含不同取代基的Cardo聚芳醚酮的气体透过性能

研究了带有不同烷基取代基的Ｃａｒｄｏ聚芳醚酮均质膜对Ｈ２，Ｏ２，ＣＯ２和ＣＨ２气体的透气性能，讨论气体透过对温度的依赖性。     

含不同取代基的Cardo聚芳醚酮──合成与表征

含不同取代基的Ｃａｒｄｏ聚芳醚酮──合成与表征王忠刚,陈天禄,徐纪平（中国科学院长春应用化学研究所长春１３００２２）关键词Ｃａｒｄｏ聚芳醚酮,合成与表征,自由体积,玻璃化转变温度酚酞型Ｃａｒｄｏ聚芳醚酮（ＰＥＫ－Ｃ）是长春应化所合成的一种新型高一Ｔ,...     

聚芳醚砜薄膜的气体透过行为

研究了一系列聚芳醚砜的Ｈ２、ＣＯ２、Ｏ２、Ｎ２和ＣＨ４气体透过性能，讨论了其气体透过的温度依赖性。与双酚Ａ聚砜（ＰＳＦ）相比，几种新型聚芳醚砜的气体透过系数和气体选择系数同时有所提高。通过聚合物的分子链段活动性和自由体积数据系列变化，讨论了气体透过速率与分子结构的关系。     

氢键型聚芳醚酮共聚物的合成与表征

氢键型聚芳醚酮共聚物的合成与表征王忠刚，陈天禄，徐纪平（中国科学院长春应用化学研究所长春１３００２２０）关键词氢键，聚芳醚酮，合成，表征高分子链之间的氢键相互作用可以有效地提高聚合物的性能［１，２］．本工作通过共聚反应，在酚酞型聚芳醚酮ＰＥＫ－Ｃ分子...     

分子结构对聚芳醚酮薄膜透气性的影响

分子结构对聚芳醚酮薄膜透气性的影响王忠刚，陈天禄，徐纪平（中国科学院长春应用化学研究所长春１３００２２）关键词聚芳醚酮，气体分离膜，结构－性能关系为了改善聚合物薄膜的透气性能，开发具有高透气性和高选择性的膜材料，人们对膜分子结构与透气性能间的关系进行...     

含氟磺化双三蝶烯型聚芳醚砜质子交换膜的制备及性能

利用3,3,4,4-四氟二苯砜、十氟联苯、6F-双酚A及6,13-双三蝶烯二酚,通过亲核取代共聚及后磺化方法制备了2个系列不同磺化度的磺化双三蝶烯型聚芳醚砜,并通过氢核磁共振波谱(1H NMR)对其化学结构进行了表征.研究发现,所得磺化聚芳醚砜均表现出了优异的热稳定性.此类膜材料具有优良的机械性能、尺寸稳定性、氧化稳定性及高温低湿度条件下高的质子传导率.透射电子显微镜的结果表明,聚合物主链中大量氟原子的引入显著改善了聚合物的相分离结构,并且随着聚合物主链中氟含量的增加,亲水区域明显增大.这也是含氟磺化双三蝶烯型聚芳醚砜质子交换膜材料在高温低湿度条件下具有高质子传导率的主要原因.     

含(4-磷酸)苯侧基聚芳醚砜的合成及杂化

本文通过含溴聚芳醚砜合成可溶性含(4-磷酸)苯侧基聚芳醚砜, 并通过与磺酸功能化聚倍半硅氧烷杂化的方法, 制备了磷酸聚合物为基体的有机-无机杂化高性能质子交换膜材料.     

主链含硅聚芳酯的合成及气体透过性能的研究

以双［对－酰氯苯基］二甲基硅烷和酚酞、四溴酚酞以及双酚Ａ为原料，合成了三种主链含硅聚芳酯，并对聚合物相关的物理性质进行了表征，制成了均质透明的薄膜．采用低真空法测定这些聚合物对Ｈ２、Ｏ２、Ｎ２、ＣＯ２、ＣＨ４的气体透过速率，并计算出气体透过系数、扩散系数、溶解系数、分离系数．从气体透过性能与聚合物分子结构关系的角度，按照气体透过的溶解－扩散机制，对聚合物的气体透过性能进行了研究，而且着重讨论了聚合物的堆积密度对气体扩散系数的影响，以及聚合物主链中极性链段的百分含量对气体溶解系数和溶解选择性的影响。     

酞侧基聚芳醚砜／对苯二甲酸乙二酯－对羟基苯甲酸嵌段共聚物共混物的研究

酞侧基聚芳醚砜／对苯二甲酸乙二酯－对羟基苯甲酸嵌段共聚物共混物的研究李刚，殷敬华，李滨耀（中国科学院长春应用化学研究所，长春，１３００２２）关键词酞侧基聚芳醚砜，热致性液晶高聚物，原位复合材料，对苯二甲酸乙二酯－对羟基苯甲酸嵌段共聚物将热塑性树脂与热...     

主链含硅的芳族聚酰胺的合成及其气体选择透过性能

采用界面缩合聚合方法，合成了一系列主链含硅的芳族聚酰胺，从化学结构与气体透过性能关系的角度研究了此类聚合物均质膜的气体透过性能，结果表明，此类聚合物膜对Ｈ２、Ｏ２、Ｎ２、ＣＯ２、ＣＨ４的气体透过系数大小顺序符合一般玻璃态聚合物规律；在刚性强的高分子链段中引进柔性基因，可提高聚合物的气体透过系数；高分子主链有较强内旋转能力的聚合物，气体透过系数大；高分子主链的化学结构相同，苯环上带有侧甲基的聚合物有高的气体透过系数；硅原子上带有侧苯基的聚合物，其气体扩散系数大于而溶解系数小于硅原子上携有侧甲基的聚合物．结论为，在刚性高分子主链中引入柔性基团和提高刚性链间隙是增大气体透过含硅聚酰胺膜速率的有利因素．     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.