610-72-0Relevant articles and documents
P -Xylene from 2,5-dimethylfuran and acrylic acid using zeolite in a continuous flow system
Al-Naji, Majd,Antonietti, Markus,Brandi, Francesco,Mendoza Mesa, Jose Alirio,Shekova, Irina
supporting information, p. 7398 - 7405 (2020/11/25)
The continuous flow synthesis of p-xylene (pXL) via Diels-Alder cycloaddition of lignocellulosic biomass-derivable 2,5-dimethylfuran (DMF) and acrylic acid (AA) was performed over different type of zeolites, i.e. Beta, ZSM-5 and Y. Among the tested zeolites, Beta zeolite showed an optimum catalytic performance in pXL synthesis from DMF and AA. In this context, Beta zeolite with a Si/Al molar ratio of 150 which is abbreviated as Beta(150), resulted in complete DMF conversion with a pXL yield of 83% and by-product 2,5-dimethylbenzoic acid (DMBA) with a yield of 17%, at 473 K in 10.1 min residence time (τ), with excess AA (0.7 M). This high catalytic activity is attributed to the high specific surface area of 1180 m2 g-1 with a three-dimensional porous architecture with a pore diameter of 6.6 × 6.7 ? and an acid site density above 40 μmol g-1. The utilized Beta(150) showed a very stable performance up to 10 h time on stream with minor deactivation after 8 h of TOS, while the pXL yield remained above 70%. The original catalytic performance of Beta(150) in the conversion of DMF to pXL was restored by applying a regeneration step for the spent catalyst, which is simple in continuous flow reactors. Finally, this sustainable continuous flow process enables an efficient and selective pXL production from DMF and AA as a dienophile at lower reaction temperature (473 K) and shorter residence time (τ = 10.1 min) in comparison to a batch fashion. This journal is
Palladium-Catalyzed ortho-C-H Methylation of Benzoic Acids
Lv, Weiwei,Wen, Si,Liu, Jing,Cheng, Guolin
, p. 9786 - 9791 (2019/08/26)
A palladium-catalyzed methylation of C-H bonds of benzoic acids with di-tert-butyl peroxide as the methylating reagent under an external oxidant and ligand-free conditions has been achieved. The reaction is found to be directed by a weakly coordinating carboxyl group, offering a facile route for the synthesis of highly functionalized ortho-methyl benzoic acids.
Preparation method for o-tolylacetic acid aryl formic acid derivative
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Paragraph 0024-0039, (2019/07/16)
The invention discloses a preparation method for an o-tolylacetic acid aryl formic acid derivative. According to the method, new C-C bonds can be formed, the organic o-tolylacetic acid aryl formic acid derivative is obtained, the good functional group tolerance is achieved, and the o-tolylacetic acid aryl formic acid derivative which cannot be easily obtained by adopting other methods can be synthesized; according to the method, adopted raw materials are easy to obtain, the yield is high, the reaction conditions are mild, the substrate range is wide, and after-treatment is simple and green.
Ionic liquid, preparation method and application
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Paragraph 0240; 0241; 0242; 0243; 0244, (2018/03/28)
The invention relates to an ionic liquid. Cations of the ionic liquid contain hexafluoroisopropyl sulfonic acid groups. According to the ionic liquid provided by the invention, the hexafluoroisopropylsulfonic acid groups are introduced into the cation part of the ionic liquid to give a super acid center to the ionic liquid, through changing anion types, the ionic liquid of which the acidity is greater than that of 98% concentrated sulfuric acid is obtained, and the highest level of the hamlet acidity (H0) in the obtained ionic liquid can reach -14.13.
Method for preparing aromatic acid by direct carboxylation of CO2
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Paragraph 0056; 0057; 0058, (2018/05/16)
The invention discloses a method for preparing aromatic acid by direct carboxylation of CO2. The method comprises the following steps: (1) adding aromatic hydrocarbon, organic alkali and lewis acid into a high pressure reaction kettle under an inert gas atmosphere, then feeding CO2 gas into the high pressure reaction kettle for reaction, and obtaining reaction liquid with aromatic acid at the endof the reaction; (2) adding water into the reaction liquid obtained in the step (1), then extracting the aromatic acid in the reaction liquid with an extracting agent to enable the aromatic acid in the reaction liquid to enter an extracting phase, separating the extracting phase from raffinate, and concentrating the extracting phase to obtain the aromatic acid. According to the method, complicatedpreparation of ionic liquid is avoided, and organic alkali is timely neutralized with halogen hydride produced by the reaction, so that the balance moves rightwards; at the end of the reaction, the organic alkali also can be recycled through alkali treatment. The method has the advantages of simple operation, mild conditions, green process, low cost and the like, and is expected to be applied toindustrial production.
Selectivity Control in the Tandem Aromatization of Bio-Based Furanics Catalyzed by Solid Acids and Palladium
Genuino, Homer C.,Thiyagarajan, Shanmugam,van der Waal, Jan C.,de Jong, Ed,van Haveren, Jacco,van Es, Daan S.,Weckhuysen, Bert M.,Bruijnincx, Pieter C. A.
