- Oxidation of cyclohexanone and/or cyclohexanol catalyzed by Dawson-type polyoxometalates using hydrogen peroxide
-
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.]
- Dermeche, Leila,Idrissou, Yasmina,Mazari, Tassadit,Moudjahed, Mohammed,Rabia, Cherifa
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- Biomass-derived dibasic acids to diesters with inorganic ligand-supported catalyst: synthesis, optimization, characterization
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Several attempts have been made to obtain aliphatic dicarboxylic diesters from esterification reaction to develop the biomass-derived platform molecules and green manufacturing processes. In this paper, Na3(H2O)6[AlMo6O18(OH)6], an Anderson-type polyoxometalate, firstly, was reported as a catalyst for diester synthesis from dicarboxylic acid to diester which showed an well productivity and selectivity characterized by 1H and 13C. Response surface methodology (RSM) integrated with the desirability function approach was used to determine the best operative conditions, and the optimal reaction parameters for maximum dipropyl succinate yield (77 ± 2.5%) were identified as 1.19?mol.% catalyst loading, 4.9:1 propanol/succinic acid ratio, 113?°C, and 9.6?h. Three batches of tests were carried for catalyst recycling with 78–75% yield even after 6 cycles of esterification. In addition, the substrate carbon chain was increased for investigation of substrate scope achieving satisfactory results and all products were characterized by 1H and 13C nuclear magnetic resonance spectroscopy.
- Chen, Zhe,Han, Sheng,Lu, Deli,Xu, Yumeng
-
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- Ruthenium-catalysed oxidative coupling of vinyl derivatives and application in tandem hydrogenation
-
The first ruthenium-catalyzed oxidative homo- and cross-coupling of exclusive vinyl derivatives giving highly valued 1,3-diene building blocks is reported. The catalytic system is based on readily available reagents and it mainly delivers the E,E isomer. This methodology also enables the synthesis of adipic acid ester derivatives in a one-pot fashion after in situ ruthenium-catalyzed hydrogenation.
- Abuhafez, Naba,Bruneau, Christian,Gramage-Doria, Rafael,Kamaraj, Raghu,Ruffin, Hervé
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p. 5772 - 5776
(2021/09/10)
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- Efficient Catalysts for the Green Synthesis of Adipic Acid from Biomass
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Green synthesis of adipic acid from renewable biomass is a very attractive goal of sustainable chemistry. Herein, we report efficient catalysts for a two-step transformation of cellulose-derived glucose into adipic acid via glucaric acid. Carbon nanotube-supported platinum nanoparticles are found to work efficiently for the oxidation of glucose to glucaric acid. An activated carbon-supported bifunctional catalyst composed of rhenium oxide and palladium is discovered to be powerful for the removal of four hydroxyl groups in glucaric acid, affording adipic acid with a 99 % yield. Rhenium oxide functions for the deoxygenation but is less efficient for four hydroxyl group removal. The co-presence of palladium not only catalyzes the hydrogenation of olefin intermediates but also synergistically facilitates the deoxygenation. This work presents a green route for adipic acid synthesis and offers a bifunctional-catalysis strategy for efficient deoxygenation.
- Deng, Weiping,Yan, Longfei,Wang, Binju,Zhang, Qihui,Song, Haiyan,Wang, Shanshan,Zhang, Qinghong,Wang, Ye
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supporting information
p. 4712 - 4719
(2021/01/20)
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- Efficient Palladium-Catalyzed Carbonylation of 1,3-Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters
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The dicarbonylation of 1,3-butadiene to adipic acid derivatives offers the potential for a more cost-efficient and environmentally benign industrial process. However, the complex reaction network of regioisomeric carbonylation and isomerization pathways, make a selective and direct transformation particularly difficult. Here, we report surprising solvent effects on this palladium-catalysed process in the presence of 1,2-bis-di-tert-butylphosphin-oxylene (dtbpx) ligands, which allow adipate diester formation from 1,3-butadiene, carbon monoxide, and methanol with 97 % selectivity and 100 % atom-economy under scalable conditions. Under optimal conditions a variety of di- and triesters from 1,2- and 1,3-dienes can be obtained in good to excellent yields.
- Yang, Ji,Liu, Jiawang,Ge, Yao,Huang, Weiheng,Ferretti, Francesco,Neumann, Helfried,Jiao, Haijun,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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supporting information
p. 9527 - 9533
(2021/03/08)
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- H2-Free Re-Based Catalytic Dehydroxylation of Aldaric Acid to Muconic and Adipic Acid Esters
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As one of the most demanded dicarboxylic acids, adipic acid can be directly produced from renewable sources. Hexoses from (hemi)cellulose are oxidized to aldaric acids and subsequently catalytically dehydroxylated. Hitherto performed homogeneously, we present the first heterogeneous catalytic process for converting an aldaric acid into muconic and adipic acid. The contribution of leached Re from the solid pre-reduced catalyst was also investigated with hot-filtration test and found to be inactive for dehydroxylation. Corrosive or hazardous (HBr/H2) reagents are avoided and simple alcohols and solid Re/C catalysts in an inert atmosphere are used. At 120 °C, the carboxylic groups are protected by esterification, which prevents lactonization in the absence of water or acidic sites. Dehydroxylation and partial hydrogenation yield monohexenoates (93 %). For complete hydrogenation to adipate, a 16 % higher activation barrier necessitates higher temperatures.
- Ho?evar, Brigita,Pra?nikar, An?e,Hu?, Matej,Grilc, Miha,Likozar, Bla?
