- Axial ligation of iron(III) porphyrin with a series of aliphatic bases: Piperazine, piperidine and pyrrolidine
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The binding of a series of nitrogen donor ligands (Piperazine (Pipz), Piperidine (Pip) and Pyrro- lidine (Pyr)) to iron porphyrin, OEPFeClO 4, where OEP is octaethylporphyrin, has been characterized by electronic spectroscopy in CH2Cl2. In nonaqueous media, in the presence of a neutral ligand, the equilibria observed are: OEPFeClO 4 + 2L [OEPFeL2]+ (β2) where the product is an ion pair and in some cases: OEPFeClO4 + L OEPFeLClO4 (K1), where the product may either be the six-coordinate or the five-coordinate [OEPFeL]+ ion pair, that L denotes neutral N-donor ligands. This behavior for the nitrogen donor ligands (L = Pipz, Pip, Pyr) is confirmed by spectrophotometric titrations data and the bind- ing constants for the substitution reaction have been reported. Pleiades Publishing, Ltd., 2012.
- Saffari,Khorasani-Motlagh,Noroozifar
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Read Online
- Putrescine Transaminases for the Synthesis of Saturated Nitrogen Heterocycles from Polyamines
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Putrescine transaminase (pATA; EC 2.6.1.82) catalyzes the transfer of an amino group from terminal diamine donor molecules to keto acid acceptors by using pyridoxal-5′-phosphate as a cofactor. The ygjG genes from Escherichia coli K12, Bacillus megaterium, and Bacillus mycoides were successfully cloned and expressed in E. coli BL21(DE3) cells. The three putrescine transaminases were all shown to prefer diaminoalkanes as substrates and thereby generated cyclic imines from the ω-amino aldehyde intermediates. The addition of a mild chemical reducing agent rapidly reduced the imine intermediate in situ to furnish a range of N-heterocycle products. We applied pATA in a biomimetic synthesis of 2,3-dihydro-1H-indolizinium-containing targets, notably the bioactive alkaloid ficuseptine.
- Slabu, Iustina,Galman, James L.,Weise, Nicholas J.,Lloyd, Richard C.,Turner, Nicholas J.
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- Cobalt-bridged secondary building units in a titanium metal-organic framework catalyze cascade reduction of N-heteroarenes
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We report here a novel Ti3-BPDC metal-organic framework (MOF) constructed from biphenyl-4,4′-dicarboxylate (BPDC) linkers and Ti3(OH)2 secondary building units (SBUs) with permanent porosity and large 1D channels. Ti-OH groups from neighboring SBUs point toward each other with an O-O distance of 2 ?, and upon deprotonation, act as the first bidentate SBU-based ligands to support CoII-hydride species for effective cascade reduction of N-heteroarenes (such as pyridines and quinolines) via sequential dearomative hydroboration and hydrogenation, affording piperidine and 1,2,3,4-tetrahydroquinoline derivatives with excellent activity (turnover number ~ 1980) and chemoselectivity.
- Feng, Xuanyu,Song, Yang,Chen, Justin S.,Li, Zhe,Chen, Emily Y.,Kaufmann, Michael,Wang, Cheng,Lin, Wenbin
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- Chemical equilibrium constants for the formation of carbamates in (carbon dioxide + piperazine + water) from 1H-NMR-spectroscopy
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H-NMR spectroscopic investigations were performed on aqueous solutions of carbon dioxide and piperazine at temperatures ranging from 283 to 333K. These investigations were performed to determine quantitatively the speciation in these solutions. The results were used to determine the chemical equilibrium constants for the formation of piperazine carbamate, piperazine dicarbamate and protonated piperazine carbamate.
- Ermatchkov, Viktor,Perez-Salado Kamps, Alvaro,Maurer, Gerd
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Read Online
- Intermolecular condensation of ethylenediamine to 1,4-diazabicyclo[2,2,2]octane over TS-1 catalysts
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The intermolecular condensation of ethylenediamine (EDA) to 1,4-diazabicyclo[2.2.2]octane or triethylenediamine (TEDA) has been carried out over various titanosilicate catalysts. Superior to Ti-MWW, Ti-Beta, Ti-FER, and Ti-MOR, TS-1 showed higher EDA conversion and TEDA selectivity. The effects of reaction parameters, Ti content, and crystal size on the EDA condensation over TS-1 have been investigated. The mechanism for the TS-1-catalyzed condensation of EDA has also been considered. The acid sites, originated from the Si-OH groups adjacent to the "open" Ti sites, were assumed to contribute to the intermolecular condensation of EDA, whereas the Lewis acid sites directly related to Ti(IV) ions were not the true active sites. The primary intermolecular condensation of EDA to 1,4-diazacyclohexane or piperazine (PIP) took place mainly inside the micropores of the MFI structure, while the secondary condensation of PIP with EDA to TEDA was favored by the acid sites located near the pore entrance and on the outer surface of crystals.
- Wang, Yong,Liu, Yueming,Li, Xiaohong,Wu, Haihong,He, Mingyuan,Wu, Peng
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- Intermolecular condensation of ethylenediamine to 1,4-diazabicyclo(2,2,2)octane over H-ZSM-5 catalysts: Effects of Si/Al ratio and crystal size
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The intermolecular condensation of ethylenediamine (EDA) to 1,4-diazabicyclo [2.2.2] octane (DABCO) or triethylenediamine (TEDA) was conducted over H-ZSM-5 catalysts. The effects of reaction parameters, Al content and crystal size on the EDA condensation over H-ZSM-5 have been investigated. The H-ZSM-5 catalyst with a medium Al content (Si/Al = 110) and a small crystal size (ca. 100 nm) showed 99% EDA conversion and afforded a TEDA yield as high as 74% under optimized conditions. The mechanism for the H-ZSM-5-catalyzed condensation of EDA has also been considered. The framework Al-related Br?nsted acid sites were assumed to contribute to selective intermolecular condensation of EDA to TEDA. The primary intermolecular condensation of EDA to piperazine (PIP) took place mainly inside the micropores of the MFI structure, while the secondary condensation of PIP with EDA to TEDA was favored by the acid sites located near the pore entrance and on the external surfaces of crystals.
