- Scalable Total Synthesis of (-)-Triptonide: Serendipitous Discovery of a Visible-Light-Promoted Olefin Coupling Initiated by Metal-Catalyzed Hydrogen Atom Transfer (MHAT)
-
An efficient and scalable total synthesis of (-)-triptonide is accomplished based on a metal-catalyzed hydrogen atom transfer (MHAT)-initiated radical cyclization. During the optimization of the key step, we discovered that blue LEDs significantly promoted the efficiency of reaction initiated by Co(TPP)-catalyzed MHAT. Further exploration and optimization of this catalytic system led to development of a dehydrogenative MHAT-initiated Giese reaction.
- Fang, Xianhe,Zhang, Nan,Chen, Si-Cong,Luo, Tuoping
-
supporting information
p. 2292 - 2300
(2022/02/09)
-
- Acid- And base-switched palladium-catalyzed γ-C(sp3)-H alkylation and alkenylation of neopentylamine
-
The functionalization of remote unactivated C(sp3)-H and the reaction selectivity are among the core pursuits for transition-metal catalytic system development. Herein, we report Pd-catalyzed γ-C(sp3)-H-selective alkylation and alkenylation with removable 7-azaindole as a directing group. Acid and base were found to be the decisive regulators for the selective alkylation and alkenylation, respectively, on the same single substrate under otherwise the same reaction conditions. Various acrylates were compatible for the formation of C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds. The alkenylation protocol could be further extended to acrylates with natural product units and α,β-unsaturated ketones. The preliminary synthetic manipulation of the alkylation and alkenylation products demonstrates the potential of this strategy for structurally diverse aliphatic chain extension and functionalization. Mechanistic experimental studies showed that the acidic and basic catalytic transformations shared the same six-membered dimer palladacycle.
- Zhang, Jinquan,Zhang, Shuaizhong,Zou, Hongbin
-
supporting information
p. 3466 - 3471
(2021/05/31)
-
- METHOD FOR MAKING BIO-BASED ACRYLIC ACID
-
Described herein are methods for the preparation of bio-based acrylic acid from bio-based methyl lactate. Some methods involve the use of an azeotropic distillate of methyl acrylate and methanol. The methods enhance bio-based acrylic acid production yield.
- -
-
Page/Page column 12-13
(2022/02/06)
-
- Method for preparing methyl acrylate from methyl acetate
-
The invention provides a method for preparing methyl acrylate from methyl acetate, which comprises the following steps: in the presence of a solid base catalyst, methyl acetate reacts with an aldehyde source to obtain methyl acrylate, and the solid base catalyst comprises the following components in parts by mass: a) a catalytic amount of alkali metal oxide; and b) 50 to 80 parts of a carrier; wherein the carrier is silicon dioxide of which the silicon hydroxyl density is 0.6-1.5 Si-OH/nm. The invention also provides a solid base catalyst, and an application and a preparation method thereof. The methyl acrylate synthesis route and the corresponding solid base catalyst have the advantages that the yield and selectivity are improved, and the catalytic activity can be maintained for a long time, so that the industrialization can be realized, and the problem that the production capacity of methyl acetate is greatly excessive is solved.
- -
-
Paragraph 0138-0168
(2021/04/28)
-
- Pd-Catalyzed Intermolecular Transthiolation of Ar-OTf Using Methyl 3-(Methylthio) Propanoate as a Thiol Surrogate
-
A method for the odorless synthesis of unsymmetrical sulfides via Csp2?O and Csp3?S bond activation is presented. Using methyl 3-(methylthio) propanoate as a MeSH surrogate, a series of substituted aryl methyl sulfides have been obtained in moderate to good yields. This catalytic protocol can also tolerate methyl 3-(methylthio)propionate derivatives to afford the corresponding aryl sulfides.
- Pan, Dandan,Xu, Shasha,Tian, Qingqiang,Li, Yahui
-
supporting information
p. 4616 - 4619
(2021/09/10)
-
- Phosphine-Catalyzed Cascade Annulation of MBH Carbonates and Diazenes: Synthesis of Hexahydrocyclopenta[c]pyrazole Derivatives
-
A phosphine-catalyzed cascade annulation of Morita-Baylis-Hillman (MBH) carbonates and diazenes was achieved, giving tetrahydropyrazole-fused heterocycles bearing two five-membered rings in moderate to excellent yields. The reaction underwent an unprecedented reaction mode of MBH carbonates, in which two molecules of MBH carbonates were fully merged into the ring system.
- Guo, Hongchao,Li, Hongxiang,Liu, Hao,Shi, Wangyu,Wang, Chang,Wang, Wei,Wu, Yongjun
-
supporting information
p. 5571 - 5575
(2021/07/31)
-
- METHOD FOR PREPARING ACRYLIC ACID AND METHYL ACRYLATE
-
The present invention provides a method for preparing acrylic acid and methyl acrylate. The method comprises passing the feed gas containing dimethoxymethane and carbon monoxide through a solid acid catalyst to generate acrylic acid and methyl acrylate with a high conversion rate and selectivity at a reaction temperature in a range from 180 to 400 and a reaction pressure in a range from 0.1 MPa to 15.0 MPa, the mass space velocity of dimethoxymethane in the feed gas is in a range from 0.05 h?1 to 10.0 h?1, and the volume percentage of dimethoxymethane in the feed gas is in a range from 0.1% to 95%.
