- Development of a new production process for N-vinyl-2-pyrrolidone
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We describe the first continuous production process for N-vinyl-2-pyrrolidone (NVP). The starting materials are γ-butyrolactone (GBL) and monoethanolamine (MEA). The process consists of two stages: the synthesis of N-(2-hydroxy-ethyl)-2-pyrrolidone (HEP) from GBL and MEA, and the vapor-phase dehydration of HEP to NVP. The key features of this technology are the dehydration catalyst and the vapor-phase reaction system. The catalyst is of very simple composition, being alkali (or alkaline earth) metal oxides-SiO 2. Though its acid and base strengths are very weak, its catalytic performance is high. We presume that the excellent catalytic performance is due to the selective adsorption of HEP to the catalyst. Moreover, an IR spectroscopic study of the HEP-adsorbed catalyst indicated that the isolated silanol of the catalyst surface plays an important role. This account describes the progress made from the laboratory study to the industrial process, along with the experimental results and discussion.
- Shimasaki, Yuuji,Yano, Hitoshi,Sugiura, Hideto,Kambe, Hideyuki
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- Correlating the Synthesis, Structure, and Catalytic Performance of Pt-Re/TiO2for the Aqueous-Phase Hydrogenation of Carboxylic Acid Derivatives
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Pt-Re bimetallic catalysts have many applications, ranging from catalytic reforming to the reduction of carboxylic acid derivatives. However, the exact role of Re in these systems has remained a matter of discussion, partly due to the plethora of suggested synthesis protocols and analysis conditions. This study presents an extensive comparison of such literature protocols and the resulting materials. In detail, characterization by N2 physisorption, X-ray diffraction, temperature-programmed reduction, CO pulse chemisorption, Fourier-transform infrared spectroscopy of adsorbed CO, scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, and in situ X-ray photoelectron spectroscopy is combined with catalytic testing to yield synthesis-structure-activity correlations. Accordingly, the investigated catalysts share common features, such as Pt0 nanoparticles (1-4 nm) decorated with partially reduced Re species (ReOx-y). The remaining rhenium oxide is spread over the TiO2 support and enhances Pt dispersion in sequential impregnation protocols. While differences in the number of active sites (Pt0/ReOx-y) mostly explain catalytic results, small variations in the extent of Re reduction and site composition cause additional modulations. The optimal bimetallic catalyst outperforms Ru/C (previous benchmark) in the reduction of N-(2-hydroxyethyl)succinimide, an important step in the production of a bio-based polyvinylpyrrolidone polymer.
- Haus, Moritz O.,Meledin, Alexander,Leiting, Sebastian,Louven, Yannik,Roubicek, Nico C.,Moos, Sven,Weidenthaler, Claudia,Weirich, Thomas E.,Palkovits, Regina
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p. 5119 - 5134
(2021/05/10)
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- Extending the chemical product tree: A novel value chain for the production of: N -vinyl-2-pyrrolidones from biogenic acids
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The sustainable production of polymers from biogenic platform chemicals shows great promise to reduce the chemical industry's dependence on fossil resources. In this context, we propose a new two-step process leading from dicarboxylic acids, such as succinic and itaconic acid, to N-vinyl-2-pyrrolidone monomers. Firstly, the biogenic acid is reacted with ethanolamine and hydrogen using small amounts of water as solvent together with solid catalysts. For effective conversion, the optimal catalyst (carbon supported ruthenium) has to hold the ability of activating H2 as well as (imide) CO bonds. The obtained products, N-(2-hydroxyethyl)-2-pyrrolidones, are subsequently converted in a continuous gas phase dehydration over simple sodium-doped silica, with excellent selectivity of above 96 mol% and water as the sole by-product. With a final product yield of ≥72 mol% over two process steps and very little waste due to the use of heterogeneous catalysis, the proposed route appears promising-commercially as well as in terms of Green Chemistry.
