AlCl3/MCM-41催化剂上桥式四氢双环戊二烯异构化反应

 分别采用介孔 MCM-41 和 SiO2 为载体制备了固载化 AlCl3 催化剂, 考察了其催化桥式四氢双环戊二烯异构化生成挂式四氢双环戊二烯反应性能. 结果表明, 180 °C 时 AlCl3/MCM-41 催化剂上挂式四氢双环戊二烯选择性可达 95.7%, 而在 AlCl3/SiO2 上仅为 86.3%. 采用 N2 吸附-脱附、Hammett 指示剂法、吡啶吸附红外光谱和化学分析等方法对催化剂进行了表征. 结果表明, AlCl3/MCM-41 催化剂较弱的表面酸性和一维孔结构有利于挂式四氢双环戊二烯的生成.     

双环戊二烯加氢异化合成金刚烷

采用固定反应器考察了双环戊二烯连续催化加氢合成桥式氢双环戊二烯反应性能,筛选出具有良好催化性能的23％Ni/γ-AI2O3催化剂。以桥式四氢双环戊二烯为原料,采用不同类型的沸石催化剂研究了金刚烷的合成,并考察了沸石骨架阳离子改性和表面负载过渡金属等对其催化性能的影响。在n(cat)/n ( reactant)=0.25,p(H2)=1.1MPa,θ=250℃,t=3h的条件下,采用三元负载型催化剂0.8%Pt-0.2%Re-3%Co/ReUSY 可得到收率为27．7％的金刚烷。     

双环戊二烯加氢异构化合成金刚烷

 采用固定床反应器考察了双环戊二烯连续催化加氢合成桥式四氢双环戊二烯反应性能,筛选出具有良好催化性能的23％Ni／γ－Al2O3催化剂．以桥式四氢双环戊二烯为原料,采用不同类型的沸石催化剂研究了金刚烷的合成,并考察了沸石骨架阳离子改性和表面负载过渡金属等对其催化性能的影响．在n（cat）／n（reactant）＝0．25,p（H2）＝1．1MPa,θ＝250℃,t＝3h的条件下,采用三元负载型催化剂0．8％Pt－0．2％Re－3％Co／ReUSY可得到收率为27．7％的金刚烷．     

固载化AlCl_3催化剂上α-蒎烯异构化反应

分别以SiO2和γ-Al2O3为载体采用两步气相法制备了固载化AlCl3催化剂,并首次将其用于α-蒎烯液相异构化反应.结果表明,该催化剂对α-蒎烯异构化反应具有非常高的催化活性,其中AlCl3/SiO2催化剂在40oC反应时α-蒎烯转化率和主产物(莰烯、柠檬烯和异松油烯)选择性分别为98.4%和93.7%;AlCl3/γ-Al2O3催化剂活性更高,在30oC反应时,即可获得95.5%的α-蒎烯转化率和94.4%的主产物选择性.固载化AlCl3催化剂的高活性与其强酸性有关.     

一种高稳定性合成直链烷基苯催化剂

以具有中、大双孔结构的γ-Al2O3为载体制备了固载化AlCl3催化剂,并在悬浮床反应器中考察了其苯与1-C1=2烷基化反应活性。结果表明,该催化剂具有较高的转化率、选择性和催化稳定性。在1000小时连续反应过程中,烯烃转化率高于94%,单烷基苯选择性达到92%,其中2-苯基异构体选择性为42%。     

γ-Al2O3改性对AlCl3/γ-Al2O3催化剂性能的影响

采用HCl和NaOH改性γ-Al2O3载体制备AlCl3/γ-Al2O3固载催化剂,用吡啶-FTIR和吡啶-TPD技术分析了催化剂的表面酸性(酸中心类型、酸强度和酸量),并以1-癸烯齐聚作为探针反应,研究了催化剂的稳定性以及催化剂对聚合反应的影响.结果表明,催化剂含有两种酸类型,即Lewis酸和Br(o)nsted酸,与未改性的催化剂相比,氢氧化钠改性载体制备的催化剂,酸量增大了47％,催化剂催化1-癸烯的齐聚反应活性增加了11.4％;而经盐酸改性制备的催化剂酸量增大112％,催化剂的活性增加了33.6％.酸强度依AlCl3/γ-Al2O3,AlCl3/γ-Al2O3(NaOH),AlCl3/γ-Al2O3 (HCl)的顺序增强.     

γ-A12O3改性对AlCl3/γ-Al2O3催化剂性能的影响

本文中,采用HCl和NaOH改性 γ-A12O3载体制备AlCl3/γ-A12O3固载催化剂,用吡啶-FTIR和吡啶-TPD技术分析了催化剂的表面酸性(酸中心类型、酸强度和酸量),并以1-癸烯齐聚作为探针反应,研究了催化剂的稳定性以及催化剂对聚合反应的影响。结果表明,催化剂含有两种酸类型,即Lewis酸和Brönsted酸,与未改性的催化剂相比,氢氧化钠改性载体制备的催化剂,酸量增大了47%,催化剂催化1-癸烯的齐聚反应活性增加了11.4%;而经盐酸改性制备的催化剂酸量增大112%,催化剂的活性增加了33.6%。酸强度依AlCl3/γ-A12O3,AlCl3/γ-Al2O3(NaOH),AlCl3/γ-Al2O3(HCl)的顺序增强。     

固载离子液体刷/过氧磷钨酸盐催化剂催化H2O2选择性氧化硫醚

以二氧化硅为载体,合成了一种新型的双层离子液体刷固载过氧磷钨酸盐催化剂.采用元素分析、IR和SEM-EDAX等手段对催化剂进行了表征.室温下,考察了该催化剂催化30％(质量分数)H2O2溶液选择性氧化硫醚为亚砜或砜的催化性能.结果表明,该催化剂具有很高的催化活性和选择性.采用1.1倍H2O2时,反应选择性地生成亚砜,仅...     

CoPc/Al2O3催化剂的制备、表征及其催化氧化性能

用原位合成法,以酸性Al2O3为载体,酞菁类金属大环配合物为活性组分,合成出CoPc/Al2O3新型环氧化催化剂,红外、紫外-可见、热重分析及XPS证实能够利用该法在Al2O3上固载CoPc催化剂,且催化剂稳定性增加,不易流失.以分子氧为氧源,异丁醛为共还原剂考察CoPc/Al2O3催化剂对环己烯的催化环氧化活性及催化剂的重复使用情况.结果表明,与均相催化剂相比,固载后环己烯转化率增加了8%,环氧环己烷选择性增加了23%,催化剂重复使用4次后,活性仅降低4%.     

双环戊二烯苯酚树脂的合成新工艺

以双环戊二烯（DCPD）和苯酚为原料,甲磺酸为催化剂,合成了双环戊二烯苯酚树脂。适宜工艺条件:苯酚与DCPD摩尔比为5、反应温度120 ℃、反应时间5 h、催化剂质量分数为1.5%,收率89%。所得的双环戊二烯苯酚树脂（DPR）经催化加氢法在H2气压力1.5 MPa、催化剂Pd/Al2O3用量为原料质量分数的0.5%、反应温度80 ℃条件下对树脂进行脱色处理。 得到浅黄色双环戊二烯苯酚树脂,收率89%,经IR和1H NMR表征分析其为目的产物,产物指标达到国际同类产品的质量标准。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.