硫脲基咪唑啉季铵盐的合成及其缓蚀作用

用戊酸、羊蜡酸、油酸、二乙烯三胺、氯化苄和硫脲为原料,合成了6种咪唑啉季铵盐化合物。 采用静态失重法和极化曲线法,比较了硫脲基烷基咪唑啉型季铵盐和烷基咪唑啉型季铵盐在80 ℃、1 mol/L的HCl溶液中对碳钢的缓蚀性能,研究了这两类缓蚀剂与无机阴离子和阴离子表面活性剂的协同作用。 结果表明,硫脲基烷基咪唑啉季铵盐类的缓蚀效果明显优于烷基咪唑啉季铵盐类,硫脲基羊脂酸咪唑啉缓蚀剂的缓蚀率可达98.3%。 当以羊脂酸、二乙烯三胺、氯化苄和硫脲为原料合成的硫脲基烷基咪唑啉型季铵盐化合物与I-质量比为1∶1复配时,缓蚀效果最佳,比单独使用硫脲基烷基咪唑啉季铵盐化合物的缓蚀率提高了1.5%。     

3-烷氧基-3-烷基异吲哚啉-1-酮的合成

为探索3-亚烷基异吲哚啉-1-酮在有机合成中的应用潜力，构建新型的异吲哚啉-1-酮类化合物，本文以3-亚烷基异吲哚啉-1-酮和醇为原料，在三氯硅烷与路易斯碱催化剂作用下发生加成反应，得到一系列3-烷氧基-3-烷基异吲哚啉-1-酮类化合物，并初步尝试了以手性路易斯碱催化该反应。综上，本文建立了一种新型异吲哚啉-1-酮类化合物的合成方法，该方法条件具有温和、操作便捷、底物适用范围广和收率普遍较高的特点。     

氟烷基三甲基硅化合物的合成和反应研究

羰基化合物的氟烷基化反应是把含氟基团引入有机分子中去的一个重要手段。文献报道的主要是通过氟烷基金属试剂来进行此反应。但氟烷基金属试剂不太稳定,容易分解。这就给它们的应用带来了许多不便。我们发现,氟烷基三甲基硅化合物(1)作为氟烷基阴离子前体,在比较温和的条件下,便可使醛发生氟烷基化反应。首先,参照文献方法,通过氟烷基格氏试剂与三甲基氯硅烷反应,方便地制得了两个新的氟烷基三甲基硅化合物 R_F-SiMe_3(1)。     

3-甲基-2(1H)-喹喔啉系列衍生物的电子轰击质谱

用电子轰击质谱（EI－MS）研究了1－烷基－3－甲基－2（1H）－喹喔啉－2－酮（烷基为H，CH3，Et,n-C5H11),1-烷基－3－甲基－6－硝基－2（1H）－喹喔啉－2－酮（烷基为CH3，Et)和1－甲基－3－甲基－6－胺基－2（1H）－喹喔啉－2－酮，结合其结构特征总结出一些裂解规律。讨论了不同取代基对这类化合物熔点的影响，结果表明：在同类喹喔啉化合物中，随着烷基链的增长，样品熔点通常会有所降低，而硝基及胺基的引入会使其熔点升高。     

全氟烷基卤化物作为含氟砌块在构建氟烷基取代杂环化合物中的研究进展

有机氟化学和杂环化学的研究对药物研发、新材料制备等方面具有重要意义.过去几年中,利用高度商业化、低毒性、廉价、稳定、易操作的全氟烷基卤化物为含氟砌块构建氟烷基取代杂环化合物取得了重要进展.本综述将全氟烷基卤化物作为含氟砌块参与构建杂环化合物的报道进行总结:(1)通过全氟烷基卤化物的单个碳卤键官能化构建杂环化合物;(2)...     

“水上”吡唑啉酮与三氟甲基酮的亲核加成（英文）

基于水相条件下发展了一种绿色高效的吡唑啉酮与三氟甲基酮的亲核加成的方法,且以高收率获得吡唑啉酮取代的叔三氟甲基醇类化合物.该方法具有的无催化剂、无色谱柱分离、环境友好以及易于后处理的优点使其在制备各种吡唑啉酮取代的叔三氟甲基醇类化合物中很有应用前景.     

1-乙酰基-5-取代吲哚啉类化合物的合成及生物活性

根据拼合原理, 以1-乙酰基吲哚啉为起始原料, 设计合成了1-乙酰基-5-{2-[4-(取代苯氧基乙基)-1-哌嗪基]烷基}吲哚啉和1-乙酰基-5-[2-(4-取代苯基-1-哌嗪基)烷基]吲哚啉两类化合物, 所有目标化合物结构均经核磁共振氢谱、元素分析、红外光谱及质谱确证. 初步生物活性测试结果表明, 所有目标化合物均具有一定的α₁-AR拮抗活性.     

