2-芳基硫杂脯氨酸结构特征的研究

对12种2-芳基硫杂脯氨酸进行了红外光谱和核磁共振谱测定,对其中两个化合物作了质谱测定。结果表明,这类化合物固态时主要以两性离子形式存在;有较强的分子离子峰,是一类较稳定的化合物。它们还存在一对非对映异构体,芳环上的取代基对芳环电子云密度的影响较大,而对四氢噻唑环的影响较小。     

亚碘酰苯氧化单和双(卟啉铁)反应的取代基效应研究

用紫外-可见分光光度分析法测定了PhIO氧化单和双(卟啉铁)两个系列共17个化合物的反应动力学并探讨了取代基的电子效应和立体效应对反应的影响规律.研究结果表明,单铁卟啉系列与PhIO的作用在动力学上的二级反应,而μ 氧代双卟啉铁系列为一级反应.无论是单卟啉铁还是双卟啉铁,反应动力学常数与取代基特性常数σ之间存在线性关系,但是卟啉环上取代基的电子效应对单和双卟啉铁的氧化反应表现出不同的影响规律.     

双消除一锅简便法合成1-丙炔基芳香化合物

报道了一种便捷合成1-丙炔基芳香化合物的新方法.在充分探讨反应条件的基础上,利用硫试剂乙基苯基砜与芳香醛组合,采用双消除反应成功地一锅合成了-系列1-丙炔基芳香化合物1a～1s.运用此法不仅合成出一些含有醚键、萘环、杂环以及含有两个1.丙炔基的化合物,重要的是芳环上含有卤原子(Br和I)的化合物也能顺利地合成出来.该方法原料易得,操作简单,产物容易分离纯化并且产率理想.     

芳胺汞化合物的合成及其分子内重排缩合反应

利用简便易得的N-取代苄基芳胺的汞化产物,经亚硝化反应得到8种N-取代苄基-N-亚硝基-2-乙酸汞基芳胺,并通过分子内缩合合成了一种苯并咪唑衍生物,其结构经元素分析、1HNMR、IR及X射线单晶衍射确证。此方法为合成咪唑类化合物提供了一条新途径。     

芳基汞化合物的性质研究——Ⅶ.邻位取代苯基氯化汞的质子分解反应

本文研究了邻位取代苯基氯化汞o-XC_6H_4HgCl(X=CH_3、H、Cl、Br、COOC_2H_5、NO_2)与HCl(NaI)在85％对氧陆圜水溶液中的质子分解反应,证明反应按S_El历程进行。视取代基不同,反应速度次序如下:CH_3>H>Cl>COOC_2H_5～Br>NO_2。从化学反应与紫外光谱的研究以及理论计算结果表明,p或π电子的邻位取代基对水原子有分子内配位,它对反应速度有重要影响。测定了15种p-、m-、o-取代苯基氯化汞在80％对氧陆圜水溶液中在40.0℃的质子分解反应的速度常数k_1,表明给电性取代基加速反应,吸电性取代基使反应减慢,这可以看作是反应中心在芳环上的芳基汞化合物的S_E1反应所具有的一个特点。     

Cp2TiCl2催化下Grignard试剂与芳醛反应的研究

Meunier 等曾研究了 Cp_2TiCl_2催化下,格氏试剂对卤代烷和羰基化合物的还原反应,并报道了与芳环或碳-碳双键或碳-碳三键共轭的羰基化合物不被格氏试剂还原。我们却发现,在较低温度下,这些芳醛或与碳-碳重键共轭的羰基化合物也会被还原,特别是在芳环上有吸电子取代基时,还原产物的产率很高。     

Galvinoxyl/K~3Fe(CN)~6/KOH复合体系相转移催化合成对称取代 偶氮苯

用Galvinoxyl自由基为催化剂,芳胺类化合物在饱和铁氰化钾的氢氧化钾溶液和二氯甲烷的两相转移催化下合成了18个对称取代偶氮苯,提供了一个快速、方便、高效的制备偶氮苯类化合物的新方法,讨论了Hammett取代基常数与反应速度的关系,同时也讨论了取代基效应对产率的影响,并对反应机理也做了合理的解释。     

