共轭2,4,5-三取代-1,3-噁唑中噁唑环的红外吸收光谱判定

本文定性地对三十种共轭2,4,5-三取代-1,3-噁唑的红外吸收光谱进行了研究。得出一系列此类分子的红外吸收位置、强度数据,将此数据与其分子结构相联系,并将此数据归属为九类振动模式,据此提出了一个用红外光谱定性判定此类噁唑衍生物中噁唑环的系统方法。     

新型吡啶环液晶化合物的合成及性能

以2-溴-5-吡啶甲醛和5-溴-2-吡啶甲醛为起始原料,合成出4种新型含吡啶环二联芳基和三联芳基化合物,总收率20%~30%。 热性能研究结果表明,二联芳基化合物未呈现出液晶相,而三联芳基化合物在加热和冷却过程中均表现向列相液晶态,且当氮原子位于正丁基的间位时,其与不含氮原子的三联苯化合物(2c)相比,熔点降低了11.7 ℃,清亮点升高6.3 ℃,液晶相区拓宽了18 ℃,表现出了良好的热性能。 光电性能测试结果表明,用吡啶环替代苯环后,化合物的光学各向异性值均较参比化合物(1c或2c)增大;当N原子位于正丁基的邻位的化合物,介电各向异性值较参比化合物增大,且液晶的阈值电压、饱和电压均降低。 通过对三环同分异构体化合物的不同构象能量态的计算分析,解释了介电各向异性的变化规律。     

New Aspects in the Chemistry of Three-membered Ring Compounds Containing a Highly Coordinate Main Group Element

The title compounds were synthesized by taking advantage of the Martin ligand. Their structures were determined by X-ray crystallography. Pentacoordinate thiasiliranides were hydrolyzed to give the corresponding thiol. Pentacoordinate chalcogenaphosphiranes were found to have polar P-chalcogen bonds, which were confirmed by their reactions with CF3SO3Me to give the corresponding 1-（methylchalcogena）alkylphosphonium triflates and by the solvent-dependent NMR studies.     

含吡啶、噻吩环大环化合物的合成及其与Cu(Ⅱ)的配合行为

以2，6－二溴甲基吡啶及2，5－二氯甲基噻吩分别与对甲基苯磺酰胺进行缩合反应得到新的大环化合物1，9，17，25－四对甲基苯磺酰基大环多胺｛[32]-Py4N4Ts4｝与1，8，15，22－四对甲基苯磺酰基大环化合物｛[28]-Th4N4Ts4｝。其中[32]－Py4N4Ts4在浓硫酸中脱去四个对甲基苯磺酰基后又得到新的大环多胺化合物[32]-Py4N4H4，并由紫外吸收光谱测定出其与Cu（Ⅱ）配合的配位比为1：2，证明形成了双核配合物。     

含吡啶环氮(王)冠的合成

本文报道了新的含吡啶环的氮(王)冠的合成。以活泼双功能团化合物2,6-二(溴四基)-吡啶和N-对甲苯磺酰基取代的多乙撑基多胺(二乙撑三胺,三乙撑四胺)二钠盐直接缩合成环,得到含吡啶环的氮(王)冠化合物:3,6,9-三对甲苯磺酰基-3,6,9,15-四氮双环[9.3.1]十五环-1(15),11,13-三烯(A)和3,6,9,12-四对甲苯磺酰基-3,6,9,12,18-五氮双环[12.3.1]十八环-1(18),14,16-三烯(B)。(A)和(B)经用30%的HBr-CH_3COOH溶液处理,得到3,6,9,15-四氮双环[9.3.1]十五环-1(15),11,13-三烯(C)和3,6,9,12,18-五氮双环[12.3.1]十八环-1(18),14,16-三烯(D)。以上化合物均经元素分析、IR和1~H NMR.等鉴定。这种直接缩合的方法,具有反应条件温和、设备简单、操作简便等优点。     

Absorption and Fluorescence Emission Spectra of Molecules Containing Azo and/or Oxadiazole Units

The ground state structures of a series of organic molecules containing azo and/or oxadiazole units were obtained by means of density functional theory B3LYP/6-31G(d) method. The first singlet excited state structures were optimized by virtue of singlet-excitation configuration interaction CIS/6-31G(d) method. The absorption and fluorescence emission spectra were then evaluated via the time-dependent density functional theory B3LYP and PBE1PBE methods with 6-311++G(3df,2p) basis set. The calculation results show that compared with those of their parent molecules A-H, B-H, C-H, D-H, the absorption and emission wavelength values of all the derivatives show red shifts. The derivatives containing both the oxadiazole and methoxyl units are good candidates for longer absorption wavelength materials. The effects of azo, oxadiazole, and methoxyl units on the absorption and emission wavelength were discussed.     

