奥司他韦的合成及炔硒醚氢芳化反应的研究

在简述奥司他韦功能的基础上,从基于天然产物为原料的合成工艺、基于非天然产物为原料的合成工艺、五步反应一锅法这三方面入手,阐述了奥司他韦的常用合成方法。在此基础上,对最优炔硒醚氢芳化反应条件以及反应底物的拓展进行了探究。

溴氨酸芳胺化反应及其在染料合成中的应用

本文介绍了溴氨酸芳胺化反应的机理、反应的实施方法及其在合成蒽醌型酸性、活性、媒介和还原染料中的应用。

聚苯乙烯二醋酸碘苯的合成及其在烯烃叠氮-芳硒化反应中的应用

The 2% cross-linked poly[styrene(iodosodiacetate)] reacted with diarylselenides and sodium azides to afford a simple and mild synthetis method of 1-azido-2- arylselenoalkanes.

高碘化合物在有机合成中的研究进展

有机高价碘化合物因为其反应条件温和、选择活性好和环境友好且相对廉价易得,受到越来越广泛的关注。由于其反应特性可作为过渡金属催化剂的替代品而被广泛应用到有机合成中。本文对常见的三价碘(Ⅲ)、五价碘(Ⅴ)和手性高碘试剂的基本情况和应用领域进行了介绍,之后对高碘化合物参与的芳烃碳氢键胺化反应以及芳烃的去芳化反应等应用进行了归纳总结。最后对高碘化合物在有机合成中的应用发展进行了展望。

Pd/1,3-双(二苯基膦)丙烷催化苯并噁唑C-2位直接芳基化反应的研究（英文）

利用简单商业可得的PdCl2和1,3-双(二苯基膦)丙烷(dppp)作催化剂,高效催化了苯并噁唑和溴苯C-2取代的芳基化反应.该催化体系表现出了很好的官能团容忍性,当催化剂用量为0.1 mol%时,反应6 h收率可达90%以上,更重要的是,当催化剂用量低至0.01 mol%时,通过延长反应时间,转化率仍然能达到90%以上.通过汞中毒实验,透射电镜和X射线光电子能谱证实了该反应是钯纳米粒子催化的过程.此外,通过控制实验证实了底物苯并噁唑在反应过程中经历了开环和关环的途径.最后,通过热过滤和高分辨质谱实验从一定程度上证实了该反应可能经历了Pd(0)-Pd(Ⅱ)的反应历程.

芳基高价碘盐诱导的亲电环化反应研究

亲电试剂诱导的环化反应是构建环状化合物的有效策略,而利用芳基高价碘盐作为亲电试剂诱导环化反应已经取得了诸多研究进展.在这些亲电环化反应中,高价碘盐不仅可以作为芳基化试剂诱导环化反应形成芳基取代环化物,还可以诱导苯并环化反应,形成苯并环状化合物.

聚亚胺醚亚胺酮的合成及性能研究

文章以4,4’-二溴对苯甲酮和4,4’-二氨基二苯醚为单体,三(二苄基丙酮)二钯为催化剂,通过Buchwald-Hartwig芳胺化反应,实现CAr-N偶联反应,合成了新型功能高分子聚亚胺醚亚胺酮。实现芳香二胺结构单元和二溴化芳香酮结构单元的共聚,对共聚物结构、基本性能进行表征,并研究CAr-N偶联构建对苯甲酮/芳基醚主链结构的可行性,探讨聚合物主链构型、热稳定性和其他性能等。

Preparation of Zn-modified nano-ZSM-5 zeolite and its catalytic performance in aromatization of 1-hexene

The promoting effect of introducing Zn into nano-ZSM-5 zeolites by conventional impregnation method and isomorphous substitution on the performance of 1-hexene aromatization was investigated. The nano-ZSM-5 zeolite was synthesized by a seed-induced method without organic templates. The Zn-modified nano-ZSM-5 zeolite catalysts, xZ n/HNZ5 and y Zn/Al-HNZ5, were prepared by the conventional impregnation method and isomorphous substitution, respectively. The structure, chemical composition and acidity of the catalysts were characterized by XRD, XRF, N2 adsorption, SEM, NH3-TPD and Py-IR, while the catalytic properties were evaluated at 480 °C and a weight hourly space velocity（WHSV） of 2.0 h-1 in the aromatization procedure of 1-hexene. Compared with xZ n/HNZ5, y Zn/Al-HNZ5 exhibited smaller particles and higher dispersion of Zn species, which led to greater intergranular mesopore and homogeneous acidity distribution. Experimental results indicated that the synergy effect between the Brnsted and Lewis acid sites of the isomorphously substituted nano-ZSM-5 zeolites could significantly increase aromatics yield and improve catalytic stability in the 1-hexene aromatization.

