对苯二酚催化加氢制备1,4-环己二醇的研究

对Pt/C、Pd/C、Ru/C、Rh/C和Raney Ni几种催化剂,以及以钌为活性组分的催化剂载体如活性碳、SiO2、Al-MCM-41、ZSM-5、MgO、TiO2在对苯二酚加氢反应中的催化活性进行了比较.结果表明Ru/C催化剂的催化活性和对目的产物的选择性最好.对Ru/C催化剂催化对苯二酚加氢反应的反应条件如反应温度,氢气压力,反应溶剂,反应时间等对反应转化率和产物选择性的影响进行了讨论.反应的适宜条件为:反应物和催化剂的物质量比为367∶1,温度为150℃、氢气压力5 MPa,乙醇为溶剂,反应时间2 h.在此反应条件下,对苯二酚的转化率为98.8%,目的产物1,4-环己二醇的选择性为77.7%.并根据产物随时间的变化规律对该反应路径进行了分析.     

氮掺杂碳纳米笼固载钌纳米粒子的费托合成性能

费托合成可以将来源广泛的合成气转化为低碳烯烃和燃油等高附加值化学品, 是后石油时代的重要化工过程, 而发展高性能的催化剂是该工程产业化的关键. 以具有高比表面积和高氮含量的氮掺杂碳纳米笼(NCNC)为载体, 采用等体积浸渍法制备了Ru的质量分数为20%的Ru/NCNC催化剂, 所得Ru纳米颗粒均匀分散, 相比于未掺杂碳纳米笼负载的Ru催化剂(Ru/CNC), Ru纳米粒子尺寸更小且分布更集中. Ru/NCNC催化剂展现出优异的费托合成催化性能, 在0.5 MPa和220 ℃的温和条件下, 具有高的催化活性、高的C₅₊选择性(55.7%)、低的CH₄选择性(13.5%)和高的催化稳定性(60 h, CO转化率保持在≈33%), 显著优于Ru/CNC. 这可归因于N掺杂提高了Ru活性中心的数量和电子态密度以及表面碱性, 增强了金属-载体相互作用, 进而提高Ru/NCNC的催化活性、长链产物(C₅₊)选择性、抗烧结能力和催化稳定性. 本研究提供了一条通过掺杂碳载体设计提升费托合成催化剂性能的有效策略.     

Fe3O4修饰的Pt-Ru/C纳米催化剂的制备及其在无溶剂条件下邻氯硝基苯选择性加氢的催化性能

采用浸渍法制备了一系列Pt/Ru质量比不同的Fe₃O₄修饰的Pt-Ru/Fe₃O₄/C催化剂, 运用透射电镜(TEM)、能量弥散X射线谱(EDX)、X射线光电子能谱(XPS)、X射线粉末衍射(XRD)等手段对Pt-Ru/Fe₃O₄/C一系列催化剂进行了表征, 并考察了Pt/Ru质量比不同对催化剂Pt-Ru/Fe₃O₄/C在无溶剂条件下催化邻氯硝基苯(o-CNB)选择性加氢制备邻氯苯胺(o-CAN)催化性能的影响. 研究结果表明, 催化剂的催化活性和对目标产物的选择性跟活性组分Pt、Ru比例有关. 随着Pt/Ru比例的减小, 目标产物o-CAN的选择性有所升高, 然而反应物o-CNB的转化率有所下降. 当Pt/Ru的质量比为2时, o-CNB的转化率降为76.5%, 而目标产物o-CAN的选择性仍然为100%. 与此同时, 我们还对Pt-Ru/Fe₃O₄/C催化剂高的催化活性和目标产物的高选择性可能的原因进行了分析.     

助剂Fe和反应修饰剂修饰的Ru催化剂上苯选择加氢制环己烯

共沉淀法制备了Ru-Fe(x)催化剂,并利用X射线衍射(XRD)、X射线荧光光谱(XRF)、N2物理吸附和透射电镜等手段对催化剂进行了表征.结果表明,Ru-Fe(x)催化剂中助剂Fe以Fe3O4形式存在.单独Fe3O4并不能提高Ru催化剂的环己烯选择性.但在加氢过程中Fe3O4可与反应修饰剂ZnSO4反应生成(Zn(OH)2)3(ZnSO4)(H2O)x(x=1 or 3).化学吸附的(Zn(OH)2)3(ZnSO4)(H2O)x(x=1 or 3)在提高Ru催化剂环己烯选择性中起着关键作用.此外,Ru-Fe(x)催化剂的性能还与浆液中的Zn2+浓度和pH值有关.在0.61 mol/L ZnSO4溶液中Ru-Fe(0.47)催化剂不但给出了56.7%的环己烯收率,而且具有良好的稳定性和重复使用性能.化学吸附在Ru表面的Fe2+同样能提高Ru催化剂的环己烯选择性.在0.29 mol/L和0.61 mol/L FeSO4溶液中Ru-Fe(0.47)催化剂上化学吸附Fe2+量近似,性能近似.因为Fe2+和Zn2+性质的差异,在0.29 mol/L和0.61 mol/L FeSO4溶液中Ru-Fe(0.47)催化剂的环己烯选择性分别低于在同浓度的ZnSO4溶液中的.     