- -
-
Paragraph 0076-0081
(2021/04/23)
-
- The effect of viscosity on the coupling and hydrogen-abstraction reaction between transient and persistent radicals
-
The effect of viscosity on the radical termination reaction between a transient radical and a persistent radical undergoing a coupling reaction (Coup) or hydrogen abstraction (Abst) was examined. In a non-viscous solvent, such as benzene (bulk viscosity bulk 99% Coup/Abst selectivity, but Coup/Abst decreased as the viscosity increased (89/11 in PEG400 at 25 °C [bulk = 84 mPa s]). While bulk viscosity is a good parameter to predict the Coup/Abst selectivity in each solvent, microviscosity is the more general parameter. Poly(methyl methacrylate) (PMMA)-end radicals had a more significant viscosity effect than polystyrene (PSt)-end radicals, and the Coup/Abst ratio of the former dropped to 50/50 in highly viscous media (bulk = 3980 mPa s), while the latter maintained high Coup/ Abst selectivity (84/16). These results, together with the low thermal stability of dormant PMMA-TEMPO species compared with that of PSt-TEMPO species, are attributed to the limitation of the nitroxide-mediated radical polymerization of MMA. While both organotellurium and bromine compounds were used as precursors of radicals, the former was superior to the latter for the clean generation of radical species.
- Li, Xiaopei,Kato, Tatsuhisa,Nakamura, Yasuyuki,Yamago, Shigeru
-
p. 966 - 972
(2021/04/29)
-
- Palladium-catalyzed remote C-H functionalization of 2-aminopyrimidines
-
A straightforward strategy was developed for the arylation and olefination at the C5-position of the N-(alkyl)pyrimidin-2-amine core with readily available aryl halides and alkenes, respectively. This approach was highly regioselective, and the transformation was achieved based on two different (Pd(ii)/Pd(iv)) and (Pd(0)/Pd(ii)) catalytic cycles.
- Das, Animesh,Jana, Akash,Maji, Biplab
-
supporting information
p. 4284 - 4287
(2020/04/27)
-
- Continuous Radio Amplification by Stimulated Emission of Radiation using Parahydrogen Induced Polarization (PHIP-RASER) at 14 Tesla
-
Nuclear Magnetic Resonance (NMR) is an intriguing quantum-mechanical effect that is used for routine medical diagnostics and chemical analysis alike. Numerous advancements have contributed to the success of the technique, including hyperpolarized contrast agents that enable real-time imaging of metabolism in vivo. Herein, we report the finding of an NMR radio amplification by stimulated emission of radiation (RASER), which continuously emits 1H NMR signal for more than 10 min. Using parahydrogen induced hyperpolarization (PHIP) with 50 % para-hydrogen, we demonstrated the effect at 600 MHz but expect that it is functional across a wide range of frequencies, e.g. 101–103 MHz. PHIP-RASER occurs spontaneously or can be triggered with a standard NMR excitation. Full chemical shift resolution was maintained, and a linewidth of 0.6 ppb was achieved. The effect was reproduced by simulations using a weakly coupled, two spin-1/2 system. All devices used were standard issue, such that the effect can be reproduced by any NMR lab worldwide with access to liquid nitrogen for producing parahydrogen.
- H?vener, Jan-Bernd,Pravdivtsev, Andrey N.,S?nnichsen, Frank D.
-
-
- Palladium Nanoparticle-Catalyzed Stereoselective Domino Synthesis of 3-Allylidene-2(3 H)-oxindoles and 3-Allylidene-2(3 H)-benzofuranones
-
A single-step, stereoselective protocol for the synthesis of unsymmetrically substituted (E)-3-allylideneoxindole and (E)-3-allylidenebenzofuran from readily accessible starting materials using palladium binaphthyl nanoparticles (Pd-BNPs) has been developed. Pd-BNP showing a wide range of functional group tolerance and an immense array of substrate scope have been explored with the successful synthesis of the drug molecule "tubulin polymerization inhibitor" free from trace metal impurities. The model reaction is extended to a gram-scale synthesis, and one of the products is utilized for derivatization. The Pd-BNP has been recycled up to 5 catalytic cycles without any loss in reaction yields and particle size of nanoparticles.
- Parveen, Naziya,Sekar, Govindasamy
-
p. 4682 - 4694
(2020/05/08)
-
- Second-Generation meta-Phenolsulfonic Acid-Formaldehyde Resin as a Catalyst for Continuous-Flow Esterification
-
A second-generation m-phenolsulfonic acid-formaldehyde resin (PAFR II) catalyst was prepared by condensation polymerization of sodium m-phenolsulfonate and paraformaldehyde in an aqueous H2SO4 solution. This reusable, robust acid resin catalyst was improved in both catalytic activity and stability, maintaining the characteristics of the previous generation catalyst (p-phenolsulfonic acid-formaldehyde resin). PAFR II was applied in the batchwise and continuous-flow direct esterification without water removal and provided higher product yields in continuous-flow esterification than any other commercial ion-exchanged acid catalyst tested.
- Hu, Hao,Ota, Hajime,Baek, Heeyoel,Shinohara, Kenta,Mase, Toshiaki,Uozumi, Yasuhiro,Yamada, Yoichi M. A.
-
supporting information
p. 160 - 163
(2020/01/02)
-
- Synthesis method of methyl alcohol-containing methyl acrylate (by machine translation)
-
The methanol-methyl acrylate mixed solution is mixed evenly and then, the mixed uniform: material is separated from the methanol,methanol azeotropic system to form a methyl, methacrylate-methanol azeotropic system which; is used to separate methanol (methyl, methacrylate ;) and the catalyst, into a reaction system to form a methyl methacrylate-methanol azeotropic system which is formed by mixing and adding methanol to a 65 °C. reaction system in a large amount. The method comprises the following steps: mixing evenly mixed materials into a reaction system to form a methyl methacrylate-methanol azeotropic system and adding methanol, to the reaction system in a large excess of methanol to form a methyl, methacrylate-methanol azeotropic system to form a methanol- PBTCA methyl 2 - acrylate mixture . (by machine translation)
- -
-
Paragraph 0017-0022
(2020/04/29)
-
- Unraveling the cation and anion effects and kinetics for ionic liquid catalyzed direct synthesis of methyl acrylate under mild conditions
-
The direct synthesis of methyl acrylate (MA) from methyl acetate and trioxane at 350-380 °C is regarded as a supplementary route for the industrial propylene oxidation process; however, it suffers from rapid catalyst deactivation. Herein, a novel ionic liquid catalyzed mild liquid-phase system was developed for the direct synthesis of MA from methyl acetate and trioxane, where N,O-bis(trimethylsilyl)acetamide (BSA) was used as a probase for α-deprotonation and enol silyl etherification of methyl acetate. The trioxane decomposition to formaldehyde and methyl acetate enolization to 1-methoxy-1-trimethylsilyloxyethene proceeded with the catalysis of [Cation]Cl/MClx (M = Cu+, Fe3+, Zn2+ and Al3+) and [Cation]F, respectively. The cations and anions were observed to have significant effects on the yield and selectivity of MA, owing to the steric hindrance, acid site category and strength confirmed by pyridine probing FT-IR characterization. As a result, up to 60.2% yield with 94.6% selectivity of MA could be achieved when [N3,3,3,3]F and [N3,3,3,3]Cl/AlCl3 with 67 mol% AlCl3 were used in the presence of BSA at 25 °C. Kinetic studies indicated that the trioxane decomposition with the activation barrier of 41.2 ± 0.3 kJ mol-1 was the rate-determining step.