Environmentally benign and economic synthesis of covalent triazine-based frameworks

Covalent triazine-based frameworks（CTFs） are important microporous materials with a wide range of applications.Here,we demonstrate an environmentally benign and economic synthetic pathway to CTFs.The monomers used for CTFs,aromatic nitriles,were obtained by cyanation using nontoxic potassium hexacyanoferrate（Ⅱ） in place of commonly used toxic cyanides.Then,the CTFs were synthesized by trimerization of the corresponding cyano monomers in molten zinc chloride.A series of CTFs was synthesized,and the highest Brunauer-Emmett-Teller surface area measured in this series was 2404 m^2/g.Among the synthesized CTFs,CTF_（DCP） exhibited excellent CO_2 adsorption properties,with a CO_2 uptake of 225 mg/g at 0℃.

Selective arylation/annulation cascade reactions of 2-alkynylanilines with diaryliodonium salts

An efficient Cu catalyzed selective arylation/annulation cascade reaction of 2-alkynylanilines with diaryliodonium salts was developed.This reaction was selective to N-arylation instead of C-arylation,which provides a simple synthetic method for N-aryl indoles.

Blanc Reaction of Aromatic Compounds Catalyzed by Ionic Liquids

Ionic liquids have been used as catalysts for Blanc reaction of toluene. The effects of reaction temperature, reaction time and dosage of the ionic liquid catalyst have been investigated, and the catalytic performance of different ionic liquid catalysts for toluene chloromethylation was also studied. The reaction was found to proceed under mild conditions with excellent conversion （up to 90%） in the absence of Lewis acids. The ionic liquids could be recycled and reused without loss of their catalytic activities.

Kinetic Model and Simulation Analysis for Toluene Disproportionation and C9-Aromatics Transalkylation

A new kinetic model for commercial unit of toluene disproportionation and C9-armatiocs transalkylation is developed based on the reported reaction scheme.A time based catalyst deactivation function taking weight hourly space velocity(WHSV)into account is incorporated into the model,which reasonably accounts for the loss in activity because of coke deposition on the surface of catalyst during long-term operation.The kinetic parameters are benchmarked with several sets of balanced plant data and estimated by the differential variable metric optimiza- tion method.Sets of plant data at different operating conditions are applied to make sure validation of the model and the results show a good agreement between the model predictions and plant observations.The simulation analysis of key variables such as temperature and WHSV affecting process performance is discussed in detail,giv- ing the guidance to select suitable operating conditions.

Construction of an operando dual-beam fourier transform infrared spectrometer and its application in the observation of isobutene reactions over nano-sized HZSM-5 zeolite

An operando dual‐beam Fourier transform infrared (DB‐FTIR) spectrometer was successfully developed using a facile method. The DB‐FTIR spectrometer is suitable for the real‐time study of the dynamic surface processes involved in gas/solid heterogeneous catalysis under real reaction conditionsbecause it can simultaneously collect reference and sample spectra. The influence of gas‐phasemolecular vibration and heat irradiation at real reaction temperatures can therefore be eliminated.The DB‐FTIR spectrometer was successfully used to follow the transformation of isobutene over nano‐sized HZSM‐5 zeolite under real reaction conditions.

Study on Aromatization of C_6 Aliphatic Hydrocarbons on ZRP Zeolite Catalyst

The performance of ZRP zeolite catalysts for aromatization of C6 aliphatic hydrocarbons was investigated in a pulsed microreactor. The influence of metal modified ZRP zeolites on aromatization reaction was also studied, coupled with comparison of aromatization tendencies of olefins, paraffins and paraffins with different degrees of chain branching. Test results had shown that the lower the silicon/aluminum ratio in the ZRP zeolite, the higher the aromatization reactivity of aliphatic hydrocarbons. Modification of ZRP zeolite by zinc and its zinc content had apparent impact on the yield and distribution of aromatics. The aromatization tendency of olefins was apparently better than paraffins, while the aromatization tendency of monomethyl paraffins was better than that of straight-chain paraffins with the exception of dimethyl paraffins, which had worse aromatization tendency because of their steric hindrance.

Estimation on Global Reaction Heat for the Aromatization Process of Liquefied Petroleum Gas

The reaction heat effect analysis for the aromatization process of Liquefied Petroleum Gas (LPG) was completed in this paper. In order to characterize this complex reaction system, one set of independent reactions was determined by means of atomic coefficient matrix method. Based on reaction thermodynamic and stoichiometric knowledge, the heat effect, Gibbs free energy change and equilibrium constant for each independent reaction was calculated for the specified conditions. Under these conditions, based on the initial and final composition data from LPG aromatization experiments, the actual extent of reaction for each independent reaction was determined. Furthermore, the global reaction heat and adiabatic temperature rise of LPG aromatization reaction system could be estimated. This work would provide a theoretical guidance for the design and scale-up of reactor for LPG aromatization process, as well as for the selection of proper operating conditions.