- Wang, Yong,Guo, Lifang,Ling, Yun,Liu, Yueming,Li, Xiaohong,Wu, Haihong,Wu, Peng
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- Gas-phase pyrolysis in organic synthesis: A route for synthesis of cyanamides
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(Chemical Equation Presented) Pyrolysis of 1,7-di-[(E)-1- morpholinomethylidene]- and 1,7-di-[(E)-1-piperidino-methylidene]-4,6,10,12- tetramethylamino-2,8-dioxo-1,7-diaza-3,5,9,11-cyclododecatetraene-3, 9-dicarbonitrile 6a,b afforded pyridone 10 in addition to cyanamides 11a,b. On the other hand, pyrolysis of 1-[E-(4-(E-3-cyano-4,6-dimethyl-2-oxopyridin-1(2H)- ylimino) methylpiperazin-1-yl] methylenamino-4,6-dimethyl-2-oxo-1,2- dihydropyridine-3-carbonitrile 8 gave 1-amino-4,6-dimethyl-2-oxo-1,2- dihydropyridine-3-carbonitrile 13 as well as piperazine. The mechanism of pyrolysis and the effect of stereochemistry of pyrolyzed substrates on the nature of the pyrolysates are discussed.
- Al-Awadi, Nouria A.,Abdelkhalik, Mervat Mohammed,El-Dusouqui, Osman M. E.,Elnagdia, Mohammad H.
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- Facile hydrogenation of N-heteroarenes by magnetic nanoparticle-supported sub-nanometric Rh catalysts in aqueous medium
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The hydrogenation of nitrogen-containing heterocyclic precursors in aqueous medium at low temperature without imposing molecular hydrogen pressure is quite challenging. Herein, we report the synthesis and performance of a novel catalyst capable of facile hydrogenation (employing tetrahydroxydiboron (THDB) as the reductant) of N-heteroarenes in water at 80 °C with good recyclability. Rhodium particles in the sub-nano range (3O4), using aqueous ammonia as a reducing agent at 50 °C. HRTEM and elemental mapping images reveal a homogeneous distribution of 3O4 nanoparticles having an average size within a narrow range of 7-9 nm. The superparamagnetic nature of the composite was confirmed by VSM analysis. The Rh@Fe3O4 catalyst was found to be highly efficient in the heterogeneous hydrogenation of nitrogen-containing heterocyclic compounds with quantitative conversion. It showed selectivity towards the hydrogenation of 1,2,3,4-tetrahydroquinoline (py-THQ) in water using THDB with a high TOF of 1632 h-1. These results are compared with the conversion and selectivity data obtained from reduction with molecular hydrogen gas pressure. The catalytic activity is extended to the successful hydrogenation of simple aromatics like benzene, toluene etc. Isotopic labelling studies were performed to determine the source of hydrogen in quinoline hydrogenation in the presence of THDB. It was found that it could be used for 16 consecutive cycles with gaseous hydrogen, without any undesired by-products; it also retained its original crystallinity.
- Nasiruzzaman Shaikh,Aziz, Md. Abdul,Kalanthoden, Abdul Nasar,Helal, Aasif,Hakeem, Abbas S.,Bououdina, Mohamed
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- Reactivity of borohydride incorporated in coordination polymers toward carbon dioxide
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Borohydride (BH4-)-containing coordination polymers converted CO2into HCO2-or [BH3(OCHO)]-, whose reaction routes were affected by the electronegativity of metal ions and the coo
- Kadota, Kentaro,Sivaniah, Easan,Horike, Satoshi
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Read Online
- Magnesium borohydride confined in a metal-organic framework: A preorganized system for facile arene hydroboration
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(Chemical Equation Presented) In close quarters: When confined in a metal-organic framework, magnesium borohydride reacts with arenes by a hydroboration pathway (see scheme), in contrast to its reactivity under analogous homogeneous solution-phase conditi
- Ingleson, Michael J.,Barrio, Jorge Perez,Bacsa, John,Steiner, Alexander,Darling, George R.,Jones, James T. A.,Khimyak, Yaroslav Z.,Rosseinsky, Matthew J.
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Read Online
- Palladium supported on magnesium hydroxyl fluoride: An effective acid catalyst for the hydrogenation of imines and N-heterocycles
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Palladium catalysts supported on acidic fluorinated magnesium hydroxide Pd/MgF2-x(OH)x were prepared through precipitation or impregnation methods. Applications to the hydrogenation of various aldimines and ketimines resulted in good catalytic activities at mild temperatures using one atmosphere of hydrogen. Quinolines, pyridines and other N-heterocycles were successfully hydrogenated at higher temperature and hydrogen pressure using low palladium loadings and without the use of any acid additive. Such reactivity trend confirmed the positive effect of the Br?nsted and Lewis acid sites from the fluorinated magnesium hydroxide support resulting in the effective pre-activation of N-heterocycle substrates and therefore in the good catalytic activity of the palladium nanoparticles during the hydrogenations. As demonstrated in the hydrogenation of imines, the catalyst was recycled up to 10 times without either loss of activity or palladium leaching. This journal is
- Agbossou-Niedercorn, Francine,Corre, Yann,Dongare, Mohan K.,Kemnitz, Erhard,Kokane, Reshma,Michon, Christophe,Umbarkar, Shubhangi B.
