FeZSM-5沸石上乙苯的吸附态及氧化脱氢

ＦｅＺＳＭ－５吸附乙苯前后的ＩＲ，ＸＰＳ，ＥＳＲ及Ｍｏｓｓｂａｕｅｒ谱表明，乙苯分子的侧链和苯环与ＦｅＺＳＭ－５的活性以（以Ｆｅ为中心的结构单元）同时发生配位络合作用，减弱了乙苯分子侧链的α和β位Ｃ－Ｈ键，使其活化，在氧存在下易发生氧化脱氢反应生成苯乙烯，Ｆｅ（Ⅲ）是乙苯氧化脱氢的活性中心，尤其是骨架不饱和配位的Ｆｅ（Ⅲ）对活化乙苯分子起到了关键作用，碱金属平衡阳离子起到了助催化剂的作用，骨架Ｆｅ     

铁硅酸盐分子筛乙苯氧化脱氢催化性能研究—平衡阳离子性…

在８２３Ｋ和乙苯／Ｏ２＝１．０的条件下考察了乙苯在ＦｅＺＳＭ－５上的催化活性，比较了平衡阳离子性质，水热处理及Ｆｅ２Ｏ３的分散程度对乙苯氧化脱氢性能的影响，结合ＸＰＳ、ＥＳＲ及ＴＰＲ测试结果讨论了ＦｅＺＳＭ－５中铁的存在状态与乙苯氧化脱氢的关系，结果表明，ＦｅＺＳＭ－５催化剂上作为Ｌ酸中心的骨架Ｆｅ（Ⅲ），水热处理产生的高分散非骨架Ｆｅ（Ⅲ）和适当强度的碱中心共同构成了乙七氧化脱氢活性中心。     

改性FeZSM－5沸石上乙苯的吸附和扩散性质及氧化脱氢催化作用

用ＸＰＳ、ＤＲＳ及Ｍｏｓｓｂａｕｅｒ谱对水热处理改性的ＦｅＺＳＭ－５中Ｆｅ（Ⅲ）的化学状态进行了研究，并定量地考察了水热处理时间对骨架铁含量的影响，比较了不同水热处理时间及不同平衡阳离子交换的ＦｅＺＳＭ－５上乙苯的吸附及扩散性质。水热处理将使骨架铁从骨架析出，但析出的骨架铁并不阻塞孔道，而是高分散在分子筛的表面上，乙苯的吸附量随水热处理时间增加而增大。阳离子交换的ＦｅＺＳＭ－５上乙苯的扩散系数及吸附量均按Ｈ、Ｌｉ、Ｎａ、Ｋ离子半径增大的顺序递减。乙苯的氧化脱氢活性主要取决于Ｆｅ（Ⅲ）活性中心的性质，也与乙苯的吸附量及扩散系数有关。     

铁硅酸盐分子筛乙苯氧化脱氢催化性能研究Ⅱ．FeZSM－5的酸碱性质和积炭对反应活性的影响

本文应用碱性气体吸附的红外光谱和ＴＰＤ技术研究了ＦｅＺＳＭ－５（Ｆ＿４）的酸性，酸性顺序为：Ｈ－Ｆ＿４＞Ｆｅ＿２Ｏ＿３／Ｆ＿４＞Ｆ＿４原粉＞水热处理的Ｋ－Ｆ＿４＞Ｌｉ－Ｆ＿４＞ＮａＦ＿４＞Ｋ－Ｆ＿４＞ＮａＯＨ／Ｆ＿４，比较了酸强度和积炭对乙苯氧化脱氢性能的影响，以及催化剂酸碱性质与积炭的关系．结果表明，乙苯氧化脱氢反应是在酸碱协同作用下进行的，积炭也参与了氧化脱氢反应，催化剂表面上Ｌ酸中心产生的具有一定Ｃ、Ｈ、Ｏ比的积炭具有高的氧化脱氢活性．碱金属阳离子改性的具有Ｌ酸中心的ＦｅＺＳＭ－５是乙苯氧化脱氢的高活性催化剂。     

FeZSM－5中不同化学环境的铁上乙苯氧化脱氢制苯乙烯的催化活性

ＦｅＺＳＭ－５中不同化学环境的铁上乙苯氧化脱氢制苯乙烯的催化活性张春雷，吴志芸，阚秋斌（吉林大学化学系，长春１３００２３）关键词ＦｅＺＳＭ－５沸石，铁，化学环境，乙苯，氧化脱氢，苯乙烯，多功能催化剂杂原子引入分子筛，除能调变分子筛的酸性和微孔孔径外，...     