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p. 1244 - 1253
(2020/12/09)
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- Diphosphine compound, catalyst system containing diphosphine compound and application of diphosphine compound
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The present invention provides a diphosphine compound, a catalyst system containing the same, and applications of the diphosphine compound, the diphosphine compound has a structure represented by a formula I or a formula II, a phosphorus atom and a benzene ring are connected through methylene, and a nitrogen-containing heteroaryl structure is matched, such that carbon monoxide can be easily activated after phosphorus and a metal are coordinated, and an alkoxy carbonylation reaction is facilitated. The catalyst system comprises a bimetallic catalyst and the diphosphine compound, and when the catalyst system is used for catalyzing conjugated olefin to prepare 1, 6-dicarboxylic ester compounds, the conversion rate of raw materials can be effectively improved, and the yield and regioselectivity of products are improved.
- -
-
Paragraph 0090-0091; 0099-0100; 0118-0119
(2021/03/13)
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- NOVEL ESTERIFICATION CATALYST AND USES THEREOF
-
Tin (II) glucarate is found to be effective alone and in combination with other tin compounds for catalyzing the reaction of carboxylic acids such as furan-2,5-dicarboxylic acid, terephthalic acid and adipic acid with alcohols such as the C1-C3 alcohols.
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Page/Page column 0026; 0028-0029
(2020/07/07)
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- Ultralow-Molecular-Weight Stimuli-Responsive and Multifunctional Supramolecular Gels Based on Monomers and Trimers of Hydrazides
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The simpler, the better. A series of simple, neutral and ultralow-molecular-weight (MW: 140–200) hydrazide-derived supramolecular gelators have been designed and synthesized in two straightforward steps. For non-conjugated cyclohexane-derived hydrazides, their monomers can self-assemble to form gels through intermolecular hydrogen bonds and dipole-dipole interactions. Significantly, conjugated phthalhydrazide can self-aggregate into planar and circular trimers through intermolecular hydrogen bonds and then self-assemble to form gels through intermolecular π–π stacking interactions. It is interesting that these simple gelators exhibit unusual properties, such as self-healing, multi-response fluorescence, and visual and selective recognition of chiral (R)/(S)-1,1′-binaphthalene-2,2′-diamine and S2? through much different times of gel re-formation and blue-green color change, respectively. These results underline the importance of supramolecular gels and extend the scope of supramolecular gelators.
- Wu, Dehua,Song, Jintong,Qu, Lang,Zhou, Weilan,Wang, Lei,Zhou, Xiangge,Xiang, Haifeng
-
supporting information
p. 3370 - 3378
(2020/10/02)
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- Synthesis of dimeric molecules via ag-catalyzed electrochemical homocoupling of organic bromides paired with electrooxidation of urea
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We present a sacrificial anode-free approach to reductive homocoupling of organohalides that does not require a co-catalyst. In this approach, a divided electrochemical cell with aprotic and aqueous compartments separated by an anion exchange membrane enables coupling of the cathodic homocoupling reaction with anodic oxidation of urea. We show that, in contrast with traditional one-compartment cells relying on sacrificial anodes, the proposed cell configuration maintains stable cell voltage in the course of galvanostatic electrolysis. A synthetic potential of this method was assessed using a series of 13 organic bromides that demonstrated a strong dependence of the reaction outcome on the structure of the organic substrate, more specifically, the dissociation energy of the C–Br bond and the redox properties of formed radicals, which are discussed in detail. While not being suitable for the synthesis of byarylstructures, this method is excellent for C(sp3)-C(sp3) coupling to corresponding dimeric products with up to quantitative yields. Simultaneous electrochemical treatment of nitrogenous waste in the adjacent half-cell provides an additional incentive for wide adaptation of this sustainable synthetic approach.
- Klinkova, Anna,Krivoshapkina, Elena F.,Medvedev, Jury J.,Medvedeva, Xenia V.,Pivovarova, Yekaterina,Steksova, Yulia P.
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- Ruthenium-catalyzed hydrogenation of CO2as a route to methyl esters for use as biofuels or fine chemicals
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A novel robust diphosphine-ruthenium(ii) complex has been developed that can efficiently catalyze both the hydrogenation of CO2 to methanol and its in situ condensation with carboxylic acids to form methyl esters; a TON of up to 3260 is achievable for the CO2 to methanol step. Both aromatic and aliphatic carboxylic acids can be transformed to their corresponding methyl esters with high conversion and selectivity (17 aliphatic and 18 aromatic examples). On the basis of a series of experiments, a mechanism has been proposed to account for the various steps involved in the catalytic pathway. More importantly, this approach provides a promising route for using CO2 as a C1 source for the production of biofuels, fine chemicals and methanol.
- Li, Yong,Liu, Qingbin,Ma, Yanping,Solan, Gregory A.,Sun, Wen-Hua,Wang, Zheng,Zhang, Qiuyue,Zhao, Ziwei,Zhong, Yanxia
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p. 6766 - 6774
(2020/08/25)
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- A general platinum-catalyzed alkoxycarbonylation of olefins
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Hydroxy- and alkoxycarbonylation reactions constitute important industrial processes in homogeneous catalysis. Nowadays, palladium complexes constitute state-of-the-art catalysts for these transformations. Herein, we report the first efficient platinum-catalysed alkoxycarbonylations of olefins including sterically hindered and functionalized ones. This atom-efficient catalytic transformation provides straightforward access to a variety of valuable esters in good to excellent yields and often with high selectivities. In kinetic experiments the activities of Pd- and Pt-based catalysts were compared. Even at low catalyst loading, Pt shows high catalytic activity.
