W-MCM-48中孔分子筛的微波合成与表征

在微波辐射下快速合成出Ｗ－ＭＣＭ－４８分子筛,通过ＸＲＤ,ＦＴ－ＩＲ和Ｎ２吸附等手段对样品进行了表征,并考察了合成条件对Ｗ－ＭＣＭ－４８相对结晶度的影响。结果表明：在微波辐射下快速合成出的Ｗ－ＭＣＭ－４８分子筛结晶及热稳定性良好,且孔道规整;Ｗ离子进入了分子筛的骨架;以十六烷基三甲基溴化铵为模板剂,最佳合成条件为ｎ（Ｎａ２Ｏ）／ｎ（ＳｉＯ２）＝０．２５,ｐ＝０．４８ＭＰａ,ｔ＝２ｈ。苯乙烯催化氧化     

硅钨杂多酸在中孔全硅分子筛HMS上的固载及其催化性能

用十二烷基胺代替传统的季铵盐合成了中孔全硅分子筛ＨＭＳ，并将硅钨杂多酸浸渍固载在ＨＭＳ上，用ＸＲＤ，ＦＴ－ＩＲ以及ＮＨ３－ＴＰＤ等手段对ＨＭＳ及不同负载量的焙烧温度的负载论剂进行了表征，即使在固载量为５０％的ＳｉＷ１２／ＨＭＳ中，ＳｉＷ１２仍保持其Ｋｅｇｇｉｎ结构产均匀分布在载体表面上，没有ＳｉＷ１２晶相生成，同时，在气－固相反应体系中研究了固载在ＨＭＳ上的ＳｉＷ１２在合成乙酸丁酯中的催化性能，实     

液－固吸附体系中不同浓度和温度条件下溶质吸附热力学函数的估算

液－固吸附体系中不同浓度和温度条件下溶质吸附热力学函数的估算陈禹银（四川乐山师专化学系，乐山６１４００４）耿信鹏（西北纺织工学院纺化系，西安７１００４８）液－固吸附体系的热力学研究，总是从等温吸附数据入手求算吸附分配常数，再计算吸附自由能变化。由于所...     

溶胶-凝胶法合成超细Li2+xRExSi1-xO3及其离子导电性

用溶胶－凝胶法合成了Ｌｉ２＋ｘＲＥｘＳｉ１－ｘＯ３（ＲＥ＝Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ；ｘ＝０～０．１５），用ＤＴＡ－ＴＧ，ＸＲＤ，ＴＥＭ及交流阻抗等技术对样品的结构、形貌、粒径及离子导电性等进行了观察和测试。基固淮体形成范围是０〈ｘ≥０．０９；平均粒径为１００ｎｍ；在固溶体范围内，样品电导率随掺 增加而增高；与传统的固相反应合成方法相比，该法可使样品的生成温度降低，离子导电性提高。     

以混合模板剂合成TS—1分子筛及其性能研究

以四丁基溴化铵（ＴＢＡＢｒ）＋四乙基氢氧化铵（ＴＥＡＯＨ，ｎ（ＴＢＡ＾＋）／ｎ（ＴＥＡ＾＋）＝１）或以四丙基溴化铵（ＴＰＡＢｒ）＋ＴＥＡＯＨ为模板剂，钛酸四丁酯和正硅酸乙酯为原料，于１７０℃水热合成出ＴＳ－１分子筛。对合成的ＴＳ－１样品进行了ＸＲＤ，ＦＴ－ＩＲ，ＳＥＭ和ＢＥＴ比表面积分析，证实了样品中钛已进入Ｓｉｌｉｃａｌｉｔｅ－１骨架。选择戊烷氧化为探针反应，考察了ＴＳ－１的催化活性。结果表明以     

