498-21-5Relevant articles and documents
Selective defunctionalization of citric acid to tricarballylic acid as a precursor for the production of high-value plasticizers
De Vos, Dirk E.,Krajnc, Andra?,Mali, Gregor,Stuyck, Wouter,Verduyckt, Jasper
, p. 7812 - 7822 (2020)
Strong concerns about the toxicity and endocrine disrupting properties of widespread phthalate plasticizers stimulate the demand for safe and preferably biobased alternatives. Citric acid forms in this respect an excellent and abundant platform chemical for the production of valuable plasticizers. Here, we report a new and direct synthesis route for propane-1,2,3-tricarboxylic acid (PTA) from citric acid via a sequential one pot dehydration-hydrogenation process. This saturated triacid can serve as a basis for the production of tricarballylate esters via esterification, which have been shown to possess excellent plasticizing properties in vinyl resins. In the presence of a solid acid H-Beta zeolite and Pd/C hydrogenation catalyst, yields up to 85% of PTA were obtained under mild reaction conditions and in water as a green solvent. Partial dealumination of the H-Beta zeolite by citric acid could be counteracted by reincorporating aluminium into the framework of the recycled H-Beta zeolite through realumination, regenerating a significant fraction of the initial activity of the catalytic system. The success of the realumination procedure was verified via MAS NMR spectroscopy.
Electrocatalytic upgrading of itaconic acid to methylsuccinic acid using fermentation broth as a substrate solution
Holzh?user, F. Joschka,Artz, Jens,Palkovits, Stefan,Kreyenschulte, Dirk,Büchs, Jochen,Palkovits, Regina
, p. 2390 - 2397 (2017)
Biomass presents a promising renewable feedstock allowing access to valuable platform chemicals. In particular, biotechnological processes enable a highly selective product formation but are carried out in aqueous electrolyte-containing solutions. Consequently, the separation of usually polar products poses severe challenges on product separation associated with a high energy demand of product purification. A direct further catalytic transformation within fermentation broth reduces the number of unit operations and the need for an energy intensive separation. We herein study the potential of a chemo- and electrochemical reduction of itaconic acid (IA) to methylsuccinic acid (MS) using acidic media or crude fermentation broth as a case study. Despite an efficient chemo-catalytic hydrogenation of neat IA over Ru/C or RANEY nickel, the presence of various salts as well as glucose prohibits a direct chemo-catalytic valorisation in fermentation broth. In contrast, the electrochemical hydrogenation enabled very benign conditions. The selection of the electrode material proved to be decisive and had, together with the voltage, a strong influence on the conversion and faradaic efficiency of electrolysis facilitating 99% faradaic efficiency. The conversion of IA only slightly declined for an IA fermentation broth instead of neat IA in a diluted sulfuric acid environment reaching 60 versus 64%. Moreover, a full conversion and yield could also be achieved by simple optimizations of the reaction period and the substrate concentration. The electrocatalytic valorisation of a crude biotechnological product stream reduces not only energy demand and unit operations but presents a promising approach to introduce renewable electrical energy in biomass utilization.
Stabilising Ni catalysts for the dehydration-decarboxylation-hydrogenation of citric acid to methylsuccinic acid
Verduyckt, Jasper,Geers, Anton,Claes, Birgit,Eyley, Samuel,Van Goethem, Cédric,Stassen, Ivo,Smolders, Simon,Ameloot, Rob,Vankelecom, Ivo,Thielemans, Wim,De Vos, Dirk E.
, p. 4642 - 4650 (2017)
A new reaction sequence of dehydration-decarboxylation-hydrogenation to transform citric acid into methylsuccinic acid has recently been developed using Pd as a noble metal catalyst in water. In this work Ni catalysts were investigated as low cost, non-noble metal alternatives. Several home-made and commercial catalysts were screened for this reaction. Citric acid was very reactive and full conversions were readily obtained in all cases. However, the selectivity to methylsuccinic acid was initially low, since typical Ni catalysts were not stable and therefore not able to hydrogenate the formed CC double bonds. Due to the lower hydrogenation activity of Ni compared to Pd, new side products appeared. Particularly, hydration of the CC double bonds made the reaction network more complex in this case. Fortunately, the formation of all hydration products-even the rather stable lactone, β-carboxy-γ-butyrolactone-was eventually shown to be completely reversible. Three routes were then studied to stabilise Ni catalysts and to enable the Ni catalyzed conversion of citric acid to methylsuccinic acid; partial neutralisation of the acid reactant, adding Fe to Ni/ZrO2 or to the reaction mixture and coating Ni particles with carbon, all proved to stabilise Ni and all resulted in high to very high methylsuccinic acid yields. Furthermore, the role of Fe was unravelled by performing reference reactions with different Fe compounds and by in depth characterisation of the NiFe/ZrO2 catalyst. Finally, the reaction conditions were optimised using the carbon-coated Ni nanoparticles and kinetic profiles were recorded to confirm the extended reaction network.
