含萘酰亚胺光功能基元的吡唑啉酮席夫碱的合成及其光谱性质

以4-溴-1,8-萘酐为原料,经亚胺化、取代和还原反应合成了中间体N-对氨基苯基-4-哌啶-1,8-萘酰亚胺(4),4与1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5缩合得到一种含萘酰亚胺光功能基元的的新型吡唑啉酮席夫碱——1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5缩N-对氨基苯基-4-哌啶-1,8-萘酰亚胺(6)。4和6的结构经1H NMR和IR确证。研究了6在不同溶剂中的光谱性质,发现其吸收光谱和荧光光谱随溶剂的极性不同而表现出不同的光谱特性。进一步研究表明6在不同溶剂中可能以不同的互变异构体存在。     

水中3-甲基-6-氨基-5-氰基-4-芳基-1-苯基-1，4-二氢吡喃[2，3-c]吡唑的洁净合成

在水溶剂中并有三乙基苄基氯化铵（TEBA）存在下，取代芳亚甲基丙二腈与3- 甲基-1-苯基-2-吡唑啉-5-酮缩合成为3-甲基-6-氨基-5-氰基-4-芳基-1-苯基-1， 4-二氢吡喃[2,3-c]吡唑，此法为相应化合物的合成提供了一种快速、方便、高效 和洁净的方法。     

水中α,β-不饱和酮与3-甲基-1-苯基-2-吡唑啉-5-酮的加成反应

在水溶剂中有三乙基苄基氯化铵（TEBA）存在下，α,β-不饱和酮与3-甲基- 1-苯基-2-吡唑啉-5-酮发生迈克尔加成反应，以良好的产率生成相应的1,3-二芳基 -3-（3'-甲基-1'-苯基-5'-羟基-2'-吡唑啉-4'-基）-1-丙酮。     

铽与4—酰代吡唑啉酮—5的三元配合物的合成与荧光性质

合成并表征了一系列铽与含不同４－酰代的１－苯基－３－甲基－吡唑啉酮－５的三元配合物Ｔｂ９Ｌ）３．２Ｈ２Ｏ和Ｔｂ（Ｌ）３．Ｄｉｐｙ「Ｌ＝１－苯基－３－甲基－４－乙酰基吡啥林酮－５（ＰＭＡＰ），１－苯基－３－甲基－４－丙酰基吡唑啉酮－５（ＰＭＰＰ），１－苯基－３－甲基－４－异丁酰基吡唑啉酮－５（ＰＭＩＢＰ），１－苯基－３－甲基－４－特戊酰基吡唑啉酮－５（ＰＭＰＶＰ），１－苯基－３－甲基－４－苯甲酰基吡     

吡唑啉-β-二酮类分子设计合成和抑菌活性

利用系统搜索和模拟退火程序对1－苯基－3－甲基－4－（4－氯苯甲酰基）－吡唑啉－5－酮和1－苯基－3－甲基－4－（4－硝基苯甲酰基）－吡唑啉－5－酮两个吡唑啉β－二酮分子进行分子力学计算和分子动力学研究。采用纸碟法测定它们的广谱抗菌活性。利用Gaussian94程序进行量子化学从头算，计算结果与抑菌活性测定结果相吻合。     

1-苯基-3-甲基-6-N,N-二正丁基胺-2(1H)-喹喔啉-2-酮的全合成

报道了2(1H)-喹喔啉类衍生物——1-苯基-3-甲基-6-N,N-二正丁基胺-2(1H)-喹喔啉-2-酮的全合成.该化合物及其中间体1-苯基-3-甲基-6-胺基-2(1H)-喹喔啉-2-酮和1-苯基-3-甲基-6-硝基-2(1H)-喹喔啉-2-酮均为新化合物,文中给出了它们的重要的分析数据,简要讨论了溶剂在关环反应以及N-烷基化反应中的重要影响,偶然发现以水作溶剂时关环主产物为1-苯基-3-甲基-5-硝基-苯并咪唑.这类化合物可应用于药物,如用作N-甲基-D-天冬氨酸(NMDA)受体及α-氨基羟甲基异噁唑丙酸(AMMPA)受体拮抗剂、杀菌剂等;还可用作植物生长抑制剂、荧光探针以及作为新型功能染料中间体等诸多领域.     

