[Cp*Rh(CO)2Me]BF4和二环庚二烯的反应机理研究

[Cp^*Rh(CO)₂Me]BF₄与二环庚二烯反应生成的含五元环产物可以作为烯烃/羰基共聚的潜在催化剂。本文采用密度泛函(DFT)方法对该类反应的机理进行了研究。研究表明，甲基转移是整个反应的决速步骤。计算得到，该步反应的活化焓变为71.67 kJ·mol^-1, 跟实验中得到的相应的焓变值(72 ± 2 kJ·mol^-1)吻合得很好。计算结果同时证实，该反应在热力学上非常有利。结构分析表明，二环庚二烯和金属中心配位后，二环庚二烯内的环张力得以释放以及螯合环的生成是导致热力学有利的主要原因。     

气相色谱法测定喷雾杀虫剂中的胺菊酯和氯菊酯

用SE-30毛细管柱、160~300℃程序升温、以邻苯二甲酸二环己酯为内标物,气相色谱法同时测定家用气雾杀虫剂中有效成分胺菊酯、氯菊酯的含量。胺菊酯、氯菊酯的平均回收率分别为94.0%、95.4%,相对标准偏差分别为2.23%、6.73%。     

Diels-Alder Addition of Dicyclopentadiene with Cyclopentadiene in Polar Solvents

Diels-Alder addition of dicyclopentadiene and cyclopentadiene in polar solvents has been studied to produce tricyclopentadiene（TCPD） that is a potential high-density fuel precursor. GC and MS analysis shows that the adducts contain two isomers, namely exo- and endo-TCPD. Theoretical simulation shows that although the transition state of endo-TCPD has a lower activation energy, exo-TCPD is thermodynamically preferred. Polar solvents can accelerate the reaction rate and improve the exo/endo ratio of TCPD because the transition state of exo-TCPD has a higher polarity than that of endo-TCPD. The solvent effect follows the order of polarity： benzyl methanol〉cyclohexanone〉toluene. The conversion rises when the temperature ranges from 120 to 150 ℃, but the selectivity of TCPD slightly decreases. Increasing the pressure can improve the conversion but the exo/endo ratio of TCPD is unchanged. The apparent kinetics in different solvents was determined via nonlinear regression. The activation energies are 99.47, 101.15, and 107.32 kJ/mol for benzyl methanol, cyclohexanone, and toluene, respectively. The optimal reaction conditions are as follows： benzyl methanol as solvent, temperature 150 ℃, and pressure 900 kPa. After an 11-hour reaction, a conversion of 58.0%, a TCPD selectivity of 95.7%, and an exo/endo ratio of 1/5.3 has been obtained.     

二环链系统的稳定性和能控性

提出了二环链系统,并利用二环链特征向量,给出了一个系统可实现二环链分解的充分必要条件,给出了可实现二环链线性系统的分解算法,研究了二环链系统的稳定性和能控性.     

某些新的连位仲、叔二胺的合成

连二胺化合物在化学工业、金属螯合剂、多氮杂环和穴状化合物化学中很重要。它们也常用于中间体的合成,以及特殊杂环化合物的合成。仲连二胺通常可用 Na、Mg、AI(Hg)Ti等诱导N取代的亚胺发生二聚反应还原制备。该方法有一些不利因素:较适合仲芳香胺而不适合叔芳香胺或脂肪胺;单分子与双分子还原相互竞争,而单分子还原产品通常是副产物;阴离子中间体形成困难。叔连二胺可在三(二烷基胺基)甲基钒(Ⅳ)或钛度剂存在下,     

过渡金属催化氮杂二环烯烃不对称开环反应的研究进展

综述了近年来过渡金属催化氮杂二环烯烃的开环反应的研究进展,重点讨论了过渡金属催化剂的种类、亲核试剂的类型、配体、底物氮杂二环烯烃及其衍生物的结构、溶剂和添加剂等因素对开环反应的影响,并对开环反应的可能的机理进行了讨论.     

色酮吡唑啉酮类衍生物的合成及抗白血病细胞活性

以色酮-吡唑啉酮作为C1合成子, 在5 mol% 的DBU催化下,与α,β-不饱和酮发生Michael加成反应, 获得了10个色酮吡唑啉酮类衍生物3a~3j,产率76%~90%, dr值为4/1~9/1, 其结构经¹H NMR, ¹³C NMR和HR-MS（ESI-TOF）表征,通过单晶进一步进行了确定化合物3b的相对构型。该类化合物包含有连续两个立体中心,包括一个季碳中心,可以为生物活性筛选提供物质基础。采用MTT法研究了3a~3f对人白血病细胞(K562)的体外抗增殖活性。结果表明：化合物3a, 3c, 3d和3i对K562增殖具有一定的抑制活性。     

合成前列碳环素中间体: 6β-(叔丁基二甲基硅氧)甲基-7-α[(四氢呋喃-2)氧基]-双环[3.3.0]辛-3-酮

The title compound (I; R = 2-tetrahydropyranyl) was prepared in 7 steps starting from lactone II.     

Assignment of cis-Epoxides and Crystal Structure of cis-4-Nitro-N-（7-oxabicyclo[4.1.0]hept-2-yl）benzamide

1 INTRODUCTION The success of strategies for total synthesis con-tinues to depend on high levels of stereoselectivityobserved in substrate-directed diastereoselective re-actions[1]. In this context, one of the most widelyused processes is diastereoselective epoxidation ofcyclic alkenes with allylic O- and N-directing group,which is very useful in building stereodefined syn-thetic blocks[2, 3] .However, in some circumstances,the assignment of resulting epoxides is not straight-forward[4～8…