钒钼杂多酸盐相转移催化环戊烯氧化制备戊二醛

设计合成了一系列含高价态钼、钒等金属的杂多酸类相转移催化剂,用于催化环戊烯(CPE)氧化制备戊二醛的反应,筛选出催化活性最优的咪唑基钼钒酸盐催化剂[C₄H₉N₂C₃H₃(CH₃)]₅VMo₇O₂₆,并对溶剂种类、H₂O₂用量、催化剂用量、反应温度、时间等进行了条件优化.在优化的反应条件[V(乙酸乙酯)∶V(水)=4∶1,n(Cat.)∶n(H₂O₂)∶n(CPE)=1∶170∶41.6,50℃,6 h]下,得到了88.7%的环戊烯转化率和62.1%的戊二醛选择性,并且催化剂在经过7次循环使用后仍能保持较高的催化活性.     

新型金属-双二硫杂戊烯(M-BDT)配合物的合成、表征及X射线的指标化

合成了4个新型NiBDT配位化合物,BDT为具有9个S原子的杂戊烯.元素分析、IR谱、UV谱确定这4个新配合物的化学式分别为[(CH₃)₄N]₂[Ni(C₅S₉)₂](1),[(C₂H₅)₄N]₂·[Ni(C₅S₉)₂](2),[(C₄H₉)₄N]₂[Ni(C₅S₉)₂](3),[(C₆H₅)(CH₃)₃N]₂[Ni(C₅S₉)₂](4).采用Ito法对配合物1的X射线粉末图进行了指标化,确定该晶体属单斜晶系,简单晶格,晶胞参数:a=0.680nm,b=0.714nm,c=2.302nm,γ=111.4°,Z=2.     

有机磷杀虫剂的研究——Ⅶ.某些苯基对位取代硫代膦酸酯的合成

1.制备一些新型的硫代膦酰氯,其中R'为C₆H₅,R"为C₂H₅O,C₂H₅,(CH₃)₂N,(C₂H₅)₂N,C₂H₅S等。     

HEDP与Fe(Ⅲ)配位化合物的制备和性质研究

制备了K₃[Fe(C₂H₅P₂O₇)₂]·4.5H₂O和K₃[Fe(C₂H₆P₂O₇)₂(OH)₂]·3H₂O两种固体配合物,用化学分析、穆斯堡尔谱、红外光谱、差热热重分析和电导测定等研究了它们的性质,推测了配合物的结构。     

新型双苯并环己酮芳亚胺镍(Ⅱ)催化降冰片烯与甲基丙烯酸丁酯共聚合

采用自制的新型双苯并环己酮芳亚胺镍催化剂双苯并环己酮-2,6-二甲基苯亚胺镍(Ⅱ)(Ni{C₁₀H₈(O)C[2,6-C₆H₃(CH₃)₂N]CH₃}₂, C1)和双苯并环己酮-2,6-二氯苯亚胺镍(Ⅱ)(Ni{C₁₀H₈(O)C[2,6-C₆H₃Cl₂N]CH₃}₂, C2)与三五氟苯硼[B(C₆F₅)₃]结合, 在一定的反应条件下可高效催化降冰片烯(NB)与甲基丙烯酸正丁酯(n-BMA)的乙烯基加成共聚合. 提出了催化聚合时存在的可能失活机理; 研究了不同单体投料比对催化活性、 产率及产物性能的影响. 根据Kelen-Tüdõs方法分别估算出2种单体在不同催化体系下的竞聚率, 即当催化体系为C1/B(C₆F₅)₃时, 竞聚率r_n-BMA=0.02, r_NB=16.28, r_NB·r_n-BMA=0.32; 当催化体系为C2/B(C₆F₅)₃时, r_n-BMA=0.01, r_NB=64.83, r_NB·r_n-BMA=0.65. 结果表明, 2种单体在2种体系催化下均为无规共聚合.     

