A new way of probing reaction networks: analyzing multidimensional parameter space

Technically relevant partial oxidation reactions represent complex reaction networks. Establishing a kinetic model for a system of multiple consecutive and parallel reaction steps is a challenging goal. The synthesis of acrylic acid by oxidation of propane using MoVTeNb mixed oxide as catalyst is such a reaction network. In an on-going study, a 10- fold parallel reactor set-up is used to vary systematically reaction conditions in a broad range over a single, well-defined MoVTeNb oxide. Selectivity and product yield in a multidimensional parameter space can give insight into the reaction network. Apparent activation energies and reaction orders of propane are derived for several conditions. Optimum reaction conditions within the investigated parameter space are specified. The results presented within this contribution contain about 200 data points measured in steady states each corresponding to reaction conditions that differ in temperature, contact time, and propane feed concentration. The fact that this data was collected in less than two months shows clearly the advantage of parallel screening of reaction conditions for mechanistic studies.     

Modeling Polycondensation of Lactic Acid

Summary: A mathematical model for the polycondensation of lactic acid accounting for water removal by diffusion is developed. The corresponding kinetic parameters are estimated by performing experiments under different sets of reaction conditions in open system. The model results are compared with the experimental ones and, after validating the model, parametric simulations are further carried out to understand the effects of operating conditions such as reaction temperature, catalyst activity, and reaction pressure.     

甲醛与新制氢氧化铜反应实验的商榷及思考

利用SPSS21.0软件设计正交实验探讨甲醛与新制氢氧化铜反应的最佳条件,并在此条件下运用化学方法进行产物分析,得出主要产物为Cu,HCOONa,H2和H2O,副产物为Cu2O的结论。研究从明确实验条件、分析实验产物等方面提供了实验探究的样例。     

Copper-catalyzed three-component reaction of ethynylstibanes,organic azides,and selenium: A simple and efficient synthesis of novel selenides and diselenides having 1,2,3-triazole rings

A simple method for the synthesis of monoselenides and diselenides having 1,2,3-triazole ring is described herein. The three component reaction of ethynylstibanes, organic azides, and selenium powder is catalyzed by CuI (10?mol%) using 1,10-phenanthroline as the ligand (10?mol%) under aerobic conditions. Either selenides or diselenides can be synthesized by selecting the appropriate amount of selenium powder for otherwise identical reaction conditions. The obtained selenides and diselenides having a 1,2,3-triazole ring are all novel compounds. By using an antimony reagent, this one-pot reaction provides regioselective double Se-arylation under simple reaction conditions.     

Sulfated polyborate catalyzed Kabachnik-Fields reaction: An efficient and eco-friendly protocol for synthesis of α-amino phosphonates

An efficient, and environmentally benign protocol for a three-component Kabachnik-Fields reaction of aldehydes, amines, and diethyl phosphite catalyzed by sulfated polyborate has been described to afford α-amino phosphonates under solvent-free reaction conditions. The major advantages of the present method are high yields, short reaction time, simple work-up procedure, inexpensive, eco-friendly and reusable catalyst and solvent-free reaction conditions and tolerance towards various functional groups present in the substrates.     

Isocyanide based multicomponent reactions of oxazolidines and related systems

N-Alkyloxazolidines react in a multicomponent reaction with carboxylic acids and isocyanides to give N-acyloxyethylamino acid amides. The previously reported reaction conditions were improved using a design of experiments approach (DoE). Under the optimised conditions, good yields of the N-acyloxyethylamino acid amide products are obtained both via a three- or four-component approach from N-alkylethanolamines, aldehydes/ketones, isocyanides and carboxylic acids. The reaction of oxazolidines without a nitrogen substituent was found to give either the expected Ugi products or the N-acyloxyethylamino acid amides depending on the choice of reaction conditions. Optimised reaction conditions were also developed for the ring-expansion of oxazolidines to morpholin-2-ones via reaction with an isocyanide followed by hydrolysis. The mechanistic pathway of the multicomponent reaction was briefly investigated using an ¹⁸O labelling experiment. The carboxylic acid component can be replaced by a range of other acidic nucleophiles including thiobenzoic acid, thiophenol or 5-phenyltetrazole, which are incorporated via an alternative pathway. These latter reactions can also be applied to 2-aminotetrahydrofurans, 2-aminotetrahydropyrans or 4-hydroxybut-2-one, further extending the structural diversity of the multicomponent reaction products.     

