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IMPROVED SAFE METHOD FOR TANDEM C-4 OXIDATION TO METHACRYLIC ACID
The present invention relates to an improved process for the production of methacrylates, in particular methacrylic acid and/or methyl methacrylate (MMA). Furthermore, the present invention relates to a process and specific embodiments of this process for the safe and efficient production of these products from C-4-based raw materials, in particular those based on isobutylene or tert-butanol as raw materials. With this novel process, it is possible to operate such processes for a longer period of time without any safety or cleaning related shutdowns. This makes it possible to carry out such processes as simple, economic and environmentally friendly as possible.
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Page/Page column 14-17

(2021/10/11)

Supported Rb- or Cs-containing HPA catalysts for the selective oxidation of isobutane
Silica-supported catalysts based on Keggin-type heteropolyacids (HPAs) containing rubidium or cesium as counter cations have been prepared by the impregnation method and evaluated in the selective oxidation of isobutane to methacrolein and methacrylic acid. The catalysts were characterized by various techniques such as XRD, N2 physisorption, TGA, Raman spectroscopy, H2-TPR, and NH3-TPD in order to study their thermal stability, structural, and textural properties, acidity and reducibility. It was evidenced that the reducibility of the Keggin type HPAs was improved by supporting the active phase on SiO2. A loading of 40 wt% was the optimum for the selective oxidation of isobutane (IBAN) to methacrylic acid (MAA). The selectivities to MAA and methacrolein (MAC) at given conversion were increased when Cs+ was used as counter cation compared to Rb+. The same trend was observed for mono- and di-vanado-substituted phosphomolybdic acid, whereby the performance followed the order: CsV1/SiO2 > RbV1/SiO2 > CsV2/SiO2 > RbV2/SiO2. The density of acid sites was correlated to the catalytic activity, which underlines the importance of the acid sites for alkane activation.
Dumeignil, Franck,Katryniok, Benjamin,Paul, Sébastien,Zhang, Li
(2021/10/29)

SYSTEMS AND METHODS FOR REGIOSELECTIVE CARBONYLATION OF 2,2-DISUBSTITUTED EPOXIDES FOR THE PRODUCTION OF ALPHA,ALPHA-DISUBSTITUTED BETA-LACTONES
Provided are methods of producing carbonyl compounds (e.g., carbonyl containing compounds) and catalysts for producing carbonyl compounds. Also provided are methods of making polymers from carbonyl compounds and polymers formed from carbonyl compounds. A method may produce carbonyl compounds, such as, for example α,α-disubstituted carbonyl compounds (e.g., α,α-disubstituted β-lactones). The polymers may be produced from α,α-disubstituted β-lactones, which may be produced by a method described herein.
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Paragraph 0082

(2021/01/29)

Tailoring Interfacial Lewis Acid-Basic Pair on ZnO/4Mg1ZrOx Allows Dehydrogenative α-Methylenation of Alcohols with Methanol to Allylic Alcohols
Allylic alcohols are the essential building blocks widely used in diverse streams of organic inventions for pharmaceuticals, fragrances, agrochemicals and polymers. Currently, allylic alcohols are industrially produced from petroleum-based feedstocks via atom uneconomic processes. More sustainable synthesis route for allylic alcohols is limited. Herein, a methodology for the direct and highly selective production of allylic alcohols has been accomplished by controlled dehydrogenative α-methylenation of alcohols with methanol. This transformation is enabled by interfacial Lewis acid-basic pair on tailor-made ZnO/4Mg1ZrOx mixed oxide. High selectivity (83～92%) of allylic alcohols is the consequence of alcohols acceptorless dehydrogenation to liberation of H2 and Meerwein-Ponndorf-Verley type hydrogen transfer onto C = O bonds of unsaturated aldehydes. Furthermore, the prepared ZnO/4Mg1ZrOx mixed oxide shows good stability after 200 h time on stream test. These observations could additionally allow us to design multifunctional solid acid-basic catalysts for the transformations of renewable oxygenates into value-added chemicals.
Fu, Aixiao,Jiang, Shifeng,Liu, Qiang,Liu, Xiaoran,Liu, Xiuyun,Mu, Xindong,Sun, Mengqing,Wang, Xicheng,Xu, Guoqiang,Zhao, Lingling
(2020/10/07)

MMA preparation method with isobutene including saturated hydrocarbon
The present invention relates to a method for preparing methyl methacrylate, including the steps of: (1) separating isobutene containing saturated hydrocarbons(n-butane and iso-butane) from flow of C4 cuts including butadiene, n-butene and isobutene through a catalytic distillation process; (2) producing methacrolein from the thus separated isobutene through primary oxidation reaction; (3) producing methacrylic acid from the thus produced methacrolein through secondary oxidation reaction; and (4) carrying out esterification of the thus produced methacrylic acid with methanol. It is possible to minimize introduction of nitrogen by virtue of high heat capacity and to reduce the size of a reactor and generation of gas in the rear end, thereby saving investment and cost and providing high cost-efficiency.(AA) Naptha steam cracker C4 mixture(BB) Butadiene(CC) Extractive distillation(DD) 2-butene(EE) Reactive distillation(FF) Isobutene, nandamp;iso-butane(GG) Produce methyl methacrylate(HH) Methyl methacrylateCOPYRIGHT KIPO 2020
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Paragraph 0033-0035; 0048

(2020/08/26)

PROCESS FOR PRODUCING METHYL METHACRYLATE
The present invention relates to a method for producing methyl methacrylate. According to the present invention, provided is a method for producing methyl methacrylate, which is capable of securing the safety of a process, while improving the catalyst life and increasing the production amount of methyl methacrylate.
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Paragraph 0181-0222

(2020/10/03)

