催化动力学法测定高纯碳酸锂中痕量银

本文基于银催化过硫酸铵氧化二价锰离子为高锰酸根的反应,催化动力学法测定银。选用磷酸介质,考察了30种共存离子对测定的影响。拟定了高纯碳酸锂中痕量银的分析方法,操作简便,结果令人满意。     

BF3活化高锰酸氧化丙烯酸反应机理的 密度泛函研究

用量子化学密度泛函理论(DFT)的B3LYP方法对高锰酸根离子与丙烯酸的环加成反应机理进行了系统研究, 全参数优化了反应势能面上各驻点的几何构型、振动频率和能量. 计算结果表明: 反应有两个竞争通道, 即[2+3]反应通道和[2+2]反应通道, 其中[2+3]通道比[2+2]通道的反应势垒降低了183.89 kJ/mol, 并通过在高锰酸根的氧原子上配位一个或两个BF3分子来研究BF3分子对反应体系的活化效应, 结合两个BF3分子使得[2+3]通道的反应势垒降低为23.97 kJ/mol, 则有利于反应按该通道进行, 然而[2+2]通道的反应势垒仍较高(>195 kJ/mol).这进一步表明该反应体系中加入一定量BF3能提高高锰酸氧化烯烃双键的化学活性.     

BF_3活化高锰酸氧化丙烯酸反应机理的密度泛函研究

用量子化学密度泛函理论(DFT)的B3LYP方法对高锰酸根离子与丙烯酸的环加成反应机理进行了系统研究,全参数优化了反应势能面上各驻点的几何构型、振动频率和能量.计算结果表明:反应有两个竞争通道,即[2+3]反应通道和[2+2]反应通道,其中[2+3]通道比[2+2]通道的反应势垒降低了183.89kJ/mol,并通过在高锰酸根的氧原子上配位一个或两个BF3分子来研究BF3分子对反应体系的活化效应,结合两个BF3分子使得[2+3]通道的反应势垒降低为23.97kJ/mol,则有利于反应按该通道进行,然而[2+2]通道的反应势垒仍较高(195kJ/mol).这进一步表明该反应体系中加入一定量BF3能提高高锰酸氧化烯烃双键的化学活性.     

锂离子电池负极碳材料的表面改性与修饰：Ⅰ.表面的氧化,还原处理对碳…

通过各种氧化／还原体系对碳材料进行表面氧化，还原处理，研究了碳材料表面的痕量有机含氧官能团对以碳材料作为锂离子电池负极的电池性能的影响。结果表明，碳材料表面大量有机含氧官能团的存在将引起电池性能的严重恶化；相应地如对电极表面进行一定的还原处理，以减少碳表面有机官能团的含量及其氧化程度则可提高电极的容量及首次循环效率。     

胺甲酰氟促进的镍催化非活化烯烃的不对称胺甲酰基-芳基化反应

过渡金属催化烯烃的不对称双碳官能团化反应提供了一种快速构建手性化合物的简便方法,近年来备受化学研究者们的关注[1].目前主要的研究思路是通过设计含苯环的底物现场生成芳基金属物种,来进行不活泼烯烃的分子内不对称双官能团化反应.对于含有非苯并底物的非活化烯烃的不对称双碳官能团化反应来实现季碳手性中心的构建,已报道的仅有少数通过酰基金属中间体的策略[2-4].2010年,Takemoto等[2]报道了一例钯催化烯烃和胺甲酰氰的不对称胺酰基氰化反应来构建季碳手性中心。     

高锰酸根褪色光度法测定食盐中的微量碘离子

在稀硫酸介质中，碘离子能快速、定量地还原高锰酸根，在加入碘离子前后，高锰酸钾溶液在波长525nm处的吸光度发生显著变化，且吸光度之差ΔA与加入的碘离子的浓度成正比，确定了最佳反应条件，建立了高锰酸根褪色光度法测定食盐中微量碘离子的新方法。方法的线性范围为0-20μg／mL，线性回归方程为ΔA=0．0165c 0．0041，相关系数r=0．9987，检出限为0．17μg／mL。用于食盐中微量碘离子的测定，加标回收率为91．0％～95．0％．相对标准偏差为0．35％～0．75％。     

非官能化烯烃的不对称催化环氧化反应

手性环氧化合物是有机合成的重要中间体,由于三元杂环的张力使其很容易与各种亲核试剂作用,通过官能团转化反应,可以从环氧化物制备一系列不同结构的手性化合物.烯烃的不对称环氧化反应可以使潜手性的烯烃转化为带有手性碳的环氧化合物,在医药、农药、香料等精细化学品的合成上具有非常重要的意义.非官能化烯烃经手性催化剂诱导的不对称环氧化反应是获得光学纯手性化合物的有效方法.这些手性催化剂包括生物酶、金属卟啉、金属Salen配合物以及有机小分子催化剂.本文综述了这几种催化剂催化的非官能化烯烃不对称催化环氧化反应近几年的研究进展,介绍了催化剂的催化机理,并就其发展趋势提出了构想.     

用于烯烃化学的新型有机铼催化剂

德国慕尼黑工业技术大学Herrmann教授最近发展了以甲基三氧化铼(Ⅶ)作为均相或异相催化剂广泛应用于烯烃复分解、烯烃氧化和醛转化为烯烃等几个过程。这些过程可用于制备某些商品重要的树脂如聚链烯(polyalkenomer)以及官能团烯烃、桥氧化物、二醇等精细化学品甲基三氧化鳞(MTO,CH_3ReO_3)是最     

钯催化苯乙烯类分子胺氟化反应研究

报道了烯烃分子间的氧化双官能团化反应, 用金属钯作为金属催化剂, 三价碘为氧化剂, 氟化银为氟源, 磺酰胺类为亲核试剂, 实现了苯乙烯的分子间胺氟化反应, 得到α-F代苯乙胺类化合物; 反应是经过烯烃的反马氏氮钯化得到碳钯键, 再经过三价碘氧化成高价钯的中间体来形成C—F键, 在分子中的特定位置引入氟原子. 该反应的一个特点是选择性地得到反马氏胺氟产物.     

可见光/镍协同催化烯烃和炔烃双官能团化反应研究进展

可见光氧化还原催化与金属镍催化的联姻,使得在极为温和条件下构建挑战性化学键成为可能.然而,大多数协同催化体系只能构建单一的碳-碳键或碳-杂原子键.近些年来,可见光/镍协同催化在烯烃及炔烃分子间双官能团化反应领域引起了广泛关注.该协同催化级联模式可以一步构建多个化学键,为复杂结构单元的快速高效构筑提供了温和且高选择性的方...     

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.