关于甲基橙合成反应条件的探讨

在有机化学实验的教学实践中,按照实验教材所述的实验步骤和实验条件进行甲基橙的合成时,实验结果不甚理想,在对该实验的各步反应条件进行认真分析后发现在偶联反应步骤,反应体系的酸性过强是导致实验失败的原因。为此在偶联反应步骤加入1mL冰醋酸和15mL5%的氢氧化钠溶液对反应体系的酸碱度进行调节,取得了理想的实验结果。     

化学反应活化能测定实验

通过测定反应温度和碘化钾浓度对反应速率的影响计算活化能,根据公式推导结果消除了试剂浓度对实验结果的影响。用Origin软件对实验数据进行拟合,从图形中得到反应速率、反应浓度、反应温度和活化能的直观对应关系。改进后的实验由单纯的验证性实验变成了自主设计综合性实验。     

乙酰苯胺制备实验的改进

乙酰苯胺制备实验是我校面向大二本科生开设的有机化学实验。如果采取传统的实验教学方法,即根据反应现象或反应时间来判定反应终点,可能会导致实验产率相差较大,且普遍偏低。因此使用薄层色谱监控反应进程和判断反应终点,可使反应重现性好和得到较高的产率。引入核磁共振仪进行定性和内标法定量分析以及红外光谱进行表征。通过对教材中经典实验的改进、延伸与拓展,提高了学生对实验研究的积极性,可在本科生实验中推广。     

格氏反应制备醇实验的改进

对有机化学必修实验“格氏反应制备醇”进行了研究。采用四氢呋喃(THF) 替代无水乙醚做反应溶剂,对教材中实验的试剂无水处理、反应的引发、试剂的用量、反应的后处理、产品的重结晶及用薄层色谱(TLC)检测产品纯度等进行了探讨和改进。结果表明,在THF中进行格氏反应制备三苯甲醇,实验现象明显,产率较高,降低了实验成本,全面提高了学生综合实验能力。     

基于绿色化学的甲烷与氯气取代反应装置优化设计

针对传统甲烷与氯气取代反应实验装置存在环境不友好、实验装置较大、过于分散、反应难以定量化等缺陷,从绿色化学角度出发,对传统甲烷与氯气取代反应装置进行优化设计,实现了该实验过程的绿色化,实验装置的微型化、综合化和反应的可控化、定量化。     

有机化学实验教学中合成实验反应进程的探讨

对现行有机化学实验教材中合成实验反应进程的监控和反应终点的判断问题进行了探讨,并以呋喃甲醇和呋喃甲酸的制备实验为例提出了对现行有机化学实验教材中合成实验的修改建议。     

甲烷与氯气取代反应实验的创新设计*

基于甲烷氯代反应的机理,对物质体系、反应容器、光照条件、实验表征等进行分析,创新设计甲烷氯代反应实验,利用数字化实验的压强和温度传感器采集的实验数据为支持,更直观地多重表征甲烷与氯气发生的“取代”过程,对于成功实现甲烷氯代反应实验具有指导意义。     

初中化学疑难实验的改进与创新

对初中化学的3个疑难实验--铜与硝酸银溶液反应实验、铁与硫反应实验、二氧化碳溶解度测定实验进行了改进和创新。     

可观察到氢气燃烧呈淡蓝色火焰的实验设计

现行高中化学教科书中钠与水的反应实验未提供验证反应所产生气体的实验装置。为使学生通过观察实验现象,直观地认识和理解钠与水反应产生的气体是氢气,在已设计"钠与水反应的实验装置"的基础上,从普通玻璃尖嘴导管焰色反应的干扰、煤油蒸气的干扰2个维度进行分析,最终设计出可以观察到氢气燃烧呈淡蓝色火焰的实验。     

钠与水(或无水乙醇)反应实验的改进

在高中化学教材[1,2]中多次出现钠与水反应及钠与无水乙醇的反应:钠与水在烧杯中进行的反应;钠与水在培养皿中进行的反应;钠与无水乙醇在试管中进行的反应。高考中以钠及其化合物为考点的题目常常出现, 其中好多是基于钠与水的反应。教材上面的3个实验用到了3种反应容器： 烧杯、培养皿和试管, 没有专门的反应容器。并且前2个实验验证了其中的产物NaOH, 而对另外的产物H2, 采用的是推测和讲解, 有的老师也用试管收集并进行验证; 后一个实验虽然也验证了H2, 但是需要"收集并验纯气体, 然后点燃。"笔者在长期的实验教学中, 对钠的相关实验做了多次探索和改进, 取得了令人满意的效果。     

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%.     

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.     

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.     

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.     

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.     

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.     

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.