偶氮聚碳酸酯的制备与性能研究

以对氨基苯甲酸、亚硝酸钠和苯酚为原料,通过重氮偶合反应合成了对羟基偶氮苯甲酸,并用红外光谱和核磁共振对所合成的对羟基偶氮苯甲酸的结构进行了表征。将羟基偶氮苯甲酸与聚碳酸酯进行熔融混合并进行酯交换反应,制备了偶氮聚碳酸酯。通过光学性能和力学性能研究发现,所制备的偶氮聚碳酸酯具有优异的光致变色性能和透明性,力学性能与聚碳酸酯相当。     

阳离子聚丙烯酰胺制备条件研究

采用氧化还原剂和偶氮类化合物组成的复合引发体系,通过水溶液聚合法制备丙烯酰胺(AM)和甲基丙烯酰氧乙基三甲基氯化铵(DMC)的共聚物。研究了氧化还原剂总质量分数、氧化剂与还原剂的质量比、偶氮类化合物的种类和质量分数、引发温度、pH值、单体质量分数等对产物特性粘数的影响。得到的较佳工艺条件:氧化还原剂总质量分数0.015%、氧化剂与还原剂质量比0.7、偶氮类化合物质量分数0.012 5%、引发温度25℃、pH值6.0、单体质量分数45%,在上述条件下,产物特性粘数为12.370 8 dL/g。用红外光谱技术对产物的结构进行表征。     

末端炔基偶氮苯化合物的合成及相转变性质研究

首次报道了可作为点击逐步聚合单体、具有不同长度间隔链的末端炔基偶氮苯类化合物的合成。首先以对羟基苯甲酸与苯酚反应制备偶氮苯原料化合物,然后以3-溴丙炔与二醇类化合物制备不同长度的末端炔基间隔链,通过其对偶氮苯原料化合物的修饰制备目标产物。所得目标产物化学结构经1HNMR、13CNMR、FT-IR、元素分析和质谱确证。利用示差扫描量热法(DSC)及偏光显微镜(POM)研究其相转变性能,结果表明,通过改变化合物间隔链长度可以调节其相转变性能,包括相变温度及液晶性能。     

侧链含偶氮生色分子的聚电解质的合成及表征

合成了偶氮苯生色分子4-羟基-4’-偶氮苯甲酸,采用自由基聚合法将生色分子与环氧氯丙烷和α-甲基丙烯酸反应,合成了含偶氮支链的聚电解质（APE）。利用傅里叶红外光谱（FT—IR）、紫外一可见光谱（UV—Vis）等分析手段对中间产物和APE进行了结构表征。采用差示扫描量热分析仪（DSC）对APE进行了热稳定性表征,其玻璃化转变温度（Tg）为189．7℃,表明具有较好的热稳定性。     

一类偶氮苯酚类化合物的合成及表征

以取代苯胺为原料,经重氮化后与取代苯酚偶联合成了5个偶氮苯酚类化合物,产物经FTIR、1 HNMR表征。结果表明,产物结构与预期一致。     

喹诺酮类化合物3-脱羧反应研究

目的:研究喹诺酮类化合物脱羧反应.方法:在喹诺酮类化合物5与邻苯二胺缩合中,以PPA为脱水剂,可以得到3-脱羧反应的产物.结果:成功地得到反应条件对3-脱羧产物生成的影响,并利用核磁共振、质谱、红外光谱等对得到的3-脱羧产物进行了结构确认.结论:为新型喹诺酮类化合物的合成研究和3-脱羧反应的研究提供参考.     

4-碘-2-甲基苯甲酸的新合成方法

设计了一种合成4-碘-2-甲基苯甲酸的新方法,合成的中间体和目标产物通过红外光谱、紫外可见光谱、核磁共振谱、质谱和元素分析得到了确证.     

天然产物(E)-4''''-甲氧基-3,5-二羟基芪的合成研究

以3,5-二羟基苯甲酸为原料,通过乙酰基保护、酰氯化,生成中间体3,5-二乙酰氧基苯甲酰氯,再与4-甲氧基苯乙烯经Heck反应、甲醇钠脱乙酰基保护,得到单一的芪类天然产物标题化合物,产率66%.研究结果对于其他芪类化合物的合成具有指导意义.     

