR studies of TTHA complexes with diamagnetic rare earth ions

TTHA complexes with diamagnetic rare earth ions (La3+, Y3+ and LU(3+)) were studied by H-1 and C-13 NMR spectroscopy. A symmetric structural model was suggested for La(TTHA) complex and an asymmetric model for Y(TTHA) and Lu(TTHA) complexes. The complex formation was dependent on the pH value of the solution. The interactions of La(TTHA) with the additional metal ions (La3+, Y3+ and Ca2+) were relatively weak, but relatively strong for that of Lu(TTHA) with the additional Lu3+.

核磁共振(NMR)研究缩聚与共缩聚高分子的数均分子量 1．全芳香族热致液晶共聚酯

通常用诸如测定溶液粘度的方法测定缩聚与共缩聚高分子的分子量十分不便.对于芳香族缩聚与共缩聚高分子经常遇到选择溶剂的困难.核磁共振波谱(NMR)是研究高分子链结构的最佳物理方法.利用AA-BB缩聚反应中数均聚合度与官能度之间的关系,基于核磁共振的实验

A HIGH-RESOLUTION SOLID-STATE NMR-STUDY OF THE MISCIBILITY, MORPHOLOGY, AND TOUGHENING MECHANISM OF POLYSTYRENE WITH POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE) BLENDS

An extended Goldman-Shen pulse sequence was used to observe indirectly the proton spin diffusion in the blends of polystyrene (PS) with poly(2,6-dimethyl-1,4-phenylene oxides) (PPO). The results indicate that the average distance between PS and PPO is less than 5 angstrom in the intimately mixed phase, but there are heterogeneous domains on a 100-angstrom scale. The data of spin relaxation of carbons, T1(C), for homopolymers and their blends suggest that there is a strong pi-pi electron conjugation interaction between the aromatic rings of PS and those of PPO, while the aromatic rings of PPO drive the aromatic rings of PS to move cooperatively. It is the cooperative motion that markedly improves the impact strength of PS.

ASSIGNMENT OF C-13 NMR-SPECTRA OF POLYMER WITH SEMIEMPIRICAL METHOD - SURVEY OF SPECTRUM OF SECONDARY CARBON OF 1,2-PBD

In chain molecules of 1, 2-PBD, there are two kinds of gauche arrangements, which is the cause of making the spectrum of the secondary carbon in main chain of the polymer split. In such a complex system, the gauche arrangements of the secondary carbon and the tertiary carbon occupy an important position. Hence, the contribution of the tertiary carbon to the chemical shifts of the secondary carbon has a decisive effect on the sequence structure distribution. In comparison the contribution of vinyl groups is ...

~(13)C-NMR化学位移与聚合物的构象——Ⅱ.1,2-聚丁二烯仲碳(—CH_2—)的~(13)C-NMR谱研究

在1,2-聚丁二烯链分子中,导致仲碳(—CH_2—)谱峰分裂的原因是存在着两种gauche排列。在这样一个复杂体系中,由于主链仲碳与叔碳的gauche排列占有重要的位置,因此主链叔碳对化学位移的贡献对于仲碳谱有着决定性的影响。相比之下,乙烯基的贡献要小得多。两种贡献分别是γ_1=—6.37——6.41ppm与γ_2=0.0——1.56ppm。在不计入侧基的影响或同时考虑乙烯基的贡献这两种情况下,均方误差MSE分别是0.166×10~(-2)和0.364×10~(-2)ppm~2。本文同时讨论了模型链的种类、链长以及温度对键概率的影响。并指出有个别反常的情况发生。文中还对间同1,2-聚丁二烯的链结构进行了分析。