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supporting information
p. 19572 - 19583
(2021/11/04)
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- One-pot dual catalysis for the hydrogenation of heteroarenes and arenes
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A simple dinuclear monohydrido bridged ruthenium complex [{(η6-p-cymene)RuCl}2(μ-H-μ-Cl)] acts as an efficient and selective catalyst for the hydrogenation of various heteroarenes and arenes. The nature of the catalytically active species was investigated using a combination of techniques including in situ reaction monitoring, kinetic studies, quantitative poisoning experiments and electron microscopy, evidencing a dual reactivity. The results suggest that the hydrogenation of heteroarenes proceeds via molecular catalysis. In particular, monitoring the reaction progress by NMR spectroscopy indicates that [{(η6-p-cymene)RuCl}2(μ-H-μ-Cl)] is transformed into monomeric ruthenium intermediates, which upon subsequent activation of dihydrogen and hydride transfer accomplish the hydrogenation of heteroarenes under homogeneous conditions. In contrast, carbocyclic aryl motifs are hydrogenated via a heterogeneous pathway, by in situ generated ruthenium nanoparticles. Remarkably, these hydrogenation reactions can be performed using molecular hydrogen under solvent-free conditions or with 1,4-dioxane, and thus give access to a broad range of saturated heterocycles and carbocycles while generating no waste.
- Chatterjee, Basujit,Kalsi, Deepti,Kaithal, Akash,Bordet, Alexis,Leitner, Walter,Gunanathan, Chidambaram
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p. 5163 - 5170
(2020/09/07)
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- Catalytic reduction of aromatic ring in aqueous medium
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A method of reducing an aromatic ring under relatively mild condition using sub-nano particles of a transition metal supported on super paramagnetic iron oxide nanoparticles (SPIONs). The catalyst is efficient for catalyzing the reduction of both carbocyclic and heterocyclic compound. In compound comprising both carbocyclic and heterocyclic aromatic rings, the catalyst displays high regioselectivity for the heterocyclic ring.
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Page/Page column 10; 16
(2020/05/04)
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- Phyllosilicate-derived Nickel-cobalt Bimetallic Nanoparticles for the Catalytic Hydrogenation of Imines, Oximes and N-heteroarenes
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The development of cost-effective, noble metal-free catalytic systems for the hydrogenation of unsaturated aliphatic, aromatic, and heterocyclic compounds is fundamental for future valorization of general feedstock. With this aim, we report here the preparation of highly dispersed bimetallic Ni/Co nanoparticles (NPs), by a one-pot deposition-precipitation of Ni and Co phases onto mesoporous SBA-15 silica. By adjusting the chemical composition in the starting mixture, three supported catalysts with different Ni to Co weight ratios were obtained, which were further subjected to treatments under reducing conditions at high temperatures. Characterization of the resulting solids evidenced a homogenous distribution of Ni and Co elements forming the NPs, the best results being obtained for Ni/Co-2 : 2 samples, for which 50 wt.percent Ni–50 wt.percent Co NPs are found located on the surface of the residual phyllosilicate. Ni/Co-2 : 2, presenting the best performances for the hydrogenation of 2-methyl-quinoline, was further evaluated in the catalytic hydrogenation of selected imines, oximes and N-heteroarenes. Due to the high dispersion of bimetallic Ni?Co NPs, excellent properties (activity and selectivity) in the conversion of the selected substrates are reported.
- Ciotonea, Carmen,Hammi, Nisrine,Dhainaut, Jérémy,Marinova, Maya,Ungureanu, Adrian,El Kadib, Abdelkrim,Michon, Christophe,Royer, Sébastien
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p. 4652 - 4663
(2020/08/19)
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- METHOD FOR THE PRODUCTION OF ETHYLENEAMINES
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The present invention relates to a process for preparing alkanolamines and/or ethyleneamines in the liquid phase, by reacting ethylene glycol and/or monoethanolamine with ammonia in the presence of an amination catalyst comprising Co, Ru and Sn.
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Paragraph 0336-0352
(2020/05/14)
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- METHOD FOR PRODUCING ETHANOLAMINES AND/OR ETHYLENEAMINES
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The present invention relates to a process for preparing ethanolamines and/or ethyleneamines in the gas phase by reacting ethylene glycol with ammonia in the presence of an amination catalyst. It is a characteristic feature of the process that the amination catalyst is prepared by reducing a calcined catalyst precursor comprising an active composition, where the active composition comprises one or more active metals selected from the group consisting of the elements of groups 8, 9, 10 and 11 of the Periodic Table of the Elements and optionally one or more added catalyst elements selected group consisting of the metals and semimetals of groups 3 to 7 and 12 to 17, the element P and the rare earth elements. It is a further characteristic feature of the process that a catalyst precursor having low basicity is used, the low basicity being achieved in that a) the catalyst precursor is prepared by coprecipitation and the active composition additionally comprises one or more basic elements selected from the group consisting of the alkali metals and alkaline earth metals; orb) the catalyst precursor, as well as the active composition, additionally comprises a support material and is prepared by impregnating the support material or precipitative application onto the support material and the support material comprises one or more basic elements selected from the group consisting of the alkali metals, Be, Ca, Ba and Sr or one or more minerals selected from the group consisting of hydrotalcite, chrysotile and sepiolite; orc) the catalyst precursor, as well as the active composition, additionally comprises a support material and is prepared by impregnating the support material or precipitative application onto the support material and the active composition of the catalyst support comprises one or more basic elements selected from the group consisting of the alkali metals and the alkaline earth metals; ord) the catalyst precursor is calcined at temperatures of 600° C. or more; ore) the catalyst precursor is prepared by a combination of variants a) and d) or by a combination of variants b) and d) or by a combination of variants c) and d).