PROCESS FOR PRODUCING METHACRYLIC ACID OR METHACRYLIC ACID ESTERS
The present invention relates to a process for producing methacrylic acid or methacrylic acid esters. The present invention is directed to a new process for the production of methacrylic acid or alkyl methacrylate starting from Acrolein, which is available from glycerol or propane.
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Page/Page column 16-17

(2020/03/02)

Catalytic synthesis of methacrolein: Via the condensation of formaldehyde and propionaldehyde with l-proline
Methacrolein (MAL) is an important chemical for the manufacture of methyl methacrylate and a key monomer in many polymerization reactions. In this study, l-proline was investigated as the catalyst for the aldol condensation of formaldehyde and propionaldehyde to produce MAL. The catalytic activity of the reaction system was closely related to the competition between the main reaction synthesizing MAL and the side reaction producing 2-methyl-2-pentenal, which could be modified by adjusting the operating parameters. The influences of several operating conditions, including temperature, reaction time and water content, on the catalytic performance of the system were systematically studied via a series of single-factor experiments, and the optimized reaction conditions were obtained. The mechanistic investigation via ESI-MS indicated that the reaction pathway followed the Mannich route. Experimental and theoretical kinetic analyses of the l-proline-catalyzed aldol condensation reaction were performed, and the reaction orders of the reactants were obtained by regression. The results showed that l-proline was an efficient catalyst for the production of MAL via aldol condensation under mild conditions.
Yu, Jiayuan,Jensen, Anker Degn,Wang, Lei,Li, Chunshan,Zhang, Suojiang
supporting information
p. 4222 - 4230
(2020/07/14)

Nickel-Catalyzed Asymmetric Reductive 1,2-Carboamination of Unactivated Alkenes
Starting from diverse alkene-tethered aryl iodides and O-benzoyl-hydroxylamines, the enantioselective reductive cross-electrophilic 1,2-carboamination of unactivated alkenes was achieved using a chiral pyrox/nickel complex as the catalyst. This mild, modular, and practical protocol provides rapid access to a variety of β-chiral amines with an enantioenriched aryl-substituted quaternary carbon center in good yields and with excellent enantioselectivities. This process reveals a complementary regioselectivity when compared to Pd and Cu catalysis.
He, Jun,Xue, Yuhang,Han, Bo,Zhang, Chunzhu,Wang, You,Zhu, Shaolin
supporting information
p. 2328 - 2332
(2020/01/08)

CONTINUOUS PROCESS FOR PREPARING METHACROLEIN
The present invention relates to a continuous process for preparing methacrolein by a Mannich condensation reaction of formaldehyde with propanal, in which a methacrolein polymerisation inhibitor is introduced during the production process and a part thereof is recycled back into the reactor where the Mannich condensation reaction is carried out.
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Page/Page column 9-10

(2020/03/15)

Catalyst-controlled regioselective carbonylation of isobutylene oxide to pivalolactone
Poly(pivalolactone) (PPVL) is a crystalline polyester with attractive physical and mechanical properties; however, prohibitively expensive syntheses of pivalolactone have thwarted efforts to produce PPVL on an industrial scale. Therefore, we developed a class of highly regioselective sandwich-type catalysts for the carbonylation of isobutylene oxide. These sterically encumbered complexes install carbon monoxide at the substituted epoxide carbon, generating a high level of contrasteric selectivity (up to >99:1). Further catalyst development improved catalyst solubility and reproducibility while maintaining high regioselectivity. In addition, a dibasic ester solvent extended catalyst lifetimes and suppressed side product formation. This contrasteric carbonylation of isobutylene oxide offers a route to sought-after pivalolactone and, therefore, PPVL.
Hubbell, Aran K.,Lamb, Jessica R.,Klimovica, Kristine,Mulzer, Michael,Shaffer, Timothy D.,MacMillan, Samantha N.,Coates, Geoffrey W.
p. 12537 - 12543
(2020/11/10)

Iodine/water-mediated deprotective oxidation of allylic ethers to access α,β-unsaturated ketones and aldehydes
The first iodine/water-mediated deprotective oxidation of allylic ethers to access α,β-unsaturated ketones and aldehydes was achieved. The reaction tolerates a wide range of functionalities. Furthermore, this protocol was found to be applicable to the oxidative transformation of allylic acetates. The proposed mechanism involves an oxygen transfer from solvent water to the carbonyl products.
Chen, Weifeng,Jiang, Kezhi,Xue, Yuntian,Yan, Yaolong,Yang, Lei
p. 14720 - 14724
(2020/04/27)

Dehydrogenative β-Arylation of Saturated Aldehydes Using Transient Directing Groups
An unprecedented cross-dehydrogenative-coupling (CDC) reaction of saturated aldehyde β-C-H with arenes to form cinnamaldehydes via the cleavages of four C-H bonds has been developed. The reaction possesses complete E-stereoselectivity for the C=C double bond. The protocol is featured by atom and step economy, mild reaction conditions, and convenient operation.
Zhang, Xing-Long,Pan, Gao-Fei,Zhu, Xue-Qing,Guo, Rui-Li,Gao, Ya-Ru,Wang, Yong-Qiang
supporting information
p. 2731 - 2735
(2019/04/30)

A study of the oxidehydration of 1,2-propanediol to propanoic acid with bifunctional catalysts
The gas-phase oxidehydration (ODH) of 1,2-propanediol to propionic acid has been studied as an intermediate step in the multi-step transformation of bio-sourced glycerol into methylmethacrylate. The reaction involves the dehydration of 1,2-propanediol into propionaldehyde, which occurs in the presence of acid active sites, and a second step of oxidation of the aldehyde to the carboxylic acid. The two reactions were carried out using a cascade strategy and multifunctional catalysts, made of W-Nb-O, W-V-O and W-Mo-V-O hexagonal tungsten bronzes, the same systems which are also active and selective in the ODH of glycerol into acrylic acid. Despite the similarities of reactions involved, the ODH of 1,2-propanediol turned out to be less selective than glycerol ODH, with best yield to propanoic acid no higher than 13percent, mainly because of the parallel reaction of oxidative cleavage, occurring on the reactant itself, which led to the formation of C1-C2 compounds.
Bandinelli, Claudia,Basile, Francesco,Cavani, Fabrizio,Concepcion, Patricia,De Maron, Jacopo,Dimitratos, Nikolaos,Lambiase, Barbara,Nieto, Jose Manuel Lopez,Tabanelli, Tommaso
(2019/06/28)