- Beller, Matthias,Dühren, Ricarda,Franke, Robert,Ge, Yao,Huang, Weiheng,Jackstell, Ralf,Liu, Jiawang,Neumann, Helfried,Schneider, Carolin,Yang, Ji
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supporting information
p. 5235 - 5238
(2020/07/30)
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- Environmentally-friendly synthesis method of dimethyl adipate
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The invention discloses a synthesis method of dimethyl adipate. The dimethyl adipate is prepared from methanol and adipic acid which serve as main raw materials by adopting a metal solid-phase catalyst prepared by dual-metal salt coprecipitation. Compared with traditional strong acid catalysts such as sulfuric acid or methylbenzenesulfonic acid, the catalyst can be repeatedly used after being recycled and avoids corrosion of equipment and production of the three types of wastes.
- -
-
Paragraph 0007-0026
(2019/03/30)
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- Coordination polymeric fluorescent gel: effect of removal of branch substituents of the central core over properties
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A fluorescent gel has been prepared by deprotonation of non-fluorescent adipic acid derived ligand (H4AL) with LiOH followed by coordination with Cd(II) in DMF. The mechanism of gelation is examined by IR, 1H NMR, UV-vis, Job’s plot, PXRD, SEM and TEM. Chelation enhanced fluorescence by Cd(II) has been established by fluorescence experiments. In addition to synthesis and characterization of this gel, we compared the gel properties by varying the core of the ligand using citric (H6CL) acid derivatives.
- Pandey, Vinay Kumar,Singh, Vikas Kumar,Chandra, Subhash,Hasan, Syed Hadi
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p. 1537 - 1546
(2019/05/21)
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- Synthesis technology for 1,6-hexanediol
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The invention relates to the technical field of organic compound preparation, and concretely discloses a synthesis technology for 1,6-hexanediol. The technology comprises the following steps: synthesis of a raw material dimethyl adipate, preparation of a reaction solution, introduction of hydrogen to a hydrogenation reaction device for evacuation, catalyst reduction, reacting of the reaction solution, and rectification of the prepared hexanediol. The technology has the characteristics of few steps, simplicity and convenience in operation, and safeness; a Cu-Co-Ni catalyst adopted in the invention has the characteristics of long service period, stability in reaction, and safeness; the synthesis technology allows the conversion rate of the dimethyl adipate to be 99.6% or more and close to 100%, the selectivity of the hexanediol to be 97% or more and the purity of the rectified hexanediol to be 98.7% or more; and excess methanol used in the present invention can be recovered, so the production cost is reduced, and the environmental problems of post-treatment is solved, thereby the technology has certain market competitiveness.
- -
-
Paragraph 0027-0030; 0041-0044; 0055-0058
(2019/09/13)
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- Direct synthesis of adipic acid esters via palladium-catalyzed carbonylation of 1,3-dienes
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The direct carbonylation of 1,3-butadiene offers the potential for a more cost-efficient and environmentally benign route to industrially important adipic acid derivatives. However, owing to the complex reaction network of regioisomeric carbonylation and isomerization pathways, a selective practical catalyst for this process has thus far proven elusive. Here, we report the design of a pyridyl-substituted bidentate phosphine ligand (HeMaRaphos) that, upon coordination to palladium, catalyzes adipate diester formation from 1,3-butadiene, carbon monoxide, and butanol with 97% selectivity and 100% atom-economy under industrially viable and scalable conditions (turnover number > 60,000). This catalyst system also affords access to a variety of other di- and triesters from 1,2- and 1,3-dienes.
- Yang, Ji,Liu, Jiawang,Neumann, Helfried,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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p. 1514 - 1517
(2020/01/08)
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- Nylon Intermediates from Bio-Based Levulinic Acid
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Use of ZrO2/SiO2 as a solid acid catalyst in the ring-opening of biobased γ-valerolactone with methanol in the gas phase leads to mixtures of methyl 2-, 3-, and 4-pentenoate (MP) in over 95 % selectivity, containing a surprising 81 % of M4P. This process allows the application of a selective hydroformylation to this mixture to convert M4P into methyl 5-formyl-valerate (M5FV) with 90 % selectivity. The other isomers remain unreacted. Reductive amination of M5FV and ring-closure to ?-caprolactam in excellent yield had been reported before. The remaining mixture of 2- and 3-MP was subjected to an isomerising methoxycarbonylation to dimethyl adipate in 91 % yield.
- Marckwordt, Annemarie,El Ouahabi, Fatima,Amani, Hadis,Tin, Sergey,Kalevaru, Narayana V.,Kamer, Paul C. J.,Wohlrab, Sebastian,de Vries, Johannes G.
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supporting information
p. 3486 - 3490
(2019/02/13)
-
- Assisted Tandem Catalytic Conversion of Acrylates into Adipic Esters
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A ruthenium-catalyzed tail-to-tail dimerization of acrylates followed by hydrogenation results in the synthesis of adipic esters in one pot. An imine-ligated ruthenium complex that has good catalytic reactivity for tail-to-tail dimerization of methyl acrylate can be readily converted to a hydrogenation catalyst resulting in the assisted tandem catalytic conversion of methyl acrylate to methyl adipate.
- Maity, Pradip K.,Tunge, Jon A.
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p. 3419 - 3423
(2018/07/31)
-
- ORGANOTIN CATALYSTS IN ESTERIFICATION PROCESSES OF FURAN-2,5-DICARBOXYLIC ACID (FDCA)
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A method for preparing sugar-based mono and diesters is described. The process entails the esterification of 2,5-furan-dicarboxylic acid (FDCA) with an alcohol in the presence of low loadings of a homogeneous organotin (IV) catalyst.
