格氏反应合成β-大马酮工艺的改进

报道了一步法格氏反应在 β 大马酮合成中的应用 ,采用一步法格氏反应代替传统的两步法格氏反应 ,缩短了反应时间 ,简化了工艺流程 ,从而提高了收率 ,获得了一条适合于工业化生产的合成路线     

Mechanism and kinetic study for the intensification of two-step synthesis of a dolutegravir intermediate in microreactor

Multi-step reaction processes are frequently encountered in the synthesis of pharmaceuticals, separate study on each step however is easily neglected. Herein, we separately investigated two reaction steps for the synthesis of an intermediate (DTG-6) of an anti-HIV drug dolutegravir (DTG) in microreactors. The first step (i.e., deprotection of DTG-4) was optimized to achieve a high DTG-5 yield (i.e., 96.7%) in the microreactor after the parametric screening on the DTG-4 concentration, methanesulfonic acid loading, molar ratio of reaction components, and so forth. Reaction kinetics was revealed based on substantial experimental data and mechanism cognition. Validation experiments showed the accuracy of this reaction kinetics. After thoroughly understanding this deprotection step, we combined it with the following annelation step in a cascade microreactor system for the two-step synthesis of DTG-6 with a much higher yield even at a remarkably shorter residence time compared with literature reports, thus indicating efficient process intensification.     

Characterization of phenol–urea–formaldehyde resin by inline FTIR spectroscopy

Phenol–urea–formaldehyde (PUF) resins were synthesized by a two‐step polymerization process. The first step was the synthesis of 2,4,6‐trimethylolphenol (TMeP) from phenol and formaldehyde, under alkaline conditions. In the second step PUF resins were synthesized by the reaction of TMeP with urea, under acidic and alkaline conditions. The influence of temperature on the synthesis of TMeP was investigated. The molar ratio between TMeP and urea was varied to study the composition effect on the second step of the PUF synthesis and final product properties. Synthesis of TMeP and PUF resins were monitored by inline FTIR‐ATR system. Analytical methods, such as differential scanning calorimetry, nuclear magnetic resonance, thermogravimetric analysis, and infrared spectroscopy were used for characterization of TMeP and PUF resins. Obtained PUF resins were cured and tested on flexural strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Direct dimethyl ether synthesis by spatial patterned catalyst arrangement: A modeling and simulation study

The effect of spatially patterned catalyst beds was investigated using direct dimethyl ether (DME) synthesis from synthesis gas as an example. A layered arrangement of methanol synthesis (MS) and dehydration catalyst was chosen and studied by numerical simulation under typical operating conditions for single‐step DME synthesis. It was revealed that catalyst layers significantly influence the DME productivity. With an increasing number of layers from two to 40, an increase in DME productivity was observed approaching the performance of a physical catalyst mixture for an infinite number of layers. The results prove that a physical mixture of MS and dehydration catalyst achieves the highest DME productivity under operating conditions chosen in this study. Essentially, the layered catalyst arrangement is comparable to a cascade model of the two‐step process, which is less efficient in terms of DME yield than the single‐step process. However, the layered catalyst arrangement could be beneficial for other reaction systems. © 2012 American Institute of Chemical Engineers AIChE J, 00: 000–000, 2012     

聚氨酯丙烯酸酯的合成研究及应用

以IPDI,PEG1000和HEMA为原料合成了可紫外光固化的聚氨酯丙烯酸酯低聚物(PUA),用作凝胶聚合物电解质中的聚合物基体。对合成的产物(PUA)进行红外图谱分析,并讨论了合成过程中反应温度,反应时间,反应物配比等因素的影响。结果表明较佳的合成条件为:n(IPDI):n(PEG1000):n(HEMA)=1:2:2.08,第一步的反应温度在60～75℃,反应时间为2 h;第二步的在55～65℃,时间为2.5 h。     

Fully Enzymatic N→C‐Directed Peptide Synthesis Using C‐Terminal Peptide α‐Carboxamide to Ester Interconversion

Chemoenzymatic peptide synthesis is potentially the most cost‐efficient technology for the synthesis of short and medium‐sized peptides with some important advantages. For instance, stoichiometric amounts of expensive coupling reagents are not required and racemisation does not occur rendering purification easier compared to chemical peptide synthesis. In this paper, a novel interconversion reaction of peptide C‐terminal α‐carboxamides into primary alkyl esters with alcalase was used to develop a fully enzymatic peptide synthesis strategy. For each elongation step a cost‐efficient amino acid carboxamide building block was used followed by the interconversion of the elongated peptide carboxamide to the corresponding primary alkyl ester. These peptide esters are the starting materials for the next enzymatic peptide elongation step.     