有机-无机型杂多酸相转移催化氧化脱硫性能研究

合成了四种有机-无机型杂多酸催化剂,包括[π-C₅H₅NC₁₆H₃₃]₃[PW₄O₁₆],[π-C₅H₅NC₁₆H₃₃]₃[PMo₄O₁₆],[π-C₅H₅NC₁₂H₂₅]₃[PW₄O₁₆]和[π-C₅H₅NC₁₂H₂₅]₃[PMo₄O₁₆]. 以有机硫的正辛烷溶液为模拟油品,H₂O₂为氧化剂,乙腈为萃取剂,在两相体系中,考察了上述四种催化剂对模拟油品中二苯并噻吩(DBT)氧化脱硫的催化活性. 结果表明,[π-C₅H₅NC₁₆H₃₃]₃[PW₄O₁₆]具有最佳的催化活性. 采用[π-C₅H₅NC₁₆H₃₃]₃[PW₄O₁₆]进行后续研究发现,反应完毕,[π-C₅H₅NC₁₆H₃₃]₃[PW₄O₁₆]以沉淀的形式析出,可以重复利用且脱硫效果很好. 研究表明,上述有机-无机型杂多酸属于相转移催化剂,氧化脱硫反应体系属于反应控制相转移催化体系. 在相同实验条件下,由于电子云密度和空间位阻效应共同的作用,DBT、噻吩(TH)、苯并噻吩(BT)和4,6-二甲基二苯并噻吩(4,6-DMDBT)脱硫由易到难的顺序为DBT >4,6-DMDBT >BT >TH,并分别通过GC-MS分析确定它们的氧化产物. 将[π-C₅H₅NC₁₆H₃₃]₃[PW₄O₁₆]进一步应用于柴油氧化脱硫,其中硫含量由355 mg/kg (mg/kg等同于ppmw)降至26 mg/kg,去除率达92.7%. 利用上述四种有机-无机型杂多酸作催化剂,研究DBT氧化反应过程动力学,确定DBT的表观反应级数均为一级,表观活化能为47.9～55.4 kJ/mol.     

中国乌头之研究——Ⅵ.雪上一枝蒿的生物碱(2)

从云南省昭通县产的雪上一枝蒿中共分得生物碱五种,其中三种为已知物,即烏头碱、次岛头碱和一枝蒿乙素,另二种为新生物碱,暂名为一枝蒿戊素和己素。一枝蒿戊素的分子式为C₂₄H₃₉O₆N,其示性式为C₁₉H₂₂(OH)₃(OCH₃)3-(N·C₂H₅);一枝蒿己素的分子式为C₂₄H₃₉O₇N,其示性式为C₁₉H₂₁(OH)₄(OCH₃)₃(N·C₂H₅);另从云南省东川县出产的雪上一枝蒿中,尚分得一新生物碱,暂称为一枝蒿庚素,分子式为C₂₁H₃₁O₃N,其示性式为C₁₉H₂₄(:O)(OH)₂(N·C₂H₅)。     

Tetrabutylammonium salts of tritransition-metal-substituted A-α-tungstogermanate:Halogen-free and single-component catalysts for the coupling reaction of carbon dioxide and epichlorohydrin

The green synthesis of chloropropylene carbonate via the coupling reaction of carbon dioxide and epichlorohydrin had been achieved using halogen-free and single-component catalysts tetrabutylammonium salts of tritransition-metal-substituted A-α-tungstogermanate [（n-C₄H₉）₄N]₃H₇GeW₉M₃（H₂O）₃O₃₇（M = Cu^Ⅱ,Ni^Ⅱ,Co^Ⅱand Mn^Ⅱ） without any solvent.The catalytic activity was significantly depended on the transition metal introduced in polyoxometalates.[（n-C₄H₉）₄N]₃H₇GeW₉Mn₃（H₂O）₃O₃₇ exhibited the highest catalytic activity with 94.9%conversion for epichlorohydrin and 98%selectivity for chloropropylene carbonate in 3 h.Plausible mechanism was proposed based on the results.     

含有金刚烷胺的多金属氧酸盐的合成和抗流感病毒活性

以金刚烷胺和1∶10 (Ln∶W), 1∶13(Ni或Mn∶V)系列多金属氧酸盐为原料, 合成了化学式分别为K₄(C₁₀H₁₈N)₅CeW₁₀O₃₆•2H₂O (APOM-5), K₄(C₁₀H₁₈N)₅PrW₁₀O₃₆•2H₂O (APOM-6), K₃(C₁₀H₁₈N)₄NiV₁₃O₃₈•H₂O (APOM-12)和K₃(C₁₀H₁₈N)₄MnV₁₃O₃₈•H₂O (APOM-13)的四种新的多金属氧酸盐, 并通过元素分析、IR光谱及¹H NMR谱对其结构进行了表征. 在狗肾(Madin-Darby canine kidney, MDCK)细胞内, 对合成化合物进行了抗流感病毒A和B的活性研究. 发现APOM-13对流感病毒A, B两型均有明显的抑制活性, 而APOM-12只在浓度较高时对流感病毒A, B两型有抑制活性, 低浓度时, 活性不明显. APOM-5,6对A型流感病毒有效, 但对B型流感病毒抑制活性不明显. 另外发现APOM-12和APOM-13对流感病毒感染MDCK细胞病变效应(CPE)具有明显抑制作用, 且浓度越大抑制作用愈明显.     