- Wang, Gang,Li, Zengxi,Li, Chunshan,Zhang, Suojiang
-
p. 7913 - 7923
(2020/12/01)
-
- Byproducts formed During Thiol-Acrylate Reactions Promoted by Nucleophilic Aprotic Amines: Persistent or Reactive?
-
The nucleophile-initiated mechanism of thiol-Michael reactions naturally leads to the formation of undesired nucleophile byproducts. Three aza-Michael compounds representing nucleophile byproducts of thiol-acrylate reactions initiated by 4-dimethylaminopyridine (DMAP), 1-methylimidazole (MIM), and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) have been synthesized and their reactivity in the presence of thiolate has been investigated. Spectroscopic analysis shows that each nucleophile byproduct reacts with thiolate to produce a desired thiol-acrylate product along with liberated aprotic amines DMAP, MIM, or DBU, thus demonstrating that these byproducts are reactive rather than persistent. Density functional theoretical computations support experimental observations and predict that a β-elimination mechanism is favored for converting each nucleophile byproduct into a desired thiol-acrylate product, though an SN2 process can be competitive (i. e. within 2.5 kcal/mol) in less polar solvents.
- Drogkaris, Vasileios,Northrop, Brian H.
-
p. 2466 - 2474
(2020/12/03)
-
- Palladium-catalyzed regioselective synthesis of B(4,5)-or B(4)-substituted: O-carboranes containing α,β-unsaturated carbonyls
-
With the help of a carboxylic acid directing group, Pd-catalyzed regioselective synthesis of B(4,5)-or B(4)-substituted o-carboranes containing α,β-unsaturated carbonyls has been reported. The-COOH, removed during the course of the reaction, is responsible for controlling the regioselectivity. The desired products could be obtained in moderate to good yields.
- Li, Jiaoyi,Lu, Jian,Tian, Song,Wang, Qian,Zhang, Chuyi,Zhang, Jianwei,Zhou, Ling
-
supporting information
p. 4723 - 4727
(2020/07/13)
-
- Acrylate Esters by Ethenolysis of Maleate Esters with Ru Metathesis Catalysts: an HTE and a Technoeconomic Study
-
A high throughput experimentation (HTE) study identified active Ru metathesis catalysts and reaction conditions for the ethenolysis of maleate esters to the respective acrylate esters. Catalysts were tested at various loadings (75–10’000 ppm) and temperatures (30–60 °C) with maleate esters dissolved in toluene (up to ca. 44 wt-%) or neat and at variable partial pressures of ethylene (0.2–10 bar). Ruthenium catalysts containing a PCy3 ligand, such as 1st or 2nd generation Grubbs catalysts, as well as the state-of-the-art catalysts containing cyclic alkyl amino carbene (CAAC) ligands, are generally inferior to Hoveyda–Grubbs 2nd generation catalyst in ethenolysis of maleates. Productive turnover numbers could exceed 1900 if the ethenolysis reaction is performed at low ethylene pressure (0.2–3 bar) and reach 5200 when a polymeric phenol additive was used. Such catalytic performance falls well within the window practiced in industry. Moreover, a crude technoeconomic analysis finds similar production cost for the ethenolysis route and conventional technology, that is, propene oxidation followed by esterification, justifying research to further improve the ethenolysis route.
- Copéret, Christophe,De Jesus Silva, Jordan,Engl, Pascal S.,Fedorov, Alexey,Lange, Jean-Paul,Togni, Antonio,Tsygankov, Alexey
-
-
- Direct and Tandem Routes for the Copolymerization of Ethylene with Polar Functionalized Internal Olefins
-
Transition metal catalyzed ethylene copolymerization with polar monomers is a highly challenging reaction. After decades of research, the scope of suitable comonomer substrates has expanded from special to fundamental polar monomers and, recently, to 1,1-disubstituted ethylenes. Described in this contribution is a direct and tandem strategy to realize ethylene copolymerization with various 1,2-disubstituted ethylenes. The direct route is sensitive to sterics of both the comonomers and the catalyst. In the tandem route, ruthenium-catalyzed ethenolysis can convert 1,2-disubstituted ethylenes into terminal olefins, which can be subsequently copolymerized with ethylene to afford polar functionalized polyolefins. The one-pot, two-step tandem route is highly versatile and efficient in dealing with challenging substrates. This work is a step forward in terms of expanding the substrate scope for transition metal catalyzed ethylene copolymerization with polar-functionalized comonomers.
- Chen, Min,Chen, Changle
-
supporting information
p. 1206 - 1210
(2019/12/24)
-
- PRODUCTION OF ALKYL ESTERS OF ACRYLIC ACID
-
A process for producing a mixture including acrylic acid or derivatives thereof, the process including the step of contacting a mixture of lactic acid or derivatives thereof and a solvent over a dehydration catalyst to produce the mixture including alkyl esters of acrylic acid, wherein the density of the solvent ranges from about 10 to about 500 kg/m3 under operating conditions.