- -
-
Paragraph 0062
(2018/06/06)
-
- Method for preparing adipic acid from glucaric acid
-
The invention discloses a method for preparing adipic acid from glucaric acid. The method comprises the following steps: making glucaric acid react with hydrogen in a water solution or an alcoholic solution to obtain the adipic acid. When the glucaric acid reacts with the hydrogen in the water solution, a system utilizes a hydrodeoxygenation catalyst to perform hydrodeoxygenation reaction; when the glucaric acid reacts with the hydrogen in the alcoholic solution, an esterification catalyst, the hydrodeoxygenation catalyst and a hydrolysis catalyst are sequentially added into the system to respectively perform esterification reaction, the hydrodeoxygenation reaction and hydrolysis reaction. The method disclosed by the invention has the advantages of green and pollution-free reaction processand environmental friendliness; furthermore, production cost is reduced.
- -
-
Paragraph 0057-0059
(2018/04/01)
-
- Sulfonic acid-functionalized organic knitted porous polyaromatic microspheres as heterogeneous catalysts for biodiesel production
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The use of renewable energy sources decreases the consequences of greenhouse gas emission from fossil fuels. Biodiesel, an easily burning and biodegradable fuel, is an alternative to conventional diesel fuel. The esterification of long-chain fatty acids and transesterification of triglycerides are two major reactions widely used to convert vegetable oils or animal fats into biodiesel. As solid acid catalysts are considered promising candidates for biodiesel production, we have synthesized a series of organic knitted porous polyaromatics (OPPs) using pyrene, anthracene, and naphthalene as monomers via Friedel-Crafts alkylation, followed by crosslinking reactions. The resultant polymers showed good surface morphology, stability and swelling property, high capacity for functionalization due to the unreacted bromomethyl groups on the surface, and excellent hydrophobicity. The sulfonated polymer microspheres obtained by the surface sulfonation showed good surface acidity; thus, they can be employed as heterogeneous solid acid catalysts for the esterification of long-chain fatty acids and transesterification of triglycerides, and they are reusable without any leaching of functional groups.
- Varyambath, Anuraj,Kim, Mi-Ra,Kim, Il
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p. 12745 - 12753
(2018/08/04)
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- High-stability ion liquid for catalyzing esterification of alcohol and acid to generate ester and preparation method
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The invention discloses high-stability ion liquid for catalyzing esterification of alcohol and acid to generate ester and a preparation method, and belongs to the technical field of esterification ofalcohol and acid. A main component of the ion liquid is N-ethylpyrrolidone p-toluenesulfonate and is obtained by synthesizing N-ethyl-2-pyrrolidinone and p-toluenesulfonic acid at the temperature of 80 to 120 DEG C in a one-step method. The high-stability ion liquid has unexpected stability in the reaction for catalyzing the synthesis of alcohol and acid into ester, has the advantages of high activity, high selectivity and low preparation cost, and can realize the esters environment-friendly industrialized production.
- -
-
Paragraph 0057; 008; 0059; 0060
(2018/11/03)
-
- Protection of COOH and OH groups in acid, base and salt free reactions
-
We report an iron-catalyzed general functional group protection method with inexpensive reagents. This environmentally benign process does not use acids or bases, and does not produce waste products. Further purification beyond filtration and evaporation is, in most cases, unnecessary. Free COOH and OH groups can be protected in a one-pot reaction.
- Zhu, Xiaotao,Qian, Bo,Wei, Rongbiao,Huang, Jian-Dong,Bao, Hongli
-
supporting information
p. 1444 - 1447
(2018/04/12)
-
- Inexpensive and rapid hydrogenation catalyst from CuSO4/CoCl2 — Chemoselective reduction of alkenes and alkynes in the presence of benzyl protecting groups
-
The simple reduction of a number of alkenes and alkynes was performed with a typical reaction time of 20 min using a copper-cobalt catalytic system. The reduction did not cleave benzyl protecting groups which are usually vulnerable to catalytic hydrogenation reactions. The catalyst can be prepared in situ by reduction of the inexpensive precursor salts CuSO4 and CoCl2 with NaBH4. Sodium borohydride was also used as an easily handled hydrogen source for the catalytic reductions. No pressure, heating or inert atmosphere is required and purification/catalyst removal is achieved using extraction procedures, making this approach simple and efficient.
- Ficker, Mario,Svenningsen, S?ren W.,Larribeau, Thomas,Christensen, J?rn B.
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supporting information
p. 1125 - 1129
(2018/02/21)
-
- Desymmetrizing Hydroformylation of Dihydromuconic Acid Diesters: Application to the Synthesis of (±)-Vindeburnol
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The desymmetrizing hydroformylation of internal alkenes derived from dihydromuconic acid is described. The study of this reaction afforded easy access to polyfunction aldehydes. After the evaluation of the reactivity of the dimethyl ester derivative with various primary amines, this methodology was used to design a rapid synthesis of (±)-vindeburnol from tryptamine in only two steps.
- Salacz, Laura,Charpentier, Cyrille,Suffert, Jean,Girard, Nicolas
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p. 2257 - 2262
(2017/02/26)
-
- Electroreductive coupling of aromatic ketones, aldehydes, and aldimines with α,β-unsaturated esters: Synthesis of 5-aryl substituted γ-butyrolactones and lactams
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The electroreductive intermolecular coupling of aromatic ketones and aldehydes with α,β-unsaturated esters in the presence of TMSCl gave the adducts as γ-trimethylsiloxy esters. The detrimethylsilylation of the adducts with TBAF afforded 5-aryl substituted γ-butyrolactones. The electroreductive coupling of N-(4-methoxyphenyl)-1-arylmethaneimines with methyl acrylate in the presence of TMSCl gave the adducts as methyl 4-aryl-4-((4-methoxyphenyl)amino)butanoates. The adducts were transformed to 5-aryl-γ-butyrolactams by cyclization with NaH and subsequent oxidation with CAN. (±)-Norcotinine was prepared from nicotinaldehyde by this method. The electroreductive coupling of aromatic ketones and aldimines with acrylonitrile in the presence of TMSCl gave 4-aryl-4-(trimethylsiloxy)butanenitriles and 4-aryl-4-((4-methoxyphenyl)amino)butanenitriles, respectively.