完全液相制备催化剂上合成二甲醚动力学研究

采用浆态床反应器,研究了用完全液相法制备的Cu-Zn-A l双功能催化剂上CO加氢直接合成二甲醚(DME)的反应动力学。按CO加氢先合成CH3OH,再由CH3OH脱水生成DME二步串联的反应机理,根据不同的中间产物及控制步骤分别建立了动力学模型,以反应物的平衡浓度代替逸度进行计算,最终选取的模型计算值和实验值吻合较好,说明采用L-H型动力学模型可以合理地描述催化剂表面的反应过程,模型参数计算结果表明,催化剂表面对CO2的弱吸附是该催化剂在浆态床中稳定性较好的主要原因之一。     

Synthesis of ternary distillation process structures featuring minimum utility cost using the IDEAS approach

A synthesis method for ternary distillation process structures is proposed on the basis of the infinite‐dimensional state‐space (IDEAS) approach. The proposed synthesis procedure consists of two steps. At the first step, the utility cost is minimized. The result of the first step contains many tiny flows among the modules because the number of flows is not included in the objective function. Then, at the second step, an evolutionary procedure for process simplification is executed. In this step, the weighted sum of flow rates is minimized recursively while updating the weights at each iteration. The practical process structure is finally determined from the result of the second simplification step. The developed synthesis procedure was applied to the separation problem of a ternary mixture consisting of benzene, toluene, and o‐xylene. It demonstrated that the proposed procedure provides a process whose liquid composition profile is quite similar to that of a Petlyuk column. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1285–1294, 2018     

完全液相法催化剂上甲醇脱水合成二甲醚的动力学及DFT研究

采用完全液相法制备AlOOH催化剂并进行了浆态床反应器中甲醇脱水制备二甲醚的反应动力学和DFT的研究。在3种甲醇脱水制备二甲醚的反应机理中,以表面反应即两个同时吸附的甲醇反应生成二甲醚作为速控步骤,所建立动力学模型的计算值和实验值吻合较好。采用DFT计算了液体石蜡环境中AlOOH(100)面的脱水反应,其反应过程和活化能结果与动力学模型结果基本一致,进一步表明采用该模型可以合理描述完全液相法制备的AlOOH催化剂表面甲醇脱水反应过程。     

Automatic Synthesis of Batch Process Operating Procedures

A three-step synthesis strategy for the automatic synthesis of operating procedures in batch processoperations is presented in this paper.The first step is pre-operation which consists of a set of checks that mustbe considered before starting the basic process operation.The second step is operation which is described by a setof basic control instructions.The third step is post-operation described by a set of instructions that must becarried out when the basic process operation is terminated.The three-step synthesis method has been imple-mented as part of a prototype recipe management system.     

Two-step multiobjective synthesis of sustainable chemical processes

This paper presents the development of a two-step multiobjective approach for the superstructural synthesis of sustainable chemical processes by means of mixed integer nonlinear programming methods. The first step is the usual economy-based synthesis. It is performed on a superstructure of technological and economic alternatives for identifying the best economic solution for use as a reference solution during the second step. The second step is sustainable multiobjective synthesis in which the superstructure is extended using sustainable alternatives. The economic and environmental criteria are identified for the multiobjective optimisation in order to generate sets of Pareto optimal solutions. The experiences gained by means of the two-step synthesis approach indicate that solutions can be obtained that have improved in both, often conflicting, criteria. This approach is illustrated using a well-known process of toluene hydrodealkylation.     

FeCl3/NaNO2催化氧化酰基肼化合物的研究

酰基肼化合物氧化制备酰基偶氮化合物是仲氰基化合物合成路线中重要一环。传统氧化方法通常使用等量氧化剂,而催化氧化对该反应进行相关研究鲜有文献报道。本文成功将氯化铁/亚硝酸钠催化氧化体系应用于该反应中。以氧气为氧源,该方法可对脂肪族类酰基肼化合物高效氧化为相应酰基偶氮产物。该法也为仲氰基化合物合成路线中氧化步骤提供一种更优的选择。     

