106-65-0Relevant articles and documents
One-pot synthesis of dimethyl succinate from D-fructose using Amberlyst-70 catalyst
He, Liangtu,Huang, Yuzhang,Len, Christophe,Liu, Lei,Miao, Xinge,Wang, Yantao,Yang, Weiran
, (2021)
Dimethyl succinate (DMS), an important building block of bio-based platform chemicals, was produced from D-fructose under one-pot and metal-free conditions for the first time. In the presence of 1.5 mmol D-fructose, 75 mg Amberlyst-70 and 10 bar O2/
Semiconductor Photocatalysis: Visible Light Induced Photoreduction of Aromatic Ketones and Electron-deficient Alkenes catalysed by Quantised Cadmium Sulfide
Shiragami, Tsutomu,Ankyu, Hirofumi,Fukami, Shinako,Pac, Chyongjin,Yanagida, Shozo,et al.
, p. 1055 - 1062 (1992)
Colloidal CdS suspensions (CdS-0) prepared at 0 deg C from methanolic Cd(ClO4)2 and Na2S solutions consist of quantised CdS microcrystallites (2-5 nm) and their loose aggregates, which catalyse the effective photoreduction of aromatic ketones and electron-deficient alkenes with triethylamine as electron donor.Under visible light induced photolysis, the methanolic CdS-0 suspension becomes brown owing to the reduction of lattice Cd2+ to Cd0, leading to the effective formation of alcohols from ketones, and dihydro compounds from alkenes.With the reduction potential2-) in the CdS-0 system, however, suppresses the formation of lattice Cd0, inducing one-electron transfer photoreductions which result in the exclusive formation of pinacols and 1,2,3,4-tetra(methoxycarbonyl)butane from the respective ketones and dimethyl maleate.The relationship between the two-electron reductions and the photogenerated lattice Cd0 is discussed in terms of the regulation of semiconductor photocatalysis.
Selective monomethyl esterification of linear dicarboxylic acids with bifunctional alumina catalysts
Santacroce, Veronica,Bigi, Franca,Casnati, Alessandra,Maggi, Raimondo,Storaro, Loretta,Moretti, Elisa,Vaccaro, Luigi,Maestri, Giovanni
, p. 5764 - 5768 (2016)
An environmentally friendly protocol for the selective protection of dicarboxylic acids is reported using methanol as a cheap esterifying agent and alumina as a heterogeneous catalyst; the selectivity of the process has been ascribed to a balanced acidity/basicity of the bifunctional alumina catalyst.
Oxidative carbonylation of ethene catalyzed by Pd(II)-PPh3 complexes in MeOH using benzoquinone as stoichiometric oxidant
Cavinato, Gianni,Facchetti, Sarah,Toniolo, Luigi
, p. 63 - 69 (2012)
The complexes [Pd(COOMe)nX2-n(PPh3) 2] (n = 0, 1, 2; X = TsO, OAc, ONO2, Cl, Br), [Pd(SO 4)(PPh3)2], [PdCl2(PPh 3)]2 and PdX2 (X = Cl, Br, I) catalyze the oxidative ethene carbonylation in MeOH using benzoquinone (BQ) as stoichiometric oxidant. The main products dimethyl succinate (DMS) and dimethyl oxalate (DMO) are formed together with minor amounts of methyl propanoate and dimethyl carbonate. The formation of DMS unambiguously proves that ethene inserts into a Pd-COOMe bond. The influence of the CO/ethene ratio at constant total pressure and of the BQ/Pd ratio on the product distribution has been studied. Model reactions of a Pd-hydride with BQ, of trans-[Pd(COOMe)(TsO)(PPh 3)2] with ethene in the presence of BQ and of trans-[Pd(COOMe)2(PPh3)2] with BQ have been studied by 31P{1H} NMR. BQ consumes the Pd-hydride and directs the catalysis toward a Pd-COOMe initiator leading to DMS. In the catalysis to DMO, BQ is likely to favour the formation of a Pd-(COOMe) 2 species having the two carbomethoxy ligands in vicinal position such to favour the elimination of the product. The proposed catalytic cycles for the formation of the products are discussed.