Polyoxometalate catalysts with co-substituted VO2+ and transition metals and their catalytic performance for the oxidation of isobutane
Cs-Salts of the Keggin-type phosphomolybdic acid with simultaneous doping of VO2+ and different transition metals are prepared, characterized and tested as catalysts for the oxidation of isobutane to methacrylic acid under isobutane-rich condit
Liu, Yanchun,He, Jingfang,Chu, Wenling,Yang, Weishen
p. 5774 - 5781
(2018/11/25)

Method for synthesizing bromoisobutylene methyl ether and application thereof in preparation of C14 aldehyde
The invention discloses a method for synthesizing bromoisobutylene methyl ether. The method comprises the following steps: (1) carrying out an aldol condensation reaction on formaldehyde and propionaldehyde so as to obtain methacrolein; (2) carrying out an addition reaction on the methacrolein obtained in the step (1) and hydrogen bromide so as to obtain bromoisobutyraldehyde; (3) carrying out a condensation reaction on the bromoisobutyraldehyde obtained in the step (2) and methanol so as to obtain dimethoxy bromo-iso-butane; and (4) carrying out an exchange and elimination reaction on the dimethoxy bromo-iso-butane obtain in the step (3) and the methanol under the action of an acid catalyst, and performing after-treatment after reaction completion, thereby obtaining the bromoisobutylene methyl ether. The initial raw materials adopted in the synthetic method are cheap and readily available, and the cost of the whole route can be effectively reduced; and meanwhile, a continuous channelization reaction is adopted, and industrialized application is facilitated.
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Paragraph 0012; 0029; 0030

(2018/07/30)

PROCESS FOR PREPARING METHACROLEIN
Provided is a process for preparing methacrolein which maximizes capture of methanol. Also provided are processes for producing methacrylic acid and methyl methacrylate.
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Page/Page column 11-12

(2018/12/13)

Catalytic Reactions of Homo- and Cross-Condensation of Ethanal and Propanal
Abstract: Processes of catalytic homocondensation of propanal and its cross-condensation with ethanal and methanal in the presence of aniline and amino acids have been studied. The dependence of the conversion of the reactants and selectivity of the homo/heterocondensation process on the catalyst nature and temperature has been revealed. It has been shown that the maximum acrolein selectivity is reached in the case of using benzoyl-substituted derivatives in water, with the proportion of the products of further condensation decreasing. The selectivity for the ethanal homocondensation product 2-butenal decreases simultaneously as a result of the formation of linear and branched oligomers of successive condensation.
Martsinkevich,Bruk,Dashko,Afaunov,Flid,Sedov
p. 1032 - 1035
(2019/01/03)

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.
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Page/Page column 8; 25; 26; 29

(2018/01/17)

EFFICIENT SYNTHESIS OF METHACROELIN AND OTHER ALPHA, BETA-UNSATURATED ALDEHYDES OVER A REGENERABLE ANATASE TITANIA CATALYST
A commercially available anatase titania catalyst is shown to be catalytically active towards the formation of methacrolein from formaldehyde and propionaldehyde with conversions and selectivities close to 90%. This titania catalyst is readily available, non-toxic, and can be used with formaldehyde and a variety of other aldehyde compounds to make α,β-unsaturated aldehyde compounds. This process benefits from low raw material costs and is economically advantaged due to the elimination of catalyst separation. An additional advantage of this method involves the ability of the catalyst to be fully regenerated after a calcination step at 450 °C in air. This process shows promising stability and selectivity during lifetime studies, particularly when performed in the presence of a hydrogen carrier gas.
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Page/Page column 26-34

(2017/08/22)

OPTIMIZED METHOD FOR PRODUCING METHACROLEIN
The present invention relates to an optimized process for the preparation of methacrolein. Methacrolein is used in chemical synthesis particularly as an intermediate for the preparation of methacrylic acid, methyl methacrylate or even active ingredients, fragrances or flavourings. In particular the present invention relates to the optimization of the process parameters by which, inter alia, a reduction of the content of harmful dimeric methacrolein in the end product may be achieved.
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Paragraph 0042-0044

(2017/10/10)

PROCESS FOR RECOVERING BYPRODUCTS FROM MMA
The present invention provides methods comprising distilling a reaction mixture of methacrolein and methanol used to make methyl methacrylate (MMA) in the presence of one or more strong or inorganic acids, the mixture comprising an aqueous organic component mixture of all of water, MMA, methacrolein methanol and acetals or hemiacetals of methacrolein to remove the acetals or hemiacetals of methacrolein to a level of 100 ppm or below, based on the amount of methyl methacrylate. The method reduces the amount of acetals or hemiacetals of methacrolein to well below equilibrium levels and eliminates the need for additional downstream distillation to refine the product of the reaction.
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Page/Page column 9

(2017/12/29)

Oxidative Dehydrogenation of 1-Butene to 1,3-Butadiene over a Multicomponent Bismuth Molybdate Catalyst: Influence of C3–C4 Hydrocarbons
Abstract: The influence of light hydrocarbons, such as n-butane, isobutane, propylene, cis- and trans-2-butenes, and isobutene on the oxidative dehydrogenation of 1-butene to 1,3-butadiene over BiMoKNiCoFePOx/SiO2catalyst has been studied using a gas flow reactor. The inhibition effect of the listed hydrocarbons on the target reaction increased in the order of n-butane ~ isobutane propylene 2-butenes isobutene. In addition, in contrast to 1-butene, isobutene has shown significant contribution to coke formation. It was suggested, that the coke formation and therefore the rate of the catalyst regeneration exercise a significant influence on the efficiency of 1-butene transformation into 1,3-butadiene in the concurrent presence of other hydrocarbons. Graphical Abstract: [Figure not available: see fulltext.]
Sobolev, Vladimir I.,Koltunov, Konstantin Yu.,Zenkovets, Galina A.
p. 310 - 317
(2017/02/18)

