- Enzymatic synthesis of 3-hydroxypropionic acid at high productivity by using free or immobilized cells of recombinant Escherichia coli
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3-Hydroxypropionic acid (3-HP) is an important platform chemical for organic synthesis and high performance polymers. Despite a wealth of reports related to 3-HP biosynthesis in microorganisms, its industrial application still requires further research because of low titer and productivity. Herein an effective enzymatic method for the synthesis of 3-HP was achieved by using free or immobilized recombinant Escherichia coli BL21(DE3) cells harboring a nitrilase gene from environmental sample (NIT190). Under the optimal conditions (100 mmol/L Tris-HCl buffer, pH 8.0, 30 °C), the maximum substrate concentration which could be completely hydrolyzed by using free cells within 24 h was 4.5 mol/L (319.5 g/L). Furthermore, immobilization of the whole cells enhanced their substrate tolerance (up to 7.0 mol/L), stability, and reusability. The immobilized cells could be reused for up to 30 batches, and 70% of enzyme activity was retained after 74 batches in distilled water. The titer (184.7 g/L) and productivity (36.9 g/(L h)) were obtained by isolation and purification of 3-HP from the first 30 batches. These results demonstrate that the immobilized cells have potential industrial application for the synthesis of 3-HP.
- Yu, Shanshan,Yao, Peiyuan,Li, Jianjiong,Ren, Jie,Yuan, Jing,Feng, Jinhui,Wang, Min,Wu, Qiaqing,Zhu, Dunming
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Read Online
- Practical syntheses of the C12-C21 epothilone subunit via catalytic asymmetric reductions: Itsuno-Corey oxazaborolidine reduction and asymmetric Noyori hydrogenation
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Two practical catalytic asymmetric reductions to introduce the epothilone C15 stereocenter are described (Itsuno-Corey reduction and Noyori hydrogenation).
- Reiff, Emily A.,Nair, Sajiv K.,Narayan Reddy,Inagaki, Jun,Henri, John T.,Greiner, Jack F.,Georg, Gunda I.
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Read Online
- Efficient, chemical-catalytic approach to the production of 3-hydroxypropanoic acid by oxidation of biomass-derived levulinic acid with hydrogen peroxide
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3-Hydroxypropanoic acid (HPA), a precursor to acrylic acid, can be produced in high yield by oxidation of the biomass-derived platform chemical levulinic acid. While treatment of levulinic acid with H2O2 under acidic conditions gives predominantly succinic acid, a remarkable reversal of selectivity is observed under basic conditions, leading either directly to HPA or, under modified conditions, initially to 3-(hydroperoxy)propanoic acid, which can be quantitatively hydrogenated to HPA. Just say no to fermentation: The first selective, chemical-catalytic approach to renewable 3-hydroxypropanoic acid (HPA) has been accomplished by gentle oxidation of biomass-derived levulinic acid with hydrogen peroxide and hydrogenolysis of the resulting hydroperoxide intermediate. HPA is a green building block of major potential for the production of renewable acrylate derivatives.
- Wu, Linglin,Dutta, Saikat,Mascal, Mark
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Read Online
- Production of 3-hydroxypropionate using a novel malonyl-CoA-mediated biosynthetic pathway in genetically engineered: E. coli strain
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3-Hydroxypropionic acid (3-HP) is a promising platform chemical with a wide range of applications. The traditional chemical synthesis of 3-HP is well-established, but the resource limitations, high price and toxicity of the used raw materials do not meet the new sustainable development goals. Accordingly, the microbial synthesis of 3-HP by fermentation will become a promising and attractive route mainly due to its environmentally friendly production, use of renewable resources, and sustainable development. Herein, to biosynthesize 3-HP directly from malonate, a novel malonyl-CoA-mediated biosynthetic pathway was successfully developed as follows. Firstly, various transporters involved in malonate transportation was systematically investigated and screened. Secondly, to biosynthesize 3-HP, an original strategy was employed by heterologously co-expressing the mutant of malonyl-CoA reductase (MCR) from Chloroflexus aurantiacus and malonyl-CoA synthetase (MatB) from Rhodopseudomonas palustris in the Escherichia coli C43 (DE3) strain, which was screened from three different MatB enzymes. Finally, to further enhance the production of 3-HP, native transhydrogenase (PntAB) and NAD kinase (YfjB) genes were expressed to increase the NADPH supply in E. coli. The final genetically modified strain SGN78 showed a significant improvement in malonate utilization and produced 1.20 ± 0.08 g L-1 of 3-HP in the flask culture. Thus, this work demonstrates the production of 3-HP in E. coli with the shortest route for the biosynthesis of 3-HP, which involved only three steps from the substrate. Also, it opens a path for the biosynthesis of 3-HP and other malonyl-CoA-based valuable chemicals directly from malonate in E. coli.
- Liang, Bo,Sun, Guannan,Wang, Zhaobao,Xiao, Jian,Yang, Jianming
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Read Online
- The selective oxidation of glycerol over metal-free photocatalysts: insights into the solvent effect on catalytic efficiency and product distribution
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Selective oxidation of glycerol to high value-added derivatives is a promising biomass conversion pathway, but the related reaction mechanism, in particular the solvent effect, is rarely studied. In this work, O-doped g-C3N4was used as a metal-free catalyst to catalyze the selective oxidation of glycerol in different solvents. It was found that solvents can affect both catalytic efficiency and product distribution. A series of controlled experiments and theoretical calculation were applied to attest that the difference in interaction between glycerol and catalysts in different solvents is the main factor: competitive adsorption and hydrogen bond network from water inhibit the adsorption and activation of glycerol on the catalyst surface and reduce the conversion efficiency, while in acetonitrile, the stronger adsorption makes the oxidation reaction continue to yield esters. Two reaction routes in different solvents over O-doped g-C3N4are proposed for the first time, which is helpful for people to better understand the related reaction mechanism.