19-取代雄烯二酮芳构酶抑制剂的定量构效关系研究

用分子动力学和量子化学AM1经验方法对系列19-位取代的雄烯二酮芳构酶抑制 剂的定量构效关系进行了研究，结果表明该位置的取代基必须符合P450芳构酶活性 位点的立体效应和疏水作用的要求。此类化合物作为较好的电子供体与芳构酶结合 ，给电子的主要基团为21-位含S取代基。这些研究结果为设计活性更高的芳构酶抑 制剂提供了有益的参考信息。     

取代苯σ·П效应分离与FMO能量的相关性△E_(X.σP)~(HO) 研究

研究了芳环上取代基诱导效应能和共轭效应能的分离,Ph(X)n的(X)n基属性从能量角度提出量化解释及应用,发现各类芳环取代基都不同程度存在两种σ_c、σ_I效应,且存有群轨道作用。     

取代苯σ·Ⅱ效应分离与FMO能量的相关性△EHOX.σP研究

研究了芳环上取代基诱导效应能和共轭效应能的分离,Ph(X)n的(X)n基属性从能量角度提出量化解释及应用,发现各类芳环取代基都不同程度存在两种σC、σI效应,且存有群轨道作用.     

Synthesis and NMR spectral studies of N-chloroacetyl-2,6-diarylpiperidin-4-ones

A series of 2,6-diarylpiperidin-4-ones having electron withdrawing chloroacetyl group at the heterocyclic nitrogen were synthesized. Unambiguous characterizations of the synthesized compounds were achieved by one-dimensional ((1)H NMR and (13)C NMR) and two-dimensional (HOMOCOSY, NOESY and HSQC spectra for compounds 8 and 9 and HOMOCOSY spectrum only for 10) NMR spectroscopic data. The conformational preferences of N-chloroacetyl-2,6-diarylpiperidin-4-ones with and without alkyl substituent at C-3 and C-5 (8-14) have also been discussed using the spectral studies. The spectral data and extracted coupling constant values suggest that the compounds 8, 12 and 14 adopt flattened boat conformation whereas the remaining compounds exist in twist-boat conformations in solution with coplanar orientation of the chloroacetyl moiety present at the heterocyclic nitrogen. The substituent parameters for the chloroacetyl moiety on the heterocyclic ring carbons have also been derived and discussed elaborately on the basis of their steric, electronic and gamma-eclipsing interaction. This substituent at the nitrogen causes a substantial change on the chemical shifts of ring carbons and the associated protons.     

取代邻苯二腈的合成

在室温条件下合成了一系列芳氧基邻苯二腈化合物,应用无素分析、1HNMR、IR确定了它们的结构,讨论了不同取代基对反应的影响.结果表明,酚的芳环上有推电子基时反应容易进行;酚的芳环上有拉电子基时反应慢或不反应.     

2-氨基取代噻唑基膦酸脂的合成

本文报导一系列2-氨基-5-取代-4-噻唑基膦酸酯和2-氨基-4-取代-5-噻唑基膦酸酯的合成. 这类化合物显示了一定的杀菌活性.     

Synthesis and Antimicrobial Evaluation of Halogen-Containing Arylidene Thiazolo Triazinediones

A series of 7-substituted arylidene-1,3-thiazolo[2,3-c]-1,2,4-triazine-4,6-diones were synthesized in an one-pot multicomponent reaction of 6-arylmethyl-3-mercapto-1,2,4-triazin-5-ones with substituted benzaldehydes and monochloroacetic acid in the presence of acetic anhydride, acetic acid, and sodium acetate. The structures of the new compounds were supported by IR, ¹H NMR, MS, and analytical data. All the new compounds were tested for their antibacterial and antifungal activity. Arylidene thiazolo triazinediones with 1,3-benzodioxolo substituent at seventh and p-chlorophenyl or 2,4-dichlorophenyl substituents at third displayed good antibacterial and antifungal activity. And also compound bearing 2,3,5-trimethoxyphenyl substituent at seventh and 2,4-dichlorophenyl substituent at third displayed good activity.     