一种新的双吡唑啉酮化合物的合成及晶体结构

4-酰基吡唑啉酮是一类含有氮杂环的β-二酮型螯合剂,近几十年来,国内外对该类化合物及其衍生物进行了广泛的研究[1-3].本室验室曾合成了一系列4-苯甲酰基吡唑啉酮缩氨基硫脲及其衍生物,发现这类含硫席夫碱具有光致变色性,并对其变色机理和反应动力学进行了详细研究[4,5].作为工作的继续,我们又合成了1-苯基-3-甲基-4-乙酰基-5-吡唑啉酮缩硫甲基氨基硫脲(PMEP-MTTSC),虽然此化合物不具有光致变色性,但在培养其单晶的过程中,却意外地得到了一种双吡唑啉酮化合物.当用不同的溶剂来培养其单晶时,又得到了这种双吡唑啉酮的一对互变色异构体.反应过程如下:     

新型吡唑啉酮衍生物的制备

以氢氧化钾为催化剂,1-苯基-3-甲基-吡唑啉-5-酮与取代苯甲醛亚胺反应合成了新型1-苯基-3-甲基-吡唑啉-5-酮衍生物——1-苯基-3-甲基-4-(1-N-氯乙胺基-1-取代苯基)甲基-吡唑啉-5-酮,其结构经1H NMR,IR,MS和元素分析表征。     

TiO2纳米晶电极上半菁衍生物分子设计中空间位阻效应的研究

设计合成了具有不同空间位阻的吡啶盐类和喹啉盐类半菁染料(E)-N-(4—磺酸 根丙基)-4-[2-4（4-N，N-二乙基氨基苯基）乙烯基]吡啶鎓盐（EPS），（E）-N-(4- 磺酸根丁基）-4-[2-(4-N,N-二乙氨基苯基）乙烯基]吡啶鎓盐（EPS4）和（E） -N-（4-磺酸根丁基）-4-[2-（4-N，N-二乙基氨基苯基）喹啉鎓盐（EQS4），研究了它们 的光物理性质，并将它们用作TiO2纳米晶电极的光敏化剂引入光电化学电池中。 研究发现:对于吡啶类半菁染料而言，无论是以三个亚甲基或是以四个亚甲基来连接 吸附基团RSO3^-和发色团时，单个的EPS和EPS4分子的光电响应行为一致．但是由于 以三个亚甲基来连接时，与EPS4相比，染料EPS的空间位阻相对较小，有利于其在 多孔膜上的吸附，最终结果是染料EPS对TiO2纳米晶电极的敏化作用好于EPS4．以喹啉 环为受电子基团的染料EQS4与同样含有四个亚甲基的以吡啶环为受电 子基团的EPS4相比，单个EQS4分子的光电响应行为虽然好于EPS4分子，但由于 EQS4分子间的空间位阻较大，影响了它在多孔电极上的吸附，致使其敏化的太阳能 电池的总光电转换效率有所下降．     

含酰基吡唑啉酮和咔唑光功能基元的新型席夫碱的合成

以苯肼、乙酰乙酸乙酯和咔唑为原料,合成了一种含酰基吡唑啉酮和咔唑双光功能基元的新型席夫碱———1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5缩N-对氨基苄基咔唑(6),其结构经1H NMR和IR确证;采用UV-vis对其电子结构进行了初步研究,与酰基吡唑啉酮或咔唑功能基元相比,6表现出特殊的电子结构。     

Synthesis, Reactions, and Anti-arrhythmic activity of Substituted Heterocyclic Systems Using 5-Chloroanisic Acid as Starting Material