- Kise, Naoki,Hamada, Yusuke,Sakurai, Toshihiko
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p. 1143 - 1156
(2017/02/18)
-
- Method for producing 1,6-hexanediol from 1,6-adipic acid by continuous esterification and hydrogenation
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The invention provides a method for producing 1,6-hexanediol from 1,6-adipic acid by continuous esterification and hydrogenation, belonging to the field of fine chemical synthesis. The method comprises the following steps: carrying out continuous esterification reaction on 1,6-adipic acid and methanol/ethanol in an acid-catalyst-filled reactive distillation tower, carrying out reduced pressure distillation purification on the dimethyl/ethyl adipate, and carrying out hydrogenation to obtain the methanol/ethanol and 1,6-adipic acid, wherein the methanol/ethanol returns to continue esterification, and the 1,6-adipic acid is used as the product. The esterification reaction product yield is 96% or above, and the hydrogenation reaction yield is greater than 99%. The method is simple to operate, implements the continuous esterification-purification-hydrogenation-separation production process, and has favorable economic benefits and industrial application prospects.
- -
-
Paragraph 0023
(2017/07/20)
-
- Efficient and selective oxidation of aldehydes with dioxygen catalysed by vanadium-containing heteropolyanions
-
The heteropolyacids “H3+n[PMo12–nVnO40]·aq” (denoted as HPA-n; n = 2, 3, 8) catalyse the oxidation of aldehydes to carboxylic acids in the presence of dioxygen with very good yields. The effect on the catalytic activity of various parameters such as the precursors, solvent, temperature or catalyst/substrate ratio was examined. The process is particularly selective for linear and aromatic aldehydes. The oxidation of adipaldehyde with dioxygen in mild conditions, in the presence of HPA-2 as a catalyst, leads to the formation of adipic acid together with a significant amount of other byproducts. Thus, several modifications of the catalytic systems have been carried out to improve their selectivity. The effect of cocatalysts was investigated and, among the species tested, complex Ni(acac)2 was found to be the most efficient yielding 60% of adipic acid.
- El Amrani, Ikram,Atlamsani, Ahmed,Dakkach, Mohamed,Rodríguez, Montserrat,Romero, Isabel,Amthiou, Souad
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p. 888 - 895
(2017/09/26)
-
- DEOXYDEHYDRATION OF SUGAR DERIVATIVES
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The disclosure provides methods for deoxydehydration of sugar-based derivatives using hydrogen gas as a reducing agent.
- -
-
Paragraph 0134; 0135; 0136; 0139; 0140
(2017/09/09)
-
- Hydrogen Gas-Mediated Deoxydehydration/Hydrogenation of Sugar Acids: Catalytic Conversion of Glucarates to Adipates
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The development of a system for the operationally simple, scalable conversion of polyhydroxylated biomass into industrially relevant feedstock chemicals is described. This system includes a bimetallic Pd/Re catalyst in combination with hydrogen gas as a terminal reductant and enables the high-yielding reduction of sugar acids. This procedure has been applied to the synthesis of adipate esters, precursors for the production of Nylon-6,6, in excellent yield from biomass-derived sources.
- Larson, Reed T.,Samant, Andrew,Chen, Jianbin,Lee, Woojin,Bohn, Martin A.,Ohlmann, Dominik M.,Zuend, Stephan J.,Toste, F. Dean
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supporting information
p. 14001 - 14004
(2017/10/17)
-
- Methylation of mono- and dicarboxylic acids with dimethyl carbonate catalyzed with binder-free zeolite NaY
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Synthesis of methyl mono- and dicarboxylates was developed consisting in treating the corresponding acids with dimethyl carbonate in the presence of a heterogenic catalyst, crystalline aluminosilicate whose mechanically strong granules to 90–95% were built of crystal aggregates of zeolite Y with modulus of about 5.0 in the Na-form. Optimum catalyst and reagents ratio and the reaction conditions were found for the preparation in high yields of methyl esters of mono- and dicarboxylic acids.
- Khusnutdinov,Shchadneva,Mayakova, Yu. Yu.,Konovalova, Yu. S.,Khazipova,Kutepov
-
p. 163 - 168
(2017/04/24)
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- A CATALYST FOR THE CARBONYLATION OF ALKENES
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The present application relates to a metal complex of Formula (I) and a catalyst composition for the carbonylation of alkenes comprising the metal complex, wherein the metal is a group 10 element such as palladium, platinum or nickel, and the complex comprises a bidentate phosphine ligand. The present invention also relates to a process for the preparation of a dicarboxylic acid or ester thereof from an alkenoic acid or ester thereof, or a process for the preparation of a carboxylic acid or ester thereof from an alkene or alkenoic acid with high selectivity and activity using said metal complex or catalyst composition. The present application also relates to a method of preparing Nylon 6-6 comprising the step of copolymerising adipic acid with hexamethylenediamine.