活性碳纤维ZnO—SACF氧化还原机理的研究

本文借助于ＩＲ，ＴＧ和ＸＰＳ，研究了ＺｎＯ－ＳＡＣＦ制备过程中及其吸附Ａｇ＾＋和Ａｕ＾３＋前后的化学结构变化。实验结果表明：从ＳＡＣＦ到ＺｎＯ－ＳＡＣＦ，纤维表面上的Ｏ／Ｃ原子比和含氧基团如Ｃ＝Ｏ和ＣＯＯ都有所减少；ＺｎＯ－ＳＡＣＦ上还原性功能基团主要是－Ｃ－ＯＨ，当ＺｎＯ－ＳＡＣＦ吸附Ａｇ＾＋后，－Ｃ－ＯＨ被氧化为－Ｃ＝Ｏ，而当其吸附Ａｕ＾３＋后，－Ｃ－ＰＨ被氧化为－Ｃ＝Ｏ和－（Ｏ＝Ｃ）－ＯＨ，     

CMC d－p π Bond in Solid State（Ⅱ） Band Structure and Metallic Properties in Incommensurate Misfit Layer Compounds（MS）_xTS_2（M＝Sn，Pb and La；T＝V，Nb，Ta and Cr）

ＣＭＣｄ－ｐπＢｏｎｄｉｎＳｏｌｉｄＳｔａｔｅ（Ⅱ）ＢａｎｄＳｔｒｕｃｔｕｒｅａｎｄＭｅｔａｌｌｉｃＰｒｏｐｅｒｔｉｅｓｉｎＩｎｃｏｍｍｅｎｓｕｒａｔｅＭｉｓｆｉｔＬａｙｅｒＣｏｍｐｏｕｎｄｓ（ＭＳ）_ｘＴＳ_２（Ｍ＝Ｓｎ，ＰｂａｎｄＬａ；Ｔ＝Ｖ，Ｎｂ...     

金属硼化物结构与稳定性的理论研究

用ＨＦ／３－２１Ｇａｂｉｎｉｔｉｏ法对金属硼化物ＭＢ２／ＭＢ２（Ｍ＝Ｌｉ，Ｎａ，Ｂｅ，Ｍｇ，Ａｌ）的７５个电子态结构进行能量梯度法优化，再用大基组二次且上互作用ＱＣＩＳＤ（Ｔ）／６－３１１Ｇ进行单点计算，得到了结构参数总能量，为了考察各原子簇的稳定性，还对２４个碎片的７０多个电子态，求得相应的ＱＣＩＳＤ（Ｔ）能量，在此基础上计算了原子化能、电离能、离解通道和碎片化能，得到了原子簇的稳定性规律。     

四乙烯溴化铵—氟化物复合模板剂合β沸石（Ⅱ）：β沸石 …

采用ＦＴ－ＩＲ、ＸＲＤ，ＳＥＭ，ＴＧ，ＩＣＰ－ＡＥＳ等技术研究了四乙经铵－氟化物复合模板剂体系合成β沸石的晶化过程。，发现本体系β沸石的合成遵循液相转变机理，在诱导期向生长期转变的转折点存在过渡态，氟离子对过渡态的形成和转变起重要作用。在诱导期初期固是富铝的，但晶生长期固相硅铝比基本不变，表明硅铝同步进入骨架。     

水溶性卟啉配合物合成及光敏化行为

在低沸点的氯仿溶剂中合成了中－四（对二甲基丙磺酸氨基）苯基卟啉（简记为Ｈ２ＴＰＳ），在乙酸溶剂中合成了相应的金属卟啉［简记为ＭｅＴＰＳ，Ｍｅ＝Ｚｎ（Ⅱ），Ｃｕ（Ⅱ），Ｎｉ（Ⅱ），Ｃｏ（Ⅱ），Ｍｎ（Ⅱ）］，并进行了表征。ＴＥＯＡ－ＭｅＴＰＳ－ＭＶ＾２＋－ＤＭＳＯ（Ｈ２Ｏ）７５：２５，Ｖ／ｖ）体系的光敏化还原ＭＶ＾２＋反应的研究结果表明，Ｚｎ（Ⅱ）ＴＰＳ，Ｍｎ（Ⅱ）ＴＰＳ及Ｈ２ＴＰＳ是较好光敏剂，且以     

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.     

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.     

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.     

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.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.