微波辅助酸催化水相一锅高效合成吖啶酸

本文建立一种以去离子水为溶剂,在微波辅助酸催化下一锅串联高效合成吖啶酸的新方法,该反应条件温和、操作简单、绿色高效。在优化反应条件下考察了多种取代基团对反应的影响,结果显示该方法具有良好的适应性,以83%～97%收率得到18个吖啶酸化合物。所有化合物结构均经过¹H NMR、¹³C NMR、HRMS、熔点等表征确认。     

Synthesis and spectroscopic studies of some new ortho functionalized triazene compounds and their reactivity with mercury (II) ion

In this work, a series of triazene derivatives in which the substituents have a wide range of electronic characters were synthesized to understand the effect of the substituent identity in controlling the changes in their electronic absorption spectra and NMR chemical shifts, as well as their tendency for interaction with some heavy metals. Elemental analysis and ¹H NMR, ¹³C NMR, and FT-IR spectroscopies were used to elucidate the chemical structures of the new compounds. Thermal analysis and protolysis of these triazenes were evaluated. The thermodynamic parameters were calculated from thermal data using Coats-Redfern method. Complexation of these compounds with mercury (II) ion in acetonitrile and deuterated dimethylsulfoxide (DMSO-d₆) solution were studied by UV–vis and ¹H NMR spectroscopy, respectively. Stoichiometry and formation constants of the complexes were calculated by the mole ratio titration method. The effects of the nature of the substituents on the formation constants were discussed.     

Study of hydrazone-Hydrazoimine tautomerism in α-Azo-6-ketomethylphenanthridines

AB Azo-coupling of a series of 6-ketomethylphenanthridines products was performed starting from 6- ketomethylphenanthridines and benzene diazonium chloride. The products were characterised using ¹H, ¹³C and ¹⁵N NMR, IR, UV and MS spectroscopic methods. The hydrazoimine forms were the only tautomer present in chloroform solution. Two rotamers were detected in chloroform solutions of the compounds studied. Analysis of the NMR data shows that the ratio of rotamers depends on electron-donating and electron-withdrawing properties of the substituent present in the benzene ring.     

New Photochromic Spiropyrans with <Emphasis Type="Italic">ortho</Emphasis>-Hydroxyaldimine Substituent

A series of new spiropyrans of indoline series with ortho-hydroxyaldimine substituent has been synthesized, their structure and photochromic properties have been studied. The structure of the obtained compounds was confirmed by the data of 1H NMR and IR spectroscopy and elemental analysis. Photochromic properties of the prepared compounds have been studied. The introduction of ortho-hydroxy group into aldimine fragment of molecule (in the 6 position of the 2H-chromene fragment) has increased the lifetime of merocyanine isomer by 40 times as compared with amino-substituted spiropyran.     

一些长链全氟烷基化合物的19-FNMR化学位移

长链全氟烷基化合物的~(19)F NMR化学位移已有很多报道,然而,文献报道的大多是CF_3-(CF_2)_n-X化合物,对于X-(CF_2)_n-Y化合物报道相对较少。长链全氟烷基化合物的~(19)F NMR谱的归属是较困难的,特别是对于X-(CF_2)_n-Y的化合物的谱,由于两端取代基的效应,图谱归属更困难。本文报道一些未报道过的长链全氟烷基化合物的~(19)F NMR化学位移的数据,并讨论它们的归属。     

New CO2-philic Compounds： Design, Synthesis and Solubility in Supercritical Carbon Dioxide

Liquid and supercritical carbon dioxide (scCO2) have attracted much attention as “green” replacement for organic solvents, offering economical and environmental benefits due to its favorable physical and chemical properties, such as recyclability, ease …