2-噻唑偶氮-5-二甲氨基苯甲酸类有机试剂氢离解常数的测定

用分光光度法测定的三个噻唑偶氮二甲氨基苯甲酸化合物的氢离解常数如下:Ⅰ.2-(5-甲基噻唑)偶氮-5-二甲氨基苯甲酸,pK_1=4.80,pK_2=1.91;Ⅱ.2-(4,5-二甲基噻唑)偶氮-5-二甲氨基苯甲酸,pK_1=4.78,pK_2=1.89;Ⅲ.2-(苯并噻唑)偶氮-5-二甲氨基苯甲酸,pK_1=4.33,pK_2=1.11。用HMO法来研究不同酸度下各种可能的离子形式,通过计算结果与分光实验数据的对照,判断了离解的过程。     

天然产物（E）-4＇-甲氧基-3,5-二羟基芪的合成研究

以3,5-二羟基苯甲酸为原料,通过乙酰基保护、酰氯化,生成中间体3,5-二乙酰氧基苯甲酰氯,再与4-甲氧基苯乙烯经Heck反应、甲醇钠脱乙酰基保护,得到单一的芪类天然产物标题化合物,产率66%.研究结果对于其他芪类化合物的合成具有指导意义.     

The mechanism and kinetics of the electrochemical cleavage of azo bond of 2-hydroxy-5-sulfophenyl-azo-benzoic acids

The electrochemical reduction of 2-hydroxy-5-[(4-sulfophenyl)azo]benzoic acid, 2-hydroxy-5-[(3-sulfophenyl)azo]benzoic acid, 2-hydroxy-5-[(2-sulfophenyl)azo]benzoic acid and 2-hydroxy-5-azo-benzoic acid has been carried out in aqueous solutions at glassy carbon electrode using cyclic voltammetry and chronoamperometry. The position of sulfo substituent relative to azo bridge as well as pH of the solution have significant impact on the electrochemical behavior of these compounds. It has been proposed that these compounds are reduced predominantly as hydrazone tautomers resulting in corresponding hydrazo compounds. The overall electrochemical reduction follows DISP2 mechanism, ultimately leading to the 5-amino salicylic acid and sulfanilic acid. The rate determining step is the homogenous redox reaction between intermediate hydrazo compound and 5-amino salicylic acid quinoneimine. The mechanism is proposed in which activated complex of 5-amino salicylic acid quinoneimine and intermediate hydrazo compound is formed with the simultaneous loss of one proton.     

非线性光学偶氮分子的合成和跃迁偶极矩的测定

以对硝基苯胺、苯胺、5 氨基嘧啶和N,N 二羟乙基苯胺为原料通过两步重氮化-偶合反应合成了两种给体-受体型非线性光学偶氮分子,用红外光谱、核磁共振、熔点、紫外光谱进行了表征,测定了分子的跃迁偶极矩,两个化合物的跃迁偶极矩分别为7 12D和8 76D,它们在不同极性溶剂中表现出明显的溶致变色效应,紫外吸收最大位移分别达到20nm和15nm。     

HPLC separation and wavelength area ratios of more than 50 phenolic acids and flavonoids

Relative retention times and wavelength area ratios for over 50 standard compounds were calculated using reverse-phase HPLC. The standard compounds analyzed included benzoic acids, cinnamic acids, benzene carboxylic acids, acetic acids, coumarins, benzaldehydes and a variety of flavonoid compounds including flavanones, flavones, isoflavones, and their glycosides. Each standard compound was chromatographed by three different gradient elutions. Compounds were detected by UV absorption at 254 nm and 280 nm. Relative retention times with respect to two different internal references and the 254nm: 280nm wavelength area ratio was determined for each standard. Soybean root and seed extracts were analyzed for the presence of the standard compounds using the chromatographic conditions described.     

单酯基多环芳香酸的合成及热分析

以4-正丙基,4-正戊基取代的双环己基甲酸、联苯甲酸和环己基苯甲酸以及对羟基苯甲醛为原料,用一次酯化、一次氧化的方法(酯化氧化法),合成了4个单酯基芳香酸类化合物:4-〔4-(反-4-丙基环己基)苯酰氧基〕苯甲酸,4〔-反-4-(反-4-丙基环己基)环己酰氧基〕苯甲酸,4-〔反-4-(反-4-戊基环己基)环己酰氧基〕苯甲酸和4-〔4-(4-戊基苯基)苯酰氧基〕苯甲酸,总产率分别为74%,76%,72%和71%。产物结构用IR,MS,1HNMR及元素分析进行了表征,DSC及偏光显微镜测定表明,4个目标化合物具有热致液晶性。     

三种偶氮化合物的合成及三阶非线性光学性能

文章选取具有非线性光学活性的偶氮化合物作为研究对象,合成了一组含不同取代基和不同推-拉电子结构的偶氮化合物,并通过红外光谱、紫外-可见吸收光谱、元素分析、核磁共振氢谱等方法对所合成的偶氮化合物结构进行了表征;用单光束Z-扫描的方法对所合成的偶氮化合物的三阶非线性光学性能进行了测试,并结合理论计算分析研究了分子结构对偶氮化合物三阶非线性光学性能的影响。     