- Fan, Mingming,Haryonob, Agus,Jiang, Pingping,Leng, Yan,Yue, Chengguang,Zhang, Pingbo
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p. 3385 - 3392
(2021/06/06)
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- Method for preparing 3-hydracrylic acid through continuous hydration of acrylic acid
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The invention relates to a method for preparing 3-hydracrylic acid through continuous hydration of acrylic acid. The reaction is carried out in a fixed bed reactor, an acid modified molecular sieve isused as a catalyst and acrylic acid is subjected to a hydration reaction to generate 3-hydracrylic acid. The modifier adopted by the acid-modified molecular sieve is a mixture of maleic acid and maleic acid diamine or a mixture of citric acid and ammonium citrate. The modified catalyst can reduce the reaction temperature and the selectivity of byproducts, inhibit self-polymerization of acrylic acid and 3-hydracrylic acid and improve the product yield.
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Paragraph 0098
(2020/04/29)
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- Expanding the repertoire of nitrilases with broad substrate specificity and high substrate tolerance for biocatalytic applications
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Enzymatic conversion of nitriles to carboxylic acids by nitrilases has gained significance in the green synthesis of several pharmaceutical precursors and fine chemicals. Although nitrilases from several sources have been characterized, there exists a scope for identifying broad spectrum nitrilases exhibiting higher substrate tolerance and better thermostability to develop industrially relevant biocatalytic processes. Through genome mining, we have identified nine novel nitrilase sequences from bacteria and evaluated their activity on a broad spectrum of 23 industrially relevant nitrile substrates. Nitrilases from Zobellia galactanivorans, Achromobacter insolitus and Cupriavidus necator were highly active on varying classes of nitriles and applied as whole cell biocatalysts in lab scale processes. Z. galactanivorans nitrilase could convert 4-cyanopyridine to achieve yields of 1.79 M isonicotinic acid within 3 h via fed-batch substrate addition. The nitrilase from A. insolitus could hydrolyze 630 mM iminodiacetonitrile at a fast rate, effecting 86 % conversion to iminodiacetic acid within 1 h. The arylaliphatic nitrilase from C. necator catalysed enantioselective hydrolysis of 740 mM mandelonitrile to (R)-mandelic acid in 4 h. Significantly high product yields suggest that these enzymes would be promising additions to the suite of nitrilases for upscale biocatalytic application.
- Rayavarapu, Pratima,Shah, Shikha,Sunder, Avinash Vellore,Wangikar, Pramod P.
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p. 289 - 296
(2020/05/18)
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- Environment-friendly and efficient synthesis method of 3-hydracrylic acid
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The invention relates to the field of fine chemicals. The invention relates to an environment-friendly and efficient synthesis method of 3-hydracrylic acid. The method comprises the following steps: sequentially adding tetrahydrofuran, a solvent, an oxygen source and required gas into a reaction container, heating to a reaction temperature, cooling to room temperature after reaction time is reached, adding a proper amount of water, and carrying out vacuum fractionation to collect a fraction with a proper temperature, thereby obtaining the 3-hydracrylic acid product with the product yield up to58%. According to the method, environment-friendly and efficient preparation of 3-hydracrylic acid is realized under mild conditions, the used raw materials can be obtained from petrochemical engineering at low cost or by biomass catalytic conversion. The reaction conditions are very mild, the process operation is very simple, the product is very easy to separate, in addition, the cyclic utilization of an experiment solvent in the industrial production can be realized, the environment-friendly and efficient synthesis of the biomass platform compound 3-hydroxypropionic acid is realized, and meanwhile, the environment problems caused in the process flow are also avoided.
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Paragraph 0030-0060
(2020/07/27)
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- Method used for producing 3-hydroxypropionic acid
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The invention belongs to the technical field of chemistry, and more specifically provides a method used for producing 3-hydroxypropionic acid. The method comprises following steps: 1, under catalyst effect, hydrogen cyanide and ethylene oxide are reacted to generated 3-hydroxypropionitrile; 2, an acid is added into the 3-hydroxypropionitrile prepared using step 1 for hydrolysis, and 3-hydroxypropionic acid and an inorganic slat are generated through reaction; 3, a reaction solution obtained in step 2 is subjected to continuous chromatography separation to obtain 3-hydroxypropionic acid and aninorganic salt solution, and the inorganic salt solution is subjected to concentration to obtain a by-product. According to the method, continuous chromatography method is adopted to process the 3-hydroxypropionitrile hydrolysis reaction solution, so that the amounts of waste water, waste gas, and waste residue can be reduced effectively, high content of the target product is obtained at high yield, and production cost is reduced.
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Paragraph 0037; 0045-0047; 0050-0052; 0053-0055
(2019/12/08)
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- Highly selective conversion of glyceric acid to 3-iodopropionic acid by hydriodic acid mediated hydrogenation
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Glycerol, generated in abundance as the by-product in the process of biodiesel production and saponification, has seen attempts to convert it into value-added chemicals. However, due to the low selectivity of hydrogenolysis of the secondary hydroxyl group, valuable 1,3-substituted chemicals are difficult to obtain from glycerol by chemocatalysis. In this work, glyceric acid (GA), a renewable biomass from glycerol, was quantitatively converted to 3-iodopropionic acid (3-IPA) at 373 K in 3 h by hydroiodic acid mediated hydrogenation. As the reductant in this process, HI is oxidized to I2 and then regenerated in situ by metal catalysts and H2. The reaction pathway was proposed by intermediate identification and verified by a kinetics study and computational method. The catalytic system was shown to be stable and can be reused several times without loss in activity. As a 1,3-substituted chemical, 3-IPA is not only a potential monomer to form poly-3-hydroxypropionic acid, but also a good platform molecule to produce useful chemicals, e.g. 3-hydroxypropionic acid (3-HPA) and acrylic acid (AA), due to its highly reactive nature.