6′-对位取代苯乙烯基吲哚啉螺吡喃的合成

利用2-亚甲基吲哚啉和取代水杨醛缩合得到十三种新的烷基苯乙烯基吲哚啉螺苯并吡喃。在苯并吡喃部分含有硝基的螺吡喃显示出逆光致变色行为,其它的则为普通光致变色化合物。同时,结果表明,化合物异构体的稳定性不仅取决于化合物本身的结构,而且还取决于介质环境的影响。     

三苯基氧膦和三氟磺酸酐参与的二茂铁咪唑啉合成

二茂铁咪唑啉可以有效地从二茂铁羧酸出发合成．二茂铁羧酸和乙二胺衍生物反应制得的二茂铁酰胺，在三苯基氧膦和三氟磺酸酐所形成的锛盐作用下有效地脱水得到二茂铁咪唑啉化合物．该反应条件温和、反应快、产率高，为二茂铁咪唑啉化合物提供了一个有效的合成方法．     

6'-对位取代苯乙烯基吲哚啉螺吡喃的合成

利用2-亚甲基吲哚啉和取代水杨醛缩合得到十三种新的烷基苯乙烯基吲哚啉螺苯并吡喃。在苯并吡喃部分含有硝基的螺吡喃显示出逆光致变色行为，其它的则为普通光致变色化合物。同时，结果表明，化合物异构体的稳定性不仅取决于化合物本身的结构，而且还取决于介质环境的影响。     

Synthesis of Fluoroalkylated Heterocycles via the Reaction of 3-(1-Hydropolyfluoroalkenyl)-1-oxo-2,4,1-benzoxazines with Dinucleophilic Reagents

The reaction of 3-(1-hydropolyfluoroalkenyl)-1-oxo-2,4,1-benzoxazines 1 with some dinucleophiles was inves-tigated.7-Fluoroalkyl-2,3-dihydro-1,4-diazepine[1,2-d]quinazolin-11-ones 2,2-fluoroalkylisoxazolo[3,2-b]quin-azolin-9-ones 3 and 2-fluoroalkylbenzoimidazoles 4 were obtained from the reaction of 1 with 1,2-diaminoethane,hydroxylamine hydrochloride and 1,2-diaminobenzene respectively.     

Synthesis of Fluoroalkylated Heterocycles via the Reaction of 3-（1-Hydropolyfluoroalkenyl）-l-oxo-2,4,1-benzoxazines with Dinucleophilic Reagents

The reaction of 3-（1-hydropolyfluoroalkenyl）-1-oxo-2,4,1-benzoxazines 1 with some dinucleophiles was investigated. 7-Fluoroalkyl-2,3-dihydro- 1,4-diazepine[ 1,2-d]quinazolin- 11-ones 2, 2-fluoroalkylisoxazolo[3,2-b]quinazolin-9-ones 3 and 2-fluoroalkylbenzoimidazoles 4 were obtained from the reaction of 1 with 1,2-diaminoethane, hydroxylamine hydrochloride and 1,2-diaminobenzene respectively.     

The effect of fluorine-substituted acrylate monomers on the electro-optical and morphological properties of polymer dispersed liquid crystals

The effects of fluorinated acrylate monomers on the electro-optical and morphological properties of polymer dispersed liquid crystal (PDLC) films are reported. The partial fluorination of host polymer matrices resulted in improved optical properties and better defined morphologies. An enhancement in contrast ratio was observed for fluorinated systems containing trifluoroethyl acrylate (TFEA) and hexafluoroisopropyl acrylate (HFIPA). Conversely, the incorporation of methyl acrylate (MA), a chemically similar non-fluorinated acrylate, resulted in no appreciable change in contrast ratio and an increase in relaxation time. Scanning electron microscopy morphological studies were conducted to understand further the influence of fluorinated monomers in PDLC systems.     

全（多）氟烷基非离子型表面活性剂的合成

通过Ｏ－烯丙基化，全氟烷基化和还原３步过程在聚乙二醇分子中引入了全（多）氟烷基，合成了１０多种全（多）氟烷基非离子型表面活性剂。     

Synthesis and structural studies of C-5 aryl- and C-6 alkyl-substituted pyrimidine derivatives

C-5 and C-6 disubstituted pyrimidine derivatives 2–7 were synthesized. Introduction of the aryl rings at C-5 of pyrimidine moiety in 5 and 6 was performed using palladium-catalyzed Stille cross-coupling reaction. The novel C-6 fluorophenylalkylated 5-phenylpyrimidine derivative (7) was prepared by lithiation of 5-phenylpyrimidine (6) and subsequent reaction of thus obtained organolithium intermediate with p-fluoroacetophenone. The structures of 3, 4 and 6 were determined by X-ray crystal structure analysis. Both methoxy groups in these structures adopt a synperiplanar conformation with respect to the N1 and N3 atoms of the pyrimidine ring. The molecules of 3 and 4 are linked through weak Br···Br interactions into zig-zag chains. The molecules of 6 are assembled into layers by one C–H···O hydrogen bond, C–H···π and aromatic π···π stacking interactions.     