Methacrylic acid
PROBLEM TO BE SOLVED: To provide a method for manufacturing methacrylic acid in a favorable productivity over an extended period.SOLUTION: The provided method for manufacturing methacrylic acid is a method for manufacturing methacrylic acid by feeding methacrolein, isobutylene, and oxygen into a methacrylic acid manufacturing reactor furnished with a catalyst layer including a catalyst for manufacturing methacrylic acid and by oxidizing the methacrolein continuously wherein the maximal temperature of the catalyst layer is 330°C or below. It is desirable for the maximal temperature of the catalyst layer to be controlled at 330°C or below by adjusting the feeding quantity of the isobutylene.
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Paragraph 0062

(2017/05/18)

Method for producing methyl acrolein
The invention relates to a production method of methylacrolein, and mainly solves the problems of poor reproducibility and low yield of the methylacrolein in the prior art. Through use of a technical scheme of the production method, the problems are well solved. The technical scheme is shown as follows: in a catalyst, at least one substance selected from SiO2 or Al2O3 is used as a carrier, the catalyst also contains an active component represented by the following general formula: Mo[12]Bi[a]Fe[b]Co[c]Ce[d]X[e]Y[f]Z[g]O[x], wherein X is at least one selected from the group consisting of W, V, Ni, Cr, Mn, Nb or Re, Y is at least one selected from the group consisting of Sn, Sr, Zn, Ti or Zr; Z is at least one selected from the group consisting of K, Rb, Na, Li, Tl or Cs. The production method can be used in industrial production of the methylacrolein.
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Paragraph 0029-0032

(2017/02/24)

Methods for Preparing Methacrolein from t-Butanol
A method for preparing methacrolein from t-butanol, specifically a method for preparing methacrolein by using t-butanol as a starting material, is disclosed, comprising passing the starting material through a fixed bed reactor filled with catalyst, wherein the fixed bed reactor is divided to n reaction zones from the inlet of the starting material to the outlet of the starting material and each zone is filled with catalysts of different catalytic activities; wherein the catalytic activity of the catalyst in the first reaction zone is higher than the catalytic activity of the catalyst in the second reaction zone, and the catalytic activity of the catalyst is gradually increased from the second reaction zone to the last reaction zone; and n is an integer between 3 to 10.
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Paragraph 0064-0065

(2016/08/03)

Small-Molecule Activation within the Group 6 Complexes (η5-C5Me5)[N(iPr)C(Me)N(iPr)]M(CO)(L) for M = Mo, W and L = N2, NCMe, η2-Alkene, SMe2, C3H6O
A series of midvalent monocyclopentadienyl monoamidinate (CPAM) group 6 complexes of the general formula Cp?[N(iPr)C(Me)N(iPr)]M(CO)(L) (II), where Cp? = η5-C5Me5 and M = Mo, W, have been prepared, and most of them have been structurally characterized. Treatment of the ditungsten "end-on-bridged" dinitrogen complex {Cp?[N(iPr)C(Me)N(iPr)]W}2(μ-η1:η1-N2) (3) with excess NCMe under a CO atmosphere produced the ditungsten bridging diimido complex {Cp?[N(iPr)C(Me)N(iPr)]W}2[μ-η1:η1-NC(Me)=(Me)N] (4). Photolysis of Cp?[N(iPr)C(Me)N(iPr)]M(CO)2, where M = Mo (6), W (7), or treatment of Cp?[N(iPr)C(Me)N(iPr)]Mo(CO)(NCMe) (1a) with excess alkene provided Cp?[N(iPr)C(Me)N(iPr)]M(CO)(L) for M = Mo and L = η2-ethene (8), M = W and L = η2-ethene (9), M = Mo and L = η2-norbornene (10), M = W and L = η2-norbornene (11), M = W and L = η2-cyclopentene (12), M = Mo and L = η2-cyclopentene (13), and M = Mo and L = η2-styrene (14). When isobutene was employed as the alkene, C-H bond activation occurred to produce Cp?[N(iPr)C(Me)N(iPr)]W(H)(η3-C4H7) (15). Photolysis of 7 in the presence of SMe2 provided Cp?[N(iPr)C(Me)N(iPr)]W[κ-C,O-C(O)Me](SMe) (16) through oxidative C-S bond activation of a coordinated SMe2, followed by 1,1-carbonyl migratory insertion into the new W-C bond. Finally, reaction of 1a with propylene oxide (C3H6O) provided the 16-electron complex Cp?[N(iPr)C(Me)N(iPr)]Mo[C(O)CH(Me)CH2O] (19) via similar oxidative C-O bond activation of coordinated C3H6O, followed by 1,1-carbonyl migratory insertion into the Mo-C bond of an intermediate metallaoxetane. Under a CO atmosphere, 19 is converted to the 18-electron complex Cp?[N(iPr)C(Me)N(iPr)]Mo[C(O)CH(Me)CH2O](CO) (20). These results provide additional support for the development of new stoichiometric and catalytic transformations that are mediated by CPAM group 6 metal complexes and that are relevant to the goal of small-molecule fixation.
Farrell, Wesley S.,Yonke, Brendan L.,Reeds, Jonathan P.,Zavalij, Peter Y.,Sita, Lawrence R.
p. 1132 - 1140
(2016/06/01)

