新型胺基修饰的超高交联聚合吸附剂吸附水中酚类化合物的研究

合成了新的胺基修饰的超高交联AH系列吸附树脂．以弱碱树脂D301和超高交联吸附树脂ND100为参照，测定了AH系列吸附树脂吸附水中苯酚、对氯苯酚、对甲苯酚、对硝基苯酚的吸附性能。结果表明：修饰的超高交联吸附树脂对苯酚．对甲苯酚、对氟苯酚的吸附量比ND100和D301更大，而D301树脂对对硝基苯酚有最大的吸附量．提出了AH系列树脂对4种酚类化合物吸附行为的作用机理．     

甲氧基修饰的大孔交联树脂对苯酚的吸附机理

由大孔氯甲基化聚苯乙烯合成了含有悬挂醚键的甲氧基修饰的大孔交联树脂.通过化学分析(氯含量的测定)、红外光谱和元素分析等手段,确证甲氧基负载在聚苯乙烯骨架上,负载量为4.10mmol/g.测定了这种树脂对正己烷中苯酚的吸附等温线,表明其对正己烷中苯酚的吸附是放热的,随着温度的升高,吸附量逐渐降低,且吸附等温线可拟合成直线.通过吸附焓的计算、不同条件下吸附等温线的比较以及理论计算等方法,确证氢键是甲氧基修饰的大孔交联树脂吸附正己烷中苯酚的主要驱动力,树脂骨架上负载的醚氧原子与苯酚的酚羟基氢原子形成了强烈氢键.     

超高交联聚苯乙烯对非水体系中苯酚的吸附热力学研究

采用“一锅法”以氯化锌为催化剂合成了超高交联聚苯乙烯。测定了超高交联聚苯乙烯对环己烷中苯酚的吸附等温曲线，利用热力学函数关系计算出了吸附焓、吸附自由能和吸附熵，比较了超高交联聚苯乙烯对苯酚和苯甲醚吸附性能的差别，推测吸附过程的主要作用为氢键作用。以小分子化合物为模型，通过分子间相互作用能的计算，论证了树脂是通过其羰基氧原子与苯酚的羟基氢原子之间的氢键作用而吸附苯酚的。     

单宁酸修饰的后交联吸附树脂的制备及对氯酚的吸附性能

采用氯甲基化的低交联苯乙烯-二乙烯苯共聚物,通过交联反应和化学修饰反应制备了单宁酸修饰的后交联吸附树脂TAMR-1和TAMR-2,并对其进行了红外光谱分析、比表面及孔径分析和热重分析。通过静态吸附实验,比较了TAMR-1和TAMR-2对2-氯酚、4-氯酚和2,4-二氯苯酚的吸附去除率。通过小柱吸附-脱附实验,探讨了TAMR-1对3种氯酚的吸附性能。结果表明,与TAMR-2相比,TAMR-1的比表面积较高,氯残留量低,后交联反应与化学修饰反应更完全。TAMR-1和TAMR-2的外推起始分解温度均超过680K。TAMR-1树脂对3种氯酚(C0均为200mg/L)的吸附去除率均超过85%,明显高于TAMR-2树脂,且对2,4-二氯苯酚的吸附量最大。4%的NaOH溶液对吸附氯酚饱和后的TAMR-1树脂具有良好的再生效果。     

单宁酸修饰的超高交联吸附树脂对酚类化合物的吸附研究

通过氯甲基化的苯乙烯-二乙烯苯共聚物的后交联及单宁酸的化学修饰反应制备了单宁酸修饰的超高交联吸附树脂(TAMR),通过红外光谱、元素分析、扫描电镜和比表面孔径分析对TAMR树脂的结构特征和表面参数及形貌进行表征.通过等温吸附实验和吸附动力学实验研究了苯酚、对硝基苯酚和对氯苯酚在TAMR树脂上的吸附性能和吸附机理.结果表明,TAMR树脂具有较高的比表面积(780.1 m2/g)和较丰富的微孔(482.3 m2/g),树脂表面修饰了较丰富的羟基.TAMR树脂对苯酚、对硝基苯酚和对氯苯酚均具有较好的吸附性能,288 K时吸附量分别可达1.43、2.07和2.48 mmol/g(c0为500 mg/L).3种酚类化合物在TAMR树脂上的吸附为典型的物理吸附,其吸附焓变和熵变均为负值.当酚类化合物以分子形态存在时,有利于其被TAMR树脂吸附.Langmuir和Freundlich方程均能较好地拟合酚类化合物在TAMR树脂上的吸附等温线.吸附动力学过程符合准一级动力学方程,颗粒内扩散过程是TAMR树脂吸附这3种酚的吸附速率的主要控制步骤.     