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Page/Page column 50-51
(2017/09/02)
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- Isomerizing Methoxycarbonylation of Alkenes to Esters Using a Bis(phosphorinone)xylene Palladium Catalyst
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The synthesis and characterization of bulky diphosphine 1,2-bis(4-phosphorinone)xylene, BPX, and its palladium complexes [(BPX)PdCl2] and [(BPX)Pd(O2CCF3)2] are described. BPX was evaluated as a ligand in Pd-catalyzed isomerizing methoxycarbonylation. A broad range of alkenes, including terminal, internal, branched, and functionalized alkenes, can be converted to esters with activities and selectivities matching or surpassing the performance of the state-of-the-art palladium bis(di(tert-butyl)phosphino-o-xylene (Pd-DTBPX) catalyst. A molecular structure of the precatalyst [(BPX)Pd(O2CCF3)2] was obtained showing a square planar geometry and a bite angle of 100.11(3)°. Rhodium carbonyl complexes [(BPX)Rh(CO)Cl] and [(DTBPX)Rh(CO)Cl] were synthesized to compare the relative electronic parameters, revealing a ν(C≡O) of 1956.8 and 1948.3 cm-1, respectively, suggesting a reduced ability of BPX to donate electron density to the metal relative to DTBPX. Competitive protonation experiments between BPX and DTBPX in the presence of CH3SO3H exclusively produce [DTBPX(H)2]2+, providing additional evidence that BPX is a much weaker base than DTBPX. This could be due to either the effect of the electron-withdrawing ketone group in the phosphorinone ring or the compression of the C-P-C bond angle induced by the ring structure. The 31P NMR (CDCl3) chemical shift of BPX is 5.6 ppm, upfield of DTBPX at 27.6 ppm. This anomalous result is attributed to a strong gamma substituent effect of C=O in the BPX ligand. The improved activity of Pd-BPX, relative to Pd-DTBPX, could be attributed to a more electrophilic PdII center, which could accelerate the rate-determining methanolysis step.
- Nobbs, James D.,Low, Choon Heng,Stubbs, Ludger P.,Wang, Cun,Drent, Eite,Van Meurs, Martin
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p. 391 - 398
(2017/04/26)
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- Towards quantitative and scalable transformation of furfural to cyclopentanone with supported gold catalysts
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Given the vital importance of furfural (FFA) upgrading towards a sustainable bio-based economy, an eco-friendly aqueous route to produce a sole valuable product from FFA is highly desirable. We herein describe an efficient approach to quantitatively convert FFA into cyclopentanone (CPO) in neat water, employing H2 as the clean reductant and supported gold nanoparticles as a simple yet versatile catalyst. The use of anatase TiO2 featuring only mild Lewis acidic sites as the underlying support is essential, not only for preventing undesirable side reactions, but also for attaining high CPO selectivity. The feasibility of using biogenic CPO and CO2 as benign carbon sources to synthesize the industrially important feedstock dimethyl adipate is also demonstrated.
- Zhang, Gao-Shuo,Zhu, Ming-Ming,Zhang, Qi,Liu, Yong-Mei,He, He-Yong,Cao, Yong
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p. 2155 - 2164
(2016/04/19)
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- Efficient and sustainable transformation of gamma-valerolactone into nylon monomers
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Herein, we reported the facile synthesis of dicarboxylic esters from biomass derived gamma-valerolactone (GVL) aiming for nylon monomer preparation via a novel synthetic route which improved the efficiency and overcame the need for toxic carbon monoxide for the synthesis of dicarboxylic esters from GVL.
- Yang, Yong,Wei, Xurui,Zeng, Fanxin,Deng, Li
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supporting information
p. 691 - 694
(2016/02/12)
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- Selective monomethyl esterification of linear dicarboxylic acids with bifunctional alumina catalysts
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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.
- Santacroce, Veronica,Bigi, Franca,Casnati, Alessandra,Maggi, Raimondo,Storaro, Loretta,Moretti, Elisa,Vaccaro, Luigi,Maestri, Giovanni
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supporting information
p. 5764 - 5768
(2016/11/06)
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- Continuous esteration preparation of adipic acid dimethyl ester method
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The invention discloses a method for preparing dimethyl adipate by continuous esterification, comprising the steps of (1) pre-esterifying mixture of adipic acid and methanol in a tubular reactor with an inner component on the catalyst-free condition, wherein the temperature is 90-180 degrees centigrade and the pressure is 0.05-3 MPa; (2), sending the pre-esterified product to upper part of a continuous catalytic rectifying tower; enabling the dried methanol to enter the lower part of the catalytic rectifying tower after being vaporized; enabling the pre-esterified material to contact the methanol steam in the catalytic rectifying tower in a counter-current manner; and further performing esterifying. The method overcomes the problems that the traditional process has device corrosion and pollution problem caused by the sulphuric acid catalyst, and has no continuous pre-esterification and large catalyst consumption.
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Paragraph 0025-0029
(2017/02/23)
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- Highly efficient metal salt catalyst for the esterification of biomass derived levulinic acid under microwave irradiation
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The esterification of levulinic acid (LA) to alkyl levulinates has been investigated in the presence of various metal salt catalysts under microwave irradiation. The reaction obtained 99.4% yield of methyl levulinate (ML) in the presence of Al2(SO4)3 catalyst in methanol solution under microwave conditions. The optimized reaction conditions were 110 °C and 10 minutes with a 20 mol% catalyst loading. Alcohols with longer carbon chains showed lower reactivities in the microwave electromagnetic field due to their poorer abilities to absorb and transmit microwave energy. Moreover, microwave irradiation provided a significantly higher reaction rate compared to conventional oil bath heating. LA aqueous solution was also converted to ML with high yields. The Al2(SO4)3 catalyst was successfully applied to the esterification of other biomass derived organic acids to their corresponding esters in high yields. Finally, the catalyst was recycled 5 times without much decrease in activity.