The method of manufacturing the oxidation products
PROBLEM TO BE SOLVED: To provide a method for manufacturing an oxidation product yielding an unprecedentedly high productivity.SOLUTION: The provided method for manufacturing an oxidation product is a method for manufacturing an oxidation product by inducing a vapor-phase oxidation reaction of an olefin and/or alcohol by using a catalyst including molybdenum, bismuth, iron, cerium, and cobalt. The olefin and/or alcohol concentration and reaction temperature at the vapor-phase oxidation reaction step are adjusted respectively within ranges of 6-10 vol.% and 430 to 500°C. The ratio of the concentration of oxygen fed into a catalyst layer with respect to the oxygen concentration at the reactor outlet is adjusted at 15-70 by feeding, into the catalyst layer, oxygen at a molar ratio of 1.1-1.8 with respect to the olefin and/or alcohol.
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Paragraph 0048-0069; 0071-0072

(2019/01/30)

A 2-methyl propanol method for the preparation of
The invention provides a preparation method for 2-methylallyl alcohol. The preparation method for 2-methylallyl alcohol comprises the following steps: oxidizing isobutene into 2-methylacrolein in the presence of a catalyst A, vapour and air; reducing 2-methylacrolein into 2-methylallyl alcohol in the presence of a catalyst B and hydrogen. Because of using isobutene as a starting material, selectively oxidizing isobutene into methylacrolein by a metallic oxide, and then directly performing a hydrogenation reaction to produce 2-methylallyl alcohol, the method is high in yield, low in cost, low in energy consumption, and environment-friendly and clean.
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Paragraph 0057; 0059

(2016/10/07)

MANUFACTURING METHOD OF α-METHYLENEALDEHYDE
PROBLEM TO BE SOLVED: To provide an economically favorable manufacturing technology of α-methylene aldehyde suppressing degeneration of secondary amine of a catalyst component while maintaining high productivity and suppressing cost of a catalyst. SOLUTION: A manufacturing of (2) by a condensation reaction formaldehyde and (1) by using a catalyst consisting of secondary amine and acid is conducted with procedure of following [1] to [3]. [1] Formaldehyde is added to a catalyst liquid and hold at 0 to 50°C. [2] (1) of 1 to 1.5 mol times as formaldehyde is added. [3] The mixture is heated. (1)(2), were R is H or a C1 to 7 aliphatic hydrocarbon group. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0035

(2017/06/20)

A process for the preparation of trifluoromethylation of the
The invention provides a preparation method of allyl alcohol. The preparation method comprises the steps of reacting acetaldehyde or propaldehyde with formaldehyde under the existence of a heterogeneous catalyst to obtain allyl aldehyde, wherein the allyl aldehyde is allyl aldehyde or methyl allyl aldehyde; reacting allyl aldehyde or methyl allyl aldehyde with hydrogen gas under the existence of a catalyst to obtain the allyl alcohol, wherein the allyl alcohol is allyl alcohol or 2-methyl allyl alcohol. The method has simple process, low cost, few byproducts, good selectivity and high yield.
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Paragraph 0089; 0094

(2017/03/14)

Structure-activity relationship study of a series of novel oxazolidinone derivatives as IL-6 signaling blockers
A series of oxazolidinone and indole derivatives were synthesized and evaluated as IL-6 signaling blockers by measuring the effects of these compounds on IL-6-induced luciferase expression in human hepatocarcinoma HepG2 cells transfected with p-STAT3-Luc. Among different compounds screened, compound 4d was emerged as the most potent IL-6 signaling blockers with IC50 value of 5.9 μM which was much better than (+)-Madindoline A (IC50 = 21 μM), a known inhibitor of IL-6.
Singh, Sarbjit,Gajulapati, Veeraswamy,Gajulapati, Kondaji,Goo, Ja-Il,Park, Yeon-Hwa,Jung, Hwa Young,Lee, Sung Yoon,Choi, Jung Ho,Kim, Young Kook,Lee, Kyeong,Heo, Tae-Hwe,Choi, Yongseok
supporting information
p. 1282 - 1286
(2016/02/23)

METHOD FOR PRODUCING METHYLMETHACRYLATE
The present invention relates to a process for producing methyl methacrylate, comprising the following steps: A) producing methacrolein andB) reacting the methacrolein obtained in step A) in an oxidative esterification reaction to give methyl methacrylate, characterized in that the two steps A) and B) take place in a liquid phase at a pressure of from 2 to 100 bar, and step B) is carried out in the presence of a heterogeneous noble-metal-containing catalyst comprising metals and/or comprising metal oxides.
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Paragraph 0212

(2016/04/20)

A propionaldehyde as raw material with formaldehyde and acrolein method of preparing methyl (by machine translation)
The invention relates to a method for preparing methylacrolein by taking formaldehyde and propionaldehyde as raw materials. A catalyst system is prepared by mixing secondary amine alcohol amines, quinine substances and organic acids, which are low in volatility and relatively stable to oxygen. In a reaction process, proper amount of polymerization inhibitor is added, so that selectivity of the methylacrolein can be remarkably improved. The method disclosed by the invention has the characteristics of being stable in catalyst, low in corrosivity, and high in methylacrolein yield.
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Paragraph 0007; 0008; 0009

(2016/10/08)

1,3-butadiene and polyelemental manufacturing method
PROBLEM TO BE SOLVED: To provide a method for substantially and efficiently manufacturing 1,3-butadiene and methacrolein by going through a specific process, in the manufacture of the 1,3-butadiene and the methacrolein from C4 hydrocarbons, as a raw material, containing n-butene and iso-butene.SOLUTION: A method of manufacturing 1,3-butadiene and methacrolein comprises at least a step (A): a step of causing at least n-butene and iso-butene to react with molecular oxygen at 300-500°C in the presence of an oxidation reaction catalyst thereby to manufacture the 1,3-butadiene and the methacrolein as a reaction product gas, a step (B): a step of bringing the obtained reaction product gas into direct contact with an aqueous medium to separate the gas into a methacrolein aqueous solution and a gas component containing the 1,3-butadiene, a step (C): a step of separating and recovering the methacrolein from the methacrolein aqueous solution obtained in the step (B), and a step (D): a step of separating and recovering the 1,3-butadiene from the gas component obtained in the step (B).
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Paragraph 0067-0069