Conversion of levulinate into succinate through catalytic oxidative carbon-carbon bond cleavage with dioxygen
Liu, Junxia,Du, Zhongtian,Lu, Tianliang,Xu, Jie
, p. 2255 - 2258 (2013)
Grand Cleft Oxo: Levulinate, available from biomass, is oxidized into succinate through manganese(III)-catalyzed selective cleavage of C-C bonds with molecular oxygen. In addition to levulinate, a wide range of aliphatic methyl ketones also undergo oxidative C-C bond cleavage at the carbonyl group. This procedure offers a route to valuable dicarboxylic acids from biomass resources by nonfermentive approaches. Copyright
Kinetic Isotope Effects and Pressure Effects in Several Hydrogen-Transfer Reactions of Tetralin and Related Compounds
Pajak, Janusz,Brower, K. R.
, p. 2210 - 2216 (1985)
The H/D kinetic isotope effects and activation volumes have been measured for several hydrogen-transfer reactions using tetralin, dihydronaphthalenes, cyclohexa-1,4-diene, and cyclohexanol as donors.The isotope effects were found to exhibit different patterns for reactions of different mechanisms.They indicate whether hydrogen is in transit in the activated complex and show the number of atoms in transit (one or two).The KIE for the reaction of tetralin with quinones is consistent with concerted transfer of two hydrogens whereas the other reactions were found to be stepwise.The activation volumes lie within the range -23 to -33 mL/mol and do not seem to differetiate among bimolecular mechanisms.The relevance to previous studies of the KIE and ΔV(excit.) for coal hydrogenation reactions is discussed.
Ozonolysis of Olefins, V : Emulsion Ozonization of Methyl Linoleate and Methyl Linolenate in Aqueous Alkaline Hydrogen Peroxide
Poklukar, Norbert,Mittelbach, Martin
, p. 719 - 724 (1991)
The ozonolysis of methyl linoleate and methyl linolenate in neutral and alkaline aqueous emulsions of hydrogen peroxide was investigated.Besides the expected products such as dimethyl malonate (3b), dimethyl azelate (3h) and methyl hexanoate (2a) further homologous methyl esters of dicarboxylic acids (3a-g), oxo carboxylic acids (4a, b, e-h) and hydroxy carboxylic acids (4c, d) could be detected by GC/MS analysis.Furthermore a method for separation of 8-hydroxyoctanoic acid (4d) by methylation and extraction of the reaction mixture containing the ozonolysis products is described. Keywords.Ozonization; Fatty esters; 8-Hydroxyoctanoic acid.
Chemical Reaction Monitoring using Zero-Field Nuclear Magnetic Resonance Enables Study of Heterogeneous Samples in Metal Containers
Blanchard, John W.,Budker, Dmitry,Burueva, Dudari B.,Eills, James,Garcon, Antoine,Koptyug, Igor V.,Kovtunov, Kirill V.,Picazo-Frutos, Román
, p. 17026 - 17032 (2020)
We demonstrate that heterogeneous/biphasic chemical reactions can be monitored with high spectroscopic resolution using zero-field nuclear magnetic resonance spectroscopy. This is possible because magnetic susceptibility broadening is negligible at ultralow magnetic fields. We show the two-step hydrogenation of dimethyl acetylenedicarboxylate with para-enriched hydrogen gas in conventional glass NMR tubes, as well as in a titanium tube. The low frequency zero-field NMR signals ensure that there is no significant signal attenuation arising from shielding by the electrically conductive sample container. This method paves the way for in situ monitoring of reactions in complex heterogeneous multiphase systems and in reactors made of conductive materials while maintaining resolution and chemical specificity.
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Samejima et al.
, p. 2722 (1969)
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Acid-catalyzed conversion of xylose in methanol-rich medium as part of biorefinery
Hu, Xun,Lievens, Caroline,Li, Chun-Zhu
, p. 1427 - 1434 (2012)
Acid treatments of xylose have been performed in a methanol/water mixture to investigate the reaction pathways of xylose during bio-oil esterification. Xylose was mainly converted into methyl xylosides with negligible humins formed below 130°C. However, humins formation became significant with the dehydration of xylose to furfural and 2-(dimethoxymethyl)furan (DOF) at elevated temperatures. The conversion of xylose to methyl xylosides protected the C1 hydroxyl group of xylose, which stabilized xylose and suppressed the formation of sugar oligomers and polymerization reactions. In comparison, the conversion of furfural to DOF protected the carbonyl group of furfural. However, the protection did not remarkably suppress the polymerization of furfural at high temperatures because of the shift of the reaction equilibrium from DOF to furfural with a prolonged residence time. In addition, the acid treatment of furfural produced methyl levulinate in methanol and levulinic acid in water, which was catalyzed by formic acid. Copyright
Conformational characteristics and configurational properties of poly(ethylene succinate) and poly(butylene succinate) and structure-property-function relationships of representative biodegradable polyesters
Sasanuma, Yuji,Nonaka, Yuta,Yamaguchi, Yuki
, p. 327 - 339 (2015)
Conformational characteristics and configurational properties of synthetic biodegradable polyesters, poly(ethylene succinate) and poly(butylene succinate), have been investigated by NMR experiments and molecular orbital calculations on their model compounds and the rotational isomeric state calculations for the two aliphatic polyesters. The results have been related to their crystal structures and thermal properties and compared with those obtained previously for poly((R)-3-hydroxybutyrate) and poly(lactic acid) to elucidate structureeproperty relationships of the representative biodegradable polyesters. In addition, selective affinities to degradative enzymes of the four polyesters have been satisfactorily explained in terms of their conformational characteristics and interactions with the depolymerases.
