离子液体中Heck反应的研究进展

过渡金属钯催化的Heck反应是碳碳偶联反应中最重要的反应之一．绿色化学是当前化学领域研究的热点和前沿,离子液体是理想的绿色溶剂．近年来在离子液体中进行Heck反应受到广泛关注并取得了一定进展．文巾就近几年离子液体中的Heck反应进行了综述．     

1-偶氮苯-3-(5-溴-2-吡啶)-三氮烯的合成及其与铜的显色反应

报道了新显色剂1-偶氮苯-3-(5-溴-2-吡啶)-三氮烯的合成。在pH11.5的Na2B4O7-NaOH缓冲溶液中,TX-100表面活性剂存在下,1-偶氮苯-3-(5-溴-2-吡啶)-三氮烯与铜发生显色反应,生成3:1的红色配合物。配合物的最大吸收波长位于540nm处,表观摩尔吸光系数为8.13×104L.mol-1.cm-1,Cu2 的浓度在0~12.0μg/25mL范围内符合比尔定律。用拟定方法测定石乳花茶和大米样品中微量铜,结果令人满意。     

邻基参与反应历程探讨

邻基参与反应的历程主要有三类。即n-参与历程、π-参与历程和σ-参与历程；分为二步：(1)反应物的邻基从反面进攻α-碳原子。形成中间体，构型转化一次．为分子内的SN2反应；(2)外部的亲核试剂Nu从邻基的反面进攻中间体。构型又转化一次，再发生一次分子内SN2反应．其结果是：该类反应总的来说属于SN1反应历程．产物的构型保持不变．     

二苯亚砜与芳族化合物缩合制备芳取代三苯基硫鎓盐

Three kind of aryl-substituted tri-benzyl sulfonium salts [ （4-phX）phSph2 ] PF6 [ X = S, O ] were prepared by the condensation of biphenyl sulfoxide with biphenyl sulfide, biphenyl ether or 1, 1＇ -biphenyl in the presence of polyphosphoric acid which can be used as dehydrate agent. The reaction condition was mild, such as reaction temperature between 40- 50 ℃ ,reactive time 2- 3 h, the yield of 4-（phenylthio）triphenylsulfonium hexafluorophosphate was 87.6%. The three kind sulfonium salts show better curing character to epoxy resin.     

若干鳞翅目昆虫性信息素——Z/E-9-烯脂肪醇醋酸酯的合成

本文提出了合成若干鳞翅目昆虫性信息素—Z/E-9-烯脂肪醇醋酸酯的新方法．即从易得的天然不饱和脂肪酸—10-十一碳烯酸出发,经臭氧化硼氢化钠还原合成相应的10-羟基癸酸,随后经乙酰化得10-乙酰氧基癸酸,再经溴代脱羧反应合成了关键中间体9-乙酰氧基溴代壬烷,最后经维悌希反应合成了目标物．其中,Z/E-9-烯十二碳醇醋酸脂为甘蔗黄螟和枣粘虫等昆虫的性信息素;Z/E-9-烯十四碳醇醋酸酯为茶小卷叶蛾和桔卷叶蛾等昆虫的性信息素;Z/E-9-烯十六碳醇醋酸酯为稻螟蛉的性信息素;Z/E-9-烯十三碳醇醋酸酯和Z/E-9-烯十五碳醇醋酸酯为类似物．     

二碘化钐引起的分子内还原偶联反应

本文综述了二碘化钐引起的分子内还原偶联反应,包括分子内酮一烯还原偶联、酮一炔还原偶联、频哪醇偶联和其它有关还原偶联反应。     

Using bio-orthogonally catalyzed lethality strategy to generate mitochondria-targeting anti-tumor metallodrugs in vitro and in vivo

Synthetic lethality was proposed nearly a century ago by geneticists and recently applied to develop precision anti-cancer therapies. To exploit the synthetic lethality concept in the design of chemical anti-cancer agents, we developed a bio-orthogonally catalyzed lethality (BCL) strategy to generate targeting anti-tumor metallodrugs both in vitro and in vivo. Metallodrug Ru-rhein was generated from two non-toxic species Ru-N₃ and rhein-alkyne via exclusive endogenous copper-catalyzed azide alkyne cycloaddition (CuAAC) reaction without the need of an external copper catalyst. The non-toxic species Ru-arene complex Ru-N₃ and rhein-alkyne were designed to perform this strategy, and the mitochondrial targeting product Ru-rhein was generated in high yield (>83%) and showed high anti-tumor efficacy in vitro. This BCL strategy achieved a remarkable tumor suppression effect on the tumor-bearing mice models. It is interesting that the combination of metal-arene complexes with rhein via CuAAC reaction could transform two non-toxic species into a targeting anti-cancer metallodrug both in vitro and in vivo, while the product Ru-rhein was non-toxic towards normal cells. This is the first example that exclusive endogenous copper was used to generate metal-based anti-cancer drugs for cancer treatment. The anti-cancer mechanism of Ru-rhein was studied and autophagy was induced by increased reactive oxygen species and mitochondrial damage. The generality of this BCL strategy was also studied and it could be extended to other metal complexes such as Os-arene and Ir-arene complexes. Compared with the traditional methods for cancer treatment, this work presented a new approach to generating targeting metallodrugs in vivo via the BCL strategy from non-toxic species in metal-based chemotherapy.     

积分第二中值定理的一种改进

著名的第二积分中值定理在《数学分析》中占有十分重要的位置,并作为很多学科计算的一个重要工具,因此它得到了多种改进和推广。本文采用了一种引入参数的办法,又得到了第二积分中值定理的一种改进形式。     

香菇中麦角甾醇生成维生素D_2的光化反应实验设计

蘑菇中的麦角甾固醇经紫外线照射后可产生维生素D2,能被人体吸收利用,是天然维生素D的重要来源之一。为了增进本科生对脂溶性维生素代谢的认识和理解,设计了从香菇中提取麦角甾醇,再经光化反应将麦角甾醇转化为维生素D2的生物化学教学实验。为简化实验步骤、方便教学,试验筛选出了样品预处理、光反应及热反应的最佳条件,确定了不经皂化处理,提取物先后用254、365 nm的紫外光照射1 h后,置于85℃水浴下处理15 min实验流程。经高效液相色谱分析,测得产物收率为4.5%。     

置换法测金属原子量实验的微型化

对置换法测金属原子量实验进行了微型化研究,改进了实验装置,实现了药品的微量化．与常量制备的方法相比较,具有节约药品、省时、装置简便、操作安全快速等优点．