(2020/03/23)

Partial oxidation of 2-methyl-1,3-propanediol to methacrylic acid: experimental and neural network modeling
Methacrylic acid (MAA) is a specialty intermediate to produce methyl methacrylate (MMA), which is a monomer for poly methyl methacrylate. Current processes to MMA and MAA rely on expensive feedstocks and multi-step processes. Here we investigate the gas-phase oxidation of 2-methyl-1,3-propanediol (2MPDO) to MAA over heteropolycompounds as effective catalysts, finding that the maximum selectivity to MAA was 41% with 63% conversion of reactant at 250 °C over Cs(NH4)2PMo12O40(VO)Cu0.5. Cesium (Cs) stabilized the catalyst structure at 250 °C, and vanadium(v) and copper (Cu) played a positive role as an oxidant and promoter, respectively. A 0.3 mm nozzle atomized the liquid reactant over the catalyst surface into a μ-fluidized bed reactor. The proposed Artificial Neural Network (ANN) model predicts MAA selectivity based on 2MPDO and oxygen compositions and catalyst components (Cs, V, Cu) as independent factors. The model accounts for 97% of the variance in the data (R2 = 0.97). Vanadium as a catalyst component and oxygen concentration are the two most significant factors. Genetic algorithms (GA) coupled with ANN modeling optimized the input parameters to improve the selectivity. The selectivity to MAA over the optimized catalyst (Cs(NH4)2PMo12O40(VO)Cu0.15) and optimum feed compositions (2MPDO/O2/Ar = 13%/10%/77%) was 43% at 250 °C.
Darabi Mahboub, Mohammad Jaber,Rostamizadeh, Mohammad,Dubois, Jean-luc,Patience, Gregory S.
p. 114123 - 114134
(2016/12/24)

Comparison of “on water” and solventless procedures in the rhodium-catalyzed hydroformylation of diolefins, alkynes, and unsaturated alcohols
Catalytic systems containing Rh(acac)(CO)2 or Rh/PAA (PAA?=?polyacrylic acid) and hydrophobic phosphine (PPh3) were used in the hydroformylation of diolefins, alkynes, and unsaturated alcohols under solventless and “on water” conditions. The total yield of dialdehydes obtained from 1,5-hexadiene and 1,7-octadiene reached 99%, and regioselectivity towards linear dialdehydes was higher in the “on water” system. The tandem hydroformylation-hydrogenation of phenylacetylene led to the formation of saturated aldehydes (3-phenylpropanal and 2-phenylpropanal) at 98% conversion with a good regioselectivity towards the linear aldehyde in the “on water” reaction. In contrast, solventless conditions appeared better in the hydroformylation of 1-propen-3-ol. 4-Hydroxybutanal, formed in this reaction with an excellent selectivity, was next transformed to tetrahydrofuran-2-ol via a ring-closure process. Cyclic products were also obtained in hydroformylation of 1-buten-3-ol. In reaction of undec-1-ol and 2-allylphenol linear aldehydes were formed with the yield 69–87%. The hydroformylation of 3-buten-1-ol performed under “on water” conditions showed very good regioselectivity towards a linear aldehyde, 5-hydroxypentanal. Further cyclization of the aldehyde to tetrahydropyran-2-ol was observed.
Alsalahi,Trzeciak
p. 41 - 48
(2016/07/06)

The bioinspired design of a reagent allows the functionalization of Cα-H of α,β-unsaturated carbonyl compounds via the Baylis-Hillman chemistry under ambient conditions
A rationally designed reagent capable of affecting alkylation at Cα of α,β-unsaturated carbonyl compounds is reported. The reaction proceeded at room temperature without any additives. The pH and H-bond formation during the reaction play a key role in the working of the reagent.
Singh, Palwinder,Kumar, Arun,Kaur, Sukhmeet,Kaur, Jagroop,Singh, Harpreet
supporting information
p. 2936 - 2939
(2016/02/20)

Process For Producing Methacrolein And/Or Methacrylic Acid
[Purpose] field period high yield, that can hold effective selectivity methacrolein and/or of methacrylic acid to provide a manufacturing method. [Constitution] 3 class butanol and/or isobutylene to used as a raw material and, same gas reaction tube 2 in the direction of the flow of oxidation catalyst to have a heating peak of of supplying fiber-forming material to reaction tube, molecular the presence of oxygen to partially oxidize raw material in methacrolein and/or methacrylic acid with a for the production in method, two 2 catalyst for oxidation of a an electric tightening device of external air exotherm peak layer Tm, when Tb temperature reactor, characterized by angle is decided within a range of Tm-Tb ≥ 15 °C methacrolein and/or of methacrylic acid manufacturing method.
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Paragraph 0041

(2017/01/05)

Bismuth-substituted "sandwich" type polyoxometalate catalyst for activation of peroxide: Umpolung of the peroxo intermediate and change of chemoselectivity
The epoxidation of alkenes with peroxides by WVI, MoVI, VV, and TiIV compounds is well established, and it is well accepted that the active intermediate peroxo species are electrophilic toward nucleophilic substrates. Polyoxotungstates, for example, those of the "sandwich" structure, [WZn(TM-L)2(ZnW9O34)2]q- in which TM = transition metal and L = H2O, have in the past been found to be excellent epoxidation catalysts. It has now been found that substituting the Lewis basic BiIII into the terminal position of the "sandwich" polyoxometalate structure to yield [Zn2BiIII2(ZnW9O34)2]14- leads to an apparent umpolung of the peroxo species and formation of a nucleophilic peroxo intermediate. There are two lines of evidence that support the formation of a reactive nucleophilic peroxo intermediate: (1) More electrophilic sulfoxides are more reactive than more nucleophilic sulfides, and (2) nonfunctionalized aliphatic alkenes and dienes showed ene type reactivity rather than epoxidation pointing toward "dark" formation of singlet oxygen from the nucleophilic intermediate peroxo species. Allylic alcohols reacted much faster than alkenes but showed chemoselectivity toward C-H bond activation of the alcohol and formation of aldehydes or ketones rather than epoxidation. This explained via alkoxide formation at the BiIII center followed by oxidative β-elimination.
Amanchi, Srinivasa Rao,Khenkin, Alexander M.,Diskin-Posner, Yael,Neumann, Ronny
p. 3336 - 3341
(2015/06/16)