Summary. A series of substituted heterocyclic systems were prepared from N1-[4-(4-fluorocinnamoyl)phenyl]-5-chloro-2-methoxybenzamide, which was prepared from the corresponding 5-chloroanisic acid (2-methoxy-4-chlorobenzoic acid) as starting material. Treating of the cinnamoyl derivative with hydrazine hydrate in dioxane afforded a pyrazoline, which was reacted with morpholine and paraformaldehyde to give the N-substituted pyrazoline. Acylation of pyrazoline with acetyl chloride in dioxane afforded the N-acetyl analogue. Also, the cinamoyl derivative was reacted with methylhydrazine, phenylhydrazine, or ethyl cyanoacetate to yield the corresponding N-methyl-, N-phenylpyrazoline, pyrane, and pyridone derivatives. Condensation of the cinnamoyl derivative with cyanothioacetamide gave the pyridinethione derivative, which was treated with ethyl chloroacetate affording the ethyl carboxylate derivative. Also, it was reacted with malononitrile or ethyl acetoacetae to give the cyano amino analougues and ethyl carboxylate, which was reacted with methylhydrazine to give the (indazolyl)phenyl derivative. On the other hand, reaction of cinnamoyl derivative with acetyl acetone afforded the cyclohexenyl derivative, which was reacted with hydrazine hydrate to give the [methylindazolyl]phenyl derivative. Condensation of the cinnamoyl derivative with guanidine hydrochloride or thiourea afforded the aminopyrimidine derivative and thioxopyrimidine. The latter was condensed with chloroacetic acid to yield a thiazolopyrimidine, which was condensed with 2-thiophenealdehyde to yield the arylmethylene derivative, however, it was also prepared directly from thiopyrimidine by the action of chloroacetic acid, 2-thiophenealdehyde, and anhydrous sodium acetate. The pharmacological screening showed that many of these compounds have good anti-arrhythmic activity and low toxicity.     

吡唑啉衍生物的电化学性质及其能带结构

有机 /聚合物电致发光是当今世界上的热门研究领域[1 ,2 ] ,因而有机 /聚合物电致发光材料的能带结构成为非常重要的研究课题[3] .目前 ,确定有机 /聚合物电致发光材料的能带结构的方法主要有电化学法[4] ,光谱法[5] ,量子化学计算法[6] ,紫外光电子能谱法[7] ,光电子发射法[8] 等 .这些方法中 ,由于电化学方法操作简单 ,对仪器设备要求不高 ,故被广泛使用 .虽然不同的测试方法测得的能带数据存在一定的系统误差 ,但由于电发光器件中考虑的是材料间的能带匹配 ,因此 ,在不同的条件下测定的能带数据相对来说是可信的 .吡唑啉化合物具有较高的…     

Synthesis,anticancer activity and docking studies of pyrazoline and pyrimidine derivatives as potential epidermal growth factor receptor (EGFR) inhibitors

A search for anticancer agents has prompted the design and synthesis of new chalcone, pyrazoline and pyrimidine derivatives as potential epidermal growth factor receptor (EGFR) kinase inhibitors. These derivatives’ binding affinities were predicted by AutoDock, which showed that chalcone, pyrazoline and pyrimidine derivatives as EGFR-kinase inhibitors have good binding energies, ranging from ?10.91 to ?7.32 kcal/mol. These compounds were synthesized and characterized using elemental analysis (CHN analysis) and spectroscopic techniques (FTIR and NMR). Among the pyrazoline derivatives, 4Aiii has revealed a superior in vitro activity, inhibiting the EGFR kinase even at a low concentration of 0.19 μM compared to the pyrimidine derivative, 5Bii. In contrast, the cytotoxic effect of these derivatives was studied against hormonal and non-hormonal breast cancer cell lines. Most of the pyrazoline derivatives were able to express their cytotoxic effect efficiently against hormonal breast cancer but only one pyrimidine derivative managed to express its activity against hormonal breast cancer.     

5-位取代吡唑啉化合物的发光行为及其在电致发光领域中的应用

合成了一系列5位不同取代的2－吡唑啉化合物，研究了取代基对吡唑啉化合物 物理性质的影响。结果表明，在吡唑啉化合物的5位引入稠环取代基提高了吡唑啉 化合物的熔点；同时，5位取代基的电位性质还影响着化合物的发光行为。DSC差热 分析结果给出1，3－二苯基－5－（9－菲基）－2－吡唑啉（TAP7）的玻璃化温度 (T_g)为96 ℃；并研究了其在电致发光器件上的应用性能。结果表明TAP7是一种具 有高热稳定性的空穴传输及蓝光发光材料。     

A Light Active Barbituric Acid Derivative as A Fluorescence Probe of Molecular Self-assembly

A light active barbituric acid derivative,5-(4-N, N-didodecylaminobenzylidene)-2,4,6-(1H,3H)-pyrimidinetrione(B), was found to be used as a fluorescence probe of molecular recognition directed self-assembly with its complementary compound, 4-amino-2,6-didodecylamino-1,3,5-triazine(M).     