- -
-
Page/Page column 7-8
(2020/01/31)
-
- METHOD FOR PREPARING LOW-GRADE UNSATURATED FATTY ACID ESTER
-
Provided is a method for preparing a lower unsaturated fatty acid ester, which comprises carrying out an aldol condensation reaction between dimethoxymethane (DMM) and a lower acid or ester with a molecular formula of R1—CH2—COO—R2 on an acidic molecular sieve catalyst in an inert atmosphere to obtain a lower unsaturated fatty acid or ester(CH2═C(R1)—COO—R2), wherein R1 and R2 are groups each independently selected from the group consisting of H- and C1-C4 saturated alkyl group.
- -
-
Paragraph 0050-0057
(2020/03/09)
-
- PROCESS FOR THE PRODUCTION OF METHYL ACRYLATE FROM METHYL LACTATE
-
The present invention is directed to a process for the production of methyl acrylate wherein methyl lactate is contacted with a ZSM-5 catalyst in the presence of methanol. It was found that the presence of methanol is essential to obtain a selective process with a high yield. With the process according to the invention methyl acrylate may be obtained as the major product of the reaction, especially if methanol is used as solvent instead of water, while acrylic acid is detected in minor quantity (usually below 10C%, but often below 5 C%). Methanol may be used as the sole solvent in the process, but preferably also a small amount of water is present in the solvent. In one aspect of the invention, between 1 and 25 wt% of water, based on the total amount of solvent is present.
- -
-
Page/Page column 14
(2019/07/04)
-
- Precisely phase-modulated VPO catalysts with enhanced inter-phase conjunction for acrylic acid production through the condensation of acetic acid and formaldehyde
-
A type of precisely phase-modulated vanadium phosphorus oxides (VPOs)was fabricated for the first time by quantitatively mixing the pure phase of γ-VOPO4, δ-VOPO4, and (VO)2P2O7 in certain ratios through a mechanical milling approach. The resulting materials were used as catalysts for very efficient condensation of acetic acid and formaldehyde to acrylic acid as well as methyl acrylate. The modulated dual phase VPO catalyst outperforms the single-phase counterpart, and by optimizing the reaction conditions especially the contact time, we can further considerably enhance the catalyst performance. Over an optimized catalyst of δ-VOPO4/γ-VOPO4 (w/w, 3/1), the (AA + MA)yield of 84.2% with the equivalent (AA + MA)formation rate of 1.71 mmol·g?1·h?1 or the (AA + MA)yield of 41.8% with the equivalent (AA + MA)formation rate of 4.25 mmol·g?1·h?1 is achievable at 360 °C on the formaldehyde input basis. This sort of catalyst is rather durable within a period of 110 h, and fully recovered by simple air-treatment at the reaction temperature. Due to the enhanced conjunction at the interface of two phases, the surface property of phase-modulated catalyst such as the P-O bond length and surface acidity is notably modified/enhanced, accounting for the promising catalytic performance.
- Liu, Jun,Wang, Pengcheng,Feng, Yina,Xu, Zhijia,Feng, Xinzhen,Ji, Weijie,Au, Chak-Tong
-
p. 171 - 182
(2019/05/14)
-
- Ruthenium(II) Catalysed Highly Regioselective C-3 Alkenylation of Indolizines and Pyrrolo[1,2-a]quinolines
-
Discovered the Ruthenium(II) catalysed highly stereo- and regioselective protocol for the oxidative C-3 alkenylation of indolizines and pyrrolo[1,2-a]quinolines. The methodology represents the first example for the directing group assisted C–C bond formation reaction of the indolizines. Under mild reaction conditions, this method provides an ample substrate scope to produce C-3 alkenyl indolizines in excellent to moderate yields. However, pyrrolo[1,2-a]quinolines underwent alkenynation at elevated temperature to furnish C-3 alkenyl derivatives. The functionalized indolizines were selectively reduced to obtain their saturated derivatives.
- Jadhav, Pankaj Pandit,Kahar, Nilesh Machhindra,Dawande, Sudam Ganpat
-
supporting information
p. 7831 - 7835
(2019/12/24)
-
- A Simple and Efficient Procedure for Rh(I)- and Ir(I)-complex Catalyzed Para-hydrogenation of Alkynes and Alkenes in Aqueous Media Resulting in Strong PHIP Effects
-
Catalytic hydrogenations with para-H2 may lead to strong para-hydrogen induced polarization (PHIP) and the hyperpolarized probe molecules may enable the application of the Magnetic Resonance Imaging (MRI) diagnostic modality for metabolism imaging. The use of water as a solvent for para-hydrogenation reactions is very challenging due to the fast exchange between the catalytically active metal hydrides and the water protons and also because of the low hydrogen solubility in water. Here we report that several water-soluble Rh(I)- and Ir(I)-complexes with N-heterocyclic carbene (NHC) and/or tertiary phosphine ligands efficiently catalyze the synthesis of hyperpolarized compounds by para-hydrogenation in aqueous media.
- Papp, Gábor,Horváth, Henrietta,Joó, Ferenc
-
p. 3000 - 3003
(2019/06/17)
-
- Selective Conversion of Carbon Dioxide to Formaldehyde via a Bis(silyl)acetal: Incorporation of Isotopically Labeled C1 Moieties Derived from Carbon Dioxide into Organic Molecules
-
The conversion of carbon dioxide to formaldehyde is a transformation that is of considerable significance in view of the fact that formaldehyde is a widely used chemical, but this conversion is challenging because CO2 is resistant to chemical transformations. Therefore, we report here that formaldehyde can be readily obtained from CO2 at room temperature via the bis(silyl)acetal, H2C(OSiPh3)2. Specifically, formaldehyde is released from H2C(OSiPh3)2 upon treatment with CsF at room temperature. H2C(OSiPh3)2 thus serves as a formaldehyde surrogate and provides a means to incorporate CHx (x = 1 or 2) moieties into organic molecules. Isotopologues of H2C(OSiPh3)2 may also be synthesized, thereby providing a convenient means to use CO2 as a source of isotopic labels in organic molecules.
