室温固相法合成席夫碱钍(Ⅳ)金属配合物

以水杨醛或邻香草醛、2,6-二氨基吡啶和硝酸钍为原料,采用室温固相法合成了2,6-二氨基吡啶双席夫碱钍(Ⅳ)配合物[ThL1(NO3)2](NO3)2.H2O,[ThL2(NO3)2](NO3)2.H2O。通过元素分析、EDTA滴定法、红外光谱、紫外光谱、热分析方法对配合物的组成和结构进行了表征。结果表明,金属钍与席夫碱配体中的亚氨基上的氮原子、酚氧基上的氧原子以及硝酸根离子形成了配位数为8的配合物。配合物的热分解过程包括失水、配体的氧化分解和氧化为氧化钍。     

2-羟基-1-萘甲醛缩2,6-二氨基吡啶钍的席夫碱配合物的合成及其抑菌活性的研究

合成了2-羟基-1-萘甲醛缩2,6-二氨基吡啶席夫碱配体L,与硝酸钍反应,生成配合物ThL,研究了配体L和配合物ThL的抗菌活性。结果表明,配体L和配合物ThL对枯草杆菌、大肠杆菌、乳酸菌有良好的抑制作用,配合物ThL的抑菌活性好于配体L,最佳抑菌活性浓度是5 mmol/L。     

双酚大环硝酸铽配合物的合成及晶体结构

以2-羟基-1,3-丙二胺和2,6-二甲酰基-4-R-苯酚（R=CH3、Cl）通过Pb2＋作模板进行缩合反应制备了四亚胺双酚双核Pb（II）配合物,再用硝酸Tb（III）置换Pb（II）离子,合成了单核Tb（III）配合物[Tb（III）（H4L）（NO3）2（H2O）]（NO3）.2（H2O）,最后再弱碱性条件下用三联吡啶置换其中的一个NO3-和一个H2O,得到目标配合物[Tb（H3L）（NO3）（C5H3N（C5H4N）2）]（NO3）.H2O,获得了单晶结构,并进行了晶体结构分析和系统物理表征。     

2,6-二乙酰基吡啶缩合苯磺酰肼铕配合物的合成及性质研究

合成了2,6-二乙酰基吡啶-苯磺酰肼Schiff碱(DAPBSH)及其与稀土Eu3+的配合物,采用元素分析、红外、核磁等表征手段确定了配体的结构,采用元素分析及热分析初步确定了配合物的结构Eu(DAPBSH)2(NO3)3·2H2O并对配合物的紫外、荧光性质做了初步研究。     

2,6-二[N-(1'-甲基-2'-羟乙基)氨甲酰基]吡啶镉(Ⅱ)配合物的合成、晶体结构及液膜传输性研究

以2,6-二[N-(1'-甲基-2'-羟乙基)氨甲酰基]吡啶为配体与Cd(NO3)2·4H2O反应,合成了一个单核镉(Ⅱ)配合物,通过元素分析、红外光谱、紫外光谱及X-射线单晶衍射法对其结构进行了表征。结构分析表明,该配合物属三斜晶系,P-1空间群,晶胞参数a=0.938 22(18)nm,b=0.944 74(19)nm,c=1.299 9(2)nm,α=105.687(7)°,β=95.154(6)°,γ=101.755(7)°。V=1.073 1(4)nm3,Z=2,Dc=1.757 g/cm3,μ=1.089 mm-1,F(000)=576.0。配合物的中心镉(Ⅱ)离子配位数为8,处于扭曲的四方反棱柱构型。考察了配体对Cd(Ⅱ)离子的液膜传输性,结果表明2,6-二[N-(1'-甲基-2'-羟乙基)氨甲酰基]吡啶可作为良好的Cd2+离子载体。     

[DyL_2(NO_3)_2]·bpy·CH_3OH·ClO_4的合成、晶体结构和荧光性能研究

以2,6-二(2-苯并咪唑)吡啶(L)和2,2′-联吡啶(bpy)为混合配体,与五水硝酸镝反应利用缓慢挥发法合成了一个镝(Ⅲ)配合物[DyL_2(NO_3)_2]·bpy·CH_3OH·ClO_4(1),并对其结构进行了X射线衍射表征、元素分析、红外和紫外光谱分析。配合物1属于三斜晶系,空间群P1。配位中心Dy(Ⅲ)通过丰富的超分子作用力构筑三维空间网络结构。由于配位原子的孤对电子参与大共轭π键与金属配位后使得配体荧光发射峰发生蓝移。     