- Li, Teng,Liu, Shengqin,Wang, Bing,Long, Jingen,Jiang, Jun,Jin, Ping,Fu, Yao,Yu, Haizhu,Yang, Weiran
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supporting information
p. 4434 - 4442
(2019/08/21)
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- Preparation method of 3- hydroxy propionic acid (by machine translation)
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The invention relates to the technical field of chemical engineering, and 3 - in particular provides a preparation method of hydroxyl propionic acid, (1) and the method comprises the following steps of: reacting 3 - hydrogen cyanide and (2) ethylene oxide (1) to 3 - form a hydroxyl propionitrile; and then separating 3 - the reaction liquid from the (3) reaction liquid (2) obtained through the bipolar membrane electrodialysis 3 - (2). By adopting the method, 3 - a high-content target product can be obtained at a high yield, the use amount of the alkali is reduced, inorganic salt is not produced, waste water, waste gas and waste residue are effectively reduced, and the production cost is reduced. (by machine translation)
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Paragraph 0047-0049; 0052-0057
(2019/12/08)
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- Synthesis method of 3-hydracrylic acid
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The invention relates to the technical field of chemical engineering, and particularly provides a synthesis method of 3-hydroxypropionic acid. The synthesis method comprises the following steps: (1) reacting hydrogen cyanide with ethylene oxide under the action of a catalyst to generate 3-hydroxypropionitrile; (2) adding acid into the 3-hydroxypropionitrile obtained in the step (1) for a hydrolysis reaction to generate 3-hydroxypropionic acid and an inorganic salt; and (3) carrying out electrodialysis separation on a reaction solution obtained in the step (2) to obtain 3-hydracrylic acid and an inorganic salt solution, and concentrating the obtained inorganic salt solution to obtain a byproduct. According to the invention, the acid hydrolysis reaction liquid of 3-hydroxypropionitrile is treated through electrodialysis, so waste water, waste gas and waste residues can be effectively reduced, a high-content target product, i.e., 3-hydroxypropionic acid, is obtained at a high yield, and production cost is reduced.
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Paragraph 0046-0056
(2019/12/29)
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- HETEROGENEOUS CATALYST FOR PREPARING ACRYLIC ACID, AND ACRYLIC ACID PREPARATION METHOD USING SAME
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The present disclosure relates to a catalyst used in the preparation of acrylic acid and acrylic acid preparation method using the same, and more specifically, discloses a catalyst capable of enhancing selectivity of acrylic acid and a production yield of acrylic acid when preparing acrylic acid from allyl alcohol using a heterogeneous catalyst including bimetallic alloy catalyst particles of gold and another metal, and an acrylic acid preparation method using the same.
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Paragraph 0091-0092; 0095-0097; 0100-0101; 0104-0105; 0108
(2018/08/03)
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- Method for using glyceric acid to prepare 3-hydroxypropionic acid
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The invention provides a method for using glyceric acid to prepare 3-hydroxypropionic acid. The method comprises the following steps that in a wild reaction condition, hydroiodic acid and glyceric acid are used for generating 3-iodopropionic acid in water; then 3-iodopropionic acid is extracted by using an organic solvent; and finally, a basic catalyst is used for catalyzing and hydrolyze 3-iodopropionic acid to be 3-hydracrylic acid. The reactants used in the method are cheap and easy to obtain, and the sources are green; the reaction time is short, efficient and energy saving effects are achieved; the amount of by-products is less, the yield rate of the first-step product 3-iodopropionic acid can reach 99%, and the yield rate of the second-step product 3-hydracrylic acid can reach 99%. The first-step product is separated by using the extraction method, and the extraction method is directly used in a two-phase system hydrolysis reaction in the second step. The product selectivity in the method is high, post-treatment is easy, and the method is easy to industrialize. The reaction system is simple, the reaction cost is low, and the preparation method has very important application value.
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Paragraph 0015; 0019-0020; 0024-0037
(2018/08/28)
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- Levulinic acid upgrade to succinic acid with hydrogen peroxide
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Levulinic acid is produced from the acidic aqueous degradation of 5-hydroxymethylfurfural, with potential applications in bio-value added chemicals synthesis. Here, we report for the first time, the Baeyer-Villiger oxidation of levulinic acid to succinic acid, with hydrogen peroxide and tungstic acid at mild conditions and without any organic solvent. We investigated the effects of time, amount of reagent-to-catalyst molar ratio and H2O2-to-levulinic acid molar ratio. The maximum succinic acid selectivity was 75% with a levulinic acid conversion as high as 48%, after 6 h at 90 °C. We propose a reaction mechanism based on results obtained from the reactivity of the intermediates. The catalyst interacts with the substrate, forming a cyclic species that enhances the formation of succinic acid versus 3-hydroxypropanoic acid.
- Carnevali, Davide,Rigamonti, Marco G.,Tabanelli, Tommaso,Patience, Gregory S.,Cavani, Fabrizio
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- Method for Producing Acrylic Acid
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The present invention relates to a method for producing acrylic acid and, more specifically, to a method for producing acrylic acid with high yield by purifying acrylic acid, 3-hydroxypropionic acid (3-HPA) and other impurities as a result of an oxidation reaction of allyl-alcohol.COPYRIGHT KIPO 2017
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Paragraph 0043; 0044; 0045
(2017/06/02)
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- RuCl3 Supported on N-Doped Graphene as a Reusable Catalyst for the One-Step Glucose Oxidation to Succinic Acid
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Impregnation of RuCl3 on N-doped graphenes results in the formation of well-dispersed, small ruthenium oxyhydroxide nanoparticles supported on N-doped graphene that may exhibit high selectivity (87 %) for the conversion of glucose into succinic acid under wet oxidation conditions (160 °C, 18 atm O2 pressure). Ruthenium loading and N-atom distribution on graphene influence the catalytic activity, the best performing catalyst having 1 wt. % Ru loading on a graphene having a large population of graphenic N atoms. The high catalytic selectivity to succinic acid was correlated with the presence of small ruthenium nanoparticles. The present catalyst improves the best one previously reported because it does not require the continuous addition of an excess of amine to reach high succinic acid selectivity and reusability.