- Rauch, Michael,Strater, Zack,Parkin, Gerard
-
supporting information
p. 17754 - 17762
(2019/11/05)
-
- Selenium-Modified Microgels as Bio-Inspired Oxidation Catalysts
-
Active colloidal catalysts inspired by glutathione peroxidase (GPx) were synthesized by integration of catalytically active selenium (Se) moieties into aqueous microgels. A diselenide crosslinker (Se X-linker) was successfully synthesized and incorporated into microgels through precipitation polymerization, along with the conventional crosslinker N,N′-methylenebis(acrylamide) (BIS). Diselenide bonds within the microgels were cleaved through oxidation by H2O2 and converted to seleninic acid whilst maintaining the intact microgel microstructure. Through this approach catalytically active microgels with variable amounts of seleninic acid were synthesized. Remarkably, the microgels exhibited higher catalytic activity and selectivity at low reaction temperatures than the molecular Se catalyst in a model oxidation reaction of acrolein to acrylic acid and methyl acrylate.
- Tan, Kok H.,Xu, Wenjing,Stefka, Simon,Demco, Dan E.,Kharandiuk, Tetiana,Ivasiv, Volodymyr,Nebesnyi, Roman,Petrovskii, Vladislav S.,Potemkin, Igor I.,Pich, Andrij
-
supporting information
p. 9791 - 9796
(2019/06/24)
-
- Method for synthesizing low-carbon alcohol acrylate from acetylene through carbonylation
-
The invention relates to a method for synthesizing low-carbon alcohol acrylate from acetylene through carbonylation. The method comprises steps as follows: acetylene, low-carbon alcohol and carbon monoxide are taken as raw materials and added to an organic solvent containing a nickel-based catalyst, low-carbon alcohol acrylate is directly synthesized from the mixture through carbonylation, whereinthe nickel-based catalyst comprises a main catalyst, an additive and a catalyst promoter, the main catalyst contains a nickel-containing compound and a multidentate ligand, the additive is triphenylphosphine, the chemical formula of the catalyst promoter is AlR(3-x)Clx, R is C2-C8 alkyl, and x is larger than or equal to 0 and smaller than or equal to 1. Compared with the prior art, the catalyticsystem is non-toxic and non-corrosion to equipment; yield of products at lower temperature and pressure is high, particularly, the catalyst system is low in cost and simple to prepare, cost of raw materials of production and operation cost can be greatly reduced, and the method has broad industrial application prospect.
- -
-
Paragraph 0033; 0034; 0036
(2018/05/30)
-
- Ruthenium(II) oxidase catalysis for C-H alkenylations in biomass-derived γ-valerolactone
-
Ruthenium(ii) biscarboxylate oxidase catalysis is a powerful tool for the assembly of functionalized arenes with oxygen as a green oxidant, but this strategy was thus far limited to its use in traditional organic solvents. Herein, we report on a green procedure for the ruthenium(ii) biscarboxylate-catalysed C-H functionalisation in biomass-derived γ-valerolactone as the reaction medium. The oxidase catalysis was characterized by ample substrate scope and proceeded efficiently with oxygen as the sole oxidant. The overall green nature of this C-H-activation methodology is reflected by H2O being the only by-product.
- Bechtoldt, Alexander,Baumert, Marcel E.,Vaccaro, Luigi,Ackermann, Lutz
-
supporting information
p. 398 - 402
(2018/02/07)
-
- Highly Catalytic Activity of Ba/Γ-Ti–Al2O3 Catalyst for Aldol Condensation of Methyl Acetate with Formaldehyde
-
Abstract: In this work, titanium-doped mesoporous Al2O3 (γ-Ti–Al2O3) was prepared by an evaporation-induced self-assembly method and used as a carrier of Ba/γ-Ti–Al2O3 catalyst to catalyze the aldol condensation of methyl acetate with formaldehyde to methyl acrylate in a fixed-bed reactor. The catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, N2 adsorption–desorption, pyridine absorption performed via Fourier transform infrared spectroscope (Py-IR), and NH3 and CO2 temperature-programmed desorption (NH3 and CO2-TPD). Experimental results indicated that the doping of the titanium species into the frame work of mesoporous Al2O3 (γ-Ti–Al2O3) had a significant influence on the catalytic activity via modifying the acid–base surface properties of the catalyst. Furthermore, the Ba/γ-Ti–Al2O3 catalyst demonstrated excellent catalytic performance, with a methyl acetate conversion rate of 50% and methyl acrylate selectivity up to 90.2%. Compared with the Ba/Al2O3 catalyst, the Ba/γ-Ti–Al2O3 catalyst had better catalytic activity, stability and potential for practical application, which was likely due to an increased number of Lewis acid sites, especially the medium acid sites. Graphical Abstract: Barium supported mesoporous γ-Ti–Al2O3 catalyst was found to be an effective catalyst for vapor phase aldol condensation of methyl acetate with formaldehyde. [Figure not available: see fulltext.].