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Paragraph 0250-0257
(2020/04/09)
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- Hydrogenation of N-Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters
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A rhodium-catalyzed method for the hydrogenation of N-heteroarenes is described. A diverse array of unsubstituted N-heteroarenes including pyridine, pyrrole, and pyrazine, traditionally challenging substrates for hydrogenation, were successfully hydrogenated using the organometallic precatalysts, [(η5-C5Me5)Rh(N-C)H] (N-C = 2-phenylpyridinyl (ppy) or benzo[h]quinolinyl (bq)). In addition, the hydrogenation of polyaromatic N-heteroarenes exhibited uncommon chemoselectivity. Studies into catalyst activation revealed that photochemical or thermal activation of [(η5-C5Me5)Rh(bq)H] induced C(sp2)-H reductive elimination and generated the bimetallic complex, [(η5-C5Me5)Rh(μ2,η2-bq)Rh(η5-C5Me5)H]. In the presence of H2, both of the [(η5-C5Me5)Rh(N-C)H] precursors and [(η5-C5Me5)Rh(μ2,η2-bq)Rh(η5-C5Me5)H] converted to a pentametallic rhodium hydride cluster, [(η5-C5Me5)4Rh5H7], the structure of which was established by NMR spectroscopy, X-ray diffraction, and neutron diffraction. Kinetic studies on pyridine hydrogenation were conducted with each of the isolated rhodium complexes to identify catalytically relevant species. The data are most consistent with hydrogenation catalysis prompted by an unobserved multimetallic cluster with formation of [(η5-C5Me5)4Rh5H7] serving as a deactivation pathway.
- Kim, Sangmin,Loose, Florian,Bezdek, Máté J.,Wang, Xiaoping,Chirik, Paul J.
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p. 17900 - 17908
(2019/11/19)
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- Effects of Ni particle size on amination of monoethanolamine over Ni-Re/SiO2 catalysts
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Ni-Re/SiO2 catalysts with controllable Ni particle sizes (4.5–18.0 nm) were synthesized to investigate the effects of the particle size on the amination of monoethanolamine (MEA). The catalysts were characterized by various techniques and evaluated for the amination reaction in a trickle bed reactor at 170°C, 8.0 MPa, and 0.5 h?1 liquid hourly space velocity of MEA (LHSVMEA) in NH3/H2 atmosphere. The Ni-Re/SiO2 catalyst with the lowest Ni particle size (4.5 nm) exhibited the highest yield (66.4%) of the desired amines (ethylenediamine (EDA) and piperazine (PIP)). The results of the analysis show that the turnover frequency of MEA increased slightly (from 193 to 253 h?1) as the Ni particle sizes of the Ni-Re/SiO2 catalysts increased from 4.5 to 18.0 nm. Moreover, the product distribution could be adjusted by varying the Ni particle size. The ratio of primary to secondary amines increased from 1.0 to 2.0 upon increasing the Ni particle size from 4.5 to 18.0 nm. Further analyses reveal that the Ni particle size influenced the electronic properties of surface Ni, which in turn affected the adsorption of MEA and the reaction pathway of MEA amination. Compared to those of small Ni particles, large particles possessed a higher proportion of high-coordinated terrace Ni sites and a higher surface electron density, which favored the amination of MEA and NH3 to form EDA.
- Ma, Lei,Yan, Li,Lu, An-Hui,Ding, Yunjie
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p. 567 - 579
(2019/04/03)
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- Effect of Re promoter on the structure and catalytic performance of Ni-Re/Al2O3 catalysts for the reductive amination of monoethanolamine
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In this paper, Ni/Al2O3 catalysts (15 wt% Ni) with different Re loadings were prepared to investigate the effect of Re on the structure and catalytic performance of Ni-Re/Al2O3 catalysts for the reductive amination of monoethanolamine. Reaction results reveal that the conversion and ethylenediamine selectivity increase significantly with increasing Re loading up to 2 wt%. Ni-Re/Al2O3 catalysts show excellent stability during the reductive amination reaction. The characterization of XRD, DR UV-Vis spectroscopy, H2-TPR, and acidity-basicity measurements indicates that addition of Re improves the Ni dispersion, proportion of octahedral Ni2+ species, reducibility, and acid strength for Ni-Re/Al2O3 catalysts. The Ni15 and Ni15-Re2 catalysts were chosen for in-depth study. The results from SEM-BSE, TEM, and CO-TPD indicate that smaller Ni0 particle size and higher Ni0 surface area are obtained in the reduced Ni-Re/Al2O3 catalysts. Results from in situ XPS and STEM-EDX line scan suggest that Re species show a mixture of various valances and have a tendency to aggregate on the surface of Ni0 particles. During reaction, the Ni0 particles on the Al2O3 support are stabilized and the sintering process is effectively suppressed by the incorporation of Re. It could be concluded that sufficient Ni0 sites, the collaborative effect of Ni-Re, and brilliant stability contribute to the excellent catalytic performance of Ni-Re/Al2O3 catalysts for the reductive amination of monoethanolamine.