- Rizescu, Cristina,Podolean, Iunia,Cojocaru, Bogdan,Parvulescu, Vasile I.,Coman, Simona M.,Albero, Josep,Garcia, Hermenegildo
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p. 3314 - 3321
(2017/09/06)
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- Prebiotic synthesis of aminooxazoline-5′-phosphates in water by oxidative phosphorylation
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RNA is essential to all life on Earth and is the leading candidate for the first biopolymer of life. Aminooxazolines have recently emerged as key prebiotic ribonucleotide precursors, and here we develop a novel strategy for aminooxazoline-5′-phosphate synthesis in water from prebiotic feedstocks. Oxidation of acrolein delivers glycidaldehyde (90%), which directs a regioselective phosphorylation in water and specifically affords 5′-phosphorylated nucleotide precursors in upto 36% yield. We also demonstrated a generational link between proteinogenic amino acids (Met, Glu, Gln) and nucleotide synthesis.
- Fernández-García,Grefenstette,Powner
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supporting information
p. 4919 - 4921
(2017/07/11)
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- PREPARATION OF COMPOUNDS FROM LEVULINIC ACID
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The present invention provides a method of making carboxylic acids from levulinic acid, such as succinic acid and 3-hydroxypropanoic acid, by reacting levulinic acid with an oxidant such as hydrogen peroxide under acidic or basic conditions.
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Paragraph 0061
(2016/08/23)
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- Carbonylation of ethylenically unsaturated compounds
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A process for the carbonylation of ethylenically unsaturated compounds including vinyl esters and a process for the production of 3-hydroxy propanoate esters or acids. The process comprises reacting said compound with carbon monoxide in the presence of a source of hydroxyl groups and of a catalyst system. The catalyst system is obtainable by combining: (a) a metal of Group 8, 9 or 10 or a compound thereof: and (b) a bidentate ligand of general formula (I): X1(X2)-Q2-A-R—B-Q1-X3(X4).
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Page/Page column 48
(2016/06/01)
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- HETEROGENEOUS CATALYST FOR PREPARING ACRYLIC ACID FROM ALLYL ALCOHOL, AND METHOD OF PREPARING ACRYLIC ACID FROM ALLYL ALCOHOL USING THE SAME
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The present invention relates to a heterogeneous catalyst for preparing acrylic acid from allyl alcohol, and a method of preparing acrylic acid from allyl alcohol using the same. More particularly, the present invention relates to a method of preparing acrylic acid from allyl alcohol at a high yield by performing a liquid phase reaction in the presence of a heterogeneous catalyst including gold supported on a carrier.
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Paragraph 0041
(2015/12/30)
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- An S188V mutation alters substrate specificity of non-stereospecific a-haloalkanoic acid dehalogenase E (DehE)
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The non-stereospecific α-haloalkanoic acid dehalogenase E (DehE) degrades many halogenated compounds but is ineffective against β-halogenated compounds such as 3-chloropropionicacid (3CP). Using molecular dynamics (MD) simulations and site-directed mutagenesis we show here that introducing the mutation S188V into DehE improves substrate specificity towards 3CP. MD simulations showed that residues W34, F37, and S188 of DehE were crucial for substrate binding. DehE showed strong binding ability for D-2-chloropropionic acid (D-2CP) and L-2-chloropropionic acid (L-2CP) but less affinity for 3CP. This reduced affinity was attributed to weak hydrogen bonding between 3CP and residue S188, as the carboxylate of 3CP forms rapidly interconverting hydrogen bonds with the backbone amide and side chain hydroxyl group of S188. By replacing S188 with a valine residue, we reduced the inter-molecular distance and stabilised bonding of the carboxylate of 3CP to hydrogens of the substrate-binding residues. Therefore, the S188V can act on 3CP, although its affinity is less strong than for D-2CP and L-2CP as assessed by Km. This successful alteration of DehE substrate specificity may promote the application of protein engineering strategies to other dehalogenases, thereby generating valuable tools for future bioremediation technologies.
- Hamid, Azzmer Azzar Abdul,Hamid, Tengku Haziyamin Tengku Abdul,Wahab, Roswanira Abdul,Shamsiromar, Mohd. Shahir,Huyop, Fahrul
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- Gold(I)/copper(II)-cocatalyzed tandem cyclization/semipinacol reaction: Construction of 6-Aza/Oxa-Spiro[4.5]decane skeletons and formal synthesis of (±)-halichlorine
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A simple and efficient strategy for the construction of 6-aza/oxa-spiro[4.5]decane skeletons under the cocatalysis of gold(I)/copper(II) was developed, and its potential utility was demonstrated by a formal synthesis of the biologically active marine alkaloid (±)-halichlorine.
- Zhu, Dao-Yong,Zhang, Zhen,Mou, Xue-Qing,Tu, Yong-Qiang,Zhang, Fu-Min,Peng, Jin-Bao,Wang, Shao-Hua,Zhang, Shu-Yu
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p. 747 - 752
(2015/03/18)
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- Production of C3 platform chemicals from CO2 by genetically engineered cyanobacteria
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Platform chemicals can be readily converted into various value-added chemicals and fuels. Photosynthetic production of platform chemicals directly from CO2 by cyanobacteria, in the presence of sunlight, holds promise for addressing global energy and environmental concerns. Herein, we report the photosynthetic production of C3 platform chemicals using engineered Synechococcus elongatus PCC7942 as the kernel. The engineered S. elongatus strain YW1 expressing glycerol-3-phosphatase produced a C3 intermediate, glycerol, with a high concentration of 1.17 g L-1 and a maximum production rate of 7733 μg L-1 H-1. Strain YW1 could serve as the kernel for the production of various C3 chemicals. By extending heterologous pathways in the cyanobacterial kernel, the carbon flux was further channelled to produce two platform chemicals: dihydroxyacetone by introducing glycerol dehydrogenase and 3-hydroxypropionic acid by introducing glycerol dehydratase and aldehyde dehydrogenase. Co-cultivation of the cyanobacterial kernel and another microbe, Klebsiella pneumoniae, was also performed to convert the C3 intermediate produced from CO2 to 1,3-propanediol, an important monomer for biodegradable material production. Besides direct photosynthetic production and co-cultivation, we demonstrated that glycerol produced by the cyanobacterial kernel can be used as a fermentation feedstock after simple concentration. The production processes presented here display great potential for carbon capture and storage and for sustainable production of chemicals and fuels.