- Huang, Yao-Bing,Yang, Tao,Cai, Bo,Chang, Xin,Pan, Hui
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p. 2106 - 2111
(2016/01/20)
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- The synthesis of di-carboxylate esters using continuous flow vortex fluidics
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A vortex fluidic device (VFD) is effective in mediating the synthesis of di-esters at room temperature. Processing under ambient conditions allows for a simple and efficient synthesis, whilst operating under continuous flow addresses scalability. The rotational speed of the sample tube and the flow rate were critical variables during reaction optimization, and this relates to the behaviour of the fluid flow at a molecular level. Whilst at specific rotational speeds the tube imparts a vibrational response into the fluid flow, the flow rate dictates residence time and the ability to maintain high levels of shear stress. The combination of mechanically induced vibrations, rapid micromixing, high levels of shear stress and water evaporation results in yields up to 90% for 3.25 minutes or less residence time. These results are key for devising greener and more efficient processes both mediated by the VFD and other continuous flow platforms.
- Britton, Joshua,Dalziel, Stuart B.,Raston, Colin L.
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p. 2193 - 2200
(2016/04/19)
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- DICARBOXYLIC ACID BISAMIDE DERIVATIVES, USE THEREOF, PHARMACEUTICAL COMPOSITION BASED THEREON AND METHODS FOR PRODUCING DICARBOXYLIC ACID BISAMIDE DERIVATIVES
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The present invention relates to novel biologically active compounds, in particular dicarboxylic acid bisamide derivatives of general formula I: or pharmaceutically acceptable salts thereof, which are able to form complexes with or chelate metal ions. The invention also relates to the use of said compounds as an agent for the prevention and/or treatment of cardiovascular, viral, cancer, neurodegenerative and inflammatory diseases, diabetes, age-related diseases, diseases caused by microbial toxins, alcoholism and alcoholic cirrhosis, anaemia, porphyria cutanea tarda, and transition metal salt poisoning. The present invention also relates to novel methods for preparing dicarboxylic acid bisamide derivatives of general formula I.
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Paragraph 0146
(2016/02/21)
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- A magnetically recoverable nanocatalyst based on functionalized mesoporous silica
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A magnetically separable 2D-hexagonally ordered thiol functionalized mesoporous silica material (Fe@TFMS) has been synthesized through co-condensation reaction of 3-mercaptopropyltriethoxysilane (MPTES) and tetraethylorthosilicate (TEOS) using cetyltrimethylammonium bromide (CTAB) as a cationic surfactant followed by immobilization of Fe3O4 nanocrystallies at the functionalized mesopore surface. Powder X-ray diffraction (XRD), N2 adsorption/desorption analysis, FT-IR, TEM, FE-SEM, TGA/DTA, CHNS, XPS and NH3-TPD tools are employed to characterize the materials. This functionalized mesoporous material exhibited high catalytic activity in the biodiesel production from a wide range of long chain fatty acids and soybean oil. The material showed high Lewis acidity of 1.02 mmolg-1 with a good Brunauer-Emmett-Teller (BET) surface area of 411 m2 g-1. Fe@TFMS exhibited excellent catalytic efficiency for this esterification reaction using methanol as a solvent cum reactant under eco-friendly and mild reaction conditions (room temperature, 25 °C).
- Bhanja, Piyali,Sen, Tapas,Bhaumik, Asim
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- ORGANIC ACIDS FROM HOMOCITRATE AND HOMOCITRATE DERIVATIVES
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This disclosure relates to methods for converting homocitric acid to adipic acid, and more particularly to methods of using metal catalysts to catalyze the conversion of homocitric acid to adipic acid.
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Page/Page column 33
(2016/01/01)
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- Sustainable production of dimethyl adipate by non-heme iron(iii) catalysed oxidative cleavage of catechol
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Adipic acid and its esters are important bulk chemicals whose principal use is in the production of the nylon-6,6 polymer. There is considerable interest in finding novel green routes from sustainable feedstocks towards these important intermediates. Herein, we describe the catalytic oxidative cleavage of catechol to muconic acids using a catalyst prepared in situ from iron(iii) nitrate, tris(2-pyridylmethyl)amine and ammonium acetate. An investigation of catalyst loading, temperature and oxygen pressure, allowed a turnover frequency of 120 h-1 to be obtained. The subsequent hydrogenation and transesterification of the obtained muconic acid products were shown to proceed well over commercially available supported catalysts. After vacuum distillation, dimethyl adipate could be isolated in 62% yield from catechol, thus demonstrating a green and sustainable route to this important bulk chemical.
- Jastrzebski, Robin,Van Den Berg, Emily J.,Weckhuysen, Bert M.,Bruijnincx, Pieter C. A.
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p. 2103 - 2109
(2015/04/14)
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- METHODS OF PRODUCING DICARBONYL COMPOUNDS
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Dicarboxylic acids, such as adipic acid, and diesters, such as adipates, may be produced by hydrogenating alkynes that may be produced from raw materials salvaged from waste stream processes. The carbons of the dicarboxylic acids are provided by alkynes generated from biomass waste and carbon dioxide recovered from waste streams such as exhaust gases.