- Ma, Lei,Yan, Li,Lu, An-Hui,Ding, Yunjie
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p. 8152 - 8163
(2018/03/09)
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- Biocatalytic Access to Piperazines from Diamines and Dicarbonyls
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Given the widespread importance of piperazines as building blocks for the production of pharmaceuticals, an efficient and selective synthesis is highly desirable. Here we show the direct synthesis of piperazines from 1,2-dicarbonyl and 1,2-diamine substrates using the R-selective imine reductase from Myxococcus stipitatus as biocatalyst. Various N- and C-substituted piperazines with high activity and excellent enantioselectivity were obtained under mild reaction conditions reaching up to 8.1 g per liter.
- Borlinghaus, Niels,Gergel, Sebastian,Nestl, Bettina M.
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p. 3727 - 3732
(2018/04/14)
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- VICINAL PRIMARY DIAMINES ASSOCIATED WITH METAL AND/OR FREE RADICAL CHELATION MOTIFS, AND ACTIVE AGAINST CARBONYL AND OXIDATIVE STRESS, AND USE THEREOF
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The invention relates to compounds of Formula I: or the salts thereof, as well as the use thereof in the pharmaceutical, cosmetic or agrofood industry.
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- Preparation method for synthesizing 2-azabicyclo[4.1.0]heptane-1-carboxylic acid hydrochloride
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The invention discloses a preparation method for synthesizing 2-azabicyclo[4.1.0]heptane-1-carboxylic acid hydrochloride. The preparation method comprises the following steps: firstly obtaining a compound III through electrophilic substitution by taking N-substituted-1,2,3,6-tetrahydropyridine (compound II) as a raw material; carrying out cycloaddition reaction of the compound III and a sulfur ylide reagent to obtain a compound IV; finally carrying out deamination protecting group and ester hydrolysis to obtain the 2-azabicyclo[4.1.0]heptane-1-carboxylic acid hydrochloride (compound I).
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Paragraph 0021; 0022; 0026-0028
(2018/07/06)
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- An Efficient Ruthenium Catalyst Bearing Tetradentate Ligand for Hydrogenations of Carbon Dioxide
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A ruthenium complex with a tetradentate bipyridine ligand was proved to be a highly efficient catalyst for the conversions of CO2. Turnover numbers up to 300 000, 9800, and 2100 were achieved for the hydrogenations of CO2 to formamides, formamides to methanol and amines, and the direct hydrogenation of CO2 to methanol, respectively.
- Zhang, Feng-Hua,Liu, Chong,Li, Wei,Tian, Gui-Long,Xie, Jian-Hua,Zhou, Qi-Lin
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supporting information
p. 1000 - 1002
(2018/09/21)
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- METHOD FOR PRODUCING PIPERAZINE AND TRIETHYLENEDIAMINE
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PROBLEM TO BE SOLVED: To provide a method for producing piperazine and triethylenediamine in combination, making it possible to provide piperazine with high selectivity and high yields. SOLUTION: Under a basic condition with pH of 8 or more, pentasil type zeolite subjected to ion exchange with alkali metal salt, and one or more amine react with each other, under a condition of 50 wt.% or more substrate concentration. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0055; 0056; 0057; 0058
(2017/07/19)
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- METHOD FOR PRODUCING BICYCLIC AMINE COMPOUND
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PROBLEM TO BE SOLVED: To provide a stable production method for a bicyclic amine compound that inhibits the generation of by-products in the production of a bicyclic amine. SOLUTION: The present invention provides a method for producing a bicyclic amine compound which employs a catalyst comprising an inorganic support and an alkali metal phosphate, and further comprising alkaline earth metal hydroxide and/or hydroxyapatite in an amount of 1.5 wt.% or more and less than 15 wt.% relative to the inorganic support. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPO&INPIT
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Paragraph 0047; 0054
(2017/11/15)
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- MANUFACTURING METHOD OF CYCLIC ETHYLENE AMINES
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PROBLEM TO BE SOLVED: To provide a method for manufacturing cyclic ethylene amines at good selectivity. SOLUTION: By using a solid catalyst containing palladium or palladium and gold with percentage of palladium of 50 to 100 mol%, ethylene diamine is deamination condensed. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0037
(2017/08/15)
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- Direct Catalytic Hydrogenation of Simple Amides: A Highly Efficient Approach from Amides to Amines and Alcohols
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A highly chemoselective and reactive direct catalytic reduction of various amides to amines and alcohols was developed by using a tetradentate ruthenium complex. The catalytic system showed excellent activity (turnover numbers up to 19 600) and great functional group tolerance under mild reaction conditions, compared to several bidentate and tridentate ruthenium-catalyzed systems.