SYNTHESIS AND CATALYTIC PROPERTY OF POLYSTYRENE SUPPORTED GLUTAMIC ACID SCHIFF BASE COMPLEX OF Mn(Ⅱ) IN AEROBIC OXIDATION OF CYCLOHEXENE

The polystyrene supported glutamic acid Schiff base complex of Mn （ Ⅱ ） （PS-Sal-Glue-Mn） was prepared with chloromethylated styrene polymer beads, 2,4-dihydroxybenzaldehyde, L-glutamic acid and manganese （ Ⅱ ） acetate tetrahyrate. The polymeric ligand and the complex were characterized by FT-IR, small area X-ray photoelectron spectroscopy （XPS） and 1CP-AES. In the presence of the manganese complex, cyclohexene （1） was effectively oxidized by molecular oxygen without reductant. The major products of the reaction were 2-cyclohexen-l-ol （2）, 2-cyclohexen-l-one （3） and 2-cyclohexen-1- hydroperoxide （4）, which was different with typical oxidation of cyclohexene. The influence of reaction temperature and additive for oxidation had been studied. The selectivity of 2-cyclohexen-1-hydroperoxide varied with reaction time and different additives. The mechanism of cyclohexene oxidation had also been discussed.

Removal of Trace Olefins from Aromatics by Catalytic Alkylation Using 1-Alkyl-3-methylimidazolium Bromochloroaluminate Catalyst

Removal of trace olefins from aromatic liquids had been investigated in the presence of various ionic liquids like 1-ethyl-3-methylimidazoliurn bromochloroaluminate （EMIMBr-AlCl3）, 1-butyl-3-methylimidazolium bromochloroaluminate （BMIMBr-AlCl3）, l-hexyl-3-methylimidazolium bromochloroaluminate （HMIMBr-AlCl3）, and 1-octyl-3-methylimidazolium bromochloroaluminate （OMIMBr-A1C13）. It was found that the longer the alkyl chain of ionic liquid cations was, the higher the olefins conversion would be. OMIMBr-AlCl3 （with 0.67 molar fraction of AlCl3） had an obvious performance on olefins removal. The influences of various reaction parameters such as the dosage of catalyst, the reaction temperature, and the reaction time on the reaction catalyzed by OMIMBr-AlCl3 were investigated. Under optimum reaction conditions, a higher than 99% conversion of olefins was achieved. The preliminary results revealed that the process could save time, consume less energy, separate products easier, and cause less pollution to the environment.

Mechanochemical Reaction of Aromatic Ketones and Aldehydes in the Presence of Zn-ZnCl_2

The solvent-free reactions of aromatic ketones and aldehydes in the presence of Zn-ZnCl2 were performed with the aid of high-speed vibration mill, Retsch MM200 mixer mill and Retsch RM100 mortar grinder to give pinacol coupling and reduction products in varying yields.

Metal Chlorides Supported Solid Catalysts for F-C Acylations of Arenes

A series of metal chlorides supported solid catalysts were prepared by simple wet impregnation method. Their catalytic performances for Friedel-Crafts acylation of toluene with benzoyl chloride were evaluated and the excellent results were obtained over FeC13/SiO2. These catalysts were characterized by BET, NH3-TPD and FT-IR of pyridine adsorption to clarify the structure-activity relationship. It was found that FeC13/SiO2 has larger pore size and pore volume than other catalysts, which increased the accessibility of the catalyst. In addition, FeC13/SiO2 ex- hibited higher molar ratio of Lewis acid sites and Brtpnsted acid sites, which might be another reason for the in- crease of toluene conversion. Furthermore, the reaction parameters, including temperature, time and molar ratio, were optimized. Under the optimized conditions, 91.2% conversion and 82.0% selectivity were obtained. Mean- while, the generality of the catalyst was demonstrated by the acylations of alkyl substituted aromatics. Finally, the catalyst was reused for four runs with slight loss in catalytic activity, which attributed to the drain of the active component.

A new approach to the bicyclo[3.3.1]nonane framework of huperzine A-like molecules via palladium-catalyzed intramolecular γ-arylation

In our synthetic studies toward huperzine A, a diastereoselective α＇-alkylation of the α-amido-γ-methyl hexenone 4 was real- ized through a dianion intermediate which significantly enhanced the reactivity. Under the attempted Heck reaction conditions, an unexpected and unprecedented palladium-catalyzed intramolecular T-arylation of 3 was observed, which generated 18 with bicyclo[3.3, l]nonane framework in satisfactory yield.