Selective oxidation and oxidative dehydrogenation of hydrocarbons on bismuth vanadium molybdenum oxide
A systematic investigation of the oxidative dehydrogenation of propane to propene and 1- and 2-butene to 1,3-butadiene, and the selective oxidation of isobutene to methacrolein was carried out over Bi1-x/3V1-xMoxO4 (x = 0-1) with the aim of defining the effects of catalyst and reactant composition on the reaction kinetics. This work has revealed that the reaction kinetics can differ significantly depending on the state of catalyst oxidation, which in turn depends on the catalyst composition and the reaction conditions. Under conditions where the catalyst is fully oxidized, the kinetics for the oxidation of propene to acrolein and isobutene to methacrolein, and the oxidative dehydrogenation of propane to propene, 1-butene and trans-2-butene to butadiene are very similar - first order in the partial pressure of the alkane or alkene and zero order in the partial pressure of oxygen. These observations, together with XANES and UV-Vis data, suggest that all these reactions proceed via a Mars van Krevelen mechanism involving oxygen atoms in the catalysts and that the rate-limiting step involves cleavage of the weakest C-H bond in the reactant. Consistent with these findings, the apparent activation energy and pre-exponential factor for both oxidative dehydrogenation and selective oxidation correlate with the dissociation energy of the weakest C-H bond in the reactant. As the reaction temperature is lowered, catalyst reoxidation can become rate-limiting, the transition to this regime depending on ease of catalyst reduction and effectiveness of the reacting hydrocarbons as a reducing agent. A third regime is observed for isobutene oxidation at lower temperatures, in which the catalyst is more severely reduced and oxidation now proceeds via reaction of molecular oxygen, rather than catalyst lattice oxygen, with the reactant.
Zhai, Zheng,Wang, Xuan,Licht, Rachel,Bell, Alexis T.
p. 87 - 100
(2015/09/28)

Α, β-unsaturated carboxylic acid manufacturing method
PROBLEM TO BE SOLVED: To obtain high selectivity of α,β-unsaturated carboxylic acid which is an objective product, when producing the α,β-unsaturated carboxylic acid by subjecting alcohol, olefin or α,β-unsaturated aldehyde to liquid phase oxidation by molecular oxygen.SOLUTION: When producing the α,β-unsaturated carboxylic acid by subjecting alcohol, olefin or α,β-unsaturated aldehyde to liquid phase oxidation by molecular oxygen, a catalyst containing palladium is used, and after starting reaction of the liquid phase oxidation, supply of a molybdenum compound into a reaction system is started.
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Paragraph 0060; 0061; 0062; 0063; 0064; 0065

(2016/12/16)

Catalytic selective oxidation of isobutane over Csx(NH 4)3-xHPMo11VO40 mixed salts
A series of mixed Keggin-type heteropolysalts Csx(NH 4)3-xHPMo11VO40 with various ammonia/caesium ratios was prepared by the precipitation method and characterized by TGA, N2 adsorption/desorption, XRD, FT-IR, and NH3-TPD techniques. Correlations between the ammonia/caesium ratio and the specific surface area, as well as with the total number of acid sites, were established. Furthermore, the introduction of Cs to the catalytic formulation was beneficial to the stabilization of the Keggin structure and helped limiting the elimination of the V atoms from the primary structure. The as-prepared samples were applied in the catalytic selective oxidation of isobutane at 340 °C under atmospheric pressure. The best results were obtained over Cs1.7(NH4)1.3HPMo 11VO40 with an isobutane conversion of 9.6% and a total selectivity to valuable products (methacrylic acid and methacrolein) of 57.1%. This was explained by the well-balanced acidity and specific surface of this catalyst, promoting the C-H bond activation (adequate acid properties) over a large number of accessible active sites (high acid sites density). the Partner Organisations 2014.
Jing, Fangli,Katryniok, Benjamin,Dumeignil, Franck,Bordes-Richard, Elisabeth,Paul, Sebastien
p. 2938 - 2945
(2014/08/18)

Chemoselective hydrogen peroxide oxidation of allylic and benzylic alcohols under mild reaction conditions catalyzed by simple iron-picolinate complexes
Chemoselective oxidation of allylic alcohols to α,β-unsaturated carbonyl compounds proceeded efficiently using hydrogen peroxide with iron-picolinate catalysts. The in situ generated [Fe(Me-Pic)3] (Me-Pic = 6-methylpicolinate) catalyzed oxidation of the alcohol moiety of primary allylic alcohols while the [Fe(Pic)3] (Pic = picolinate) and [Fe(Me-Pic)2(Pic)] did not show sufficient catalytic activity. the Partner Organisations 2014.
Tanaka, Shinji,Kon, Yoshihiro,Nakashima, Takuya,Sato, Kazuhiko
p. 37674 - 37678
(2014/11/07)