新型超支化聚合物聚氨酯的合成

研究了由丁二酸酐和二乙醇胺为起始原料合成超支化聚合物的方法；采用分步反应合成出了几种聚氨酯类超支化聚合物。考察了反应时间、带水剂、封端剂及其配比对反应结果的影响。试验结果表明，第1步反应时间为3h，第2步缩和脱水反应时间为8h(甲苯为带水剂)，第3步用脱水剂封端脱水为48h；甲苯为较好的带水剂；带水剂、封端剂及其配比对产品粘度、溶解性、颜色等影响不大；产物的比浓对数粘度在0．02dL/g左右。     

二苯甲烷双马来酰亚胺的合成工艺研究

以顺丁烯二酸酐和4,4'-二氨基二苯基甲烷(DDM)为原料,采用甲苯为溶剂、共沸蒸馏法,分别用一步法和两步法合成N,N'-4,4'-二苯甲烷双马来酰亚胺(BDM)。通过产物核磁氢谱、红外色谱、示差扫描量热(DSC)及产物收率的计算和双键含量、酸值、凝胶时间、凝胶温度等的测定,对BDM一步法、两步法合成工艺进行了研究并对两种方法中生成的副产物进行了分析。结果表明,一步法比两步法产品产率有很大提高,得到的残渣较少,主要是由DDM与BDM的加成反应生成的低聚物,重新利用价值较小;两步法副产物较多,如高温条件下BMA发生分子间脱水形成的线形低聚物,其可以水解成BMA重新利用。     

4,4′,4″-三氨基三苯胺的合成

本文从对氯硝基苯和对硝基苯胺出发,经过两步反应合成了三偶氮类光导材料的重要中间体4,4′,4″-三氨基三 苯胺,其中第一反应采用KF/季铵盐催化法,收率48.4％,第二步反应采用钯碳催化加氢法,收率91.4％。     

Chemical Vapor Synthesis of FeOx–BaTiO3 Nanocomposites

Nanocomposite powders of FeO_x–BaTiO₃ (FO‐BTO) have been prepared by chemical vapor synthesis (CVS) in a single‐step process. The optimal parameters (reactor temperature, reactor length, precursor ratio) for the synthesis were investigated in an initial step for the individual systems, iron oxide (FO), and barium titanate (BTO); and in a second step optimized for the synthesis of the nanocomposites. The solid iron precursor was thermally evaporated, whereas the solid Ba‐ and Ti precursors were vaporized using laser flash evaporation to obtain ultrafine crystalline FO, BTO, and FO‐BTO nanoparticles. The possibility to influence the mass ratios of the two phases in FO‐BTO mixture by adjusting the ratio of the precursor in the two precursor delivery units has been investigated. The potential of CVS for the synthesis of nanocomposites containing iron oxide and barium titanate ultrafine crystalline nanopowders with particle size bellow 10 nm is demonstrated.     

Synthesis and properties of unsaturated epoxyfumarate resins

Synthesis and properties of epoxyfumarate and epoxymaleate resins obtained by the addition of acidic ester of maleic acid to the commercially available resin, Epidian 5, is presented. In acidic ester preparation, n‐hexanol was used. The resins were synthesized in one‐ and two‐step procedures. In the two‐step procedure, acidic hexyl maleate was synthesized separately and then used for the addition reaction with epoxy resin. In the one‐step synthesis, acidic ester was formed during the synthesis process. Properties of the obtained resins were compared. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3077–3084, 2000     

邻苯二甲酸二丁酯合成的动力学研究

采用高效液相色谱法测定了邻苯二甲酸酐（A）与正丁醇（B）合成邻苯二甲酸二丁酯（DBP）反应过程中的产品分布。研究了其反应机理,第一步,自A生成单酯酸（R）是快反应,第二步自R生成DBP是慢反应。建立了分水条件下酯化合成反应的反应动力学模型,试验数据表明DBP的合成表现为二级不可逆反应,测出第二步反应速率常数k2=0．0007 L·mol^-1·min^-1。     

四乙酰乙二胺的合成研究

以乙二胺、乙酸、乙酸酐为原料,在同一反应釜内,采用两步法合成四乙酰乙二胺。结果表明,当ｎ（乙二胺）∶ｎ（乙酸）∶ｎ（乙酸酐）＝１∶２５∶４,反应温度为１２０℃（第一步）和１４０℃（第二步）,反应时间为９～１０ｈ时,产品产率可达７５％。     

分步氟化法合成3,4-二氟苯腈的研究

以3,4-二氯苯腈为起始原料,通过分步氟化,实现了高收率制备3,4-二氟苯腈的方法。相比于先前的报道,本工艺不仅收率提高,同时有效地控制了体系焦化、聚合、变黑等高温下不利因素的影响。