- Haus, Moritz Otto,Louven, Yannik,Palkovits, Regina
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p. 6268 - 6276
(2019/12/03)
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- Mild Hydrogenation of Amides to Amines over a Platinum-Vanadium Bimetallic Catalyst
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Hydrogenation of amides to amines is an important reaction, but the need for high temperatures and H2 pressures is a problem. Catalysts that are effective under mild reaction conditions, that is, lower than 30 bar H2 and 70 °C, have not yet been reported. Here, the mild hydrogenation of amides was achieved for the first time by using a Pt-V bimetallic catalyst. Amide hydrogenation, at either 1 bar H2 at 70 °C or 5 bar H2 at room temperature was achieved using the bimetallic catalyst. The mild reaction conditions enable highly selective hydrogenation of various amides to the corresponding amines, while inhibiting arene hydrogenation. Catalyst characterization showed that the origin of the catalytic activity for the bimetallic catalyst is the oxophilic V-decorated Pt nanoparticles, which are 2 nm in diameter.
- Mitsudome, Takato,Miyagawa, Kazuya,Maeno, Zen,Mizugaki, Tomoo,Jitsukawa, Koichiro,Yamasaki, Jun,Kitagawa, Yasutaka,Kaneda, Kiyotomi
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supporting information
p. 9381 - 9385
(2017/08/01)
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- Method for Producing Bio-Based Homoserine Lactone and Bio-Based Organic Acid from O-Acyl Homoserine Produced by Microorganisms
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The present invention relates to a method of producing bio-based homoserine lactone and bio-based organic acid through hydrolysis of O-acyl homoserine produced by a microorganism in the presence of an acid catalyst. According to the present invention, O-acyl homoserine produced by a microorganism is used as a raw material for producing 1,4-butanediol, gamma-butyrolactone, tetrahydrofuran and the like, which are industrially highly useful. The O-acyl homoserine produced by a microorganism can substitute conventional petrochemical products, can solve environmental concerns, including the emission of pollutants and the exhaustion of natural resources, and can be continuously renewable so as not to exhaust natural resources.
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Paragraph 0232; 0233; 0234; 0235
(2014/10/16)
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- Catalytic hydrogenation of carboxamides and esters by well-defined Cp*Ru complexes bearing a protic amine ligand
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A novel catalytic method for the straightforward hydrogenation of carboxamides and esters to primary alcohols has been developed. Chiral modification in the ligand sphere of the well-defined Cp*Ru catalyst molecule opens up a new possibility for the development of an enantioselective hydrogenation of racemic substrates via dynamic kinetic resolution.
- Ito, Masato,Ootsuka, Takashi,Watari, Ryo,Shiibashi, Akira,Himizu, Akio,Ikariya, Takao
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supporting information; experimental part
p. 4240 - 4242
(2011/06/21)
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- 2,3,4,5-TETRAHYDRO-1H-1,5-BENZODIAZEPINE DERIVATIVE AND MEDICINAL COMPOSITION
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The present invention has its object to provide a 2,3,4,5-tetrahydro-1H-1,5-benzodiazepine derivative represented with the Formula (1) , or the pharmaceutically acceptable salt, which is effective as a therapeutic and prophylactic agent for diabetes, diabetic nephropathy, or glomerulosclerosis.
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- Method for purifying N-(2-hydroxyethyl)-2-pyrrolidone
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A method for purifying N-(2-hydroxyethyl)-2-pyrrolidone (HEP) is disclosed. The method comprises crystallizing crude HEP to produce HEP crystals and a mother liquor, and separating the HEP crystals from the mother liquor. In one method of the invention, crystallization is induced by adding an HEP seed crystal to the crude HEP. In a preferred method, the crystallization is performed in the presence of 14 wt. % of added water. HEP can be successfully crystallized to a purity greater than 99.9%.