布洛芬-扑热息痛孪药的合成

以布洛芬（IPF）和扑热息痛（PCM）为原料,无水丙酮和乙酸乙酯为溶剂,二环己基碳二亚胺（DCC）为脱水剂,4-二甲氨基吡啶（DMAP）为催化剂,合成了布洛芬-扑热息痛孪药（PHI）,以重结晶法对目标产物进行纯化,产物结构经IR和1H NMR确定。 探讨了原料比例、脱水剂用量、催化剂用量、反应时间和溶媒用量对目标物产率的影响,并采用正交试验筛选最优合成工艺,最终确定的最优反应条件为:n(PCM)∶n(IPF)=1∶1.5,催化剂的最佳用量为布洛芬质量的10%,反应时间为8 h,溶媒体积为70 mL（V(乙酸乙酯)∶V(丙酮)=1∶1）,在该条件下,目标物PHI的产率为66.53%。     

PREPARATION OF STARCH SUCCINATE WITH INTERMEDIATE DS BY AQUEOUS SLURRY REACTION

The succinylation of cornstarch by slurry reaction has been studied using sodium hydroxide as catalyst.Several reaction parameters affecting the succinylation were investigated including the concentration of starch in water,the ratio of succinic anhydride to starch,the reaction time and the reaction temperature,The favorable conditions for an intermediate degree of substitution(DS) and reasonably high reaction efficiency(RE) are pH 8.5-9.0,50% starch by weight to water.succinic anhydride to starch 1/1(w/w),reaction time 4h,reaction temperature 30℃ .Under these conditions,the DS of 0.45 and RE of 28% were achieved.The addition of an adequate amount of crosslinking agent imparted starch succinate water absorbency.     

The effect of cyclodextrins on the hydrolysis of carboxylic acid esters

Cyclodextrins and their derivatives act as inverse phase-transfer catalysts in the hydrolysis of carboxylic acid esters. The reaction is affected by temperature, choice of cyclodextrin and also by the stirring rate. Lipophilic esters are better hydrolyzed under inverse phase-transfer catalysis conditions than under classic phase-transfer catalysis (PTC) conditions. Some typical features of the reaction are emphasized and compared with classical PTC reactions.     

迈克尔加成法合成乙二胺枝状化合物

以乙二胺和丙烯酸异辛酯为原料,甲醇为溶剂,在无催化剂条件下,经迈克尔加成反应合成了低代的树枝状化合物.探讨了反应条件对产率的影响,发现适宜的条件为:n(乙二胺)∶n(丙烯酸异辛酯)=1∶5.0~6.5,反应温度为5~10℃,反应时间为48 h左右,产率可达55%.     

Selective oxidative cyclization by FeCl3 in the construction of 10H-indeno[1,2-b]triphenylene skeletons in polycyclic aromatic hydrocarbons

A novel family of polycyclic aromatic hydrocarbons of various shapes based on the 10H-indeno[1,2-b]triphenylene skeleton has been synthesized via a reaction sequence of Diels-Alder reaction, decarbonylation, followed by an oxidative cyclization. In particular, the reaction conditions for regioselective oxidative cyclization promoted by FeCl3 are investigated, and this reaction is employed as an effective method to afford the above molecules under mild conditions. Their photophysical properties in dilute solution are also reported.     

Palladium nanoparticles decorated on reduced graphene oxide: An efficient catalyst for ligand‐ and copper‐free Sonogashira reaction at room temperature

This article focuses on a room temperature copper‐free Sonagashira cross‐coupling reaction in ethanol, catalysed by palladium nanoparticles homogeneously deposited on reduced graphene oxide. The catalyst showed efficient catalytic activity towards the said coupling reaction, and was well characterized using various techniques, and could be reused up to six times with almost constant yield of the desired product. The attractions of this protocol are that the reaction completes within short reaction time under ligand‐ and copper‐free conditions and it avoids harsh reaction conditions.     

Mild and efficient cyclization reaction of 2-ethynylaniline derivatives to indoles in aqueous medium

Results of the optimized cyclization reaction of 2-ethynylaniline derivatives to indoles catalyzed by copper(II) salts are described. The reactions can be carried out in a mixture of H₂O and MeOH in the presence of 1-ethylpiperidine at room temperature. These conditions can be applied to a bulky substrate, which is difficult to be cyclized efficiently by existing reaction conditions. Furthermore, this reaction condition was applied to a catalyst recycling reaction system.     

