达比加群酯的合成

以3-硝基-4-氯苯甲酸为起始原料,经酰氯化、酰胺缩合、甲胺化、催化氢化、缩合关环、氰基氨解和酯化等7步反应合成了达比加群酯,总收率44.2%,其结构经1H NMR,MS和IR确证。     

胸苷酸合成酶抑制剂——Nolatrexed的合成工艺改进

以2-溴4-硝基甲苯为起始原料,经还原、缩合、成环、过酸氧化、氨解、缩合、取代等反应合成了胸苷酸合成酶抑制剂--Nolatrexed(总收率9.5%),其结构经1H NMR,IR和Ms表征.     

泮托拉唑钠的合成工艺改进

以5-二氟甲氧基-2-巯基-1H-苯并咪唑和2-氯甲基-3,4-二甲氧基吡啶盐酸盐为原料,经缩合,氧化和成盐反应合成了泮托拉唑钠,其结构经1HNMR和MS表征。缩合,氧化和成盐反应的收率分别为88.8%,79.2%,89.7%。     

左氟沙星的微波催化合成

以2,3,4,5-四氟苯甲酰乙酸乙酯为原料,在微波辐射下,经N,N-二甲基甲酰胺二甲缩醛缩合,S-(+)-2-氨基丙醇置换,环合和水解后再与N-甲基哌嗪缩合制得左氟沙星(1),总收率48.1%.1和中间体的结构经1H NMR和MS表征.     

三苯胺亚胺类化合物的合成

以三苯胺为起始原料,经硝化、还原和胺醛缩合反应合成了4个三苯胺亚胺类化合物,其结构经1H NMR和IR确证。     

氟丙嘧草酯的合成新工艺

以2-氯-5-硝基苯甲酸甲酯为原料,经还原、缩合得2-氯-5-(乙氧羰基)氨基苯甲酸甲酯(3);3与3-氨基-4,4,4-三氟巴豆酸乙酯进行环合得脲嘧啶环中间体(4);4经甲基化、水解、酰化和缩合反应合成了氟丙嘧草酯,总收率55.2%,纯度99.1%。中间体和产物结构经1H NMR和EI-MS确证。     

超声波促进合成新型吡咯α,β-不饱和酮

以乙酰乙酸酯为原料,通过亚硝化反应、Knorr缩合反应和氧化反应制得中间体3-甲基-5-甲酰基-1H-吡咯-2,4-二甲酸酯(4a~4d);在超声波促进下,4a~4d与丙酮经Aldol缩合反应合成了4个新型吡咯α,β-不饱和酮,其结构经IR,1H NMR和HR-ESI-MS表征。     

新型Venetoclax哌嗪衍生物的合成

以溴乙酸乙酯和苄胺为起始原料，经氨基化、氨基酸缩合、环化、还原、脱苄基、苯甲酸甲酯衍生物取代、氯苯衍生物取代、水解、磺胺缩合和吡喃氨基化反应，合成了一个新型的含螺环哌嗪结构的磺胺类Venetoclax衍生物，总收率3.4%，其结构经¹H NMR和HR-MS(ESI)表征。     

新方法合成4-氰基-1-茚酮

以邻氰基氯苄和丙二酸二乙酯为原料,经缩合、碱水解、脱羧和Friedel-Crafts酰化反应合成了4-氰基-1-茚酮,总收率32.1%,其结构经1H NMR和13C NMR确证。     

托比司他的合成工艺改进

以2-氰基异烟酸甲酯为原料,经水解、酰化、脱保护和缩合反应合成了托比司他,总收率32%,其结构经1H NMR和ESI-MS确证。     

Study on the reaction kinetics between PBT and epoxy by a novel rheological method

In the present study, the reaction kinetics of polybutylene terephthalate (PBT) and epoxy system was studied by a novel rheological method. The reaction process was determined by rheological test and the results showed that there were three stages in the reaction between PBT and epoxy, which were reaction-controlling stage (stage I), reaction-stagnation stage (stage II) and diffusion-controlling stage (stage III). In addition, the stage I was selected to study the reaction kinetics by the rheological method. The results showed that the reaction between PBT and epoxy could be classified as a pseudo-first-order reaction due to the excessive amount of epoxy group. Furthermore, the reaction apparent activation energy of the stage I determined by the rheological method was 143 kJ/mol. To confirm these results, the reaction kinetics was also evaluated by the endgroup determination method, and the results showed that the reaction could also be classified as a pseudo-first-order reaction. Moreover, the apparent activation energy of the reaction was 116 kJ/mol, which was similar to that of the value obtained by the rheological method.     

一种以三聚氯氰为桥基的新型小分子功能活性染料的合成

以对氨基苯甲酸甲酯和水合肼为原料,经酰胺化反应制得对氨基苯甲酸甲酰胺,进一步与水杨醛通过还原氨化反应生成席夫(1）;以罗丹明B和水合肼为原料,1经闭环反应制得罗丹明B酰肼（2）; 2在四氢呋喃溶剂中与三聚氯氰经缩合取代反应生成一缩产物（3）; 3进一步在四氢呋喃中与1于45~50 ℃回流6 h,经取代反应生成二缩产物,其结构经¹H NMR, MS, IR和元素分析表征。     

荧光增白剂4,4′-二(4-磺酸钠苯乙烯基)二苯甲酮的合成

用Heck反应合成了4,4′-二(4-磺酸钠苯乙烯基)二苯甲酮.对Heck反应条件进行了改进,使用壳聚糖负载钯为催化剂并考察了催化剂的回收再利用情况.通过研究影响该反应的各种因素,如反应时间、反应温度、原料配比等,优化了实验条件,得到了较好的结果.     