Monitoring of itaconic acid hydrogenation in a trickle bed reactor using fiber-optic coupled near-infrared spectroscopy
Wood, Joseph,Turner, Paul H.
, p. 293 - 298 (2003)
Near-infrared (NIR) spectroscopy has been applied to determine the conversion of itaconic acid in the effluent stream of a trickle bed reactor. Hydrogenation of itaconic to methyl succinic acid was carried out, with the trickle bed operating in recycle mode. For the first time, NIR spectra of itaconic and methyl succinic acids in aqueous solution, and aqueous mixtures withdrawn from the reactor over a range of reaction times, have been recorded using a fiberoptic sampling probe. The infrared spectra displayed a clear isolated absorption band at a wavenumber of 6186 cm-1 (wavelength 1.617 μm) resulting from the =C-H bonds of itaconic acid, which was found to decrease in intensity with increasing reaction time. The feature could be more clearly observed from plots of the first derivatives of the spectra. A partial least-squares (PLS) model was developed from the spectra of 13 reference samples and was used successfully to calculate the concentration of the two acids in the reactor effluent solution. Itaconic acid conversions of 23-29% were calculated after 360 min of reaction time. The potential of FT-NIR with fiber-optic sampling for remote monitoring of three-phase catalytic reactors and validation of catalytic reactor models is highlighted in the paper.
Ligandgesteuerte Ringkontraktion von Nickela-Fuenf- in Vierringkomplexe-neuartige Startsysteme fuer die praeparative Chemie
Hoberg, Heinz,Ballesteros, Alfredo,Sigan, Andrei,Jegat, Corine,Baerhausen, Dieter,Milchereit, Armin
, p. C23 - C29 (1991)
Nickela-compounds with a five-membered ring, 4, are formed on Ni0 from CO2 and alkenes in the presence of the heterodifunctional ligand (cyclo-C6H11)2PCH2-CH2-2-pyridyl (2).A ring contraction occurs on addition of a promotor, such as BeCl2 or on heating.The greater reactivity of the nickela-complex with a four-membered ring, 6, can be used in the former reactions with CO2, CO or CH2=CH2.Such a sequence of reactions can be employed for the catalytic reaction of ethene with acrylic anilide on a (C6H11)3P/Ni0 system.
Stereochemistry of bertyadionol and related compounds
Ghisalberti,Jefferies,Toia,Worth
, p. 3269 - 3274 (1974)
Two new diterpenes related to bertyadionol have been isolated and their structure determined. Degradation of bertyadionol to 2R-methylsuccinic acid provided the configuration at C-2 for this compound. The absolute stereochemistry of bertyadionol and its c
Mechanistic aspects of hydrogen addition during enantioselective rhodium-catalysed reduction of C=C double bonds with formic acid/triethylamine or molecular hydrogen
Lange, Susanne,Leitner, Walter
, p. 752 - 758 (2002)
Deuterium labelling experiments reveal a remarkably different hydrogen addition mode during homogeneously catalysed C=C bond reduction of itaconic acid derivatives 1a-d using molecular hydrogen (hydrogenation) or formic acid/triethylamine (transfer hydrogenation). The expected vicinal addition of two hydrogen atoms across the double bond prevails for all substrates in conventional hydrogenation, whereas the deuterium pattern depends largely on the nature of the carboxyl group in the β (or allylic) position during transfer hydrogenation. Vicinal addition is observed only in case of itaconic acid 1a and α-methylitaconate 1c, while 1,3-addition is preferred with dimethylitaconate 1b and β-methylitaconate 1d. Significant amounts of polydeuterated products are formed also during hydrogenation and transfer hydrogenation. Monitoring the deuterium pattern as a function of time reveals that deuterium scrambling is responsible for polydeuteration, but not for the change of the addition mode. The use of monodeuterated formic acid isotopomers shows that the incorporation from the hydridic formyl position occurs preferentially at the terminal end of the double bond (C-3) whereas the protic hydrogen is directed either in the higher substituted olefinic (C-2) or the methylene (C-1) position. Control experiments using mesaconic (2) and citraconic (3) acids demonstrate that double bond migration in 1a-d is negligible under the reaction conditions. These results are best rationalised on the basis of a common mechanism for hydrogenation and transfer hydrogenation that involves (i) the generation of Rh-H intermediates, (ii) reversible hydride transfer to coordinated substrate to form two isomeric σ-alkyl intermediates, and (iii) irreversible product liberation through protolytic Rh-C cleavage. The key intermediates are similar if not identical for hydrogenation and transfer hydrogenation. The change of the hydrogen transfer pattern can be explained on the basis of the relative rates of the individual steps within the catalytic cycle as compared to the rate of isomerisation of the σ-alkyl intermediates. The Royal Society of Chemistry 2002.