- Wang, Yu,Tao, Fei,Ni, Jun,Li, Chao,Xu, Ping
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p. 3100 - 3110
(2015/05/27)
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- Efficient, metal-free production of succinic acid by oxidation of biomass-derived levulinic acid with hydrogen peroxide
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A practical, scalable, metal-free synthesis of succinic acid from the biomass-derived platform chemical levulinic acid is described. Treatment of levulinic acid with the inexpensive, simple oxidant hydrogen peroxide under the catalytic action of trifluoroacetic acid gives succinic acid in high yield and enables facile product isolation by simple distillation of the volatile catalyst and byproducts.
- Dutta, Saikat,Wu, Linglin,Mascal, Mark
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supporting information
p. 2335 - 2338
(2015/04/22)
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- CARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS
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PROBLEM TO BE SOLVED: To provide a process for the carbonylation of ethylenically unsaturated compounds including vinyl esters and a process for the production of 3-hydroxypropanoate esters or 3-hydroxypropanoic acids. SOLUTION: The process comprises reacting the compound with carbon monoxide in the presence of a source of hydroxyl groups and of a catalyst system. The catalyst system is obtainable by combining: (a) a metal of Group 8, 9 or 10 or a compound thereof: and (b) a bidentate ligand of general formula (I): X1(X2)-Q2-A-R-B-Q1-X3(X4). COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0242
(2016/10/09)
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- THERMAL SALT-SPLITTING OF (ALKYL)AMMONIUM 3-HYDROXYPROPIONATE
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A salt-splitting liquid (SSL) and a process that uses the SSL to "split" (alkyl)ammonium 3-hydroxypropionate salts into ammonia (or amines) and 3-hydroxypropionic acid (3-HP) that minimizes increases in viscosity and condensation reactions of the 3-HP. Converting (alkyl)ammonium 3-hydroxypropionate in an aqueous mixture to 3-HP includes admixing a polar aprotic organic solvent and an azeotroping solvent with the aqueous mixture. The azeotroping solvent forms an azeotrope mixture with water of the aqueous mixture. The SSL is heated to convert the (alkyl)ammonium 3-hydroxypropionate to 3-HP and ammonia, where heating produces a vapor phase containing at least water, ammonia and the azeotroping solvent. At least a portion of the water and the ammonia is removed from the vapor phase during the heating, and at least a portion of the azeotroping solvent is returned from the vapor phase back to SSL to maintain the azeotrope mixture with the water.
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Page/Page column 12
(2014/10/04)
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- Perspectives on the kinetics of diol oxidation over supported platinum catalysts in aqueous solution
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The catalytic oxidation of a variety of terminal alcohols was performed over Pt/C with 10 bar dioxygen at 343 K in aqueous solvent at low pH. The influences of Pt particle size, carbon support, alcohol structure, and start-up conditions were explored. Although the turnover frequency was not affected by particle size or the carbon support, the structure of the alcohols affected their initial rate of conversion. Both the rate of oxidation of α,ω-diols and selectivity of the diols to the diacids increased with increasing carbon chain length. The rate of 1,6-hexanediol oxidation was independent of dioxygen pressure and the order of reaction with respect to diol concentration depended on the start-up conditions. A kinetic model involving two types of metal sites was proposed to account for the experimental observations.
- Ide, Matthew S.,Davis, Robert J.
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- Solvent effect and reactivity trend in the aerobic oxidation of 1,3-propanediols over gold supported on titania: Nmr diffusion and relaxation studies
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In recent work, it was reported that changes in solvent composition, precisely the addition of water, significantly inhibits the catalytic activity of Au/TiO2 catalyst in the aerobic oxidation of 1,4-butanediol in methanol due to changes in diffusion and adsorption properties of the reactant. In order to understand whether the inhibition mechanism of water on diol oxidation in methanol is generally valid, the solvent effect on the aerobic catalytic oxidation of 1,3-propanediol and its two methyl-substituted homologues, 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol, over a Au/TiO2 catalyst has been studied here using conventional catalytic reaction monitoring in combination with pulsed-field gradient nuclear magnetic resonance (PFG-NMR) diffusion and NMR relaxation time measurements. Diol conversion is significantly lower when water is present in the initial diol/methanol mixture. A reactivity trend within the group of diols was also observed. Combined NMR diffusion and relaxation time measurements suggest that molecular diffusion and, in particular, the relative strength of diol adsorption, are important factors in determining the conversion. These results highlight NMR diffusion and relaxation techniques as novel, non-invasive characterisation tools for catalytic materials, which complement conventional reaction data. In solvent company: The solvent effect on the aerobic catalytic oxidation of 1,3-propanediol and its two methyl-substituted homologues, 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol, over a Au/TiO 2 catalyst has been studied. The results show that diol conversion is significantly lower when water is present in the initial diol/methanol mixture. A reactivity trend within the group of diols was also observed. Copyright
- D'Agostino, Carmine,Kotionova, Tatyana,Mitchell, Jonathan,Miedziak, Peter J.,Knight, David W.,Taylor, Stuart H.,Hutchings, Graham J.,Gladden, Lynn F.,Mantle, Mick D.
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p. 11725 - 11732
(2013/09/12)
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- Synthesis and antitumour activity of β-hydroxyisovalerylshikonin analogues
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A series of novel β-hydroxyisovalerylshikonin analogues bearing oxygen-containing substituents at the side-chain hydroxyl of shikonin were designed and synthesized. The cytotoxicities of these compounds were evaluated in vitro against multi-drug resistant (MDR) cell lines DU-145 and HeLa. Most compounds exhibited significant inhibitory activity on both cell lines. The structure-activity relationship showed the analogues with ether substituents displayed the most potent antitumour activity and selective cytotoxicity towards DU-145. Among the compounds with ether substituents, increasing the steric hindrance in the carbon bearing β-hydroxyl or replace the β-hydroxyl with acetoxy or methoxy would lead to the decline of cytotoxicity.
