相转移条件下Cu(Ⅰ)催化的末端炔的偶联反应研究

本文报道端炔与烯(炔)丙基衍生物在Cu(Ⅰ)催化和相转移条件下发生偶联反应合成1,4-烯炔、二炔化合物的方法。考察了溶剂、催化剂、反应底物、反应时间和温度等多种因素对偶联反应的影响, 用正交试验法优选出最佳反应条件,此反应条件具有条件温和、催化剂用量少、收率高、无烯(炔)丙基重排副产物生成等特点。用此方法合成了十一种1,4-烯炔、二炔化合物。     

相转移条件下Cu(Ⅰ)催化的末端炔的偶联反应研究

本文报道端炔与烯(炔)丙基衍生物在Cu(Ⅰ)催化和相转移条件下发生偶联反应合成1,4-烯炔、二炔化合物的方法。考察了溶剂、催化剂、反应底物、反应时间和温度等多种因素对偶联反应的影响, 用正交试验法优选出最佳反应条件,此反应条件具有条件温和、催化剂用量少、收率高、无烯(炔)丙基重排副产物生成等特点。用此方法合成了十一种1,4-烯炔、二炔化合物。     

过渡金属催化端炔的氧化交叉偶联反应研究进展

炔基化合物是有机合成中重要的一类官能团化合物,端基炔通过氧化交叉偶联反应可以制备各种各样新的炔基化合物.总结了近年来端基炔参与的氧化交叉偶联反应,主要介绍了Pd,Cu,Fe等过渡金属催化的端炔氧化交叉偶联反应研究进展.     

Cu催化吲哚啉的炔丙基烷基化/脱氢对映选择性合成手性N-炔丙基吲哚化合物(英文)

基于吲哚啉的Cu催化不对称炔丙基烷基化及DDQ脱氢策略,成功合成了手性N-炔丙基吲哚化合物.通过使用一个结构刚性的酮亚胺三齿P,N,N-配体,反应获得了很好的对映选择性.该方法反应条件温和、底物适用范围广、产物收率高、立体选择性好,为手性N-炔丙基吲哚化合物的合成提供了一条简捷、高效的新途径.     

蛋白-脂质体复合物毛细管电泳筛选单胺氧化酶抑制剂

基于酶与底物间的相互作用,建立了蛋白-脂质体复合物毛细管电泳筛选单胺氧化酶(MAO)抑制剂的新方法.分别将不同浓度的4种N-炔丙基胺类化合物添加至含有蛋白-脂质体复合物的毛细管电泳缓冲液中,抑制MAO活性.考察MAO底物犬尿胺(Kyn)在含有不同浓度N-炔丙基胺类化合物缓冲液中的迁移时间比率(RMTR).结果表明,化合物N-炔丙基-N-甲基-R-2-庚胺(R-2-HMP)和N-炔丙基-R-2-庚胺(R-2-HPA)能够明显抑制MAO活性,导致MAO与Kyn的相互作用减弱,Kyn的RMTR值随着R-2-HMP和R-2-HPA的增加呈现出明显增加的趋势.化合物N,N-二炔丙基-R-2-己胺和N,N-二炔丙基-R-2-辛胺对MAO活性抑制不明显,Kyn的RMTR随这两种浓度增加变化不大.此结果与柱外孵育测定化合物活性结果一致.与传统MAO筛选剂筛选方法相比,本方法快速,成本低,酶消耗量少且不受分离电压等于扰因素的影响.     

铟促进的烯丙基硒醚的合成

烯丙基溴和炔丙基溴在铟促进下与二硒化合物反应，生成烯丙基和炔丙基硒醚。反应无需严格的无水无氧条件，烯丙基溴以α-位与二硒化合物反应，产率55%～91%。     

双酚A二炔丙基醚与4,4′-联苯二苄叠氮的合成及聚合反应研究

合成了两种单体双酚A二炔丙基醚与4,4′联苯二苄叠氮,研究了一种新的低温聚合体系———双酚A二炔丙基醚与4,4′联苯二苄叠氮在烘箱中的本体聚合行为.通过红外、核磁共振以及质谱、元素分析等表征了单体的结构.利用傅立叶红外技术(FTIR)跟踪了聚合反应过程中特征基团的变化,采用差示扫描量热技术(DSC)研究了聚合反应工艺及其动力学,热失重分析(TGA)考察了聚合产物的热稳定性能.通过Kissinger法和0zawa法获得了反应的一些动力学参数.结果表明,双酚A二炔丙基醚与4,4′联苯二苄叠氮易发生1,3偶极环加成聚合反应,在聚合物结构中形成三唑五元环,它们的聚合起始温度在70℃左右,聚合反应的主反应是一级反应,表观活化能ΔE=84.6kJmol,指前因子A=4.865×1010min-1.同时发现,聚合物具有较好的热稳定性能.     