Efficient conversion of bio-renewable citric acid to high-value carboxylic acids on stable solid catalysts
Li, Zhaowei,Liu, Haichao,Wen, Xin
, p. 1650 - 1658 (2022/03/07)
Citric acid is an important biomass-derived platform chemical for the synthesis of high-value organic acids, such as itaconic acid (ICA), 2-methylsuccinic acid (MSA) and tricarballylic acid (TCA). However, these reactions frequently encounter low efficiency and severe leaching of catalysts imposed by the acidity of citric acid under hydrothermal conditions, limiting their practical applications. Here, we report that highly acid- and etching-resistant monoclinic zirconium dioxide (m-ZrO2) exhibited high catalytic efficiency in the conversion of citric acid to ICA via sequential dehydration and decarboxylation steps, providing a high yield of 70.3% at 180 °C on m-ZrO2 (calcined at 300 °C). The correlation between the activity of the m-ZrO2 catalysts and their acid-basicity demonstrates that the synergistic effect of acidic and basic sites facilitates the rate-determining dehydration step for the citric acid conversion to ICA. On the bifunctional catalysts, Pt and Pd nanoparticles supported on P25 and anatase TiO2, citric acid can be selectively converted to MSA and TCA, respectively, with yields as high as 83.1% and 64.9%. The hydrogenation activity of the bifunctional catalysts was found to be crucial for regulating the relative rates of the decarboxylation and hydrogenation steps involved in the selective conversion of citric acid to MSA and TCA. These catalysts showed excellent stability and recyclability in acidic aqueous solutions. This study provides a rationale for tuning catalytic functions required for the green production of important carboxylic acids from citric acid and other biomass-derived feedstocks. This journal is
CATALYST AND METHOD OF HYDROGENATING UNSATURATED COMPOUND WITH MULTI-CARBOXYLIC ACID GROUPS
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Paragraph 0024-0040; 0042, (2021/06/26)
A method of hydrogenating unsaturated compound with multi-carboxylic acid groups is provided, which includes introducing hydrogen to an unsaturated compound with multi-carboxylic acid groups in the presence of a catalyst to hydrogenate the alkene or alkyne group of the unsaturated compound with multi-carboxylic acid groups without hydrogenating the carboxylic acid groups of the unsaturated compound with multi-carboxylic acid groups. The catalyst includes a support, and palladium and metal oxide loaded on the support.
Catalytic Aerobic Oxidation of Lignocellulose-Derived Levulinic Acid in Aqueous Solution: A Novel Route to Synthesize Dicarboxylic Acids for Bio-Based Polymers
Che, Li,Jiang, Min,Jiang, Yu,Pang, Jifeng,Song, Lei,Wang, Rui,Zhang, Tao,Zhao, Yu,Zheng, Mingyuan,Zhou, Guangyuan,Zhou, Mo
, p. 11588 - 11596 (2021/09/22)
The world is facing grand and ever-increasing pressures on energy and environmental issues. Using carbon-neutral biomass to prepare monomers such as dicarboxylic acids for degradable polymers is of great significance and an urgent but challenging task. Herein, we report a catalytic route for the synthesis of 2-hydroxy-2-methylsuccinic acid, an excellent monomer: e.g., it is able to remarkably enhance the comprehensive properties of polybutylene succinate as shown herein. By catalytic aerobic oxidation of levulinic acid, a bulk platform chemical derived from lignocellulose, the target product was obtained with a very high selectivity of up to ca. 95%. The mild reaction conditions below 100 °C in water and the low-cost reusable heterogeneous catalyst further make the process highly attractive for applications. This process was also found to be effective for the conversion of homologues of levulinic acid to dicarboxylic acids. We studied the C-C bond rearrangement and the roles of catalysts in the reaction that are highly likely involved in a superoxide anion radical mechanism. This study may provide inspiration for the synthesis of bio-based dicarboxylic acids via alternative routes.