含四元环的多环芳香化合物的研究进展

含四元环的多环芳香化合物通常能够表现出独特的光物理和化学性质,在很多领域具有潜在应用价值.分别针对线型、角型、螺旋型和环型含四元环多环芳香化合物的合成方法、分子堆积方式、光电性质及载流子迁移率等方面进行归纳总结.研究表明,表面合成法更利于制得规则形貌的多环芳香化合物;线型类分子表现出了较高的载流子迁移率;角型分子通常显...     

含呋喃环系西佛碱型大环化合物的合成

利用 Mn~(++)和 Ba~(++)作为模板离子,合成了一类新型的含呋喃环系西佛碱型大环化合物L~1 和配合物 L~2 Ba(ClO_4)_2、L~3 Ba(ClO_4)_2 和 L~4 Ba(ClO_4)_2.L~2～L~4 的 Ba~(++)配合物经与 Na_2 SO_4 水溶液反应解络,得到自由配体 L~2、L~3 和 L~4。配体 L~2 和 L~3 分别与 Sr~(++)作用,得到配合物 L~2 Sr(ClO_4)_2 和 L~3 Sr(ClO_4)_2。上述大环配体和各种配合物均经元素分析、IR、~1HNMR、MS 等证实了它们的结构和组成。     

含吡啶环系和中心功能基氮杂冠醚的合成研究

合成了氮杂大环化合物Ⅰ－Ⅳ，并通过＾１Ｈ ＮＭＲ、ＭＳ和元素分析表征了它的结构，对其中间体（７）的合成方法进行了改进，使收率得到了大幅度提高，探讨了在不同温度下的成环反应，结果表明，室温有利于成环和提高反应收率。     

含四硫富瓦烯大环化合物的合成与研究进展

简要介绍了含有四硫富瓦烯(TTF)单元的大环化合物的分类, 概括了各类含四硫富瓦烯大环化合物的合成方法, 主要包括含有1,3-二硫杂环戊烯-2-硫酮单元的大环化合物在亚磷酸三烷基酯参与下的偶合反应, 以及带有氰乙基硫等取代基的预先合成的官能化TTF与二卤代低聚醚的反应. 综述了含四硫富瓦烯大环化合物的电化学性能及其在分子识别方面应用研究的最新进展, 提出了含四硫富瓦烯大环化合物的发展趋势.     

Studies on Synthesis and Biological Activities of Novel Triazole Compounds Containing Pyrimidine or N,N-Dialkyldithiocarbamate Ring

IntroductionAs an important type of fungicides,triazolecompounds are highly efficient,low poisonous andinward absorbents[1— 4] .At present,the studies ontriazole derivatives have mainly been concentratedon the compounds with triazole group as the onlyactive group.The report of triazloe compoundsthat contain both a triazole group and other activegroups in a single molecule has rarely been found.Some pyrimidines have been used as high efficientand low poisonous fungicides[5] in control of pow-d…     

新型含七元醚环的脯氨酸衍生物的合成

以L-谷氨酸和苯甲醛为起始原料,经7步反应合成了重要中间体(2S,5R)-1-苄基-5-(2-羟乙基)吡咯烷-2-羧酸叔丁酯(1),总产率19%;1经TBDMSCl保护羟基后,用10%Pd/C催化氢解去除苄基制得游离胺(2S,5R)-5-(2-二甲基叔丁基硅氧烷基乙基)吡咯烷-2-羧酸叔丁酯(3);3与Boc-β-Cl-ala,在碱性条件下偶合得氯代烃消去产物(2S,5R)-1-[(2-叔丁氧甲酰胺基)丙烯酰基]-5-(2-二甲基叔丁基硅氧烷基乙基)吡咯烷-2-羧酸叔丁酯(4),或在中性条件下偶合得(2S,5R)-1-[(R)-2-叔丁氧甲酰胺基-3-氯丙酰基]-5-(2-二甲基叔丁基硅氧烷基乙基)吡咯烷-2-羧酸叔丁酯(5);4或5经四丁基氟化铵去除TBDMS保护并发生关环反应合成了新型的七元醚环化合物(4R,7S,9R)-4-甲基-4-叔丁氧甲酰胺基-5-羰基-3-氧杂氮杂卓[1,4]并吡咯[1,2-d]-7-羧基叔丁酯(简称6);6于室温在氯仿中静置2 d~3 d自发转换为其构象异构体(4S,7S,9R)-6(简称6’,6/6’=1/9),其结构经1H NMR,13C NMR,2D NMR和HR-ESI-MS表征。     