二吡啶胺为配体的新型镍配合物的合成及结构

以2,2'-二吡啶胺(Hdpa)和对氨基苯甲酸钠(PABA为4-氨基苯甲酸阴离子)为原料,和氟化镍反应合成了一种新型的镍配合物[Ni(PABA)(Hdpa)2]F(CH3OH)。通过X-射线单晶衍射、红外光谱、元素分析、质谱(ESI),对该配合物进行了结构表征。晶体结构表明,该配合物为阴离子-阳离子型化合物。     

Eu(Ⅲ)、Tb(Ⅲ)配合物的制备、表征及荧光性能研究

以吡啶-2,6-二甲酸为起始原料合成了一种新型β-二酮配体4-(2-乙酰基-3-氧代丁基)吡啶-2,6-二甲酸甲酯(L),其结构通过红外光谱和核磁共振氢谱得以确定。同时制备了该配体与稀土离子Eu(Ⅲ)和Tb(Ⅲ)的配合物,通过元素分析、红外光谱确定了它们的组成结构,用荧光光谱研究分析了配合物Eu(L)3.2H2O和Tb(L)3.3H2O的光致发光性能。     

吡啶希夫碱铁配合物的合成与表征

用2,6-吡啶二甲醛和对甲苯胺反应,合成二亚胺吡啶类配体L(2,6-二[1-(4-甲基苯基)亚胺基]吡啶),采用室温挥发法制备配体L与过渡金属Fe(Ⅱ)的配合物,并对所合成的吡啶希夫碱铁配合物进行了红外光谱、元素分析等测试,用X-射线单晶衍射技术确定了配合物的晶体结构。结果表明:铁配合物属于三斜晶系,其空间群为P-1,中心铁离子为五配位,位于配体的三个氮原子和两个游离的氯离子组成的变形的的三角双锥的中心,同时通过分子间氢键可以连接成一维链状结构。     

N,N′-二(O-氨基吡啶)-3,6-二氧杂辛二酰胺轻稀土硝酸盐配合物的合成与表征

由轻稀土硝酸盐和开链冠醚N,N′-二(α-氨基吡啶)-3,6-二氧杂辛二酰氨(BDD)在非水介质中合成了组成为Ln(NO3)3@BDD@(H2O)n(M＝La～Eu,Pm除外,n＝1,2)的六种固体配合物.以元素分析,IR,1H NMR,摩尔电导及TG-DTA等对配合物进行了表征.结果表明,配体在配合物中以六齿方式进行配位.     

目标导向合成及差异导向合成在药物合成中的应用

介绍了目标导向合成和差异导向合成的基本概念,扼要阐述了目标导向合成在药物合成上的应用,着重综述了差异导向合成的固相有机合成法和液相有机合成法在合成有机小分子库以备药物筛选中的应用。认为差异导向合成在药物研究领域的作用必将变得更加重要。     

依替米贝合成新工艺的研究

依替米贝(Ezetimibe)是一种新型选择性胆固醇吸收抑制剂,在参考相关文献的基础上,以4-羟基苯甲醛、4-氟苯胺和氯化苄为原料一步合成得到N-(4-氟苯基)-4-苄氧基苯亚甲胺(化合物2),4-(4-氟苯甲酰基)丁酸与特戊酰氯反应成混酐后在氯化锂存在下直接和(S)-4-苯基-噁唑烷酮反应再经过CBS/BH3体系还原得到(4S)-3-[(5S)-5-(4-氟苯基)-5-羟基-1-氧代戊基]-4-苯基-2-噁唑烷酮(化合物4),经三甲基硅烷基保护羟基后直接和化合物2在TiCl2(OiPr)2催化下缩合后经三水合四丁基氟化铵催化环合和Pa/C催化氢化脱保护制得,总收率92.4%×91.6%×77.7%×85.3%=56%。最终产品和部分中间体经过熔点、MS和1H-NMR测定。该工艺路线不仅减少了关键原料的使用,提高了收率,同时也增强了有羟基保护基的中间体的稳定性,简化了反应操作,更加易于工业化。     

Methanol Synthesis

Abstract

Methanol is a basic industrial chemical that is produced in the United States at an annual rate of over one billion gallons [1]. It is used as a solvent in many industrial processes, as a starting material for the production of other compounds, notably formaldehyde, and as a freezing point suppressing agent for gasoline lines and window washing liquids, as well as for many other purposes. Traditionally, methanol has been produced by catalytic hydrogenation of carbon monoxide.     

Hydrothermal Synthesis

The underlying theory of hydrothermal synthesis is presented and the apparatus used is described. By way of illustration the determination of the solubility of quartz in superheated steam at high pressures and the determination of the compositions of coexisting gas and liquid phases in the system H₂O–Na₂O–SiO₂ at 400°C. are discussed.     

