全氟磺酸树脂/SiO2催化合成邻苯二甲酸二辛酯

全氟磺酸树脂/SiO2催化合成邻苯二甲酸二辛酯;固体酸;全氟磺酸离子交换膜;全氟磺酸树脂/SiO2复合物催化剂;邻苯二甲酸二辛酯     

全氟4-甲基-3,6-二氧杂-△~7-辛酸甲酯的合成

在离子交换膜法制碱中,全氟羧酸离子交换膜是比全氟磺酸离子交换膜(Nafion)优良的电解隔膜。它不需经过化学改性就能直接应用于食盐电解,且可在电解制取30～40％浓碱的情况下保持90％以上的电解电流效率。全氟羧酸离子交换膜为四氟乙烯与一种含有羧酸甲酯的全氟烯醚的共聚物:     

丙烯酸含漫改性的全氟磺酸膜

全氟磺酸膜(“耐氟昂”)是最先工业化生产的全氟型离子交换膜:它具有突出的耐氧化性。目前已成功地用于电解氯化钠制备氢氧化钠。全氟磺酸膜虽有不少优点,但是性能还不够理想,主要是电流效率低。这是由于膜中的磺酸基具有很强的亲水性,可使阴极室的氢氧根向阳极室逆扩散,从而使电流效率降低。为了改进膜的性能,我们曾采用全氟磺酸(Na型)膜含浸丙烯酸,苯乙烯和二乙烯基苯,制备改性的全氟磺酸膜,以阻止氢氧根扩散。结合测定交换容量,含水率和扩散系数等,来研究含浸液组成对膜性能的影响。并根据电解氯化钠制备氢氧化钠的试验结果,比较了改性膜和未经改性膜的性能。     

全氟4-甲基-3,6-二氧杂-△~7-辛基磺酰氟及有关化合物的合成

全氟4-甲基-3,6-二氧杂-△~7-辛基磺酰氟是合成全氟磺酸离子交换树脂的共聚单体,此单体在文献中除有关专利简单报导外,尚未见其合成和结构鉴定等方面的详细资料。我们在合成全氟磺酸离子交换树脂的过程中,对它以及其有关化合物的合成进行了研究。     

BF3/离子交换树脂固体酸催化剂的研究

ＢＦ_３／离子交换树脂固体酸催化剂的研究温陵生，马淑杰，张强，吕慧娟，徐征（吉林大学化学系，长春１３００２３）关键词三氟化硼，聚苯乙烯磺酸树脂，全氟磷酸树脂，超强酸催化剂用于催化剂的离子交换树脂有大孔聚苯乙烯磺酸树脂ＰＳＳＡ和全氟磺酸树脂ＰＦＩＥＰ（?..     

新型全氟烷基磺酸盐乳化剂—N-2

在制备全氟磺酸离子交换树脂(膜)共聚单体CF_2=CF_2O-CF_2CF(CF_3)OCF_2CF_2SO_2F的过程中,生成一定量的副产物CF_2=CF-O[CF_2CF(CF_3)O]_2CF_2CF_2SO_2F。为化废为利,降低成本,我们利用此副产物为原料,研制成了一种新的全氟烷醚基磺酸钾表面活性剂N-2:CF_3CF_2O[CF_2CF(CF_3)O]_2CF_2CF_2SO_3K。现将制备方法、性能测试结果介绍如下: 一、制备方法:     

侧链含有全氟磺酸的聚芳醚砜质子交换膜材料的制备及性能

利用含溴苯侧基的聚芳醚砜(PES-Br)和1,1,2,2-四氟-2-(1,1,2,2-四氟-2-碘乙氧基)乙烷磺酸钾(PSA-K)进行Ullman偶联反应, 制备了新型含全氟磺酸侧链的聚芳醚砜(PES-PSA), 全氟磺酸的引入量为50%. 在离子交换容量(IEC)为0.907 meq./g, 80 ℃, 相对湿度为100%时, PES-PSA质子传导率达到0.039 S/cm, 表现出较高的质子传导能力. 其较低的IEC值使膜材料表现出良好的热稳定性和尺寸稳定性.     

用全氟磺酸离子交换树脂多相催化合成不对称醚

醚类化合物是有机化学工业和医药工业上常用的溶剂。又如甲基叔丁基醚沸点低、辛烷值高可作无铅汽油,特别是高级无铅航空汽油的添加剂。Cottle、Wolff等人曾用硫酸、磷酸、有机金属化合物和聚苯乙烯磺酸型离子交换树脂作催化剂,通过醇和烯烃的加成反应合成了对称的和不对称的醚。本文采用酸性比聚苯乙烯磺酸强,但对反应容器无任何腐蚀,操作简便,无三废的全氟磺酸离子交换树脂(以后简称全氟磺酸)作催化剂,合成了甲基叔丁基醚;乙基叔丁基醚;异丙基叔丁基醚和仲丁基叔丁基醚。     

杂萘联苯聚芳醚质子交换膜材料的研究

质子交换膜是质子交换膜燃料电池的核心部件之一，其性能的优劣直接关系燃料电池的工作性能。目前质子交换膜燃料电池多采用全氟磺酸离子膜，全氟磺酸膜虽然具有较高的质子传导性和良好的化学稳定性，但是也具有价格昂贵、甲醇渗透高和高温下质子传导性能下降等缺点。为了克服全氟磺酸膜的不足，国内外相继开展了非氟质子交换膜的研究，如磺化聚醚醚酮（SPEEK）、磺化聚醚醚酮酮（SPEEKK）、磺化聚砜（SPSU）和磺化聚酰亚胺（SPI）等。     

杂萘联苯聚芳醚质子交换膜材料的研究

质子交换膜是质子交换膜燃料电池的核心部件之一,其性能的优劣直接关系燃料电池的工作性能.目前质子交换膜燃料电池多采用全氟磺酸离子膜,全氟磺酸膜虽然具有较高的质子传导性和良好的化学稳定性,但是也具有价格昂贵、甲醇渗透高和高温下质子传导性能下降等缺点.     

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.     

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.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.