双酚A二炔丙基醚与4,4''''-联苯二苄叠氮的合成及聚合反应研究

合成了两种单体-双酚A二炔丙基醚与4,4'-联苯二苄叠氮,研究了一种新的低温聚合体系--双酚A二炔丙基醚与4,4'-联苯二苄叠氮在烘箱中的本体聚合行为.通过红外、核磁共振以及质谱、元素分析等表征了单体的结构.利用傅立叶红外技术(FT-IR)跟踪了聚合反应过程中特征基团的变化,采用差示扫描量热技术(DSC)研究了聚合反应工艺及其动力学,热失重分析(TGA)考察了聚合产物的热稳定性能.通过Kissinger法和Ozawa法获得了反应的一些动力学参数.结果表明,双酚A二炔丙基醚与4,4'-联苯二苄叠氮易发生1,3-偶极环加成聚合反应,在聚合物结构中形成三唑五元环,它们的聚合起始温度在70℃左右,聚合反应的主反应是一级反应,表观活化能△E=84.6kJ/mol,指前因子A=4.865×1010min-1.同时发现,聚合物具有较好的热稳定性能.     

高烯丙基醇和高炔丙基醇的无溶剂合成

在活化锌粉的促进下,通过羰基化合物的烯丙基化和炔丙基化反应,实现了高烯丙基醇和高炔丙基醇的快速无溶剂合成,收率72％～88％。产物的结构经1^H NMR,MS和元素分析确证。     

金属单质锡促进的水相中醛的Barbier类型炔丙基化反应

报道了一种简单、 高效且快速的醛的炔丙基化反应体系. 使用廉价的金属单质锡粉, 在路易斯酸SnCl₂·2H₂O促进下, 实现了水相中醛羰基化合物的Barbier类型炔丙基化反应, 高收率、高区域选择性地得到单一的高炔丙基醇产物(收率99%). 该方法具有底物适用范围广、反应条件温和(30℃)、环境友好(以水为介质)及反应速度快(30 min内反应原料基本消失)等优点. 另外, 在使用肉桂醛为底物且将反应温度升至55℃时, 意外地得到了中等收率的新型高度对称的烯炔醚化合物.     

手性乙烯基二联苯单体的合成与螺旋选择性聚合反应

设计、合成了一系列含有手性烷氧基末端的乙烯基二联苯单体,进行了普通自由基、原子转移自由基以及负离子聚合反应.所有单体中,只有手性烷氧基苯基位于乙烯基邻位的聚合物的比旋光度与其单体相比有比较大的区别,且在对应于其侧基的紫外吸收处呈现明显不同于单体的Cotton效应,说明可能形成了某一方向占优的螺旋构象.在所研究范围内,聚合条件和聚合物分子量对聚合物的旋光度没有明显的影响.比较负离子聚合和自由基聚合所获得聚合物的比旋光度发现,负离子聚合有利于增加聚合物螺旋链构象的完整性.切除能形成螺旋链的聚合物侧基上的手性烷氧基,所得到的聚合物虽然不含手性原子但依然表现出光学活性,说明其具有一定的手性记忆效应.     

Synthesis and Polymerization Reactions of Cyclic Imino Ethers. 4. Aromatic Poly(ester amide)s of the AA+BB Type on the Basis of 2-Oxazolines

Poly(ester amide)s were prepared by thermally initiated polymerization from two aromatic bis(2-oxazoline)s and four aromatic dicarboxylic acids. Polymerizations were performed in bulk and in solution. The structure of the polymers formed was confirmed by spectral analysis. The synthesis is limited by the thermal stability of the starting compounds. Limitation of the solution polymerization is the solubility of the starting compounds and the products in the solvent used. The prepared polymers have very good thermal properties.     

Comparison of molecular imprinted particles prepared using precipitation polymerization in water and chloroform for fluorescent detection of nitroaromatics

A comparative study was conducted to study the effects that two different polymerization solvents would have on the properties of imprinted polymer microparticles prepared using precipitation polymerization. Microparticles prepared in chloroform, which previous results indicated was the optimal solvent for molecular imprinting of nitroaromatic explosive compounds, were compared to water, which was hypothesized to decrease water swelling of the polymer and allow enhanced rebinding of aqueous template. The microparticles were characterized and were integrated into a fluorescence sensing mechanism for detection of nitroaromatic explosive compounds. The performance of the sensing mechanisms was compared to illustrate which polymerization solvent produced optimal imprinted polymer microparticles for detection of nitroaromatic molecules. Results indicated that the structures of microparticles synthesized in chloroform versus water varied greatly. Sensor performance studies showed that the microparticles prepared in chloroform had greater imprinting efficiency and higher template rebinding than those prepared in water. For detection of 2,4,6-trinitrotoluene, the chloroform-based fluorescent microparticles achieved a lower limit of detection of 0.1 μM, as compared to 100 μM for the water-based fluorescent microparticles. Detection limits for 2,4-dinitrotoluene, as well as time response studies, also demonstrated that the chloroform-based particles are more effective for detection of nitroaromatic compounds than water-based particles. These results illustrate that the enhanced chemical properties of using the experimentally determined optimal polymerization solvent overcome deformation of imprinted binding sites by water swelling and benefits of using the polymerization solvent for rebinding of the template.     