Efficient synthesis of 5-fluoroalkylated 1H-1,2,3-triazoles and application of the bromodifluoromethylated triazole to the synthesis of novel bicyclic gem-difluorinated 1H-pyrano[3,4-d][1,2,3]-triazol-4-one compounds

A series of 5-fluoroalkylated 1H-1,2,3-triazoles were synthesized in good yield by the regiospecific 1,3-dipolar cycloaddition reaction of (Z)-ethyl 3-fluoroalkyl-3-pyrrolidino-acrylates with aryl or benzyl azides. In the cases of benzyl azides, addition of Na₂CO₃ was crucial for a high yield of the triazoles. Tetrakis(dimethylamino)ethylene (TDAE) promoted reaction of bromodifluoro-methylated triazole with aldehydes affording a new class of β,β-difluoro-β-triazolyl alcohol derivatives, which were lactonized with catalytic amount of p-toluenesulfonic acid in toluene at 80-90°C to give a series of novel bicyclic gem-difluorinated 1H-pyrano[3,4-d][1,2,3]-triazol-4-one compounds in good yield.     

Two-dimensional lattice Monte Carlo simulation of the compatibility of A/B/functionalized A ternary polymer mixtures coupled with chemical reaction

Compatibility of A/B and functionalized A ternary polymer mixtures was studied by Monte Carlo simulation in a two-dimensional lattice. Polymer A was a nonreactive polymer, whereas polymer B was a reactive polymer and immiscible with polymer A. Functionalized polymer A could react with the end group of polymer B, leading to the formation of block copolymers. Simulation results showed the phase domain sizes dropped considerably with increasing functionalized polymer A content, indicating that the compatibility between polymer A and B could be markedly improved with the introduction of functionalized polymer A. Moreover, it was shown that the resulting block copolymers tended to distribute at the phase interface between polymer A and B, and the block copolymer conformation depended on the structures of polymer B and functionalized polymer A. In case 1, i.e., both polymer B and functionalized polymer A were with single end group, it could be found that the block A and block B of resulting A–B copolymer inserted into polymer A and polymer B phase domains, respectively. In case 2, i.e., functionalized polymer A was with single end group and polymer B was with double end groups, it was found that the resulting A–B–A triblock copolymer tended to connect two neighbor separated polymer A phase domains. However, in case 3, namely functionalized polymer A was with double end groups and polymer B was with single end group, it was found that the resulting B–A–B triblock copolymer was likely to form a folding conformation. These lead to the different compatibilizing effects for different polymer structures. Comparing with case 1 and case 2, functionalized polymer A with double end groups (case 3) had less effective to compatibilize the A/B polymer blends. For the purpose of comparison, same simulations were carried out in a three-dimensional lattice. The results showed the compatibility behavior of the mixtures was similar to those in the two-dimensional lattice with the addition of functionalized polymer A. However, the conformation of the resulting block copolymers was different from that in the two-dimensional lattice.     

尼泊金乙酯分子印迹固相萃取小柱的研制及应用

研制了一种对尼泊金乙酯具有特异性识别性能的分子印迹固相萃取小柱。用本体聚合法制备尼泊金乙酯分子印迹聚合物,通过静态平衡吸附实验及固相萃取实验表征其固相萃取性能,并结合UV法对滴眼液中的尼泊金乙酯进行测定。结果显示,尼泊金乙酯模板聚合物的吸附能力强于空白聚合物;印迹固相萃取柱对尼泊金乙酯标准溶液(0.04mmol/L)一...     

小孔沸石微结构的CO_2吸附表征

以3种已知结构的小孔沸石3A、4A和5A为研究对象,以N2和CO2为吸附质,通过吸附数据测定,研究了小孔沸石微孔结构的吸附表征方法.结果表明,N2吸附无法检测4A沸石的孔,而CO2吸附可以检测.对于4A和5A沸石,在35s内CO2吸附就可以达到平衡.HK(Horvath-Kawazoe)柱状模型不能表征4A和5A沸石的孔结构,但是HK球形模型可以,基于最大吸附量、D-A(Dubinin-Astakhov)方程和Langmuir-Freundlich模型计算了4A和5A沸石的微孔孔容,其中根据最大吸附容量和D-A方程计算的微孔孔容与文献值最接近.