- Shi, Liyang,Tan, Xuefeng,Long, Jiao,Xiong, Xiong,Yang, Song,Xue, Peng,Lv, Hui,Zhang, Xumu
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supporting information
p. 546 - 548
(2017/01/18)
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- MANUFACTURING METHOD OF PIPERAZINE AND TRIETHYLENE DIAMINE
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PROBLEM TO BE SOLVED: To provide a manufacturing method of piperazine and triethylene diamine, in which piperazine is obtained more selectively and at a higher yield. SOLUTION: Ethylene diamines and steam-treated ZSM-5 type zeolite are brought into contact to make react. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0047; 0048; 0049
(2017/10/07)
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- METHOD FOR PRODUCING HYDROXYALKYLTRIETHYLENEDIAMINE HAVING IMPROVED HUE
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PROBLEM TO BE SOLVED: To provide a production method which makes it possible to improve the hue of a cyclic alkanolamine such as a hydroxyalkyltriethylenediamine and efficiently obtain a high-purity bicyclic compound. SOLUTION: A method for producing the bicyclic diamine includes bringing a crude hydroxyalkyltriethylenediamine reaction liquid comprising a hydroxyalkyltriethylenediamine represented by formula (1) into contact with oxygen at 110-170°C and then distilling and purifying it (R1-R10 independently represent H, a C1-4 alkyl group or a C1-4 hydroxyalkyl group). SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0048
(2017/12/12)
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- Preparation method of ethylene carbonate (propylene carbonate)
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The invention discloses a preparation method of ethylene carbonate (propylene carbonate), and belongs to a novel method for synthesizing cyclic allyl carbonate. According to the method, alkyl polyamine-carbamate prepared in a lab and ethylene oxide (propylene oxide) carry out reactions in the presence of a catalyst to prepare an organic chemical product namely ethylene carbonate (propylene carbonate) with a high additional valve. Moreover, an absorption solvent (alkyl polyamine) can be obtained. The catalyst has a high activity and selectivity, so the yield of ethylene oxide (propylene oxide) is high and can reach more than 90%. The yield of byproduct (alkyl polyamine) can reach more than 95%. The byproduct (alkyl polyamine) can be recovered to cyclically absorb CO2. The fixed C1 resources are converted into an importation chemical product by the preparation method, the greenhouse effect is effectively relieved; at the same time, the problem of large energy consumption for desorption of CO2 in an organic amine solution is solved, and the recovered byproduct can be used to absorb CO2 circularly.
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Paragraph 0026; 0027
(2017/08/27)
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- Tailor-Made Ruthenium-Triphos Catalysts for the Selective Homogeneous Hydrogenation of Lactams
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The development of a tailored tridentate ligand enabled the synthesis of a molecular ruthenium-triphos catalyst, eliminating dimerization as the major deactivation pathway. The novel catalyst design showed strongly increased performance and facilitated the hydrogenation of highly challenging lactam substrates with unprecedented activity and selectivity. Bulky catalysts: A tailored sterically demanding tridentate ligand enabled the synthesis of a novel molecular ruthenium-triphos catalyst, which eliminates dimerization as the major deactivation pathway. The novel catalyst design showed increased performance and facilitated the hydrogenation of highly challenging lactam substrates with unprecedented activity and selectivity.
- Meuresch, Markus,Westhues, Stefan,Leitner, Walter,Klankermayer, Jürgen
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supporting information
p. 1392 - 1395
(2016/02/14)
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- LJ the reaction application of Mitsunobu reaction (by machine translation)
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The invention relates to application of a novel heterogeneous reaction in an LJ molecule in a mitsunobu reaction. Phosphorus pentahalide substitutes for a classic mitsunobu reaction coupling reagent, so that the yield in most of the mitsunobu reactions is improved, the cost is reduced, and the standard of clean production process is reached.
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Paragraph 0044; 0045
(2016/12/01)
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- mellow amination by homogeneous catalysis of the method for the production of primary amines
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The invention relates to a method for producing primary amines by means of the alcohol amination of alcohols with ammonia, with water being eliminated. The method comprises the steps of: (a) a homogenously-catalysed reaction of a reaction mixture which contains at least one alcohol, ammonia, at least one non-polar solvent, and at least one catalyst containing at least one element selected from groups 8, 9 and 10 of the periodic table in the liquid phase, a product mixture (P) thus being obtained; (b) separating the phases of product mixture (P) which was obtained in step (a), if necessary after a reduction in temperature, a reduction in pressure and/or the addition of at least one polar solvent with a miscibility gap in relation to the non-polar solvent, and thus obtaining at least one polar product phase (A) and at least one non-polar phase (B) containing at least one portion of the catalyst that was introduced, with said non-polar phase (B) being separated off, (c) returning at least one portion of the non-polar phase (B) into the reaction in step (a), and (d) separating the amination product from the polar product phase (A). The non-polar solvent introduced in (a) and the catalyst introduced in step (a) are selected such that the catalyst in the non-polar phase (B) becomes enriched.
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Paragraph 0265; 0270
(2016/10/09)
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- METHOD FOR PRODUCING ALKANOL AMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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PROBLEM TO BE SOLVED: To provide a method for producing alkanol amines by alcohol amination of diols using ammonia under elimination of water. SOLUTION: The invention relates to a method for producing alkanol amines which comprise a primary amino group (-NH2) and a hydroxyl group (-OH), by alcohol amination of diols comprising two hydroxyl groups (-OH) using ammonia under elimination of water. The reaction is homogeneously catalyzed in the presence of at least one complex catalyst which contains at least one element selected from groups 8, 9 and 10 of the periodic table and at least one donor ligand. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0088; 0101
(2016/10/27)
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- Method for synthesizing N-hydroxyethylpiperazine and piperazine by means of co-production
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The invention discloses a method for synthesizing N-hydroxyethylpiperazine and piperazine by means of co-production. With diethanolamine and ethanol amine as raw materials, in a solvent and in a fixed bed reactor with a hydrogen service atmosphere, the raw materials are catalyzed to perform cyclization by a catalyst to obtain N-hydroxyethylpiperazine and piperazine. The prepared catalyst has the advantages of good selectivity and long service life. The synthetic method has the advantages of small reaction pressure of the whole process and high safety, can be used for continuous synthesis, and can co-produce piperazine while preparing N-hydroxyethylpiperazine. The prepared products have the quality conforming to the industrial product first-class standards, and the contents of N-hydroxyethylpiperazine and piperazine are not less than 99.5%; the purities of N-hydroxyethylpiperazine and piperazine are 99.0% or more. The method is simple in process and suitable for industrialized continuous production.