Fe－ZSM－5分子筛中Fe的化学环境研究

本文应用ＥＳＲ、ＸＰＳ、ＤＲＳ、Ｍｏｓｓｂａｕｅｒ谱和首次运用ＴＰＲ技术结合ＸＰＳ、ＸＲＤ对Ｆｅ－ＺＳＭ－５中Ｆｅ的化学环境进行了研究。结果表明，碱性介质条件下合成的Ｆｅ－ＺＳＭ－５分子筛中，铁仅有一种价态Ｆｅ（Ⅲ），但却有多种存在形式。非骨架Ｆｅ（Ⅲ）包括分子筛孔道内及外表面上沉积的氧化铁；骨架Ｆｅ至少有两种状态，即骨架不饱和配位Ｆｅ（Ⅲ）和骨架畸变四配位的Ｆｅ（Ⅲ）．各种测试方法的结果表明Ｆｅ主要位于分子筛的骨架上，非骨架Ｆｅ（Ⅲ）很少．     

Fe—ZSM—5分子筛中Fe的化学环境研究

本文应用ＥＳＲ、ＸＰＳ、ＤＲＳ、Ｍｏｓｓｂａｕｅｒ谱和首次运用ＴＰＲ技术结合ＸＰＳ、ＸＲＤ对Ｆｅ－ＺＳＭ－５中Ｆｅ的化学环境进行了研究。结果表明，碱性介质条件下合成的Ｆｅ－ＺＳＭ－５分子筛中，铁仅有一种价态Ｆｅ（Ⅲ），但却有多种存在形式。非骨架Ｆｅ（Ⅲ）包括分子筛孔道内及外表面上沉积的氧化铁；骨架Ｆｅ至少有两种状态，即骨架不饱和配位Ｆｅ（Ⅲ）和骨架畸变四配位的Ｆｅ（Ⅲ）．各种测试方法的结果表明Ｆｅ主要位于分子筛的骨架上，非骨架Ｆｅ（Ⅲ）很少．     

改性FeZSM—5沸石上乙苯的吸附和扩散性质及氧化脱氢催化作用

用ＸＤＰＳ、ＤＲＳ及Ｍｏｓｓｂａｕｅｒ谱对水热处理改性的ＦｅＺＳＭ－５中Ｆ（Ⅱ）的化学状态进行了研究，并定量地考察了水热处理时间对骨架铁含量的影响，比较了不同水热处理时间及不同平衡阳离子交换的ＦｅＺＳＭ－５上乙苯的吸附及扩散性质。水热处理将骨架析出，但析出的骨架铁并不阻塞孔道，而高分散在分子筛的表面上，乙苯的吸附量随水热处理时间增加而增大。     

铁硅酸盐分子筛乙苯氧化脱氢催化性能研究：II.FeZSM—5的酸碱性质和…

本文应用碱性气体吸附的红外光谱和ＴＰＤ技术研究了ＦｅＺＳＭ－５（Ｆ４）的酸性，酸性为：Ｈ－Ｆ４〉Ｆｅ２Ｏ３／Ｆ４〉Ｆ４原粉〉水热处理的Ｋ－Ｆ４〉Ｌｉ－Ｆ４〉Ｎａ－Ｆ４〉Ｋ－Ｆ４〉ＮａＯＨ／Ｆ４。比较了酸强度和积炭对乙苯氧化脱氢性能的影响，以及催化剂酸碱性质与积炭的关系。结果表明，乙苯氧化脱氢反应是在酸碱协同作用下进行的，积炭也参与了氧化脱氢反应，催化剂表面上Ｌ酸中心产生的具有一定Ｃ、Ｈ、Ｏ比的积炭     

铁硅酸盐分子筛乙苯氧化脱氢催化性能研究：I.催化剂的表征及反应温…

本文合成了五种不同Ｓｉ／Ｆｅ比的Ｆｅ－ＺＳＭ－５分子筛，并进行了离子交换改性。ＸＲＤ和ＩＲ谱测试均表明Ｆｅ进入了分子筛骨架。用连续流动法考察了反应温度、ＥＢ／Ｏ２比对乙苯氧化脱氢活性的影响。结果表明，在８２３Ｋ和ＥＢ／Ｏ２＝１的条件下苯乙烯有最大收率。     

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.