Zn（ClO4）2—DAPTU（MAPTU）—H2O三元体系30℃时的相平衡研究

测定了三元体系Ｚｎ（ＣｌＯ４）２－Ｌ－Ｈ２Ｏ（Ｌ＝ＤＡＰＴＵ，Ｎ，Ｎ＇－二安替比林硫脲，Ｌ＝ＭＡＰＴＵ，Ｎ－甲基Ｎ＇－安替比林硫脲）在３０℃时的溶解度和饱和溶液的折学率，绘制了相应的溶度图和折光率、组成图。体系的浓度曲线和折光率曲线均由３支组成，民Ｌ（Ｌ＝ＤＡＰＴＵ，ＭＡＰＴＵ）、Ｚｎ（ＣｌＯ４）２．Ｌ２．ｎＨ２Ｏ（Ｌ＝ＤＡＰＴＵ，ｎ＝２；Ｌ＝ＭＡＰＴＵ，ｎ＝０）和Ｚｎ（ＣｌＯ４）２．６Ｈ２Ｏ相应     

半导体催化膜上泵氧甲烷氧化偶联反应的研究 Ⅱ.联合体系的反应

在常压及６５０℃下，以含１％Ｏ２的甲烷－氧混合气进料，考察了在ＣａＯ，ＳｒＯ，ＺｎＯ，ＴｉＯ２，ＣｅＯ２和ＭｎＯ２膜上外加电流为－９０～９０ｍＡ范围内联合体系的甲烷氧化偶联反应，结果表明，在ｐ型和ｎ型半导体催化膜上，发生ＮＥＭＣＡ效应的增强因子有一极值，联合体系中泵氧ＯＣＭ反应的Ｃ２烃选择性低于开路体系中反应的Ｃ２烃选择性，根据总反应速率求出了总传递系数及电化学影响效率，电化学影响效率随ｎ型电导率     

甲烷部分氧化制合成气Ⅱ．镍系催化剂的反应性能

主要用第四周期金属元素的氧化物与Ａｌ２Ｏ３的复合氧化物催化剂上甲烷氧化的结果证实了催化剂设计中的预测：（１）催化剂首先应能解离活化甲烷，（２）催化剂要能较快地活化Ｏ２分子．只有同时满足这两个条件，催化剂才可能有较好的甲烷部分氧化活性．第四周期元素中只有镍具有这样的性质．Ｃｕ，Ｍｎ，Ｃｒ，Ｌａ，Ｃａ，Ｚｎ等氧化物的添加可明显提高Ｎｉ－Ａｌ２Ｏ３催化剂的甲烷部分氧化性能，其中Ｃｕ的助催化性能最好．催化剂ＮｉＯ－ＣｕＯ－Ａｌ２Ｏ３，ＮｉＯ－ＭｎＯ－Ａｌ２Ｏ３，ＮｉＯ－Ｃｒ２Ｏ３－Ａｌ２Ｏ３的反应活性和选择性顺序，与金属Ｃｕ，Ｍｎ，Ｃｒ上ＣＯ和Ｈ２脱附的顺序是一致的     

Zn（ClO_4）_2－DAPTU（MAPTU）－H_2O三元体系30℃时的相平衡研究

测定了三元体系Ｚｎ（ＣｌＯ４）２－Ｌ－Ｈ２Ｏ（Ｌ＝ＤＡＰＴＵ，Ｎ，Ｎ′－二安替比林硫脲；Ｌ＝ＭＡＰＴＵ，Ｎ－甲基－Ｎ′－安替比林硫脲）在３０℃时的溶解度和饱和溶液的折光率，绘制了相应的溶度图和折光率－组成图．体系的溶度曲线和折光率曲线均由３支组成，分别与Ｌ（Ｌ＝ＤＡＰＴＵ，ＭＡＰＴＵ）、Ｚｎ（ＣｌＯ４）２·Ｌ２·ｎＨ２Ｏ（Ｌ＝ＡＰＴＵ．ｎ＝２；Ｌ＝ＭＡＰＴＵ，ｎ＝０）和Ｚｎ（ＣｌＯ４）２·６Ｈ２Ｏ相对应．从溶度图上发现两个未见报道的固液异组成溶解的化合物，经化学分析、元素分析、ＴＧ－ＤＴＡ、ＩＲ表征，结果表明，三元化合物Ｚｎ（ＤＡＰＴＵ）２（ＣｌＯ４）２．２Ｈ２Ｏ中ＤＡＰＴＵ是以两个羧基氧与Ｚｎ２＋离子配位，而在二元化合物Ｚｎ（ＭＡＰＴＵ）２（ＣｌＯ４）２中ＭＡＰＴＵ则以氧和硫原子与Ｚｎ（２＋）离子配位。     