硝酸水热处理活性炭对其负载的Ba-Ru-K氨合成催化剂性能的影响

采用N2物理吸附、Boehm滴定、He-TPD-MS、CO化学吸附和透射电镜等手段考察了硝酸水热处理对活性炭(AC)及其负载的Ru基催化剂的孔结构、表面含氧基团、Ru分散度的影响,并评价了Ba-Ru-K/AC催化剂氨合成反应性能.结果表明,经硝酸水热处理后,AC表面含氧基团明显增多,但其孔结构变化不大.随着水热处理硝酸浓度的增加,AC表面含氧基团的数量增加,而相应催化剂的Ru分散度有所降低,Ru粒子尺寸增大.当硝酸浓度为2.0mol/L时,Ru分散度较高,且粒子尺寸(2.0nm)适宜,分散均匀,因此催化剂活性较高.在10MPa和10000h1条件下,400和375oC时,出口氨浓度分别达到17.80%和11.10%,较4.6mol/L硝酸回流处理AC负载的Ru基催化剂分别提高了16.8%和21.3%.水热处理AC的适宜条件为硝酸浓度2.0mol/L,150oC处理4h,填充度为70%.因此,通过调节水热处理时所用硝酸浓度可有效调控AC表面含氧基团的数量及其负载Ru的粒子尺寸.     

电化学发光-分子印迹传感器的制备及其在海洛因检测中的应用

利用掺杂多壁碳纳米管(MWNTs)的Nafion膜在玻碳电极上固定联吡啶钌(Ru(bpy)2+3),制得Ru(bpy)2+3/Nafion/MWCNT修饰电极。为了提高修饰电极的选择性,通过溶胶-凝胶技术,对该电极进一步修饰了溶胶-凝胶分子印迹膜,制得电化学发光-分子印迹传感器。优化了扫速、pH值、富集时间等检测条件,传感器显示出既具电化学发光技术的灵敏性和分子印迹技术的选择性。在优化条件下,即pH 7.0的磷酸盐缓冲溶液中,以100 mV/s扫速,富集5 min,对海洛因进行检测,在1.0×10!10~1.0×10!14mol/L范围内有良好线性关系,检出限可达到4.0×10!15mol/L(S/N=3)。传感器直接应用于唾液和尿液中海洛因的测定,回收率达到97%~104%。     

聚乙二醇-水介质中水溶性膦稳定的钌催化芳香酮的不对称加氢反应

在聚乙二醇-400-水介质中,以(1S,2S)-1,2-二苯基乙二胺的磺酸钠盐为手性修饰剂,考察了水溶性三(间-磺酸钠苯基)膦稳定的Ru催化苯乙酮及其衍生物的不对称加氢反应.结果表明,该催化剂体系具有良好的催化活性和对映选择性.在优化反应条件下,苯乙酮转化率和对映选择性分别为100％和84.9％.经正己烷萃取后,催化剂...     

巴豆醛选择性催化加氢的研究

利用P-2-Ni催化剂对巴豆醛常压催化加氢生成正丁醛的反应进行了研究。实验表明,该催化剂对巴豆醛的α,β-烯键有很高的选择性和催化活性,同时,合成了P-2-Co、P-2-Co-Ni催化剂,并选择了巴豆醛的加氢条件。     

ZrO_2负载Pt催化巴豆醛选择性加氢

以高比表面积ZrO2为载体,采用浸渍法制备了负载型Pt催化剂,应用于常压下气相巴豆醛加氢反应,考察了Pt负载量和H2还原温度等对巴豆醛选择性加氢性能的影响.实验结果表明,Pt负载量(质量分数)为3%的3Pt/ZrO2催化剂经500℃还原后,具有较高的巴豆醛选择性加氢性能:巴豆醛转化率为27%,巴豆醇的选择性为55%.X射线粉末衍射(XRD)分析,CO化学吸附,NH3程序升温脱附(NH3-TPD)表征结果表明Pt/ZrO2催化剂上Lewis强酸中心和适宜的Pt颗粒(约为8nm)有利于巴豆醛选择性加氢生成巴豆醇.     

水溶性含钌-铂双金属催化剂催化卤代芳香硝基化合物选择性加氢

考察了水溶性Ru/Pt-TPPTS双金属催化剂催化卤代芳香硝基化合物的加氢性能.实验结果表明,在Ru-TPPTS中添加铂或钯后,反应活性明显提高,尤其是Ru/Pt-TPPTS双金属催化剂更表现出显著的双金属协同效应.在pH₂=1.0MPa,70℃,反应2h的条件下,双金属催化剂0.50Ru/0.50Pt-TPPTS催化对-氯硝基苯加氢生成对-氯苯胺的反应转化率达到100%.对于取代基和取代位置不同的一些卤代硝基苯加氢,该双金属催化剂也表现出很高的催化活性和生成卤代苯胺的选择性,脱卤反应的程度很小.     

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%.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.