HMS和NaY固载酒石酸钛配合物的研究

利用化学键合和“瓶中造船”方法,成功地将酒石酸钛配合物接枝到HMS(heragonal mesoporous silicas)上或包络合于微孔NaY内.FT-IR表征表明酒石酸钛在HMS上是通过与载体表面羟基发生交换作用而被固载的;在NaY载体上则是通过包络合被封装在载体的超笼内.UV-Vis可见漫反射表征表明两类固载型催化剂有着相似的钛配位环境.在催化肉桂醇环氧化反应中,HMS键合型催化剂的反应转化率比NaY包络型催化剂的高;但后者在环氧化选择性上要高于前者.回收样品的重复使用实验结果表明,两类固载型催化剂在重复使用过程中均存在不同程度的失活.     

沸石催化剂上醇的醚化反应

研究了乙醇，正丁醇，仲丁醇和正戊醇有ＺＳＭ－５和Ｂｅｔａ沸石上的醚化反应。用ＮＨ３－ＴＰＤ和ＩＲ测定了ＺＳＭ－５沸石的表面酸性，讨论了沸石表面Ｂ酸和Ｌ酸和与醚化活性的关系。结果表明，乙醇的脱水反应既可以在Ｂ酸中心上进行，也可以在Ｌ酸中心中心上进行，既可以在强酸中心上进行，亦可以在弱酸中心上进行。     

三异丙氧钐催化下醇的选择性乙酰化反应

本文报道了三异丙氧钐(5%)催化下，以乙酸乙酯为乙酰化试剂醇的选择性乙酰化反应。此法操作简便，产率良好。     

Acridin-9-ylmethoxycarbonyl （Amoc）： A New Photochemically Removable Protecting Group for Alcohols

Synthesis and photochemistry of acridin-9-ylmethoxycarbonyl(Amoc)as a new photochemically removableprotecting group for alcohols were described.Three carbonates of alcohols 1—3 were synthesized throughcondensation of 9-hydroxymethylacridine and chloroformates of alcohols,including benzyl alcohol,phenethylalcohol and one galactose derivative.The photolysis of protected alcohols can efficiently release the correspondingalcohol in the efficiencies(Q_(u1)ε)of 100—200(quantum yield Q_(u1)=0.011—0.023,and molar absorptivity ε=9.1×10~3—9.8×10~3 mol~(-1)·L·cm~(-1))under 360 nm light.     

Catalytic Preparation of Optically Active 1,1′—Binaphthalene—2,2′—Diol by Chiral Benzoimidazole—Cu（Ⅱ）Complex

Inthepastseveraldecades ,muchattentionhasbeenpaidtoopticallyactive ,C2 asymmetric1,1′ bi naphthalene 2 ,2′ diolanditsderivativesbecauseoftheirapplicationininducingchiralityinasymmetricsynthesis[1,2 ] .Enantiomericallypure1,1′ binaphtha lene 2 ,2′ diolhasbeen preparedbymanymethodsrangingfromtheclassicalresolutionviacrystalliza tionofthediastereoisomericsalts[3] toasymmetricox idativecoupling[4～ 6 ] .However ,theuseofexpensivechiralreagentsandthetediousnessoftheprocessessetalimitontheuseof…     

多相催化剂的MOVS制备方法

介绍了非均匀相催化剂的ＭＯＶＳ制备方法，以该法制得的ＭｏＯ３催化剂在甲醇选择氧化制甲醛、ＣＯ加氢制高级和喹啉加氢脱氮中均显示出常规催化剂更为优异的催化性能，并探讨了ＭＯＶＳ催化剂的内在特性与催化性能的关系。     

Synthesis and Characterization of Fluoro- and Chloro- bimetallic Alkoxides as Precursors for Luminescent Metal Oxide Materials via Sol-Gel Technique

Heterobimetallic alkoxides are broadly recognized as versatile precursors for luminescence materials, and efforts are being made to develop novel routes by applying the concept of geometrical molecular design, for their synthesis and to design a single source precursor suited to photoluminescent materials. Novel and new series of bimetallic alkoxides has been prepared by metathesis route. They exhibit a lower sensitivity towards hydrolysis and so they are easier to handle as compared to other alkoxides. All the compounds were characterized by elemental analysis, FT-IR and multinuclear NMR spectroscopies. FT-IR revealed that the molecular structure of these metal alkoxides was retained to a large extent in 4 ： 1 halogenated alcohol-benzene solution. The heteronuclear NMR spectroscopy provided useful information about chemical shifts for better understanding the likely structure based on interactions with their coordinate metals. The mass spectra show similar types of fragmentation pattern. SEM-EDS analyses showed consistency with the formulation. XRD patterns show an enhanced homogeneity at high temperature. TGA measurements show that thermal decomposition occured in steps that depended entirely on the chemical compositions and the synthesis routes. SEM observation reveals that the morphology and particle size strongly depend on synthesis routes for their precursors.     

带手性酰胺醇侧链的1，5－二氮环辛烷的合成

用手性α－氨基醇和氯乙酰氯作用得到的手性酰胺醇（2a－2f）和1，5－二氮 环辛烷反应，合成了带手性侧臂的1，5－二氮环辛烷衍生物N，N’-二[（S）／（ R）－N－（1－羟甲基羟基）－乙酰胺－2]－1，5－二氮环辛烷（1a－1f）。     

二茂钛苄氧基衍生物的合成及性质研究

Ｃｐ２ＴｉＣｌ２及（ＭｅＣｐ）２ＴｉＣｌ２在Ｅｔ３Ｎ或ＮａＮＨ２存在下与苄醇类化合物反应，高产率地合成了６个未见文献报道的二茂钛（Ⅳ）苄氧基衍生物，甲基二茂钛（Ⅳ）苄氧基化合物，经元素分析，ＨＮＭＲ和ＩＲ光谱确定了化合物的结构，并对其部分性质进行了讨论。     

K-Mo基催化剂的表面酸性与其合成醇选择性

对500℃和800℃焙烧制得的氧化态K－MoO3／γ－AlO3，K－MoO3／SiO2及非负载K－Mo催化剂进行硫化后，测试其合成醇活性．结果表明500℃焙烧制得的负载型催化剂显示较高的合成低碳烃活性和较低的合成低磷醇选择性，经800℃焙烧后，合成低磷醇的选择性大幅度提高．500℃焙烧的非负载K－Mo催化剂显示较高的合成醇选择性，经800℃焙烧后，促碳醇的选择性保持不变．用氨的吸附及TPD方法测定了各样品的酸性，并与催化剂活性对照，发现催化剂酸性越强，酸量越大，则其合成醇选择性越低．催化剂上的乙醇分解实验证实，催化剂的酸量大小与它的醇分解活性成正变关系，这些结果说明催化剂酸性对其合成醇性能有直接的影响．