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Paragraph 0043
(2015/05/06)
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- Ligand-Controlled Palladium-Catalyzed Alkoxycarbonylation of Allenes: Regioselective Synthesis of α,β- and β,γ-Unsaturated Esters
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The palladium-catalyzed regioselective alkoxycarbonylation of allenes with aliphatic alcohols allows to produce synthetically useful α,β- and β,γ-unsaturated esters in good yields. Efficient selectivity control is achieved in the presence of appropriate ligands. Using Xantphos as the ligand, β,γ-unsaturated esters are produced selectively in good yields. In contrast, the corresponding α,β-unsaturated esters are obtained with high regioselectivity in the presence of PPh2Py as the ligand. Preliminary mechanistic studies revealed that these two catalytic processes proceed by different reaction pathways. In addition, this novel protocol was successfully applied to convert an industrially available bulk chemical, 1,2-butadiene, into dimethyl adipate, which is a valuable feedstock for polymer and plasticizer syntheses, with high yield and TON (turnover number).
- Liu, Jie,Liu, Qiang,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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supporting information
p. 8556 - 8563
(2015/07/15)
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- A new hypercrosslinked supermicroporous polymer, with scope for sulfonation, and its catalytic potential for the efficient synthesis of biodiesel at room temperature
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We have designed a new hypercrosslinked supermicroporous polymer (HMP-1) with a BET surface area of 913 m2 g-1 by FeCl3via a catalyzed Friedel-Crafts alkylation reaction between carbazole and α,α′-dibromo-p-xylene. Upon sulfonation HMP-1 yielded a very efficient solid acid catalyst for the production of biodiesels via esterification/transesterification of free fatty acids (FFA)/esters at room temperature.
- Bhunia, Subhajit,Banerjee, Biplab,Bhaumik, Asim
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supporting information
p. 5020 - 5023
(2015/03/30)
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- Metal/bromide autoxidation of triglycerides for the preparation of FAMES to improve the cold-flow characteristics of biodiesel
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Triglyceride autoxidation using a homogeneous Co/Mn/Zr/bromide catalyst in acetic acid (93%) of low grade tallow, canola oil or soy bean oil in a batch reactor at 150 °C for 2 h, produced lower molecular weight products relative to the fatty acids of the starting triglycerides. For the autoxidation of tallow the main products after esterification were monoesters Me(CH 2)mC(O)OMe (m = 5-12) and diesters MeOC(O)(CH 2)nC(O)OMe, (n = 7-12). Oxidation of the saturated fatty acids in triglycerides was confirmed and modelled using methyl palmitate. Post-treatment esterification of tallow autoxidation products to produce biodiesel (BD) esters resulted in improved cold temperature properties by a mean of 13.0 °C, i.e. a mean cloud point (CP) 1.0 °C (cf. unmodified tallow biodiesel: CP 14 °C).
- Phung, Peter,Rowlands, William N.,Thiyakesan, Appadurai,Benndorf, Paul,Masters, Anthony F.,Maschmeyer, Thomas
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p. 162 - 168
(2014/07/07)
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- Palladium-catalyzed alkoxycarbonylation of conjugated dienes under acid-free conditions: Atom-economic synthesis of β,γ-unsaturated esters
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Carbonylation reactions constitute important methodologies for the synthesis of all kinds of carboxylic acid derivatives. The development of novel and better catalysts for these transformations is of interest for both academic and industrial research. Here, a benign palladium-based catalyst system for the alkoxycarbonylation of conjugated dienes under acid-free conditions has been developed. This atom-efficient transformation provides straightforward access to a variety of β,γ-unsaturated esters in good to excellent yields and often with high selectivities. As an industrially relevant example the (formal) synthesis of dimethyl adipate and ε-caprolactam from 1,3-butadiene is demonstrated.
- Fang, Xianjie,Li, Haoquan,Jackstell, Ralf,Beller, Matthias
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supporting information
p. 9030 - 9034
(2014/09/17)
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- PROCESS FOR THE PREPARATION OF FORMYLVALERIC ACID AND ADIPIC ACID
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The invention relates to a process for the production of 5-formylvaleric acid and adipic acid or esters thereof from an isomeric mixture of pentenoic acid or esters thereof said mixture comprising at least 4-pentenoic acid or esters thereof, and further comprising 3-pentenoic acid and/or 2-pentenoic acid or esters thereof, theprocess comprising: (a) subjecting the isomeric mixture of pentenoic acid to a hydroformylation reaction comprising a hydroformylation catalyst which is non-isomerizing towards the pentenoic acid or esters thereof to obtain a mixture comprising 5-formylvaleric acid or esters thereof and further comprising 3-pentenoic acid and/or 2-pentenoic acid, or esters thereof; (b) separating the 3-pentenoic acid and/or 2-pentenoic acid, or esters thereof from the 5-formylvaleric acid or esters thereof; (c) subjecting the separated pentenoic acids or esters thereof to a carbonylation reaction comprising an isomerizing carbonylation catalyst to obtain adipic acid or esters thereof; (d) optionally isolating the adipic acid or ester thereof; and (e) optionally isolating the separated 5-formylvaleric acid or esters thereof. The process allows for efficient production of two different intermediates for producing polyamide using a single process, with good selectivity, little waste, in an economically efficient fashion. The process is very suitable to use an isomeric pentenoic acid mixture obtained from valerolactone, and can be used to produce renewable polyamide intermediates using a single process.
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Page/Page column 8; 10
(2014/08/06)
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- ALCOHOL-MEDIATED ESTERIFICATION OF CARBOXYLIC ACIDS WITH CARBONATES
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A process for making esters from organic acids by means of reacting a carboxylic acid with dialkylcarbonate in an alcohol-containing solvent without any extrinsic acid or base catalyst is described. A benefit of the preparation process is that it can make the separation and extraction of ester products simpler and more facile vis-a-vis conventional isolation techniques.
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Page/Page column 12
(2014/05/24)
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