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Page/Page column 2-3
(2008/06/13)
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- METHOD OF PURIFYING N-(2-HYDROXYETHYL)-2-PYRROLIDONE
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A method for obtaining high purity N-(2-hydroxyethyl)-2-pyrrolidone satisfactory for use as an intermediate material for N-vinyl-2-pyrrolidone from a reaction liquid formed of a reaction between γ-butyrolactone and 2-aminoethanol, i.e., a liquid containing N-(2-hydroxyethyl) -2-pyrrolidone, compounds having boiling points lower than that of N-(2-hydroxyethyl)-2-pyrrolidone and compounds having boiling points higher than that of N-(2-hydroxyethyl)-2-pyrrolidone. The method is characterized by distilling said reaction liquid using a distillation column, whereby obtaining a liquid containing the compounds having the lower boiling points than that of N-(2-hydroxyethyl)-2-pyrrolidone and N-(2-hydroxyethyl)-2 -pyrrolidone as a distillate liquid from the column top and a liquid containing compounds having boiling points higher than that of N-(2-hydroxyethyl)-2-pyrrolidone as a bottom liquid.
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- Process for production of cyclic N-vinyl carboxylic acid amide
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There is provided a process for producing a cyclic N-vinyl carboxylic acid amide stably in safety and low cost, using, as starting raw materials, a cyclic carboxylic acid ester and monoethanolamine both available inexpensively and easily. The process comprises subjecting a cyclic carboxylic acid ester and monoethanolamine to an intermolecular dehydration reaction (a first-step reaction) in a liquid phase to produce a cyclic N-(2-hydroxyethyl) carboxylic acid amide and then subjecting the cyclic N-(2-hydroxyethyl) carboxylic acid amide to an intramolecular dehydration reaction (a second-step reaction) in a gas phase in the presence of an oxide catalyst containing an alkali metal element and/or an alkaline earth metal element and silicon, to produce a cyclic N-vinyl carboxylic acid amide.
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- gem-cyclodialkylation A facile synthetic route to N-substituted heterocycles
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N-alkylated and N-arylated pyrroles, pyrrolidines, and piperidines are synthesized in high yield by the reaction between cyclic ethers and primary amines over a heterogeneous titania catalyst.
- Hargis, Duane C.,Shubkin, Ronald L.
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p. 2991 - 2994
(2007/10/02)
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- β-ENAMINOESTERS BICYCLIQUES : SYNTHESE ET REDUCTION STEREOSPECEFIQUES. ACCES A L'ISORETRONECANOL, LA TRACHELANTHAMIDINE, LA LUPININE ET L'EPILUPININE
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The functionalized N-alkyl-β-enaminoesters 11 are precursore of nitrogen-bridged bicyclic β-enaminoesters 7.The compounds 7 are prepared either by intramolecular alkylation of β-enaminoesters 11 or by termolysis of β-enaminoesters 6.A stereospecific reduction of 7 under thermal control leads to bicyclic β-aminoesters 13, 14, 15 or 16 which are good precursors of natural aminoalcohols like lupinine 4 or isoretronecanol 2.
- Celerier, J. P.,Haddad, M.,Saliou, C.,Lhommet, G.
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p. 6161 - 6170
(2007/10/02)
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- Photoreactions of Succinimides with an N-Acyl Group in the Side Chain. Synthesis and Stereochemistry of Tricyclic Pyrrolopyrazine Ring Systems
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Photocyclization of succinimides with an N-acyl group in the side chain gave bi- and tricyclic pyrrolopyrazines, some of which were converted to tricyclic amines by reduction.The stereochemistry of pyrrolopyrazine derivatives is discussed on the basis of the results of X-ray analysis and carbon-13 nuclear magnetic resonance spectroscopy.Keywords - succinimide; photocyclization; pyrrolo-pyrazine; hydrogen abstraction; X-ray analysis; 13C-NMR spectrum; tricyclic diamine
- Takechi, Haruko,Tateuchi, Sumiko,Machida, Minoru,Nishibata, Yoshihiko,Aoe, Keiichi,et al.
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p. 3142 - 3152
(2007/10/02)
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- Preparation of 2-pyrrolidones
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2-pyrrolidone and N-substituted 2-pyrrolidones such as N-methyl 2-pyrrolidone and N-(beta-hydroxyethyl)-2-pyrrolidone are prepared by the catalyzed reaction of methyl 4-oxobutyrate with ammonia or a primary amine and hydrogen.
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