Total synthesis of leustroducsin B

Leustroducsin B was synthesized via a convergent route based on division of the leustroducsin molecule into three segments A, B, and C. Two coupling reactions (Julia coupling reaction and Nozaki-Hiyama-Kishi (NHK) reaction) were employed for coupling of segments A and B: segment A1 for the Julia coupling reaction was prepared by a combination of Sharpless asymmetric epoxidation and an epoxide-cleavage reaction with an organoaluminum reagent, while segment A2 for the NHK reaction was synthesized from optically active alcohol that had previously been prepared by lipase-catalyzed kinetic resolution. Segment B, whose structure was modified with some functional groups, was synthesized from (R)-malic acid by a combination of Wittig reaction and Sharpless asymmetric dihydroxylation, and segment C, containing a cyclohexane moiety, was prepared by asymmetric Diels-Alder reaction. Segment B was first coupled with segment A1 via the Julia coupling reaction, but the yield was low due to unexpected epimerization. The NHK reaction of segment A2 proceeded to give the coupling product in good yield. This product was coupled with segment C via Wittig and Stille coupling reactions, and finally, phosphorylation was carried out by partial hydrolysis of a cyclic phosphate to give leustroducsin B.     

N溴代丁二酰亚胺氧化醇反应的热动力学研究

氧化反应是有机化学中的一种重要反应类型,也是有机化学、化学工程和生物学家们研究的重点之一.但因其机理复杂,至今未见到用热动力学理论探索氧化反应体系的报道. N溴代丁二酰亚胺(NBS)是良好的溴化试剂,在不同反应条件下,它既可和不饱和键发生加成反应,也可在水溶液中作为次溴酸的来源,还可作为有效的氧化剂和脱氢剂.Reich和Reichstein首先报道了用N溴代乙酰亚胺将仲醇缓慢氧化为酮,Fieser等人报道了NBS的氧化作用.本文用RD-1型热导式自动量热计研究了35℃下NBS氧化异丙醇及环己醇2个反应体系,计算了反应速率常数,对反应的动力学及其机理提出了较合理的解释.     

聚对苯二甲酸丙二醇酯的甲醇解聚研究

在高压反应器中研究了聚对苯二甲酸丙二醇酯的甲醇解聚反应规律，考察了反应温度、时间等对解聚反应的影响。结果表明，单体收率随反应温度的升高、反应时间的延长而增加；利用凝胶色谱分析了反应后固体产物的组成，利用羧甲基浓度随反应时间的变化建立了动力学方程，计算得到解聚反应的活化能为87.8kJ/mol。     

硅胶负载的亚胺环钯催化剂的制备、表征及催化性能

利用SiO2表面硅羟基与有机硅烷作用制得氨基化SiO2,再与邻甲氧基苯甲醛反应,可得到键合在SiO2微粒表面的席夫碱配体,该配体与Li2PdCl4甲醇溶液反应得到SiO2负载的亚胺环钯催化剂.采用傅里叶变换红外光谱、X射线固体粉末衍射和X射线光电子能谱等手段对催化剂进行了表征,并用于催化碘代苯(PhI)与丙烯酰胺(AM)反应生成反式-肉桂酰胺的反应中,考察了溶剂、温度、原料比、缚酸剂及其用量、催化剂用量和反应时间对催化性能的影响,从而得到适宜的反应条件,并探讨了反应机理.     

HCN + OH→CN + H2O反应理论研究

The reaction path of the reaction HCN + OH→ CN + H2O was traced with Fukui's theory of intrinsic reaction coordinate by using ab initio MO method (at UMP4/6-31G** level) with gradient technique. On this basis, the dynamics properties along the reaction path was investigated by reaction path Hamiltonian theory. The rate constants of this reaction at different temperatures were calculated by conventional and variational transition state theory with tunneling correction. The theoretically calculated rate constants are in good agreement with experimental results, this shows that the title reaction is an one step, direct reaction.     

金属醋酸盐催化合成聚丁二酸乙二醇酯预聚体和碳酸二甲酯

研究了醋酸盐催化碳酸乙烯酯（EC）和丁二酸二甲酯（DS）同时合成聚丁二酸乙二醇酯 (PES) 预聚体和碳酸二甲酯(DMC)的耦合反应新工艺。 采用气相色谱-质谱联用定性分析馏分组成;红外光谱、核磁共振表征了预聚物的结构;采用乌式粘度计测试了预聚物的特性粘数;气相色谱定量测定馏分碳酸二甲酯的收率以考察耦合反应的进度。 以对该反应催化效果最佳的无水醋酸锂为催化剂考察了物料配比、反应温度、反应时间、催化剂用量对耦合反应的影响,结果表明,最佳的工艺条件为：反应温度195～200 ℃,n(EC)∶n(DS)=2∶1,n(cat)∶n(EC+DS)=0.02∶1,反应时间为2 h,耦合反应所得的DMC收率为48.0%,聚丁二酸乙二醇酯预聚物的特性粘数为0.3787。     

聚2,2-二甲基三亚甲基碳酸酯与壳寡糖的接枝共聚反应研究

用新戊二醇和三光气为原料,反应生成2,2-二甲基三亚甲基碳酸酯.再以四氢呋喃为溶剂,酶为催化剂引发聚2,2-二甲基三亚甲基碳酸酯（PDTC）与壳寡糖接枝生成接枝共聚物.研究了温度、时间、配比对接枝共聚物的产率和分子量的影响.就产率而言,最佳反应条件是60℃、-NH2/DTC的摩尔比值为1∶10、36 h、DTC/酶的质量比值为200;就重均分子量而言,最佳反应条件是60℃、-NH2/DTC摩尔比为1∶10、36 h、DTC/酶质量比值为150.对产品进行红外光谱、凝胶色谱与溶解性能测试.