The synthesis,characterization and structures of some 4-[((E)-1-{2-hydroxy-5-[(E)-2-(aryl)-1-diazenyl]phenyl}methylidene)amino]benzoic acid

The structures of several azo-benzoic acids, 4-[((E)-1-{2-hydroxy-5-[(E)-2-(aryl)-1-diazenyl]phenyl}methylidene)amino]benzoic acid along with their precursors 2-hydroxy-5-[(E)-(aryldiazenyl)]benzaldehydes were confirmed using ¹H, ¹³C NMR, UV–VIS and IR spectroscopic techniques. UV–VIS absorption spectra were measured in pure organic solvents while complementary spectroscopic experiments using mixed solvent systems as well as in the presence of base were undertaken to characterize the different species present in solution. Both acid–base dissociation and azo–hydrazone tautomerism occurred in solution, with the extent of the individual equilibria being dependent on the solvent composition and/or pH of the medium. Molecular structures and geometries were optimized using the B3LYP density functional theory method employing the 6-31G(d) basis set.     

热对偶氮化合物光致变色性能的影响

用125 W的高压汞灯照射,用紫外-可见分光光度计测试合成的2个偶氮化合物的光致变色性。结果表明,热对2个偶氮化合物的光反应具有干扰作用,当消除热干扰,2个偶氮化合物具有较好的光致变色性,在热的作用下具有热致变色性;而在光和热同时作用时,2个化合物均未表现出变色性质。因此,在测试偶氮化合物光致变色性质时要避免热的干扰作用。     

Synthesis of chloromethylstyrene‐tetraethyleneglycol dimethacrylate copolymer beads having various phenolic derivatives immobilized via amide bond and their antioxidation activity

Resins having phenolic derivatives were prepared by treating a resin (RAS‐4G), having benzylamino groups, with benzoic acids containing phenolic hydroxyl groups. The RAS‐4G was prepared by treating macroreticular chloromethylstyrene‐tetraethyleneglycol dimethacrylate (4G) copolymer beads with potassium phthalimide in N,N‐dimethylformamide, followed by reflux in an ethanol/hydrazine monohydrate mixture. 4‐Hydroxy benzoic acid, (2,4‐, 3,4‐, and 3,5‐)dihydroxy benzoic acids, 3,4,5‐trihydroxy benzoic acid, etc., were used as benzoic acids with phenolic hydroxyl groups. The antioxidation ability of the resins having phenolic derivatives was investigated against the generation of 1,4‐dioxane hydroperoxide. The resins showed high inhibition ability against the generation of hydroperoxide. In particular, the resin (RAS‐4G‐3,4‐DHBA) having two phenolic hydroxyl groups had the highest inhibition ability. The resins were found to act as radical scavengers during the generation of 1,4‐dioxane hydroperoxide by UV irradiation in the presence of oxygen. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2097–2104, 2005     

A novel barbituric acid-based azo dye and its derived polyamides: Synthesis,spectroscopic investigation and computational calculations

5-[(3,5-dicarboxyphenyl)azo]-barbituric acid, an azo-based aromatic diacid was prepared and fully characterized by FT IR, ¹H and ¹³C NMR along with UV–vis absorption spectroscopy. The effects of varying pH and solvent upon the absorption spectrum of the azo dye were investigated. The optimized molecular structures of possible tautomeric forms and HOMO–LUMO energies of expecting preferred forms of the synthesized heterocyclic azo dye have been calculated using density functional theory, (B3LYP) methods with TZVP basis set level and Polarizable Continuum Model (PCM) model for solvation effect. The calculations showed that the most probably preferred form of the azo dye in gas phase and solution was a hydrazone-keto form. FT IR and UV–vis spectroscopy, DSC, TGA and XRD techniques were used to obtain the characteristics and structural features of the monomer-synthesized polyamides. The influence of organic solvents on the absorption spectra of the polymers along with viscosity measurements (0.19–0.44 dl/g), solubility and film formability of the synthesized polyamides were also investigated.     

双羟乙氨基-硝基型偶氮生色分子的二阶非线性极化率

设计并合成了6种具有D-π-A型和D-π-A-π-D型共轭结构的双羟乙氨基给体-硝基受体型偶氮化合物,用溶致变色法测算了分子的二阶非线性极化率。实验结果表明,双羟乙氨基和硝基是一对有效的给体、受体组合,它们与偶氮共轭链相连组成的分子具有较大的二阶非线性极化率,其中,具有D-π-A-π-D二维共轭结构的化合物,它包含两条从给体到受体的共轭链,二阶非线性极化率β1 064达到297.4×10(-30)esu,并且这个分子的透明性在6个分子中也是最好的,光学损耗最小。