系列Ln(Ⅲ)配位聚合物(Ln=Eu,Sm,Tb,Pr,Gd)的合成及其荧光分析

采用水热法合成了4个具有1D结构的Ln(Ⅲ)配位聚合物,[Eu₂(C₉H₇O₂)₆(C₉H₇O₂H)(C₂H₅OH)]n(1)、[Sm(C₉H₇O₂)₃]n(2)、[Tb(C₉H₇O₂)₃]n(3)和[Gd(C₉H₇O₂)₃]n(4)(C₉H₈O₂=肉桂酸)。 通过X射线单晶衍射确定了它们的结构。 这4个Ln(Ⅲ)配合物中,Ln(Ⅲ)的配位数均为9,桥配体均为肉桂酸根,但其配位方式有差异。 对配合物进行了IR、UV-Vis-NIR和荧光光谱等表征。 分析了各配合物的荧光发射,结果表明,在可见区,配合物1发射较明显的红光,配合物2、3发射绿光,配合物4发射蓝光,但很弱。 讨论了具有刚柔相混杂性质的肉桂酸配体对配位聚合物的构筑及稀土离子发光的影响。     

磷钨反应控制相转移催化剂的制备及表征

制备了三缺位Keggin型反应控制相转移催化剂[C7H7(CH3)3N]9PW9O34(记为Q9PW9),利用FT-IR、31P NMR、XRD和TG对催化剂进行了表征,并确定了反应的催化活性中心。 分析结果表明,催化剂Q9PW9在反应后其结构仍然得到了很好的保持,反应中形成的[C7H7(CH3)3N]9PW9O34 (O2)x活性中心使催化剂具有反应控制相转移功能。以H2O2水溶液为氧化剂,在氧化苯甲醇制备苯甲醛反应中,发现该催化剂具有良好的催化活性。当H2O2与苯甲醇的物质的量比为0.9时,苯甲醇的转化率为86.2%,苯甲醛的选择性≥99%。反应结束后催化剂以沉淀的形式析出,催化剂的回收率保持在86%左右。将催化剂循环使用三次,苯甲醇的转化率和催化剂的回收率均无明显变化,说明Q9PW9具有良好的稳定性。     

Heteropolymolybdate as a New Reaction-controlled Phase-transfer Catalyst for Efficient Alcohol Oxidation with Hydrogen Peroxide

Aldehydes are very important raw materials or intermediates, which have widespread applications in the perfumery, pharmaceutical, dyestuff and agrochemical industries1. Oxidation of alcohol is one of the most frequently used synthetic reactions in the lab…     

钨过氧酸盐离子液体催化过氧化氢氧化苯甲醇制苯甲酸

用甲基三辛基氯化铵和钨酸钠一步法合成甲基三辛基季铵钨酸盐离子液体[(CH3)N(n-C8H17)3]2W2O11,以该离子液体为催化剂,在无反应溶剂条件下催化过氧化氢氧化苯甲醇生成苯甲酸。 考察了反应温度、催化剂用量以及氧化剂过氧化氢用量对苯甲酸产率的影响。 确定优化条件：反应温度70 ℃,苯甲醇用量5 mmol,催化剂用量是底物的0.4%(摩尔分数),30%过氧化氢用量2 mL,苯甲醇的转化率可达99%,苯甲酸选择性为98%。 该方法具有反应条件温和、产率高和选择性好的优点。     

Ru/ZrO2·xH2O催化剂催化肉桂醛选择性加氢制肉桂醇

采用共沉淀法制备了7.5%Ru/ZrO2·xH2O催化剂,运用N2物理吸附-脱附法、X射线衍射、X射线光电子能谱和高分辨透射电子显微镜等技术对催化剂进行了表征,并用于催化肉桂醛选择加氢制肉桂醇反应中,考察了温度、H2压力和溶剂对肉桂醛转化率和肉桂醇选择性的影响.结果表明,肉桂醛转化率随着温度或H2压力的升高而升高,而肉...     