Efficient palladium catalysts for the copolymerization of carbon monoxide with olefins to produce perfectly alternating polyketones
Drent, E.,Broekhoven, J.A.M. van,Doyle, M.J.
, p. 235 - 251 (1991)
A class of highly efficient homogeneous palladium catalyst systems has been developed for the production of perfectly alternating copolymers of carbon monoxide with ethylene.Mixtures of carbon monoxide, ethylene and propene are converted into the correspo
Oxidative degradation of nylon-6 and nylon-6,6 with nitrogen dioxide in supercritical carbon dioxide
Yanagihara, Naohisa,Abe, Naoto,Takama, Hironori,Shimamura, Yuichiro,Yoshida, Masaaki
, p. 1128 - 1129 (2007)
Nylon-6 and nylon-6,6 were subjected to oxidative degradation with NO 2 in supercritical CO2. It was found that valuable short-chain α,ω-diacid mixture could be obtained in good yield under relatively mild conditions. Copyright
Electrosynthesis of esters of mono- and dioxoalkanoic and alkanedioic acids on the basis of nitro-substituted alkyl carboxylates and cycloalkanones
Ogibin,Ilovaiskii,Merkulova,Nikishin
, p. 728 - 733 (2003)
A one-pot electrochemical method for the synthesis of methyl monooxoalkanoates with the carbonyl group in position 4, methyl dioxoalkanoates with the oxo groups in positions 4,7-, 6,9-, 7,10-, and 12,15, and methyl 4-oxoalkanedioates was developed. This method is based on amperostatic electrolysis in an undivided cell of the salts of esters of nitroalkanoic acids and their adducts with CH2=CHX (X = Ac, CO2Me).
Renewable Polyethers via GaBr3-Catalyzed Reduction of Polyesters
Dannecker, Patrick-Kurt,Biermann, Ursula,von Czapiewski, Marc,Metzger, Jürgen O.,Meier, Michael A. R.
, p. 8775 - 8779 (2018)
Herein, a novel approach is reported for the synthesis of medium- and long-chain aliphatic polyethers 2 based on the GaBr3-catalysed reduction of polyesters 1 with TMDS as the reducing agent. Thus, various linear and branched aliphatic polyesters 1 were prepared and systematically investigated for this reduction strategy, demonstrating the applicability and versatility of this new polyether synthesis protocol. Medium- and long-chain chain polyethers were obtained from the respective polyesters without or with minor chain degradation, whereas short-chain polyesters, such as poly-l-lactide 1 i and poly[(R)-3-hydroxybutanoate] 1 j, showed major chain degradation. In this way, previously unavailable and uncommon polyethers were obtained and studied.
Chemical synthesis of fully biomass-based poly(butylene succinate) from inedible-biomass-based furfural and evaluation of its biomass carbon ratio
Tachibana, Yuya,Masuda, Takashi,Funabashi, Masahiro,Kunioka, Masao
, p. 2760 - 2765 (2010)
We have produced fully biomass-based poly(butylene succinate) (PBS) from furfural produced from inedible agricultural cellulosic waste. Furfural was oxidized to give fumaric acid. Fumaric acid was hydrogenated under high pressure with a palladium-rhenium/carbon catalyst to give 1,4-butanediol, and with a palladium/carbon catalyst to give succinic acid. Dimethyl succinate was synthesized from fumaric acid by esterification and hydrogenation under normal pressure. Fully biomass-based PBS was obtained by polycondensation of biomass-based 1,4-butanediol and biomass-based succinic acid or dimethyl succinate. The biomass carbon ratio calculated from 14C concentrations measured by accelerator mass spectroscopy (AMS) verified that the PBS obtained in this study contained only biomass carbon. The polycondensation of biomass-based 1,4-butanediol and petroleum-based terephthalic acid or dimethyl terephthalate gave partially biomass-based poly(butylene terephthalate), which is an engineering plastic.