2,4-二硝基-6-溴苯胺生产废水中有机物的吸附回收工艺研究

通过Friedel-Crafts后交联反应制备了超高交联吸附树脂(YSS150)及二甲胺修饰的超高交联吸附树脂(YSS99),以Amberlite XAD-4树脂做参照,通过等温吸附-脱附、动态吸附-脱附及树脂稳定性实验,在筛选的基础上,研究了YSS150树脂对2,4-二硝基苯胺(2,4-dinitroaniline,DA)及2,4-二硝基-6-溴苯胺(2,4-dinitro-6-bromoaniline,DBA)的吸附效果及对2,4-二硝基苯胺及2,4-二硝基-6-溴苯胺的吸附回收工艺的可靠性.结果表明:YSS150树脂对水中2,4-二硝基苯胺及2,4-二硝基-6-溴苯胺具有较高的吸附容量,吸附等温线符合Freundlich方程,甲醇或8%盐酸具有较好的脱附效果.     

氨基修饰超高交联树脂对没食子酸的吸附性能

以亲水性小分子有机酸没食子酸作为研究对象,研究了氨基修饰超高交联树脂对没食子酸的吸附行为和机理.结果表明,氨基修饰超高交联树脂WJN-10对没食子酸有较高的吸附容量和吸附作用力;π-π共轭作用是树脂WJN-10吸附没食子酸主要作用力;WJN-10吸附没食子酸是物理吸附主导;吸附速率主要受控于颗粒内扩散过程;WJN-10对没食子酸有较好的吸附-脱附性能.     

硫辛酸在三种不同树脂上的吸附热力学和动力学研究

通过静态吸附实验,研究了大孔交联聚苯乙烯树脂(XAD-4)、氧修饰超高交联聚苯乙烯树脂(NDA-100)和胺基修饰超高交联聚苯乙烯树脂(ND-90)对乙醇．水溶液中硫辛酸的吸附热力学及动力学特性,结果表明：硫辛酸在XAD-4树脂上是单层吸附,符合Langmuir等温吸附方程,吸附过程符合准一级动力学吸附方程。硫辛酸在NDA-100和ND-90树脂上的吸附也符合Langmuir等温吸附方程,但并不只是单层吸附,同时兼有毛细管凝聚和微孔填充作用,吸附过程可分为大孔和中孔区的吸附以及微孔区的吸附两个阶段,两个阶段都符合准一级动力学吸附方程。     

氨基酸螯合吸附树脂对苯酚的吸附行为研究

合成了一种L-酪氨酸修饰的螯合吸附树脂(AJS-02),并与超高交联树脂NDA-150作对比,研究了其对苯酚的吸附和脱附行为.静态实验结果表明,在研究的浓度范围内,吸附平衡数据符合Langmuir等温吸附方程且吸附为放热过程.溶液的初始浓度为100 mg/L、吸附温度为288 K时,苯酚在AJS-02和NDA-150上的平衡吸附量分别为76.98和91.97 mg/g,苯酚在两种树脂上的吸附是比表面积和表面官能团共同作用的结果.动力学数据表明吸附动力学符合液膜扩散方程和颗粒内扩散方程,液膜扩散为吸附速率的主要控制步骤.动态吸附-脱附实验表明,AJS-02树脂对苯酚的动态穿透吸附量和饱和吸附量分别为5.26×10-2和6.60×10-2mmol/mL,采用95%乙醇作脱附剂,脱附率可达91.5%以上.     

氨基修饰超高交联树脂对单宁酸的吸附行为及机理研究

选用单宁酸作为天然有机酸中典型中分子、高水溶性有机酸,系统研究了氨基修饰超高交联树脂对单宁酸的吸附行为和机理.吸附等温线表明氨基修饰超高交联树脂WJN-08对单宁酸有较高的吸附容量,其静态饱和吸附量比传统商业吸附剂高15%以上;吸附表面分析表明离子键、π-π共轭作用和阳离子-π键是重要吸附作用力;吸附热力学试验表明树脂WJN-08吸附单宁酸是化学吸附主导,吸附焓变在20~22 kJ mol-1;吸附动力学试验表明树脂WJN-08吸附单宁酸速率同时受控于颗粒内扩散和膜扩散过程.动态小柱吸附-脱附实验表明树脂WJN-08对单宁酸有较好的吸附-脱附性能,饱和吸附量和穿透吸附量分别为24.43 mg g-1和19.56 mg g-1,脱附率为98.6%。     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.