混杂聚合

混杂聚合是指同一体系内有两种或两种以上不同类型的聚合反应同时进行的过程,如自由基聚合与阳离子聚合,自由基聚合与缩聚等。混杂聚合能够在原位形成高分子合金,并有可能得到互穿网络结构（ＩＰＮ）,从而使聚合产物具备较好的综合性能。     

Living polymerization of substituted acetylenes

For many years, considerable research efforts have been dedicated to π‐conjugated polymers because of their extraordinary electronic, optical, and structural properties. The employed transition‐metal‐based initiating systems comprise not only simple transition‐metal salts but also rather sophisticated mixtures of two, three, or four compounds and even highly defined single‐component systems such as transition‐metal alkylidene complexes. Extensive fine‐tuning of the electronic and steric properties of initiator–monomer systems eventually allowed the tailor‐made synthesis of conjugated materials via living polymerization techniques. This article focuses on recent developments in the field of the living polymerization of substituted acetylene derivatives. Ill‐defined group 5 and 6 transition metal halide‐based initiators, well‐defined transition‐metal alkylidene complexes, and rhodium(I)‐based systems that induce the living polymerization of numerous substituted acetylenes are reviewed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5723–5747, 2005     

Synthesis, microwave-assisted polymerization, and polymer properties of fluorinated 2-phenyl-2-oxazolines: a systematic study

We present a detailed systematic study of the synthesis and ability of fluorinated 2-phenyl-2-oxazolines to undergo polymerization. The synthesis of these compounds is based on a two-step procedure that gives the desired 2-oxazolines in moderate-to-good yields. All the compounds were fully characterized by IR and NMR ((1)H, (13)C, and (19)F) spectroscopy, mass spectrometry, and elemental analysis. The 2-oxazolines were subsequently used as monomers for living cationic ring-opening polymerization (CROP) with microwave irradiation as the heat source (T=140 degrees C), nitromethane as the solvent, and methyl tosylate as the initiator. The linear first-order kinetic plots of the polymerizations accompanied by a linear increase of the molecular weight with conversion and low polydispersity index (PDI) values (generally below 1.30) indicate a living polymerization mechanism. The resulting polymerization rates reflect a strong sensitivity to the quantity of fluorine substituents in general and the presence or absence of ortho-fluoro substituents of the phenyl ring in particular. All the polymers were isolated and characterized by size-exclusion chromatography and MALDI-TOF mass spectrometry. Finally, a detailed investigation of selected polymer properties was performed by using differential scanning calorimetry, thermogravimetric analysis, and contact-angle measurements, thus resulting in structure-property relationships. Whereas the thermal properties of the polymers are mostly influenced by the presence of ortho-fluoro substituents, the surface properties are mainly determined by the presence of para- and/or meta-fluoro substituents.     

Light‐Harvesting Organic Photoinitiators of Polymerization

Two new photoinitiators with unprecedented light absorption properties are proposed on the basis of a suitable truxene skeleton where several UV photoinitiators PI units such as benzophenone and thioxanthone are introduced at the periphery and whose molecular orbitals MO can be coupled with those of the PI units: a red‐shifted absorption and a strong increase of the molecular extinction coefficients (by a ≈ 20–1000 fold factor) are found. These compounds are highly efficient light‐harvesting photoinitiators. The scope and practicality of these photoinitiators of polymerization can be dramatically expanded, that is, both radical and cationic polymerization processes are accessible upon very soft irradiation conditions (halogen lamp, LED…︁) thanks to the unique light absorption properties of the new proposed structures.     

N-取代基马来酰亚胺均聚合研究进展

N-取代基马来酰亚胺聚合物具有良好的热性能,近些年来随着材料性能的要求提高,对这类单体的研究也越来越多,本论文综述了N-取代基马来酰亚胺在自由基、阴离子聚合、配位聚合等方面的均聚合研究进展。     

微乳液聚合研究进展

从聚合机理和所得聚合物性能两个方面,分析总结了微乳液聚合与乳液聚合的差别.并介绍了微乳液聚合研究的国内外研究动态.     

新型烯烃聚合催化剂研究进展

由于过渡金属催化剂在烯烃聚合方面具有高活性和良好的分子剪裁性,通过调节催化剂的微结构或温度、压力等聚合环境的变化,可以在分子层次上实现烯烃聚合物的分子设计与组装,实现聚合物物理性质的调控,最近引起了人们的广泛关注。本文介绍了过渡金属催化剂的合成及其负载化,水相烯烃聚合及活性聚合等方面的研究进展。