Na_（1＋x）Al_xZr_（2－x）P_3O_（12）的水热合成与表征

采用水热法合成了系列磷酸盐化合物Ｎａ_（１＋ｘ）Ａｌ_ｘＺｒ_（２－ｘ）Ｐ_３Ｏ_（１２），该系列化合物具有ＮＡＳＩＣＯＮ型三维骨架结构。考查了反应物料配比、晶化时间、晶化温度等实验条件对产物物相及掺入Ａｌ含量对化合物的结构与性能的影响．实验结果表明：在０≤ｘ≤０．３３的范围内，可水热合成出Ｎａ_（１＋ｘ）Ａｌ_ｘＺｒ_（２－ｘ）Ｐ_３Ｏ_（１２）纯相，而且具有良好的热稳定性。该系列化合物的离子电导率测试结果表明，其电导率与掺入的Ａｌ含量有关。     

La(ClO4)3-OCBAAP-H2O体系(30℃)溶度及Ln(OCBAAP)4(ClO4)3·nH2O的合成和表征

测定了三元体系Ｌａ（ＣｌＯ４）３－ＯＣＢＡＡＰ－Ｈ２Ｏ在３０℃时的溶解度．结果表明，该体系有一个新固相（不一致溶解化合物）Ｌａ（ＯＣＢＡＡＰ）４（ＣｌＯ４）３·６Ｈ２Ｏ形成．参考该体系溶度图确定合成条件，合成了系列化合物Ｌｎ（ＯＣＢＡＡＰ）４（ＣｌＯ４）３·ｎＨ２Ｏ（Ｌｎ＝Ｌａ，ｎ＝６；Ｌｎ＝Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｙｂ，ｎ＝２）．通过化学分析、元素分析、ＴＧ－ＤＴＧ、ＩＲ和密度对化合物进行了表征，计算了Ｌａ（ＯＣＢＡＡＰ）４（ＣｌＯ４）３热分解过程各阶段的表观活化能．     

新型层柱微孔材料─GaW_9Z_3（Z＝Co~（2＋），Fe~（3＋））柱撑Zn

新型层柱微孔材料─ＧａＷ_９Ｚ_３（Ｚ＝Ｃｏ~（２＋），Ｆｅ~（３＋））柱撑ＺｎＡｌ阴离子粘土的合成、表征及催化性能的研究张继余，余新武，张淑云，胡长文，梁兆君，王恩波（东北师范大学化学系，长春１３００２４）关键词阴离子粘土，杂多化合物，过渡金属，催化性...     

NdCl3-FeCl3-石墨层间化合物的合成

采用熔盐交换法成功地合成了ＮｄＣｌ３ＦｅＣｌ３ＧＩＣ, 用ＸＲＤ 技术和Ｘ射线能谱仪（ＥＤＳ） 对其层间结构及各元素的相对含量进行了表征。研究表明, 其结构为２,３ ,４ 阶混合结构,３ 阶ＮｄＣｌ３ 的特征层间距为１－６５３６ ±０－００２４ ｎｍ , 并探讨了稀土氯化物石墨层间化合物的形成机制。     

新型层柱材料ZnAl－XW_（11）Co的合成、表征及催化活性

新型层柱材料ＺｎＡｌ－ＸＷ_（１１）Ｃｏ的合成、表征及催化活性胡长文，刘彦勇，王作屏，张继余，王恩波（东北师范大学化学系，长春１３００２４）关键词层柱化合物，杂多阴离子，Ｋｅｇｇｉｎ结构，乙酸，正了醇，酯化化学组成通式为的阴离子粘土具有独特的层柱结构?..     

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。     

太阳能热电耦合合成苯甲酸

通过恒电位电解甲苯实现了苯甲酸的太阳能热电耦合合成, 考察了电极材料、 反应温度及电解电压对苯甲酸合成的影响. 采用气相色谱、 红外光谱和紫外光谱对电解产物进行分析检测, 证实了太阳能热电氧化甲苯的主要产物为苯甲酸. 实验结果表明, 以石墨作为阳极材料, 反应温度为90 ℃, 电解电压为2.0 V时, 氧化甲苯合成苯甲酸的产率可达51.6%.     

三羰基全甲基硅基环戊二烯基钼衍生物的合成与表征

通过三羰基（五甲基二硅基）环戊二烯基钼负离子盐与卤代烃（ＥｔＩ，ＰｈＣＨ２Ｃｌ，ＣｌＣＨ２ＣＯＯＥｔ，Ｉ（ＣＨ２）４Ｉ）进行基化反应合成其烷基钼化合物。用六甲基三硅二氧烷桥联双（三羰基环戊二烯基钼）负离子经冰醋酸处理，硫酸铁氧化偶联成钼－钼键双核化合物，经碘裂解后钼－钼键生成六甲基三硅二氧烷桥联双（三羰基环戊二烯基碘钼）化合物。以元素分析，ＩＲ和１ＨＮＭＲ谱表征了化合物的结构。     

含氨茂铁异核金属配合物合成和性质研究

Ｐｄ（Ⅱ）、Ｐｔ（Ⅱ）ＤＭＡＦ配合物已合成，并已定结构。本文采用ＭＸ２（Ｍ－Ｎｉ（Ⅱ），Ｃｏ（Ⅱ），Ｚｎ（Ⅱ）、Ｃｕ（Ⅱ）；Ｘ＝Ｃｌ，Ｂｒ，Ｉ）在ＣＨ２Ｃｌ２中和ＤＭＡＦ作用合成［ＭＸ２．２ＤＭＡＦ］型配合物。由ＮｉＣｌ２．２ＤＭＡＦ．Ｃ７Ｈ８晶胞参数推知属于对称链状四配位结构。ＩＲ谱表明，该化合物化学式为ＭＸ２．２ＤＭＡＦ。ＣＶ表明配合物中Ｍ（Ⅱ）和Ｆｅ（Ⅱ）存在。由于金属离子互相影响。Ｅｐ／２     

用KF/Al_2O_3催化合成N-乙基咔唑方法研究

用ＫＦ／Ａｌ２Ｏ３催化合成Ｎ┐乙基咔唑方法研究钟增培周健能（中山大学化学化工学院应化系广州５１０２７５）咔唑是染料、香料、医药等产品的中间体［１］，它及其衍生物是一类杂环芳香烃化合物，有些咔唑衍生物还是很好的有机光导材料，Ｎ－乙基咔唑是合成染料硫化还...     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.