A New Reaction-controlled Phase-transfer Catalyst System

A new reaction-controlled phase-transfer catalyst system was designed and synthesized.In this system, heteropolytungstate [C7H7N(CH3)3]9PW9O34 was used for catalytic epoxidation of cyclohexene with H2O2 as the oxidant. The conversion of H2O2 was 100% and the yield of cyclohexene oxide was 87.1% based on cyclohexene. Infrared spectra showed that both fresh catalyst and the recovered catalyst do have completely same absorption peak, indicating the structure of catalyst is very stability and can be recycled.     

Factors affecting the catalytic epoxidation of olefins by iron porphyrin complexes and H2O2 in protic solvents

The catalytic epoxidation of cyclohexene by iron(III) porphyrin complexes and H2O2 has been investigated in alcohol solvents to understand factors affecting the catalyst activity in protic solvents. The yields of cyclohexene oxide and the Fe(III/II) reduction potentials of iron porphyrin complexes were significantly affected by the protic solvents, and there was a close correlation between the product yields and the reduction potentials of the iron porphyrin catalysts. The role of alcohol solvents was proposed to control the electronic nature of iron porphyrin complexes that determines the catalyst activity in the epoxidation of olefins by H2O2. We have also demonstrated that an electron-deficient iron porphyrin complex can catalyze the epoxidation of olefins by H2O2 under conditions of limiting substrate with high conversion efficiency in a solvent mixture of CH3OH and CH2Cl2.     

Lacunary Keggin Polyoxotungstate as Reaction-controlled Phase-transfer Catalyst for Catalytic Epoxidation of Olefins

A new reaction-controlled phase-transfer catalyst system, lacunary Keggin polyoxotungstate [C7H7N(CH3)3]9PW9O34 has been synthesized and used for catalytic epoxidation of olefins with H2O2 as the oxidant. Infrared spectra were used to analyze the behavior of the phase transfer of catalyst. In this system, the catalyst not only can act as homogeneous catalyst but also as heterogeneous catalyst to be easily filtered and reused. The epoxidarion reaction is clean and exhibits high conversion and selectivity as well as excellent catalyst stability.     

Preparation of high purity 1,2-diols by catalytic oxidation of linear terminal alkenes with H202 in the presence of carboxylic acids under solvent-free conditions

The oxidation of terminal alkenes was smoothly catalyzed by a recyclable and environmentally friendly catalytic system: [(C18H37)2N(CH3)2]3[PW4O16]/H2O2/formic acid. This new catalytic system is not only capable of catalyzing oxidation of terminal alkenes with a phase-transfer character, but also under solvent-free conditions, avoiding the use of chlorinated solvents. Many different kinds of terminal alkenes could be converted to the corresponding 1,2-diols of high purity in high yields. The catalyst could be easily separated and reused after reaction. Both fresh and used [(C18H37)2N(CH3)2]3[PW4O16] catalyst was characterized by Raman and FTIR.     

Mn-Al和Cu-Mn-Al复合氧化物催化苯甲醇选择氧化反应

用溶胶-凝胶法制备了不同组成的Mn-Al和Cu-Mn-Al复合氧化物两组催化剂,用于苯甲醇选择氧化反应.用X射线衍射(XRD)、N2物理吸附(BET)、扫描电镜(SEM)、H_2程序升温还原(H_2-TPR)、O_2程序升温脱附(O_2-TPD)和X射线光电子能谱(XPS)技术对催化剂进行了结构表征,考察了催化剂组成对催化活性的影响.结果表明:以甲苯为溶剂,O_2为氧化剂,353 K反应5 h,Mn_2Al和Cu_(0.3)Mn_(0.7)Al_2催化剂上的苯甲醇转化率分别为36.6%和40.9%,苯甲醛选择性均为100%.进一步研究表明:催化剂活性与其H2还原性和O_2吸附性有关,高活性的催化剂吸附氧多,生成的活性氧易参与反应.     

Oxidative desulfurization of dibenzothiophene with hydrogen peroxide catalyzed by selenium(IV)-containing peroxotungstate

With stoichiometric H(2)O(2) as oxidant, dibenzothiophene (DBT) is oxidized to its corresponding sulfone with high efficiency, catalyzed by a sub-valence heteronuclear peroxotungstate, [C(18)H(37)N(CH(3))(3)](4)[H(2)Se(IV)(3)W(6)O(34)], under mild biphase conditions and the catalyst shows remarkable selectivity of catalytic oxidation towards DBT, cinnamyl alcohol and quinoline.