, p. 277 - 286 (2017/01/17)
Bio-based furanics can be aromatized efficiently by sequential Diels–Alder (DA) addition and hydrogenation steps followed by tandem catalytic aromatization. With a combination of zeolite H-Y and Pd/C, the hydrogenated DA adduct of 2-methylfuran and maleic anhydride can thus be aromatized in the liquid phase and, to a certain extent, decarboxylated to give high yields of the aromatic products 3-methylphthalic anhydride and o- and m-toluic acid. Here, it is shown that a variation in the acidity and textural properties of the solid acid as well as bifunctionality offers a handle on selectivity toward aromatic products. The zeolite component was found to dominate selectivity. Indeed, a linear correlation is found between 3-methylphthalic anhydride yield and the product of (strong acid/total acidity) and mesopore volume of H-Y, highlighting the need for balanced catalyst acidity and porosity. The efficient coupling of the dehydration and dehydrogenation steps by varying the zeolite-to-Pd/C ratio allowed the competitive decarboxylation reaction to be effectively suppressed, which led to an improved 3-methylphthalic anhydride/total aromatics selectivity ratio of 80 % (89 % total aromatics yield). The incorporation of Pd nanoparticles in close proximity to the acid sites in bifunctional Pd/H-Y catalysts also afforded a flexible means to control aromatic products selectivity, as further demonstrated in the aromatization of hydrogenated DA adducts from other diene/dienophile combinations.
A Simple and Mild Approach for the Synthesis of p-Xylene from Bio-Based 2,5-Dimethyfuran by Using Metal Triflates
Ni, Lingli,Xin, Jiayu,Dong, Huixian,Lu, Xingmei,Liu, Xiaomin,Zhang, Suojiang
, p. 2394 - 2401 (2017/06/13)
The production of aromatic platform chemicals from biomass-derived feedstocks is of considerable importance in biomass conversion. However, the development of effective routes with simple steps and under mild conditions is still challenging. In this work, we report an original route for the direct synthesis of p-xylene from 2,5-dimethylfuran and acrylic acid catalyzed by scandium(III) triflate (Sc(OTf)3) in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim]NTf2) under mild conditions. An overall 63 % selectivity towards p-xylene and 78 % selectivity towards aromatics were obtained at 90 % conversion of 2,5-dimethylfuran by enhancing the dehydration and introducing an extra one-pot decarboxylation step. Furthermore, various dienes and dienophiles were employed as reactants to extend the substrate scope. The aromatic compounds were obtained in moderate yields, which proved the potential of the method to be a generic approach for the conversion of bio-based furanics into renewable aromatics.
A carbon dioxide by the method of preparing the arylcarboxylic acid
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Paragraph 0048-0049, (2017/03/22)
The invention discloses a method for preparing arylformic acid from carbon dioxide, belonging to the technical field of comprehensive utilization of carbon dioxide. The method comprises the following concrete steps: reacting sodium arylsulfinate with CO2 (0.1MPa) in a Schlenk tube subjected to dehydration and deoxidation treatment in the presence of a catalytic system comprising copper salt, a nitrogen-containing ligand and alkali, and acidifying reaction liquid by a diluted hydrochloric acid solution to obtain arylformic acid. A catalyst used in the catalytic system is simple and easily available, high in catalytic activity, low in consumption, relatively mild in reaction condition and good in universality on sodium arylsulfinate. Raw materials in the preparation method disclosed by the invention are easily available, the reaction condition is mild, a reaction substrate is good in universality, the reaction time is short, the yield of a target product is high, and the reaction operation and the post-treatment process are simple.
A Facile Solid-Phase Route to Renewable Aromatic Chemicals from Biobased Furanics
Thiyagarajan, Shanmugam,Genuino, Homer C.,Van Der Waal, Jan C.,De Jong, Ed,Weckhuysen, Bert M.,Van Haveren, Jacco,Bruijnincx, Pieter C. A.,Van Es, Daan S.
supporting information, p. 1368 - 1371 (2016/02/12)
Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels-Alder (DA) aromatization route, to effectively block retro-DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal-based dehydrogenation catalyst and solid acid dehydration catalyst in toluene. Herein it is demonstrated that the hydrogenated DA adducts can instead be conveniently converted into renewable aromatics with up to 80 % selectivity in a solid-phase reaction with shorter reaction times using only an acidic zeolite, that is, without solvent or dehydrogenation catalyst. Hydrogenated adducts from diene/dienophile combinations of (methylated) furans with maleic anhydride are efficiently converted into renewable aromatics with this new route. The zeolite H-Y was found to perform the best and can be easily reused after calcination. Just heat and tumble: Furanics-derived hydrogenated Diels-Alder adducts can be conveniently converted, over acidic zeolites, into renewable aromatics using a solid-phase conversion strategy. The zeolite H-Y was found to perform the best and can be easily reused after calcination.
Iron-Catalyzed Ortho C-H Methylation of Aromatics Bearing a Simple Carbonyl Group with Methylaluminum and Tridentate Phosphine Ligand
Shang, Rui,Ilies, Laurean,Nakamura, Eiichi
supporting information, p. 10132 - 10135 (2016/08/31)
Iron-catalyzed C-H functionalization of aromatics has attracted widespread attention from chemists in recent years, while the requirement of an elaborate directing group on the substrate has so far hampered the use of simple aromatic carbonyl compounds such as benzoic acid and ketones, much reducing its synthetic utility. We describe here a combination of a mildly reactive methylaluminum reagent and a new tridentate phosphine ligand for metal catalysis, 4-(bis(2-(diphenylphosphanyl)phenyl)phosphanyl)-N,N-dimethylaniline (Me2N-TP), that allows us to convert an ortho C-H bond to a C-CH3 bond in aromatics and heteroaromatics bearing simple carbonyl groups under mild oxidative conditions. The reaction is powerful enough to methylate all four ortho C-H bonds in benzophenone. The reaction tolerates a variety of functional groups, such as boronic ester, halide, sulfide, heterocycles, and enolizable ketones.