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Paragraph 0021; 0024; 0025
(2017/01/12)
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- Synthesis of piperazine and method of triethylene diamine
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The invention discloses a method for synthesizing piperazidine and triethylenediamine. The method aims to solve the problems of low efficiency and need for expensive high-vacuum rectifiers in the process of converting ethanolamine into piperazidine and triethylenediamine in the prior art. The method comprises the following steps: mixing and gasifying ethanolamine and ammonia, and carrying out amination reaction in a fixed-bed reactor R by using a catalyst A (using a mesoporous-microporous composite molecular sieve MOR/MCM-41 as a support) and a catalyst B (using a mesoporous-microporous composite molecular sieve ZSM-5 MCM-41 as a support); carrying out rectification separation on the reactor outlet product in a rectification tower T1 to distil off unconverted ammonia, piperazidine and triethylenediamine from the tower top, and circulating unreacted ethanolamine and amination byproduct obtained from the tower bottom to the inlet of the fixed-bed reactor R to continue reaction; and sending the top fraction of the rectification tower T1 into a rectification tower T2, and separating to obtain the piperazidine and triethylenediamine. The method is used for synthesizing piperazidine and triethylenediamine.
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Paragraph 0030-0032
(2017/03/08)
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- A catalytic hydrogenation preparing piperazine or alkyl piperazine method
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The invention discloses a method for preparing piperazidine or alkyl piperazidine by catalytic hydrogenation, which comprises the following steps: carrying out catalytic hydrogenation reaction on raw materials dihydroxy ethyl piperazidine or/and hydroxyethyl piperazidine under the action of a catalyst, and carrying out after-treatment to obtain the piperazidine or/and alkyl piperazidine, wherein the active component in the catalyst is one or more of Cu, Ni and Co. The dihydroxy ethyl piperazidine or hydroxyethyl piperazidine is used as the raw material to prepare the piperazidine or alkyl piperazidine by catalytic hydrogenation, thereby providing a brand-new synthesis technique of piperazidine or alkyl piperazidine. Meanwhile, the method can be utilized to implement the recovery of the waste liquor or byproduct containing dihydroxy ethyl piperazidine or hydroxyethyl piperazidine. Besides, the existing method can be utilized to separate the alkyl piperazidine in the product, thereby further enhancing the value of the product and lowering the preparation cost.
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Paragraph 0036-0037
(2017/04/26)
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- METHOD FOR PRODUCING PIPERAZINE AND TRIETHYLENEDIAMINE
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PROBLEM TO BE SOLVED: To provide a joint production method of piperazine and triethylenediamine capable of obtaining piperazine more selectively and also at a high yield. SOLUTION: Diethylenetriamine and at least one kind of amine selected from the group consisting of ethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and their alkylated bodies are mixed, the mixture is contacted with ZSM-5 type zeolite in which the ion exchange rate in the alkali metal salt is 50% or higher, and reaction is caused. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0049; 0054; 0058; 0059
(2017/05/26)
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- METHOD FOR PRODUCING PIPERAZINE AND TRIETHYLENE DIAMINE
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PROBLEM TO BE SOLVED: To provide a method for producing piperazine and triethylene diamine that allows piperazine to be obtained selectively with high yields. SOLUTION: At least one amine selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and their alkylate is brought into contact with zeolite having BEA structure for a reaction. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0046-0063
(2018/10/17)
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- Synthesis of common-sized heterocyclic compounds by intramolecular cyclization over halide cluster catalysts
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Five- to seven-membered common-sized heterocyclic compounds containing an oxygen, sulfur, or nitrogen were synthesized by the intramolecular condensation of α,ω-hydroxy, mercapto, or amino alkanes, respectively, over halide cluster complexes as a thermally stable molecular solid weak acid catalyst in the gas phase at temperatures ≥150 °C. From ω- mercapto and ω-amino alcohols, cyclic sulfides and amines were obtained, respectively. These unimolecular reactions are thermodynamically and kinetically favored.
- Nagashima, Sayoko,Sasaki, Tomoaki,Kamiguchi, Satoshi,Chihara, Teiji
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supporting information
p. 764 - 766
(2015/06/22)
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- Production of phenylpiperazines
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PROBLEM TO BE SOLVED: To provide a method for selectively producing piperazines with high yield.SOLUTION: An N-(2-hydroxyalkyl)vicinal diamines are subjected to dehydrative cylization reaction in the presence of a Raney metal catalyst and a dehydrating agent.
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Paragraph 0055
(2017/06/29)
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- METHOD OF PRODUCING PIPERAZINE
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PROBLEM TO BE SOLVED: To provide a method of producing piperazine with various industrial uses at good yields. SOLUTION: In a method of producing piperazine from 1,2-dichloroethane and ethylenediamine, a reaction is made to occur in the absence of water. COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0028-0035
(2018/10/04)
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- Production of piperazinecarboxylic
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Method for preparing piperazine of formula I by reacting diethanolamine (DEOA) of formula II with ammonia in the presence of hydrogen and a metal-containing supported catalyst. Before the catalyst is reduced with hydrogen, the catalytically active mass of the catalyst contains oxygen-containing aluminum, copper, nickel and cobalt compounds and 0.2 to 5.0 wt.% oxygen-containing tin compounds calculated as SnO, and the reaction is carried out in the liquid phase at an absolute pressure ranging from 160 to 220 bar, at a temperature ranging from 180 to 220°C, ammonia is used at a molar ratio ranging from 5 to 25 in relation to the DEOA used in the process, the method being carried out in the presence of 0.2 to 9.0 wt.% hydrogen relative to the total amount of DEOA and ammonia used in the process.
