溶剂系统向量选择性参数Q值的研究

提出了溶剂和溶剂系统向量参数表示方法,给出了正相及反相二元溶剂系统Ｑ值参数表。得到经验公式：Ｒ＿ｆ＝ａ＋ｂｌｎＱ＋ｃＱ。     

溶剂效应的TLSER描述及其在几类异构化反应中的应用

建立了适合于描述党溶剂效应的理论线性溶剂化能相关(TLSER)模型。并用该模型对四类异构化反应在不同溶剂下的反应自由能或活化自由能与溶剂的分子结构之间的关系进行了研究,确证了模型的合理性。     

混合溶剂作淋洗剂的体积排除色谱(SEC)中溶剂化高分子峰和溶剂峰的关系

以混合溶剂作淋洗剂的体积排除色谱(SEC)中高分子样品一般会出现2个峰, 分别是溶剂化高分子峰和自由溶剂峰. 理论分析结果表明, 溶剂化高分子峰面积( A3eff )是“裸高分子”峰面积(A3)和被束缚溶剂峰面积(A1*)的加和, 被束缚溶剂峰面积(A1*)和自由溶剂峰面积(A2*)大小相等符号相反. 以聚苯乙烯(3)-氯仿(1)-甲醇(2)体系为研究对象, 分别对A3eff, A3及A2*进行了实验测定, 证实了理论推断的正确性, 表明由高分子峰和由溶剂峰来求算优先吸附系数是等价的.     

酰胺-盐溶剂体系中的缔合解离平衡和溶剂化效应

本文研究了酰胺-盐溶剂体系中盐的缔合解离平衡和离子的溶剂化效应,以及这些因素对该溶剂体系溶解能力的影响。研究结果表明,盐在溶剂体系中存在多级缔合-解离平衡,阳离子周围有较强的溶剂化效应。自由离子浓度最大和溶剂化效应最强时的盐浓度对应于聚合时的最佳盐用量。     

电子自旋共振作为探针研究卤代溶剂的专属性效应

4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基(4-OH-TEMPO)电子自旋共振的超精细耦合常数AN与溶剂极性的微观反应常数ET(30)和溶剂受体数AN呈现线性正相关. 并且在介电常数或偶极矩接近时, 含卤溶剂中超精细耦合常数AN普遍偏高. 除了一般的溶剂效应外, 在含卤溶剂中超精细耦合常数AN偏大的原因与专属性的卤键作用有关. 理论计算结果辅助印证了这一结论.     

溶剂-导体界面电子转移溶剂重组能的球-界面模型

在连续介质理论基础上, 根据热力学基本原理, 用一个外加电场Eex将非平衡态2[Enon2, Dnon2]变成约束平衡态[E*2, D*2], 推导出了正确普适的溶剂重组能公式. 基于球-界面近似, 推导出了正确的溶剂-导体界面电子转移溶剂重组能公式. 和Marcus的公式相比, 本文的结果多了(εs-εop)/(εop(εs-1))因子. 对极性溶剂, 预测的溶剂重组能约为Marcus模型所得结果的一半. 以C343(Coumarin 343)-TiO2体系为算例, 计算了溶剂重组能并与实验值进行了比较.     

129Xe NMR法研究醇二元混合溶液

129Xe NMR可以作为研究液体结构状态的探针．甲醇是一个与水结构差别最小的有机溶剂．本文研究了129Xe在甲醇-丁醇,甲醇-戊醇,甲醇-辛醇,甲醇-癸醇混合溶剂中化学位移随组成的变化,并测定了混合溶剂的密度和折射率．129Xe化学位移随混合溶剂的摩尔分数的变化为四条曲率很近的曲线,而化学位移随混合溶剂的体积分数的变化为斜率随多碳醇碳原子数增加的直线．这表明甲醇-多碳醇二元混合溶剂中不存在疏溶剂作用,而构成分子均匀分布的体系．129Xe在甲醇-丁醇,甲醇-癸醇中的化学位移与混合溶剂折射率的一种函数的关系为两条斜率很接近的直线,表明Xe在溶液中主要受范德华力作用．     

溶剂气浮法去除水中的刚果红的研究

以十六烷基三甲基溴化铵为表面活性剂, 与阴离子型染料刚果红形成缔合物, 对该缔合物的溶剂气浮过程进行研究. 研究多种参数对溶剂气浮过程的影响, 如气浮速率、共存溶质的量、pH等参数对溶剂气浮去除率的影响. 研究表明表面活性剂与染料的物质的量之比为2∶1, 约24 min水中刚果红的去除率可达97%;NaCl会大大降低溶剂气浮的去除率;溶剂气浮的速率随着气流速率的增加而增加, 但高速率反而降低溶剂的去除率;共存溶质乙醇存在会使去溶剂去除率降低, 有机溶剂的量对溶剂气浮影响较小;pH中性去除率最佳;考察了不同温度下溶剂气浮的热力学及动力学, 研究表明, 溶剂气浮过程遵从一级动力学, 计算了该过程中的气浮表观活化能为7.48 kJ/mol.     

RbCl由H2O至混合溶剂(H2O-DMF)标准迁移熵的测定

电解质迁移热力学性质的测定,对于离子溶剂化的研究具有重要意义.迁移自由能主要反映离子与溶剂分子间的相互作用,迁移熵则主要反映不同溶剂分子间的相互作用,迁移熵随温度及溶剂组成的改变可为溶剂的原有结构推测及溶液秩序改变提供信息.我们曾运用离子选择性电极测定了部分碱金属卤化物在水及含水混合溶剂中的热力学性质[1-3].本文用离子选择性电极方法,通过测定不同温度下电池的标准电动势,根据溶液热力学原理,求得ＲｂＣｌ由Ｈ2Ｏ至混合溶剂(Ｈ2ＯＤＭＦ)的标准迁移自由能ΔＧｔ及其温度系数,计算ＲｂＣｌ的标准迁移熵ΔＳｔ.结果尚未见…     

溶剂对煤液化影响的研究

用共振搅拌反应器研究了煤液化过程中溶剂的作用,结果表明,用大分子直链脂肪烃、单环苯系列化合物作溶剂,煤转化率较低。比较不同环数化合物作溶剂对应的煤转化率可得,单环苯系列< 两环萘系列<三环蒽、菲。使用芘溶剂和萘溶剂转化率相近;酚类化合物不适合作煤液化的溶剂;同系列物相比,煤转化率次序为,部分氢化芳香化合物作溶剂>带侧链的芳香化合物作溶剂>芳香化合物作溶剂>完全氢化芳香化合物(环烷烃)作溶剂。气氛对煤转化率的影响与所用溶剂的种类有关,用十氢萘和甲基萘做溶剂时,气氛的影响很小,使用四氢萘时,气氛的影响很大。     

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%.     

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.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.