- Rao, Zhen,Liu, Xin,Zhou, Wen,Yi, Jing,Li, Shao-Shun
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experimental part
p. 3934 - 3941
(2011/11/12)
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- Efficient nitrile hydration mediated by RuII catalysts in micellar media
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Efficient nitrile hydration to the corresponding amide derivatives is observed in water using poorly soluble [RuCl2(η6- arene)(PR3)] catalysts 1 with the aid of surfactants to ensure substrate and catalyst solubilization, and enabling ligand effect study on catalytic activity. Amide yields of 40 to 95% can be observed with a variety of aromatic and aliphatic nitriles using the optimized catalyst system, [RuCl 2(p-cymene)(PPh2OEt)]/Triton X-114. Catalyst separation and recycling is possible.
- Cavarzan, Alessandra,Scarso, Alessandro,Strukul, Giorgio
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experimental part
p. 790 - 794
(2010/09/05)
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- Selective oxidation of glycerol under acidic conditions using gold catalysts
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(Figure Presented) Skip the bases! H-mordenite-supported PtAu nanoparticles are highly active and selective in the oxidation of glycerol under acidic conditions, which allows the direct preparation of free acids (see picture). The high selectivity for Cs
- Villa, Alberto,Veith, Gabriel M.,Prati, Laura
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supporting information; experimental part
p. 4499 - 4502
(2010/08/22)
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- Degradation of an ether-alcohol (3-ethoxypropan-1-ol) by photo-Fenton-generated OH radicals: Products analysis and formation pathways; relevance to atmospheric water-phase chemistry
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We have chosen 3-ethoxypropan-1-ol (EtOPrOH) as a typical shortcarbon- chain ether-alcohol used as industrial solvent and have analyzed the degradation products resulting from its attack by OH radicals generated by the photo-Fenton reaction. The laboratory conditions were representative of those found in tropospheric water droplets. Twelve products have been identified by use of GC- MS analysis, either directly or after extraction by SPME fibers, and by HPLC-UV analysis with a special column for carboxylic acids and after reaction of carbonyl groups with 2,4-dinitrophenylhydrazine. These products contain one to three carbon atoms (instead of five in EtOPrOH), among which one or two are oxidized. According to the reaction pathways proposed, seven products-including methanal- can result from attack by one OH only, three products imply attack by a second OH, as expected from their higher oxidation number, and it is suggested that reaction between two organic radicals is needed for formation of only two products. The relevance of this investigation to the fate of EtOPrOH and similar ether-alcohols in the troposphere is briefly discussed. Springer Science+Business Media B.V. 2010.
- Carteau, David,Pichat, Pierre
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experimental part
p. 141 - 153
(2011/10/19)
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- Process for converting a hydroxycarboxylic acid, or salts thereof, to an unsaturated carboxylic acid and/or its esters
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A process for converting a salt of a hydroxycarboxylic acid to an unsaturated carboxylic acid, or esters thereof. The process involves converting an ammonium salt of a hydroxycarboxylic acid in aqueous solution to a corresponding hydroxycarboxylic acid and ammonium cation in aqueous solution; and separating the ammonium cation from the aqueous solution, leaving the hydroxycarboxylic acid in aqueous solution. The converting and separating steps may be accomplished by employing a hydrophobic acid or an acid ion exchange resin, each of which must have an acid dissociation constant, i.e., pKa, at least 0.5 less that that of the salt of the hydroxycarboxylic acid. Where a hydrophobic acid is used, it must be immiscible in water, and its salt must also be immiscible in water, and the resulting multi-phase solution comprises an aqueous phase comprising the corresponding hydroxycarboxylic acid, as well as a non-aqueous phase comprising a neutralized acid. Alternatively, where the ion exchange resin is used, the aqueous solution of the ammonium salt of a hydroxycarboxylic acid is contacted with the resin, thereby converting the salt to a hydroxycarboxylic acid and capturing the ammonium cations on the resin. In either case, the aqueous solution is treated, such as by heating, to separate and recover the hydroxycarboxylic acid. The non-aqueous phase or resin is treated to separate and recover ammonia useful for preparing additional ammonium salt of a hydroxycarboxylic acid.
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Page/Page column 4
(2009/04/24)
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- Solvent effects on the enthalpy and entropy of activation for the hydrolysis of β-lactones
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The hydrolysis of β-propiolactone and β-butyrolactone in binary water∈+∈dioxane mixtures was investigated by kinetic studies. The following conclusions were reached: First, β-propiolactone is more reactive than β-butyrolactone across the range of water∈+∈dioxane compositions. This observation was rationalized in terms of the electric charge flow caused by the β-butyrolactone's methyl substituent. Second, hydrolysis of these lactones is essentially enthalpy controlled. Third, an increase in the dioxane percentage, which relaxes the intermolecular hydrogen bonds in the ordered structure of water, reduces the enthalpy of activation ΔH # and simultaneously increases the entropy of activation ΔS #(absolute value) for solvent compositions up to 60% dioxane. Fourth, plotting ΔH #/ΔS # against the solvent composition yields an N-shaped curve. This results is a consequence of the quadratic and cubic terms appearing in the expressions of ΔH # and ΔS # as functions of the solvent media composition. Fifth, an ABC classification was set up to characterize the behavior of ΔH #/ΔS # for the solvolysis of these lactones.
- Manso, Jose A.,Perez-Prior, M. Teresa,Del Pilar Garcia-Santos, Maria,Calle, Emilio,Casado, Julio
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p. 451 - 457
(2008/09/19)
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- CARBOXYLIC ACIDS PREPARED USING A SALT-SPLITTING PROCESS
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Processes for preparing carboxylic acids in which a single phase mixture including an ammonium salt of a carboxylic acid is heated in the presence of a non-aqueous solvent to split the salt and form the acid. The acid may be dehydrated to form unsaturated counterparts.