Gold-nanoparticle-based catalysts for the oxidative esterification of 1,4-butanediol into dimethyl succinate
Brett, Gemma L.,Miedziak, Peter J.,He, Qian,Knight, David W.,Edwards, Jennifer K.,Taylor, Stuart H.,Kiely, Christopher J.,Hutchings, Graham J.
, p. 1952 - 1958 (2013)
The oxidation of 1,4-butanediol and butyrolactone have been investigated by using supported gold, palladium and gold-palladium nanoparticles. The products of such reactions are valuable chemical intermediates and, for example, can present a viable pathway for the sustainable production of polymers. If both gold and palladium were present, a significant synergistic effect on the selective formation of dimethyl succinate was observed. The support played a significant role in the reaction, with magnesium hydroxide leading to the highest yield of dimethyl succinate. Based on structural characterisation of the fresh and used catalysts, it was determined that small gold-palladium nanoalloys supported on a basic Mg(OH)2 support provided the best catalysts for this reaction. Twice as nice: The oxidation of 1,4-butanediol and butyrolactone has been investigated over supported gold, palladium and gold-palladium nanoparticles. The oxidation of both hydroxyl groups of α,γ-diols has previously proved to be difficult. Small AuPd alloy nanoparticles on a basic Mg(OH)2 support provide the best catalysts for this reaction. Copyright
ELECTROSYNTHESIS OF DIESTERS OF SATURATED DICARBOXYLIC ACIDS FROM OXALIC ACID AND ETHYLENE
Grinberg, V. A.,German, L. S.,Kanevskii, L. S.,Polishchuk, V. R.,Skundin, A. M.,Vasil'ev, Yu. B.
, p. 259 - 262 (1980)
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Matsuda
, p. 571 (1969)
High activity and selectivity of Ag/SiO2 catalyst for hydrogenation of dimethyl oxalate
Yin, Anyuan,Guo, Xiaoyang,Dai, Weilin,Fan, Kangnian
, p. 4348 - 4350 (2010)
Ag/SiO2 prepared by a sol-gel process is highly effective for selective gas-phase hydrogenation of dimethyl oxalate to corresponding alcohols. The catalysts are of great potential as industrially viable and novel catalysts for the production of methyl glycolate and ethylene glycol.
Visible-Light-Induced Two-Electron-Transfer Photoreductions on CdS: Effeects of Morphology
Shiragami, Tsutomu,Pac, Chyongjin,Yanagida, Shozo
, p. 504 - 506 (1990)
Freshly prepared CdS suspensions (CdS-0) consisting of quantized particles and their loose aggregation catalyze photoreductions of aromatic ketones and olefins in methanol under visible light irradiation using triethylamine as sacrificial electron donor, yielding alcohols and dihydro compounds, respectively, which are more selective than photocatalysis of commercially available crystalline CdS (Aldrich) (CdS-Ald).Deuterium incorporation experiments in photolysis of dimethyl maleate in methanol-O-D revealed that CdS-0 catalyzes sequental two-electron-transfer photoreduction, affording dideuterated dimethyl succinate, while CdS-Ald induces both photoreduction and photoisomerization through disproportionation between one-electron-transfer-reduction intermediates, yielding much trideuterated dimethyl succinate and monodeuterated dimethyl fumarate and maleate.
Selective Alkene Insertion into Inert Hydrogen-Metal Bonds Catalyzed by Mono(phosphorus ligand)palladium(0) Complexes
Komine, Nobuyuki,Ito, Ryo,Suda, Hiromi,Hirano, Masafumi,Komiya, Sanshiro
, p. 4160 - 4168 (2017)
Isolated mono(phosphorus ligand)palladium(0) complexes catalyzed alkene insertions into hydrogen-tungsten bonds. These insertions using WHCp(CO)3 with ethyl acrylate and dimethyl fumarate smoothly gave the corresponding alkyltungsten complexes. Kinetic studies involving the stoichiometric reactions and DFT calculations suggest the following steps: (i) formation of a mono(phosphorus ligand)mono(alkene)palladium(0) species, (ii) subsequent reaction of a metal hydride with the palladium(0), (iii) insertion of the coordinated alkene into the resulting palladium hydride, and (iv) reductive elimination between the alkyl and metal on the palladium center to release the alkylmetal species with regeneration of a palladium(0) by a reaction with alkene.