Neutral amphiphilic polysaccharides: chemical structure and emulsifying properties

Dextran, a neutral bacterial polysaccharide, is chemically modified by reaction with an aromatic epoxide (phenylglycidylether). The reaction conditions are either homogeneous, using dimethylsulfoxide as a common solvent, or heterogeneous, dispersing the epoxide into an aqueous solution of dextran. The grafting yield is much higher in homogeneous conditions. The viscometric characteristics of the amphiphilic polysaccharides are examined in water and in dimethylsulfoxide. These properties clearly depend on both the degree of substitution and the reaction conditions at a given degree of substitution. Highly modified dextrans (with more than 30% hydroxyl substituted) exhibit characteristic solubility in organic liquids that are non-solvents for the unmodified dextran. Changing the degree of hydrophobic substitution of the amphiphilic polysaccharide, direct and inverse submicronic emulsions are prepared. The stability of direct and inverse emulsions is analysed by following the evolution of the droplet size. Ostwald ripening is the major ageing process for both emulsions.     

Determination of Hydroxyl Groups in Epoxy Resins by Potentiometric Titration Using a Reaction with Maleic Anhydride

A reaction of maleic anhydride with epoxy–dian resins in methyl ethyl ketene was investigated. It was shown by potentiometric titration that the resulting maleic esters are stable to hydrolysis in acid and weakly acid organic solutions. This reaction can be used for the quantitative determination of hydroxyl groups in epoxy resins. Epoxy groups do not interfere with the formation of maleic esters under the conditions of determination. The optimal reaction conditions were found. The reaction kinetic was investigated, the reaction rate constants were determined at various temperatures, and the activation energy was found. The value of the activation energy indicates that the reaction is characterized by a low potential barrier.     

Revisiting the reaction between diaminomaleonitrile and aromatic aldehydes: a green chemistry approach

The reaction between diaminomaleonitrile (DAMN) and aldehydes and the resulting monoimines are well known. Since the standard reaction conditions involve the use of toxic solvents (typically methanol), we have sought to apply green chemistry principles to this reaction by either using water as the solvent without any catalysts or employing "solvent-free" conditions. The monoimines derived from DAMN are of interest as precursors for obtaining different heterocyclic systems and linear polymers. The methodologies used have significant advantages with regards to cost and environmental considerations.     

THE NITROMETHANE INITIATOR OF THE FRIEDEL-CRAFTS NAPHTHALENE REACTION USING MICROWAVES

The alkylation of naphthalene using halogen derivatives may be achieved under very simple conditions by the Friedel–Crafts reaction. The products are obtained by irradiation of the paste containing the reaction mixture and a small quantity of nitromethane to initiate the reaction.     

Amberlite-IR 120 catalyzed three-component synthesis of α-amino phosphonates in one-pot

A simple, efficient, and environmentally benign method for a three-component reaction of an amine, an aldehyde or a ketone, and diethyl phosphite catalyzed by Amberlite-IR 120 resin has been developed to afford α-amino phosphonates in high yields and short reaction times under solvent-free reaction conditions. The major advantages of the present method are good yields, inexpensive, ecofriendly and reusable catalyst, mild and solvent-free reaction conditions and tolerance towards various functionalities present in the substrates.     

Expeditious and efficient synthesis of Strecker’s α-aminonitriles catalyzed by sulfated polyborate

A straightforward, mild, efficient, and environmentally benign protocol for a three-component Strecker reaction of aldehydes or ketones, amines, and trimethylsilyl cyanide catalyzed by sulfated polyborate has been described to afford α-aminonitriles under solvent-free reaction conditions. The major advantages of the present method are excellent yields, shorter reaction time, simple experimental procedure, easy workup procedure, recyclability of the catalyst, solvent-free reaction conditions and ability to tolerate a variety of functional groups which gives economical as well as ecological rewards.     

Organocatalyzed Friedel-Crafts arylation of benzylic alcohols

Electron-rich aromatic and heteroaromatic rings are functionalized directly with a variety of benzylic alcohols under mild conditions. The reaction is catalyzed by commercially available pentafluorophenylboronic acid, which is stable under ambient conditions and recoverable. The reaction itself is highly atom economical and produces water as the only byproduct. A Friedel-Crafts mechanism is proposed.