- Bao, Qiang,Qi, Hui,Zhang, Chunlei,Ning, Chunli,Zhang, Yi,Jiang, Ye,Wu, Yifan,Gui, Wenying,Wang, Zhenlu
-
p. 3402 - 3412
(2018/09/11)
-
- (Meth) acrylate production (by machine translation)
-
(Meth) acrylates [to] (meth) acrylate can be obtained by coloring of high quality manufacturing method. The first step following the first step 3 - [solution] 1, 3 - (meth) acrylates are the first step in production of the first step below 1. ○ 1 the first step in the presence of an acidic catalyst, (meth) acrylic acid (meth) acrylate produced by reacting alcohol dehydration esterification step○ (meth) acrylate containing a reaction product obtained in the first step 1 2 first acidic catalyst removal step○ (meth) acrylate containing a reaction product obtained in step 2 a first 3 and second, hydroxylamine or hydrazine is added to[Drawing] no (by machine translation)
- -
-
Paragraph 0079; 0080; 0081
(2018/10/16)
-
- Catalytic Gas-Phase Production of Lactide from Renewable Alkyl Lactates
-
A new route to lactide, which is a key building block of the bioplastic polylactic acid, is proposed involving a continuous catalytic gas-phase transesterification of renewable alkyl lactates in a scalable fixed-bed setup. Supported TiO2/SiO2 catalysts are highly selective to lactide, with only minimal lactide racemization. The solvent-free process allows for easy product separation and recycling of unconverted alkyl lactates and recyclable lactyl intermediates. The catalytic activity of TiO2/SiO2 catalysts was strongly correlated to their optical properties by DR UV/Vis spectroscopy. Catalysts with high band-gap energy of the supported TiO2 phase, indicative of a high surface spreading of isolated Ti centers, show the highest turnover frequency per Ti site.
- De Clercq, Rik,Dusselier, Michiel,Makshina, Ekaterina,Sels, Bert F.
-
supporting information
p. 3074 - 3078
(2018/03/13)
-
- One-step aldol condensation reaction of dimethoxymethane and methyl acetate over supported Cs/ZSM-35 zeolite catalysts
-
This study was performed for the development of a green and promising approach for the synthesis of methyl acrylate and acrylic acid by a one-step aldol condensation reaction of dimethoxymethane and methyl acetate over cesium oxide-supported on ZSM-35 zeo
- Ma, Zhanling,Ma, Xiangang,Liu, Hongchao,Zhu, Wenliang,Guo, Xinwen,Liu, Zhongmin
-
p. 1129 - 1137
(2018/05/28)
-
- Method for carbonylation-synthesizing acrylic ester by acetylene
-
The invention discloses a method for carbonylation-synthesizing acrylic ester by acetylene, and relates to the technical field of the organic synthesis. The method comprises the following steps: using the acetylene, carbon monoxide and lower alcohol as reaction raw materials, under the action of a catalyst, executing the acetylene carbonylation reaction in a solvent and directly generating the acrylic ester, wherein the catalyst is a nickel non-halogen compound and a salt ligand of Beta-diketone and corresponding compounds. An original method for synthesizing the acrylic ester has the problems, such as long reaction time, carbon deposition in the reaction process and serious corrosion of devices. The method has the advantages of easy acquisition of used catalyst components, rapid catalytic reaction speed, short used time, no carbon deposition in the reaction process, and no device corrosion by a catalyst system.
- -
-
Paragraph 0047; 0048
(2018/03/01)
-
- Method for synthesizing acrylic acid low-carbon alcohol ester through carbonylation of acetylene
-
The invention relates to a method for synthesizing acrylic acid low-carbon alcohol ester through carbonylation of acetylene. A nickel-containing compound and a bidentate ligand containing nitrogen and a VIA-th group element serve as catalysts, and acetylene, carbon monoxide and low-carbon alcohol are subjected to carbonylation reaction in a solvent to synthesize the acrylic ester at one step. The method has the characteristics of low catalyst cost, high reaction speed, no carbon deposition in the reaction process and the like.
- -
-
Paragraph 0025-0026
(2017/08/29)
-
- OZONE-ACTIVATED NANOPOROUS GOLD AND METHODS OF ITS USE
-
The invention relates to nanoporous gold nanoparticle catalysts formed by exposure of nanoporous gold to ozone at elevated temperatures, as well as methods for production of esters and other compounds.
- -
-
Page/Page column 23
(2018/01/17)
-
- Enhanced Acrylate Production from 2-Acetoxypropanoic Acid Esters
-
Reaction conditions and reactor geometry for producing acrylates in high yield from lactic acid-derived 2-acetoxypropanoic acid (APA) esters are presented. An acrylate ester yield of 75% is achieved from methyl and benzyl APA esters at 550 °C in a fixed bed reactor filled with nonporous silica particles, carbon dioxide as a diluent gas, and acetic acid as a co-feed with the APA ester. The yield from methyl and benzyl APA esters is remarkably higher than from ethyl or butyl esters of APA, which have hydrogen atoms on the β-carbon of the ester functional group and thus can undergo alkene elimination, leading to reduced acrylate yield. Under optimum conditions, APA conversion to acrylates is stable over 30 h of continuous operation with little carbon deposition on the contact material.
- Nezam, Iman,Peereboom, Lars,Miller, Dennis J.
-
supporting information
p. 715 - 719
(2017/05/29)
-
- Vapor phase aldol condensation of methyl acetate with formaldehyde over a Ba-La/Al2O3 catalyst: The stabilizing role of la and effect of acid-base properties
-
Vapor phase aldol condensation of methyl acetate with formaldehyde was studied over Ba-La/Al2O3 with different amounts of lanthanum catalysts. The catalysts were characterized by X-ray diffraction (XRD), N2 adsorption-deso
- Bao, Qiang,Zhu, Wanchun,Yan, Jianbiao,Zhang, Chunlei,Ning, Chunli,Zhang, Yi,Hao, Mengmeng,Wang, Zhenlu
-
p. 52304 - 52311
(2017/11/22)
-
- PROCESS FOR PREPARING MONO AND DICARBOXYLIC ACIDS
-
The present application relates to a process for preparing a dicarboxylic acid or dicarboxylic ester according to general formula (IV) R1OOC-(CH2)m-CH2CH2-(CH2)y-COOR4 (IV), comprising the steps of subjecting alkenoic acid or alkenoate of formula (II) R1OOC-(CH2)m-CH=CH-(CH2)x-H (II) to a metathesis reaction in the presence of a metathesis catalyst to form a longer-chain alkenoic acid or alkenoate of formula (III) R1OOC-(CH2)m-CH=CH-(CH2)y-H (III) where xa carbonylation reaction in the presence of a carbonylation catalyst and a carbonyl source to form said compound of Formula (IV). Alternative embodiments provide: a process for preparing an alkenoic acid or alkenoate comprising the step of subjecting a lactone to a ring opening reaction; a process for preparing a monocarboxylic acid or monocarboxylic ester according to general formula (XI) R1OOC-(CH2)m-CH2-(CH2)y-CH3 (XI) by subjecting an alkenoic acid or alkenoate to alkene hydrogenation; and a process for preparing an alcohol or ether according to general formula (XII) R1O-CH2-(CH2)m-CH2-(CH2)y-CH3 (XII) by subjecting an alkenoic acid or alkenoate to hydrogenation. The use of the respective mono/dicarboxylic acid, mono/dicarboxylic ester, ethers or alcohols in a variety of applications is also disclosed.