Palladium nanodendrites uniformly deposited on the surface of polymers as an efficient and recyclable catalyst for direct drug modification via Z-selective semihydrogenation of alkynes
García-Calvo, José,Calvo-Gredilla, Patricia,Vallejos, Saúl,García, José Miguel,Cuevas-Vicario, José Vicente,García-Herbosa, Gabriel,Avella, Manuel,Torroba, Tomás
, p. 3875 - 3883 (2018)
The preparation of new monodisperse polycrystalline palladium nanoparticles uniformly distributed on the surface of polymers, by simply adding a palladium(ii) solution in water to the polymers, is described. The polymer supported palladium nanoparticles material was used as an efficient portable and reusable catalyst for the stereoselective semihydrogenation reaction of internal alkynes to (Z)-alkenes in green solvents.
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Pac,C.,Ihama,M.,Yasuda,M.
, p. 6495 (1981)
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Ito,Y. et al.
, p. 2912 - 2914 (1975)
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Oxidation of cyclohexanone and/or cyclohexanol catalyzed by Dawson-type polyoxometalates using hydrogen peroxide
Dermeche, Leila,Idrissou, Yasmina,Mazari, Tassadit,Moudjahed, Mohammed,Rabia, Cherifa
, (2022/03/07)
The oxidation of cyclohexanone, cyclohexanol or cyclohexanone/cyclohexanol mixture using as catalyst, Dawson-type polyoxometalates (POMs) of formula, α- and β-K6P2W18O62, α-K6P2Mo6W12O62 and α1-K7P2Mo5VW12O62 and hydrogen peroxide, carried out at 90 °C with a reaction time of 20 h, led to a high number of mono- and di-acids which were identified by GC-MS. Levulinic, 6-hydroxyhexanoic, adipic, glutaric and succinic acids, major products were evaluated by HPLC. Regardless of the substrate nature, all POMs exhibited high catalytic activity with 94–99% of conversion, whereas the formation of the different products is sensitively related to both the composition and symmetry of the POMs and the substrate nature. The main products are adipic acid in the presence of α-K6P2Mo6W12O62 and α1-K7P2Mo5VW12O62, levulinic acid in the presence of α1-K7P2Mo5VW12O62 and β-K6P2W18O62 and 6-hydroxyhexanoic acid in the presence of α- and β-K6P2W18O62. Graphical abstract: High catalytic activity was observed with?α- and?β-K6P2W18O62, α-K6P2Mo6W12O62 and α1-K7P2Mo5VW12O62 Dawson-type for the oxidation of cyclohexanone, cyclohexanol or cyclohexanone/cyclohexanol mixture, in the hydrogen peroxide presence, to several oxygenated products. Adipic, levulinic and 6-hydroxyhexanoic acids are the main products. The peroxo- species formed in situ could be the active sites.[Figure not available: see fulltext.]
FLOW CHEMISTRY SYNTHESIS OF ISOCYANATES
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Paragraph 0175; 0240-0242, (2021/06/22)
The disclosure provides, inter alia, safe and environmentally-friendly methods, such as flow chemistry, to synthesize isocyanates, such as methylene diphenyl diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and tetramethylxylene diisocyanate.
Environment-friendly production method for greatly reducing sewage discharge of dimethyl succinylsuccinate
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Paragraph 0018-0020; 0023-0025, (2021/04/03)
The invention provides an environment-friendly production method for greatly reducing sewage discharge of dimethyl succinylsuccinate. According to the technical scheme, succinic acid and methyl alcohol react under the nitrogen protection condition to generate dimethyl succinate, the dimethyl succinate serves as a reaction solvent, sodium methoxide is dropwise added into the reaction solvent underthe ultrasonic oscillation condition, after dropwise adding is completed, a reflux reaction continues to be conducted for a period of time, and the reaction sufficiency can be improved through microcosmic vibration of fluid; after the reaction is finished, stirring, slurrying and suction filtration are performed, washing with absolute methanol is performed, and fractionation is performed so as torecover methanol and dimethyl succinate; the filter cake is neutralized with dilute sulfuric acid, and reduced pressure distillation is performed to obtain a final product. On the basis, a pickling solution is prepared from a residual solution obtained by reduced pressure distillation, and calcium chloride is added into the excessive pickling solution, so that a calcium sulfate byproduct can be obtained; meanwhile, the high-temperature residual liquid after fractionation is used for heating the dimethyl succinate in the next stage, so that the waste heat is effectively utilized, and the sewagedischarge amount is reduced.