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Page/Page column 7; 7-8
(2008/06/13)
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- Unexpected preference of the E. coli translation system for the ester bond during incorporation of backbone-elongated substrates
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There have been recent advances in the ribosomal synthesis of various molecules composed of nonnatural ribosomal substrates. However, the ribosome has strict limitations on substrates with elongated backbones. Here, we show an unexpected loophole in the E. coli translation system, based on a remarkable disparity in its selectivity for β-amino/hydroxy acids. We challenged β-hydroxypropionic acid (β-HPA), which is less nucleophilic than β-amino acids but free from protonation, to produce a new repertoire of ribosome-compatible but main-chain-elongated substrates. PAGE analysis and mass-coupled S-tag assays of amber suppression experiments using yeast suppressor tRNAPheCUA confirmed the actual incorporation of β-HPA into proteins/oligopeptides. We investigated the side-chain effects of β-HPA and found that the side chain at position α and R stereochemistry of the β-substrate is preferred and even notably enhances the efficiency of incorporation as compared to the parent substrate. These results indicate that the E. coli translation machinery can utilize main-chain-elongated substrates if the pKa of the substrate is appropriately chosen.
- Sando, Shinsuke,Abe, Kenji,Sato, Nobuhiko,Shibata, Toshihiro,Mizusawa, Keigo,Aoyama, Yasuhiro
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p. 6180 - 6186
(2008/02/03)
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- Method for conversion of beta-hydroxy carbonyl compounds
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A process is disclosed for conversion of ammonium salts of β-hydroxy carbonyl compounds forming useful conversion products including, e.g., α, β-unsaturated carbonyl compounds and/or ammonium salts of α, β-unsaturated carbonyl compounds recovered at a high molar yield. Conversion products find use, e.g., as feedstock and/or end-use chemicals.
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Page/Page column 9-10
(2008/06/13)
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- Method and apparatus for conversion of beta-hydroxy carbonyl compounds
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A process and apparatus are disclosed for conversion of β-hydroxy carbonyl compounds forming useful conversion products including, e.g., acrylic acid [CAS No. 79-10-7], acrylates, and acrylamide [CAS No. 79-06-01]. Conversion products find use, e.g., as feedstock and/or end-use chemicals.
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Page/Page column 9-10
(2010/11/28)
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- PROCESS FOR THE PREPARATION OF HYDROXY CARBOXYLIC ACID
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The present invention provides a three step process for the preparation of hydroxy carboxylic acid. The present invention involves the hydroformylation of enol ester (e.g. vinyl acetate) using a cobalt catalyst (e.g. Co2(CO)8), optionally a promoter or a ligand containing O, N, N—O, P, As or Sb atom/s, to obtain a mixture of 2-acetoxy carboxaldehyde (e.g. 2-acetoxy propanal) and 3-acetoxy carboxaldehyde (e.g. 3-acetoxy propanal), oxidizing the product acetoxy carboxyaldehydes to the corresponding acetoxy carboxylic acid, in presence or absence of a Gr. 8 metal catalyst, followed by hydrolyzation of the product acetoxy carboxylic acids to the corresponding desired hydroxy carboxylic acids, in presence of an acidic catalyst and separating the catalyst and reusing it for another hydrolysis step.
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Page/Page column 3; 4; 5; 6
(2008/06/13)
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- METHOD OF TREATING AN ALDEHYDE MIXTURE, USE OF THE TREATED ALDEHYDE, AND AN ALCOHOL
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A method of treating an aldehyde mixture comprising a carboxylic acid and a metal cation, which method comprises: contacting the aldehyde mixture with a basic separating medium, and subsequently or simultaneously contacting with an acidic separating medium; use of the treated aldehyde mixture to prepare an alcohol; and the alcohol.
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Page/Page column 7-8
(2008/06/13)
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- Reactivity of lactones and GHB formation
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(Chemical Equation Presented) The behavior of lactones in their hydrolysis reactions is a good indicator of their reactivity as electrophilic molecules. The hydrolysis of four- to six-membered lactones was investigated in neutral (water) and slightly acid media and in water/dioxane media. The following conclusions were drawn: (i) The reactivity of β-propiolactone in neutral water is more than four times greater than that of β-butyrolactone, due to the flow of charge caused by the latter's methyl substituent. Reactivity is enthalpy-controlled. (ii) The reactivity of β-lactones diminishes in water/dioxane media when the percentage of dioxane increases. The increase in the dioxane percentage relaxing the intermolecular hydrogen bonds in the ordered structure of the water reduces ΔH# and simultaneously increases the -ΔS# value. (iii) An inverse solvent kinetic isotope effect in the acid-catalyzed hydrolysis of γ-butyrolactone and δ-valerolactone was observed, this being indicative of acyl cleavage. (iv) The ΔH# and ΔS# values permit discrimination between alkyl and acyl cleavage, (v) A correlation was found between the chemical reactivity of lactones and their carcinogenic activity. (vi) The results suggest that orally ingested γ-butyrolactone remains largely in its nonhydrolyzed form in the stomach before passing into the blood. (vii) The concentration equilibrium constant of GHB formation at human body temperature is Keq (37°C) = 0.40. (viii) Study of GHB formation shows that, contrary to earlier results, this is an endothermic process, with ΔrH= 3.6 kJ mol-1.
- Perez-Prior, M. Teresa,Manso, Jose A.,Del Pilar Garcia-Santos,Calle, Emilio,Casado, Julio
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p. 420 - 426
(2007/10/03)
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- ALKOXYCARBONYLATION OF VYNIL ESTERS
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A process for the alkoxycarbonylation of a vinyl ester comprising reacting a vinyl ester with carbon monoxide in the presence of an alkanol and a catalyst system. The catalyst system used in the said process is obtainable by combining: a) a metal of Group VIII B or a compound thereof, and b) a bidentate ligand of general formula (I) wherein, R is a covalent bridging group; R1 together with Q2 to which it is attached form an optionally substituted 2-Q2-tricyclo[3.3.1.1 {3,7}]decyl group or derivative thereof(2-PA); R2 and R3 independently represent univalent radicals upto 20 atoms or jointly form a bivalent radical of up to 20 atoms; and Q1 and Q2 each independently represent phosphorous, arsenic or antimony. The process is carried out for the production of a 3-hydroxy propanoate ester or acid of formula (II) CH2 (OH)CH2 C(O) OR28.The process may also be carried out for the production of a lactate ester or acid of formula (III).