- -
-
Page/Page column 33; 34
(2018/02/03)
-
- Aldol condensation of acetic acid with formaldehyde to acrylic acid over Cs(Ce, Nd) VPO/SiO2 catalyst
-
Cs, Ce, and Nd cation-modified VPO/SiO2 catalysts were prepared by a deposition method. The VPO/SiO2 catalyst was composed of VOPO4 and (VO)2P2O7 phases. When Cs, Ce, and Nd cations were added in the VPO/SiO2 catalyst, Cs4P2O7, CePO4, and NdPO4 were formed and V5+/V4+ ratio increased, respectively. The basicities of the metallic cation-modified catalysts increased while their acidities exhibited maximum values with the increase in the ratios of metallic cation to vanadium. The metallic cation-modified VPO/SiO2 catalysts exhibited higher catalytic activities for the aldol condensation reaction of acetic acid with formaldehyde to acrylic acid than the VPO/SiO2 catalyst. The high acidity and basicity of the metallic cation-modified VPO/SiO2 catalysts favored the formation of acrylic acid.
- Wang, Aili,Hu, Jing,Yin, Hengbo,Lu, Zhipeng,Xue, Wuping,Shen, Lingqin,Liu, Shuxin
-
p. 48475 - 48485
(2017/11/03)
-
- A green route to methyl acrylate and acrylic acid by an aldol condensation reaction over H-ZSM-35 zeolite catalysts
-
A one-step aldol condensation reaction to produce MA and AA is a green and promising strategy. Here, the aldol condensation reaction was first conducted with DMM and MAc over different types of zeolite catalysts. The H-ZSM-35 zeolite demonstrates excellent catalytic performance with a DMM conversion of 100% and a MA + AA selectivity of up to 86.2% and superior regeneration ability, with great potential for industrial operation.
- Ma, Zhanling,Ma, Xiangang,Liu, Hongchao,He, Yanli,Zhu, Wenliang,Guo, Xinwen,Liu, Zhongmin
-
p. 9071 - 9074
(2017/08/17)
-
- Reactivity of 7-Azanorbornenes in Bioorthogonal Inverse Electron-Demand Diels–Alder Reactions
-
In the preparation of multicomponent compounds, the accumulation of components through sequential click reactions is an attractive strategy. In this work we examined the reactivity of various N-substituted 7-azanorbornenes in inverse electron-demand Diels–Alder (iEDDA) reactions with tetrazines to explore the potential of 7-azanorbornenes as clickable hub molecules. The iEDDA reaction of 7-azanorbornene is expected to proceed faster when the nitrogen atom at the 7-position is substituted with an electron-donating substituent. Contrary to this expectation, the electron-donating alkyl-bearing derivative reacted much more slowly than those bearing electron-withdrawing acyl groups. The results of DFT calculations indicate that the reaction rates correlate well with an increase in sp2 character of the 7-nitrogen atoms: The ease of conversion of the more stable exo conformer into the more reactive endo conformer may lower the activation energy of the first rate-determining hetero-Diels–Alder step. Indeed, the reaction rates of N-acylated 7-azanorbornenes, which have a more planar nitrogen atom, were found superior to those of other derivatives and comparable to those of norbornenes. Finally, we successfully labeled a tetrazine on a protein surface by fluorophore-conjugated 7-azanorbornene in the presence of other proteins.
- Karaki, Fumika,Ohgane, Kenji,Imai, Hirotaka,Itoh, Kennosuke,Fujii, Hideaki
-
p. 3815 - 3829
(2017/07/22)
-
- NOVEL SINGLE STEP ESTERIFICATION PROCESS OF ALDEHYDES USING A HETEROGENEOUS CATALYST
-
The present invention relates to a novel simple, efficient and single-step process for esterification of aldehydes using a heterogeneous catalyst with high yields. More particularly, the present invention relates to a novel simple, efficient and single-step process for esterification of aldehydes using Titanium superoxide with greater than 80% yields.
- -
-
Page/Page column 16; 19
(2016/06/20)
-
- The 2V-P,N polymer supported palladium catalyst for methoxycarbonylation of acetylene
-
Heterogenization of homogeneous catalyst by immobilizing complex on the surface of polymer supports promotes the design of the catalysts which combine the advantages of heterogeneous and homogeneous catalysts. The porous 2-vinyl-functional diphenyl-2-pyri
- Chen, Xingkun,Zhu, Hejun,Wang, Tao,Li, Cunyao,Yan, Li,Jiang, Miao,Liu, Jia,Sun, Xueping,Jiang, Zheng,Ding, Yunjie
-
-
- System and method for preparing acrylic acid lower alcohol ester from acetylene
-
The invention discloses a system and method for preparing acrylic acid lower alcohol ester from acetylene. The system comprises an acetylene dissolution tank, a reactor, a first gas-liquid separator, a second gas-liquid separator, a carbon monoxide extraction device and a compressor. The acetylene dissolution tank is provided with an acetylene inlet, a non-polar organic solvent inlet and a liquid outlet. The reactor comprises an acetylene solvent inlet, a carbon monoxide gas inlet and a gas outlet. The first gas-liquid separator comprises a gas inlet, a gas outlet and an acrylic acid lower alcohol ester outlet. The second gas-liquid separator comprises a gas inlet and a gas outlet. The product, by-products and a solvent can be separated by means of different distillation temperatures; besides, carbon monoxide and the organic solvent are recycled, so that raw materials are saved, and cost is lowered.