Chemoselective hydrogen peroxide oxidation of allylic and benzylic alcohols under mild reaction conditions catalyzed by simple iron-picolinate complexes
Chemoselective oxidation of allylic alcohols to α,β-unsaturated carbonyl compounds proceeded efficiently using hydrogen peroxide with iron-picolinate catalysts. The in situ generated [Fe(Me-Pic)3] (Me-Pic = 6-methylpicolinate) catalyzed oxidation of the alcohol moiety of primary allylic alcohols while the [Fe(Pic)3] (Pic = picolinate) and [Fe(Me-Pic)2(Pic)] did not show sufficient catalytic activity. This journal is
Tanaka, Shinji,Kon, Yoshihiro,Nakashima, Takuya,Sato, Kazuhiko
p. 37674 - 37678
(2014/12/11)

Selective acceptorless dehydrogenation and hydrogenation by iridium catalysts enabling facile interconversion of glucocorticoids
An iridium(III) pentamethylcyclopentadienyl catalyst supported by 6,6'-dihydroxy-2,2'-bipyridine displays exquisite selectivity in acceptorless alcohol dehydrogenation of cyclic α,β-unsaturated alcohols over benzylic and aliphatic alcohols under mild aqueous reaction conditions. Hydrogenation of aldehydes and ketones occurs indiscriminately using the same catalyst under hydrogen, although chemoselectivity could be achieved when other potentially reactive carbonyl groups present are sterically inaccessible. This chemistry was demonstrated in the reversible hydrogenation and dehydrogenation of the A ring of glucocorticoids, despite the presence of other alcohol/or carbonyl functionalities in rings C and D. NMR studies suggest that an iridium(III) hydride species is a key intermediate in both hydrogenation and dehydrogenation processes.
Ngo, Anh H.,Adams, Michael J.,Do, Loi H.
supporting information
p. 6742 - 6745
(2015/02/19)

Process for preparation of methyl methacrylate by esterification during oxidation
The invention relates to a process for preparation of methacrylic acid, comprising the steps: a) providing a feed composition comprising a main compound selected from isobutylene and tert-butyl alcohol and at least one co-compound selected from the group consisting of methanol, dimethyl ether and formaldehyde; b) subjecting the feed composition provided in step a) with at least a first part of said at least one co-compound to a catalytic reaction zone and obtaining an oxidation phase comprising methyl methacrylate and methacrylic acid. The invention also relates a process for preparation of methyl methacrylate, further comprising the step of: c) esterification of at least a part of the oxidation phase obtained in step b), to an apparatus for preparation of methacrylic acid, to an apparatus for preparation of methyl methacrylate, to a process carried out in the apparatus, to methacrylic acid, to methyl methacrylate, to methacrylate esters, to a process for preparation of a polymer comprising at least one methacrylic acid, methyl methacrylate and/or methacrylate ester monomer unit, to a polymer comprising at least one methacrylic acid, methyl methacrylate and/or methacrylate ester monomer, to a process for preparation of a composition, to a composition, to chemical products, and to the use of at least one of methacrylic acid, methyl methacrylate, methacrylate ester, a polymer and/or a composition in chemical products.
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Paragraph 0112-0122

(2014/09/17)

METHOD FOR MAKING METHYL METHACRYLATE FROM PROPIONALDEHYDE AND FORMALDEHYDE VIA OXIDATIVE ESTERIFICATION
A process for forming methyl methacrylate can comprise: reacting ethylene, carbon monoxide, and hydrogen, in the presence of a first catalyst comprising a metal carbonyl; removing a first reaction product comprising propionaldehyde; reacting the first reaction product with formaldehyde; removing a second reaction product comprising methacrolein; reacting the second reaction product with oxygen and methanol in the presence of a second catalyst to form a third reaction product comprising methyl methacrylate. Another process for forming methyl methacrylate can comprising: reacting ethylene with carbon monoxide to form propionaldehyde; reacting the propionaldehyde with formaldehyde to form methacrolein; and reacting the methacrolein with methanol and oxygen to form the methyl methacrylate.
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Paragraph 0041

(2014/08/06)

OH-initiated photooxidations of 1-pentene and 2-methyl-2-propen-1-ol: Mechanism and yields of the primary carbonyl products
The products of the gas-phase reactions of OH radicals with 1- pentene and 2-methyl-2-propen-1-ol (221MPO) at T=298±2 K and atmospheric pressure were investigated by using a 4500 L atmospheric simulation chamber that was built especially for this work. The molar yield of butyraldehyde was 0.74± 0.12 mol for the reaction of 1-pentene. This work provides the first product molar yield determination of formaldehyde (0.82±0.12 mol), 1-hydroxypropan-2-one (0.84±0.13 mol), and methacrolein (0.078±0.012 mol) from the reaction of 221MPO with OH radicals. The mechanism of this reaction is discussed in relation to the experimental results. Additionally, taking into consideration the complex mechanism, the rate coefficients of the reactions of OH with formaldehyde, 1-hydroxypropan-2- one, and methacrolein were derived at atmospheric pressure and T=298±2 K.; the obtained values were (8.9±1.6)×10-12, (2.4±1.4)×10-12, and (22.9±2.3)×10-12 cm3 molecule-1 s-1, respectively.
Peirone, Silvina A.,Cometto, Pablo M.,Lane, Silvia I.
p. 3848 - 3854
(2015/02/19)

METHOD FOR PRODUCING t-BUTANOL FROM ISOBUTANOL, METHOD FOR PRODUCING METHACROLEIN AND METHACRYLIC ACID FROM ISOBUTANOL, AND APPARATUS FOR PRODUCING THEM
A method for efficiently producing t-butanol as a raw material of a methacrylic resin from isobutanol is described, including a step (1) of dehydrating isobutanol to obtain butenes, and a step (2) of hydrating the butenes to obtain t-butanol. A method for producing methacrolein and methacrylic acid is also described, which further includes a step (3) of dehydrating and oxidizing the obtained t-butanol to obtain methacrolein and methacrylic acid. An apparatus for performing the steps (1) to (3) is also described.
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Paragraph 0040-0045

(2014/12/09)