γ—（3,4—亚甲二氧基—苯基）丙基三乙氧基硅烷的合成

利用天然可再生资源黄樟油素与三乙氧基硅烷进行硅氢加成反应,合成了γ-(3,4-亚甲二氧基－苯基）丙基三乙氧基硅烷。合成操作简便,产率52％。用红外光谱对化合物进行了表征。     

δ-癸内酯的合成

采用廉价易得的己二酸二甲酯为原料 ,用金属钠在甲苯中进行Dieckmann酯缩合 ,加入DMF为溶剂在 80～ 85℃直接与溴代正戊烷反应生成 2 戊基 2 甲氧酰基环戊酮 (Ⅰ ) ,经过脱羧反应和Beayer-Villiger氧化反应得到δ 癸内酯 (Ⅲ ) ,产品纯度为w(δ 癸内酯 ) >98% (GC法 ) ,香气纯正。反应总产率达 48%。列出了各中间体的IR数据 ,最终产品由FT -IR、1 HNMR和EI-MS进行了结构确证     

Methanol Synthesis

Methanol is a basic industrial chemical that is produced in the United States at an annual rate of over one billion gallons [1]. It is used as a solvent in many industrial processes, as a starting material for the production of other compounds, notably formaldehyde, and as a freezing point suppressing agent for gasoline lines and window washing liquids, as well as for many other purposes. Traditionally, methanol has been produced by catalytic hydrogenation of carbon monoxide.     

微波辐射下1，5—苯并硫氮杂zhuo—β—内酰胺衍生物的合成

（4R）-苯基恶唑烷酮乙酰氯，1，5-苯并硫氮杂zhuo、三乙胺在微波辐射下反应得标题化合物。实验表明微波辐射大大加快了反应速率和提高了反应产率。     

硫代香叶醇的合成

以异戊烯醇为原料，经过卤化、硫代、缩合、水解等步骤合成了硫代香叶醇。反应操作分两大阶段进行：第一阶段2，6-二甲基-2，6-庚二烯基硫脲的合成；第二阶段硫代香叶醇的合成。通过水解、调节溶液的pH值、萃取、蒸馏得到产品，收率85％以上，质量分数95％，产品结构用IR确认。     

Methanol Synthesis

Methanol, like ammonia, is one of the key industrial chemicals produced by heterogeneous catalysis. As with the original ammonia catalyst (Fe/K/Al₂O₃), so with methanol, the original methanol synthesis catalyst, ZnO, was discovered by Alwin Mittasch. This was translated into an industrial process in which methanol was produced from CO/H₂ at 400?°C and 200 atm. Again, as with the ammonia catalyst where the final catalyst which is currently used was achieved only after exhaustive screening of putative “promoters”, so with methanol, exhaustive screening of additives was undertaken to promote the activity of the ZnO. Early successful promoters were Al₂O₃ and Cr₂O₃ which enhanced the stability of the ZnO but not its activity. The addition of CuO was found to increase the activity of the ZnO but the catalyst so produced was short lived. Current methanol synthesis catalysts are fundamentally Cu/ZnO/Al₂O₃, having high CuO contents of?~60?% with ZnO?~?30?% and Al₂O₃?~?10?%. Far from promoting the activity of the ZnO by incorporation of CuO, the active component of these Cu/ZnO/Al₂O₃ catalysts is Cu metal with the ZnO simply being involved as the preferred support. Other supports for the Cu metal, e.g. Al₂O₃, MgO, MnO, Cr₂O₃, ZrO₂ and even SiO₂ can also be used. In all of these catalysts the activity scales with the Cu metal area. The original feed has now changed from CO/H₂ to CO/CO₂/H₂ (10:10:80), radiolabelling studies having provided the unlikely discovery that it is the CO₂ molecule which is hydrogenated to methanol; the CO molecule acts as a reducing agent. The CO₂ is transformed to methanol on the Cu through the intermediacy of an adsorbed formate species. These Cu/ZnO/Al₂O₃ catalysts now operate at?~230° and between 50 and 100 atm. This important step change in the activity of methanol synthesis has resulted in a significant reduction in the energy required to produce methanol. The “step change” however has been incremental. It has been obtained on the basis of fundamental knowledge provided by a combination of surface science techniques, e.g. LEED, scanning tunnelling microscope, TPD, temperature programmed reaction spectroscopy, combined with catalytic mechanistic studies, including radiolabelling studies and chemisorption studies including reactive chemisorption studies, e.g. N₂O reactive frontal chromatography.