Zn_2Al－PW_（12－n）V_nO_（40）（n＝1～4）的合成与表征

Ｚｎ_２Ａｌ－ＰＷ_（１２－ｎ）Ｖ_ｎＯ_（４０）（ｎ＝１～４）的合成与表征郭军，孙铁，沈剑平，蒋大振闵恩泽（吉林大学化学系，长春，１３００２３）（石油化工科学研究院）关键词Ｐ－Ｗ－Ｖ杂多阴离子，柱撑水滑石，合成同多和杂多阴离子柱撑水滑石（简称ＰＯＭｓ－...     

水蒸汽对负载型催化剂丙烷脱氢性能的影响：Ⅰ.反应性能的研究

研究了ＭｇＡｌ２Ｏ４，ＺｎＡｌ２Ｏ４负载的Ｐｔ－Ｓｎ催化剂在氮气及水蒸汽中的丙烷脱氢性能。考察了还原温度，反应温度，催化剂载量对Ｐｔ－ＳＳｎ／ＭｇＡｌ２Ｏ４催化剂丙烷脱氢性能的影响。     

ZrO2对Mn—O／γ—Al2O3催化剂中表面氧性能的影响

用ＴＰＤ－ＭＳ和ＴＰＲ技术研究了Ｍｎ－Ｏ／γ－Ａｌ２Ｏ３和Ｍｎ－Ｏ／ＺｒＯ＋γ－Ａｌ２Ｏ３催化剂中表面氧的脱附、还原性能和再生氧化恢复性能，并用ＸＲＤ对催化剂的固相结构进行了表征。结果表明，Ｍｎ－Ｏ／γ－Ａｌ２Ｏ３或Ｍｎ－Ｏ／ＺｒＯ２＋γ－Ａｌ２Ｏ３催化剂上存在ＭｎＯ２、Ｍｎ２Ｏ３和少量Ｍｎ３Ｏ４物种。ＺｒＯ２的存在不影响Ｍｎ－Ｏ／γ－Ａｌ２Ｏ３的ＴＰＲ的ＴＰＤ的特征峰，但使ＭｎＯ２的量明显增加，     

钙钛矿型（La0.8M0.2）MnO2和（La0.2Sr0.2）（Mn1—xFex）O3的XRD和IR光谱 …

合成了（Ｌａ０．８Ｍ０．２）ＭｎＯ３和（Ｌａ０．８ｓＲ０．２）（ｍＮ１－ｘＦｅｘ）（Ｏ３（Ｘ＝０．１，０．２，０．３，０．４，０．５）两类氧化物，经ＸＲＤ确认为钙钛矿型氧化物，应用ＦＴ－ＩＲ对其进行研究，对主要的红外特征振动υ（Ｍｎ－Ｏ）和δ（Ｏ－Ｍｎ－Ｏ）进行了分析表征。     

细胞色素P－450单加氧酶的模拟－在锰卟啉催化环己烷加氧反应中不同氧原子供体的作用

以ＭｎＴＰＰＣ１为催化剂研究了不同氧原子供体ＰｈＩＯ、ＮａＯＣｌ和Ｈ２Ｏ２在环己烷加氧反应中的作用。根据动力学考察和ＵＶ－Ｖ１Ｓ、ＩＲ、ＥＳＲ分析认为，ＰｈＩＯ和ＮａＯＣ１可能分别与ＭｎＴＰＰＣ１形成具有转移氧原子能力的单核或双核的高氧化态氧代锰卟啉配合物，而Ｈ２Ｏ２与ＭｎＴＰＰＣ１作用则形成非活性物种。讨论了ＭｎＴＰＰＣ１－单氧原子供体催化环己烷加氧反应机理。     

改性电解二氧化锰研究

用电解法制备一种掺杂铋的改性二氧化锰材料（Ｂｉ－ＥＭＤ），通过Ｘ射线衍及光电子能谱分析，Ｂｉ－ＥＭＤ属于γ－ＭｎＯ２，Ｂｉ以Ｂｉ２Ｏ３形式存在于改性中，且材料中Ｂｉ含量随电解时Ｂｉ＾３＋浓度增加而增加，当电解液中Ｂｉ＾３＋浓度为０．００８ｍｏｌ．Ｌ＾－１时，材料中Ｂｉ含量１４．３％（重量百分比），用Ｂｉ－ＥＭＤ装配民ＡＡ型Ｚｎ／ＭｎＯ２试验电池，通过循环寿命实验，Ｂｉ－ＥＭＤ表现出良好的可逆性。     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.