- -
-
Paragraph 0049-0055
(2017/06/13)
-
- System and method for preparing methyl acrylate by carbonylation of acetylene
-
The invention discloses a system and method for preparing methyl acrylate by carbonylation of acetylene. The system comprises an acetylene dissolving tank, a reactor, a first gas-liquid separator, a second gas-liquid separator, a carbon oxide extraction apparatus and a compressor, wherein the acetylene dissolving tank is provided with an acetylene inlet, a non-polar organic solvent inlet and a liquid outlet; the reactor comprises an acetylene solvent inlet, a carbon oxide gas inlet and a gas outlet; the first gas-liquid separator comprises a gas inlet, a gas outlet and a methyl acrylate outlet; and the second gas-liquid separator comprises a gas inlet and a gas outlet. By adopting the system and method, a product, a byproduct and a solvent can be separated by virtue of different distillation temperatures, and carbon oxide and organic solvents can be recycled, so that the raw materials are saved, and the cost is reduced.
- -
-
Paragraph 0049-0054
(2017/06/29)
-
- A method for the synthesis of acrylic ester
-
The invention discloses an acrylate synthesis method. The method is characterized by directly synthesizing acrylate by adopting batch reaction, using CO2 and ethylene as raw materials, acetonitrile as a solvent, a metal Ni complex as a catalyst and anhydrous sodium carbonate as a promoter, and adding a methylation reagent to continuously react for 10-24 hours after reacting for 15-30 hours, wherein the mole ratio of ethylene to carbon dioxide is (1 to 1)-(1 to 5), preferably (1 to 2)-(1 to 4); the reaction temperature is 40-130 DEG C, preferably 50-120 DEG C; the reaction pressure is 0.5-6.0MPa, preferably 1.0-5.5MPa. In the method, acrylate is directly synthesized under the action of the methylation reagent by using CO2 and ethylene as the raw materials. The method has the advantages of low reaction temperature, high product yield, and the like.
- -
-
Paragraph 0022-0041
(2019/02/04)
-
- PROCESSES FOR CONVERSION OF BIOLOGICALLY DERIVED MEVALONIC ACID
-
The invention relates to a process comprising reacting mevalonic acid, or a solution comprising mevalonic acid, to yield a first product or first product mixture, optionally in the presence of a solid catalyst and/or at elevated temperature and/or pressure. The invention further relates to a process comprising: (a) providing a microbial organism that expresses a biosynthetic mevalonic acid pathway; (b) growing the microbial organism in fermentation medium comprising suitable carbon substrates, whereby biobased mevalonic acid is produced; and (c) reacting said biobased mevalonic acid to yield a first product or first product mixture.
- -
-
Paragraph 0134
(2016/06/13)
-
- Titanium superoxide-a stable recyclable heterogeneous catalyst for oxidative esterification of aldehydes with alkylarenes or alcohols using TBHP as an oxidant
-
Titanium superoxide efficiently catalysed the oxidative esterification of aldehydes with alkylarenes or alcohols, under truly heterogeneous conditions, to afford the corresponding benzyl and alkyl esters in excellent yields. Mechanistic studies have established that this "one pot" direct oxidative esterification process proceeds through a radical pathway, proven by a FTIR spectral study of a titanium superoxide-aldehyde complex as well as spin trapping experiments with TEMPO. The intramolecular version of this protocol has been successfully demonstrated in the concise synthesis of 3-butylphthalide, an anti-convulsant drug.
- Dey, Soumen,Gadakh, Sunita K.,Sudalai
-
p. 10631 - 10640
(2015/11/17)
-
- Preparation of Cs-La-Sb/SiO2 catalyst and its performance for the synthesis of methyl acrylate by aldol condensation
-
A variety of cesium supported catalysts with amorphous SiO2 as a carrier were prepared by vacuum impregnation and ultrasonic impregnation methods, which were used for the synthesis of methyl acrylate by aldol condensation of methyl acetate and formaldehyde. The as-prepared catalysts were characterized by XRD, N2 adsorption-desorption, NH3-TPD, CO2-TPD, XPS, ICP and TG. The results indicated that the bifunctional Cs-La-Sb/SiO2 showed a high conversion of methyl acetate as well as a high yield of methyl acrylate, which was attributed to the weak acid-base sites and the formation of basic Cs-O-Si species with the addition of antimony and lanthanum, respectively. Furthermore, Cs-La-Sb/SiO2-(V) prepared by vacuum impregnation showed a high initial catalytic activity, but its activity sharply decreased due to the loss of active species. Comparatively, Cs-La-Sb/SiO2-(U) prepared by ultrasonic impregnation showed a good stability owing to the cavitation effect of ultrasonic waves. The conversion of methyl acetate and yield of methyl acrylate remained above 20% and 9.0% (based on methyl acetate) for 100 h without obvious deactivation. Moreover, carbon deposition was the main factor for the deactivation of Cs-La-Sb/SiO2-(U), and the coked catalyst could be regenerated by calcination in air. This journal is
- Wang, Yanan,Lang, Xuewei,Zhao, Guoqing,Chen, Huanhui,Fan, Yiwei,Yu, Linqing,Ma, Xiuxiu,Zhu, Zhirong
-
p. 32826 - 32834
(2015/04/27)
-