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Page/Page column 38
(2010/02/15)
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- PROCESS FOR SEPARATING AND RECOVERING 3-HYDROXYPROPIONIC ACID AND ACRYLIC ACID
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Disclosed is a process for separating and recovering 3-hydroxypropionic acid from an aqueous solution comprising 3-hydroxypropionic acid and acrylic acid, comprising counter current extracting the aqueous solution with ethyl acetate extractant. Further disclosed is a process for separating and recovering 3-hydroxypropionic acid and acrylic acid from an aqueous solution comprising 3-hydroxypropionic acid and acrylic acid.
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Page 6-7; 10-12
(2008/06/13)
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- PROCESS FOR PREPARING 3-HYDROXYCARBOXYLIC ACIDS
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Disclosed is a process for hydrating an alpha, beta-unsaturated carboxylic acid, such as acrylic acid, in water, in the presence of a catalyst selected from carbon dioxide, a sulfur oxide, a nitrogen oxide, gaseous hydrochloric acid, an inorganic or organic base having a pKa greater than 7, to prepare a 3-hydroxycarboxylic acid such as 3-hydroxypropionic acid. Also disclosed is a process for recovering 3-hydroxypropionic acid from a solution comprising the 3-hydroxypropionic acid.
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- Hydration of propargylic alcohols by ruthenium catalysts, with dominant anti-Markovnikov regioselectivity, formation of α,β-unsaturated products and catalytic decarbonylation to 1-alkenes
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Ruthenium catalysts - water-soluble ruthenium sulfophthalocyanine and heterogeneous ruthenium hydroxyapatite complexes - proved to be effective for the hydration of propargylic alcohols in entirely aqueous media. 1-Phenyl-2-propyn-1-ol underwent an unprecedented catalytic hydration- decarbonylation-dehydration reaction, giving rise to styrene and carbon monoxide; 2-propyn-1-ol and 3-butyn-2-ol gave predominantly the products of anti-Markovnikov addition, together with products of hydration-dehydration (α,β-rearrangement) and, to a minor extent, the decarbonylation products, ethene or propene, respectively. Hydrations were also conducted in D2O, giving indications of the mechanism of the reactions and apparently ruling out the allenylidene route for the α,β- rearrangement. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- D'Alessandro, Nicola,Di Deo, Milena,Bonetti, Monica,Tonucci, Lucia,Morvillo, Antonino,Bressan, Mario
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p. 810 - 817
(2007/10/03)
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- METHODS OF MANUFACTURING DERIVATIVES OF β-HYDROXYCARBOXYLIC ACIDS
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Preparation of derivatives of β-hydroxycarboxylic acid, including β-hydroxycarboxylic acid esters, α,β-unsaturated carboxylic acids, esters of α,β-unsaturated carboxylic acid, and alkoxy derivatives.
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Page/Page column 14
(2008/06/13)
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- Process for recovering butyl acrylate substantially free from acrylic acid
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A process for producing continuously recovering n-butyl acrylate substantially free of acrylic acid from an esterification reaction mixture.
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- Interaction of 2,2,6,6-tetramethylpiperidine-1-oxyl chlorite with alcohols
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The kinetics of the oxidation of a series of alcohols (viz., ethanol, propan-2-ol, butan-1-ol, butan-2-ol, heptan-4-ol, decan-2-ol, propan-1,3-diol, butan-2,3-diol, cyclohexanol, benzyl alcohol, and borneol) with the oxoammonium salt 2,2,6,6-tetramethylpiperidine-1-oxyl chlorite in acetonitrile was studied by spectrophotometry. The products of oxidation of primary alcohols are the corresponding aldehydes and carboxylic acids, and the products of oxidation of secondary alcohols are ketones. The reaction rate is described by the second order equation. The rate constants and activation parameters were determined. The rate constant as a function of the alcohol nature is described by the one-parameter Taft equation.
- Ganiev,Suvorkina,Igoshina,Kabal'nova,Imashev,Tolstikov
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p. 982 - 985
(2007/10/03)
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- N-dealkylation of an N-cyclopropylamine by horseradish peroxidase. Fate of the cyclopropyl group
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Cyclopropylamines inactivate cytochrome P450 enzymes which catalyze their oxidative N-dealkylation. A key intermediate in both processes is postulated to be a highly reactive aminium cation radical formed by single electron transfer (SET) oxidation of the nitrogen center, but direct evidence for this has remained elusive. To address this deficiency and identify the fate of the cyclopropyl group lost upon N-dealkylation, we have investigated the oxidation of N-cyclopropyl-N-methylaniline (3) by horseradish peroxidase, a well-known SET enzyme. For comparison, similar studies were carried out in parallel with N-isopropyl-N-methylaniline (9) and N,N-dimethylaniline (8). Under standard peroxidatic conditions (HRP, H2O2, air), HRP oxidizes 8 completely to N-methylaniline (4) plus formaldehyde within 15-30 min, whereas 9 is oxidized more slowly (14C]-3, [1′-13C]-3, and [2′,3′-13C]-3 as substrates, radiochemical and NMR analyses of incubation mixtures revealed that the complete oxidation of 3 by HRP yields 4 (0.2 mol), β-hydroxypropionic acid (17, 0.2 mol), and N-methylquinolinium (16, 0.8 mol). In buffer purged with pure O2, the complete oxidation of 3 yields 4 (0.7 mol), 17 (0.7 mol), and 16 (0.3 mol), while under anaerobic conditions, 16 is formed quantitatively from 3. These results indicate that the aminium ion formed by SET oxidation of 3 undergoes cyclopropyl ring fragmentation exclusively to generate a distonic cation radical (14+?) which then partitions between unimolecular cyclization (leading, after further oxidation, to 16) and bimolecular reaction with dissolved oxygen (leading to 4 and 17 in a 1:1 ratio). Neither β-hydroxypropionaldehyde, acrolein, nor cyclopropanone hydrate are formed as SET metabolites of 3. The synthetic and analytical methods developed in the course of these studies should facilitate the application of cyclopropylamine-containing probes to reactions catalyzed by cytochrome P450 enzymes.
- Shaffer,Morton,Hanzlik
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p. 8502 - 8508
(2007/10/03)
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