AN EXAMPLE OF HOW PHOTOPHYSICAL PROPERTIES CAN INFLUENCE THE MAGNITUDE OF SOLVENT ISOTOPE EFFECTS UPON PHOTO-OXIDATION REACTIONS

Abstract Substantial isotope effects have been observed for the dye sensitised photo-oxidation of 1,3-diphenyl-2-pyrazoline in both polar and non polar solvents, implicating singlet oxygen as a reactive intermediate. By way of contrast, a solvent isotope effect upon the direct photo-oxidation of the pyrazoline was only observed when a protic solvent (methanol) was used. It was found that the photophysical properties (e.g. quantum yields and fluorescence lifetimes) of pyrazolines are sensitive to the isotopic composition of protic solvents but not aprotic solvents. The solvent isotope effect observed for the direct photo-oxidation reaction in methanol may not therefore be a true indication of the participation of singlet oxygen. Since this reaction may not be singlet oxygen mediated, an alternative mechanism is proposed.     

Environment‐Sensitive Behavior of DCNP in Solvents with Different Viscosity,Polarity and Proticity

A pyrazoline derivative, 3‐(1,1‐dicyanoethenyl)‐1‐phenyl‐4,5‐dihydro‐1H‐pyrazole (DCNP), is studied by using optical spectroscopy methods in several solvents at room and at low temperatures. The DCNP molecule reveals a complex photophysics behavior, which is sensitive to solvent polarity, proticity, temperature and viscosity and arises from the presence of two rotational degrees of freedom of the dicyanovinyl group—the torsion around the double C=C bond and the s‐trans–s‐cis isomerization around the single C?C bond—that differently behave in various environmental conditions. The fluorescence yield of a few percent and sub‐nanosecond decay times observed at room temperature make the compound useful for optical studies of liquid environments. The proticity of polar solvents can be detected with two‐exponential fluorescence decays. At low temperatures, DCNP can be used as solvent viscosity or temperature fluorescent sensor.     

非平面扭曲构象对1，3－二苯基吡唑啉衍生物荧光性质的影响

研究了１，３－二苯基吡唑啉（ＤＰＰ）和１－苯基－３－（４－硝基苯基）吡唑啉（ＰＮＰ）在室温及７７Ｋ时不同溶剂中的荧光光谱，发现在非极性溶剂中７７Ｋ时ＤＰＰ的荧光强度远比其在室温时的低，而ＰＮＰ则完全没有荧光，表明这些化合物激发态的构象松驰，形成非平面扭曲构象对分子的发光性质十分重要。同时发现这两个化合物具有不同的关键性扭曲部位，形成各自有利于发光的构象，Ｎ－１上及Ｃ－３上苯环的扭曲分别对ＤＰＰ和ＰＮＰ的发光态的形成起着重要作用。     

二苯基吡唑啉衍生物发光态构象的研究

本工作在合成了几种不同结构吡唑啉衍生物的基础上,测定了它们在相同极性,不同粘度介质中的荧光量子产率并表明:和1-位氮原子相联苯基的旋转松弛对该类化合物的发光具有决定意义,通过对化合物在极性与非极性溶剂内和在冻结与流动条件下(低温与室温下)荧光强度的比较,证明了二苯基吡唑啉化合物的发光态具有扭曲构象。     

EXCIPLEX FORMATION OF A POLYESTER WITH A TEREPHTHALATE MAIN CHAIN HAVING A PENDANT N, N-DIMETHYLAMINO GROUP

The fluorescence behaviours of a new polymer poly [oxy-2 (4-N, N-dimethylaminobenzyl) propane-1 , 3-diyloxy-terephthaloyl] (Ⅰ) in solution were studied. Inter-and intra -molecular exciplex is formed between the singlet excited state of N, N- dimethylanilino group (abbreviated to DMA) and the ground state of terephthalate group (abbreviated to TP). The intensity ratio of the long wavelength exciplex fluorescence to the short wavelength emission of DMA group is used as an index for the inter-and intra-molecular interaction of chromophores. The results are compared with model polymer polyoxy-2-(4-N ,N-dimethylaminobenzyl) propanc-1 , 3-diyloxyadipoyl (Ⅱ), model monomer compound 4-N, N-dimethylaminobenzylmethyl terephthalate(Ⅲ) and diethyl 2-( 4-N, N-dimethylaminobenzyl) malonate (Ⅳ). Polymer association derived by electron donor and acceptor interaction (EDA) is further verified as a key role in the interpolymer exciplex formation . The fluorescence decay time of (Ⅰ) and monomer (Ⅲ) are measured in solutions.