离子液中磷酸铝方英石的低温合成及表征

 在溴化 1-丁基-3-甲基咪唑离子液体中, 于低温 80 °C 反应 30 min 即可制得结晶完好的磷酸铝方英石. 详细考察了有机胺和 HF 的加入量、反应原料磷铝比和反应时间等对合成固体磷酸盐骨架结构的影响. 粉末 X 射线衍射和高分辨固体核磁共振结果表明, 合成的方英石晶体为 α 晶相, 磷铝物种大部分位于分子筛骨架上, 并以四配位的形式通过 Al–O–P 键相连.     

离子热合成微球方钠石

在1-甲基-3-乙基咪唑溴盐离子液体([emim]Br)中合成了球形的方钠石分子筛,分别通过X射线衍射仪(XRD)和扫描电子显微镜(SEM)等表征手段对产物进行了表征。结果表明,在反应物料配比相同的条件下,离子热合成有利于球形方钠石结构的形成。在反应物料中nNa2SiO3·9H2O/nNaAlO2为1.1(即nSiO2/nAl2O3=2.2)和5.0时(即nSiO2/nAl2O3=10)时,离子热合成得到了粒径为0.2和1.4μm的球形方钠石分子筛,而水热合成分别得到了X型分子筛和一种未知结构的产物。     

有机胺在离子热合成 LTA 型磷酸铝分子筛中的助模板作用

 在 1-丁基-3-甲基溴化咪唑 ([bmim]Br) 离子液体中引入有机胺合成了 LTA 型磷酸铝分子筛 (AlPO4-42), 采用热重分析、核磁共振光谱、红外光谱以及荧光光谱对所得晶化产物进行了表征, 并考察了体系的晶化动力学. 结果表明, 有机胺以特定的聚集形态协同离子液体阳离子起到助模板剂的作用, 并填充在 AlPO4-42 分子筛孔道中. 晶化产物随晶化时间的演变表明, 体系中有机胺浓度的变化改变了动力学路径. 高浓度有机胺所形成的聚集体组装周围的无机物种, 促进了 sod 或 lta 笼结构的形成, 并导致立方相的 LTA 骨架晶化.     

介孔硅铝分子筛的合成、表征及其作为固体酸催化苯酚与1-辛烯的烷基化反应

以异丙醇铝、硅酸四乙酯和十六烷基三甲基溴化胺为原料,以乙酰丙酮为螯合剂,采用溶胶-凝胶法合成了硅铝比分别为25,50,100和150的介孔硅铝分子筛,并用其催化苯酚与1-辛烯的液相烷基化反应.X射线衍射、N2吸附、高分辨透射电镜及27Al核磁共振光谱表征结果表明,该介孔分子筛具有蠕虫状骨架结构.在160℃时,硅铝比为25的介孔硅铝分子筛催化剂上苯酚可以完全转化为单烷基苯酚.     

高温离子热快速合成AlPO4-42分子筛

本文采用离子热合成法,以磷酸为磷源、异丙醇铝为铝源,在溴化1-丁基-3-甲基咪唑鎓([BMIM]Br)离子液体中于280℃快速合成了AlPO_4-42分子筛,并用该方法快速合成了其他类型的磷酸铝分子筛。通过X射线衍射、扫描电镜、比表面积孔隙率分析、固体核磁等表征手段研究了不同物料配比、模板剂、晶化时间对合成AlPO_4-42分子筛的影响以及AlPO_4-42分子筛的比表面积、孔容大小和孔道中的填充物。结果发现,在4min时已经形成了AlPO_4-42分子筛的结构。合成出的AlPO_4-42分子筛具有十四面体的形貌,这与采用常规方法得到的AlPO_4-42分子筛晶体的立方体形貌明显不同,而且AlPO_4-42分子筛的比表面积和孔容都有所改变。在合成AlPO_4-42分子筛的过程中离子液体和模板剂协同导向产物的形成。     

离子液体催化邻二甲苯氯甲基化反应

制备了8种不同链长的溴化烷基咪唑盐和4种丁基类甲基咪唑六氟磷酸盐、四氟硼酸盐、全氟丁基磺酸盐及氯化盐离子液体,研究了咪唑盐类离子液体催化邻二甲苯、氯化氢、多聚甲醛为起始原料的氯甲基化反应. 考察了离子液体类型、催化剂用量、反应温度及反应时间对反应的影响. 反应产物采用气相色谱法进行定量分析;采用GC-MS测试技术进行了定性分析. 结果表明,[C12mim]Br(溴化1-十二烷基-3-甲基咪唑盐)是最适合的催化剂. 其最佳反应条件是:离子液体摩尔分数为4%(与邻二甲苯的摩尔比),温度70 ℃,反应时间10 h,产物收率可达89.8%,TON数达到22.4.     

离子热法合成AEL磷酸铝分子筛膜及其机理研究

以δ-氧化铝为基底和铝源, 使用离子热基底自转晶法, 在[EMIm]Br离子液体中合成了AEL磷酸铝分子筛膜. 采用X射线(XRD)和扫描电镜(SEM)等方法对所得的AEL分子筛膜进行了表征, 研究了合成条件对膜的影响. 研究发现在氢氟酸和磷酸离子液体混合溶液中一步反应可以合成c轴高度取向的AEL分子筛膜, 在氢氟酸和磷酸离子液体溶液中分别顺序两步反应可以合成无取向的AEL分子筛膜. 离子热基底自转晶法分子筛膜的形成符合固相转化机理, 氟离子可以促进分子筛膜的生长, 并影响分子筛膜的取向.     

NaY 分子筛超笼内离子液体和金属配合物自组装制备溶剂分子和金属配合物一体化催化剂

 采用自组装-瓶中造船法在 NaY 分子筛超笼内, 将溴化 1-癸基-3-甲基咪唑离子液体和邻菲罗啉钯组合成一体化催化剂, 并用于苯胺羰化反应. 结果表明, 相对于以离子液体为溶剂, 邻菲罗啉钯配合物/NaY 分子筛为催化剂的体系, 该一体化催化剂在离子液体和邻菲罗啉钯配合物用量显著降低的条件下, TOF 可达 23 000 h?1, 而相应均相催化剂体系的 TOF 仅为 3 060 h-1.     

短链羟基甲基咪唑离子液体的合成与电化学性能

通过2-(2-氯乙氧基)乙醇和2-溴乙醇分别与1-甲基咪唑反应,合成乙醇基甲基咪唑溴(EMIMBr)和乙氧基乙醇基甲基咪唑氯(EEMIMCl)2种羟基咪唑离子液体,用1H NMR和FT-IR表征结构,TG和DSC进行热性能测试,并研究了其电化学性能.结果表明,羟基类咪唑离子液体具有高的热稳定性,这种含醚氧键和羟基的短链离子液体有利于电导率的提高,导电机理符合Vogel-Tmman-Fulcher (VTF)方程.乙醇基甲基咪唑溴和乙氧基乙醇基甲基咪唑氯的室温电导率分别为1.2×10-4和1.7×10-4 S/cm.对于碳酸丙二醇酯、乙氧基乙醇基甲基咪唑氯和钾盐体系,室温电导率最高可达3.82×10-3 S/cm.乙氧基乙醇基甲基咪唑氯的电化学窗口为3.4V.     

在离子液体中合成多取代苯基异丙基醚

以1-甲基3-丁基咪唑四氟硼酸盐离子液体为反应介质,由多取代苯酚与2-溴丙烷反应合成了12个多取代苯基异丙基醚,其结构经1H NMR和IR确证.     

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.