Synthesis and Characterization of Novel Schiff Base Macrocyclic Compounds Containing Thiophene

Several novel Schiff base macrocyclic compounds containing thiophene were synthesized from d/ethyl 3,4-dialkoxythiophene-2,5-dicarboxylate, cyanuric chloride, diethylarnine and p-nitrophenol by reduction, oxidation, substitution and cyclization, and their structures were characterized by IR, NMR and electrospray ionization-rnass spectrorneter（ESI-MS）. The studies on their UV-Vis absorption spectra show that Schiff base rnacrocycles 6-10 have selective recognition for Fe^3＋.     

Hydrazinolysis of Compounds Containing Oxazolidine Ring

We have studied hydrazinolysis of (4S,5S)-3-benzyl-4-hydroxymethyl-5-(4-nitrophenyl)oxazolidine, (1R,4S,5S)-1-(4-nitrophenyl)-1-aza-3,7-dioxabicyclo[3,3,0]octane, and (1R,4S,5S)-1-benzyl-4-(4-nitrophenyl)-1-azonia-3,7-dioxabicyclo[3,3,0]octane. We have shown that neutral compounds are decomposed with opening of the oxazolidine ring, while quaternary ammonium salts react with hydrazine in several directions.     

含苯氧基萘并萘醌和偶氮苯双变色基化合物的合成和性质

通过６－氯－５，１２－萘并萘醌与４－羟基偶氮苯及其衍生物的反应合成了３种含苯氧基萘并萘醌和偶氮苯光致变色基的双变色基化合物，６－［４－（苯偶氮基）苯氧基］－５，１２－萘并萘醌（５），６－［４－（ｐ－乙氧基苯偶氮基）苯氧基］－５，１２－萘并萘醌（６）和６－［４－（ｐ－硝基苯偶氮基）苯氧基］－５，１２－萘并萘醌（７）．这些化合物的苯氧基萘并萘醌变色基的ＵＶ诱导光致变色性较弱；基于氨与苯氧基萘并萘醌ａｎａ显色体的不可逆反应，化合物５和６ＤＭＳＯ溶液在３６５ｎｍ紫外光辐照光稳态（ＰＳＳ）下的ａｎａ醌式摩尔分数估计分别为２２％和１７％．这些结果说明，苯偶氮基对苯氧基萘并萘醌变色基的光致变色性质有着极强的影响．另一方面，与４－羟基偶氮苯母体不同，这些双变色基化合物在ＤＭＳＯ中偶氮苯变色基的顺式异构体是相对稳定的     

Synthesis and Properties of Novel Luminescent Compounds Containing Triphenylamine and Bipyridine Units

Blue luminescent compounds T1-T4 containing triphenylamine donors,bipyridine acceptors and olefinic linkers were synthesized and characterized by 1H NMR,13C NMR and high resolution mass spectrometry(HR...     

Synthesis, Structure and Properties of Two Photochromic Compounds Containing A Pyrazolone-ring

IntroductionThe investigation of organic photochromic materials has increased considerably in recentyears because of their potential commercial application in several areas,such as high-densityoptical storage media,optical switching,etc.[1 ,2 ] .Though numerous organic photochromicmolecular systems or photoactive devices have been explored so far,those systems classifiedaccording to the photochromic structural units mainly belong to a small number of families:fulgides,spiropyrans and spiroxazi…     

抗癌大环化合物的环合方法

大环化合物具有广泛的生物活性.一些具有抗癌活性的天然大环化合物已开发成上市药物或应用于临床研究.在抗癌大环化合物的合成中,环合步骤是整个合成过程中的关键,同时也是难点所在.目前已经发展出了一些方便实用的环合方法.文章以具有抗癌作用的大环化合物为例,简要介绍各种常用的大环环合方法及应用.     

锰,钴,镍钨硅杂多酸盐的合成及性质研究

对3种过渡金属钨硅杂多酸钾盐的组成及性质进行了研究,与12-钨硅酸钾比较表明,在Keggin阴离子骨架中,以空位或过渡金属Mn~(2+)、Co~(2+)、Ni~(2+)取代一个W~(6+)后,其W—O、Si—O键振动吸收频率、组成元素内层电子结合能、W—O多面体的可还原性、晶形、晶格大小及热稳定性都出现了明显变化,这些变化与过渡元素的性质相关联.