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Paragraph 0096-0098
(2018/12/12)
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- Production of phenylpiperazines
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PROBLEM TO BE SOLVED: To provide a method for selectively producing piperazines with high yield.SOLUTION: Vicinal diamines and vicinal diols are subject to dehydrative cylization reaction in the presence of a Raney metal catalyst and a dehydration agent.
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Paragraph 0064
(2017/06/24)
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- · Uniform catalyst by using alcohol aminosilicone di-, tri-and a method of manufacturing a polyphenylenepolyamine
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The invention relates to a method for producing primary amines, which contain at least one functional group of the formula (-CH2-NH2) and at least one further primary amino group, by the alcohol amination of reactants, which contain at least one functional group of the formula (-CH2-OH) and at least one further functional group (-X), wherein (-X) is selected from hydroxyl groups and primary amino groups, using ammonia with removal of water, wherein the reaction is carried out in a homogeneously catalyzed manner in the presence of at least one complex catalyst containing at least one element selected from groups 8, 9 and 10 of the periodic table and at least one donor ligand.
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Paragraph 0099; 0111
(2016/10/09)
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- Amination process for manufacturing amines using catalyst
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Disclosed is a process for the preparation of an amine (particularly diamines and polyamines) by reacting an alkanolamine or a polyol with ammonia in the presence of a catalyst composed of two active metals from the group of transition metals, namely nickel and chromium supported on a microporous refractory substrate, in a hydrogenated, trickle bed reactor.
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Paragraph 0044-0049
(2014/08/07)
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- METHOD FOR PREPARING N-(2-AMINOETHYL)ETHANE-1,2-DIAMINE
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The invention discloses a method for preparation of N-(2-aminoethyl)ethane-1,2-diamine (DETA), which comprises steps of preparing a mixture by dissolving iminodiacetonitrile (IDAN) in an organic solvent and adding an anion exchange resin of OH type and a stabilizing agent for IDAN, subjecting the mixture to hydrogenation in the presence of a hydrogenation catalyst and a first aid at a temperature of 50-150°C, preferably 70-90°C, and under a pressure of 5-25 Mpa, preferably 9-14 Mpa to obtain DETA. In comparison with the known methods, the process of the present invention may inhibit the decomposition of IDAN, eliminate the poisoning factors for the catalyst, so as to prolong the service life of the catalyst, improve the efficiency of the process and obtain the product with high purity.
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Paragraph 0041
(2014/01/23)
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- Process for Preparing Piperazine
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Process for preparing piperazine of the formula I by reacting diethanolamine (DEOA) of the formula II with ammonia in the presence of hydrogen and a supported, metal-containing catalyst has been found, wherein the catalytically active mass of the catalyst, prior to its reduction with hydrogen, comprises oxygen-containing compounds of aluminum, copper, nickel and cobalt and in the range from 0.2 to 5.0% by weight of oxygen-containing compounds of tin, calculated as SnO, and the reaction is carried out in the liquid phase at an absolute pressure in the range from 160 to 220 bar, a temperature in the range from 180 to 220° C., using ammonia in a molar ratio to DEOA used of from 5 to 25 and in the presence of 0.2 to 9.0% by weight of hydrogen, based on the total amount of DEOA used and ammonia.
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Paragraph 0106; 0107
(2014/01/08)
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- Process for Preparing Piperazine
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Process for preparing piperazine of the formula I by reacting diethanolamine (DEOA) of the formula II with ammonia (NH3) in the presence of hydrogen and a supported, metal-containing catalyst, wherein the catalytically active mass of the catalyst, prior to its reduction with hydrogen, comprises 20 to 85% by weight of oxygen-containing compounds of zirconium, calculated as ZrO2, 1 to 30% by weight of oxygen-containing compounds of copper, calculated as CuO, 14 to 70% by weight of oxygen-containing compounds of nickel, calculated as NiO, and 0 to 5% by weight of oxygen-containing compounds of molybdenum, calculated as MoO3, and the reaction is carried out in the liquid phase at an absolute pressure in the range from 160 to 220 bar, a temperature in the range from 180 to 220° C., using ammonia in a molar ratio to DEOA used of from 5 to 20 and in the presence of 0.2 to 9.0% by weight of hydrogen, based on the total amount of DEOA used and ammonia.
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Paragraph 0100-0109
(2014/01/08)
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- METHOD FOR PRODUCING ETHYLENEAMINES
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The present invention relates to method for producing ethyleneamines that includes: reacting ethylenedichloride with ammonia water under conditions optimizing the molar ratio of ethylenedichloride to ammonia in a defined range to produce amine compounds, ammonium chloride, and water; and isolating the amine compounds, ammonium chloride, and water, respectively. The present invention provides a continuous process for producing ethyleneamines using ethylenedichloride and ammonia by efficiently controlling the composition of the ethyleneamine product in accordance with the supply and demand of ethyleneamines to optimize the distribution of ethyleneamines.
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Page/Page column 16
(2013/12/03)
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- REDUCTIVE AMINATION OF DIETHANOLAMINE AND RESULTING PRODUCT MIXTURE
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The invention provides a method for the reductive amination of diethanolamine to form a product composition that includes piperazine (PIP) and aminoethylethanolamine (AEEA). A catalyst with a transitional alumina/second metal oxide support and a mixture of catalytic metals is used for the reaction which results in low levels of non-PIP and non-AEEA side products.
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Page/Page column 25; 26
(2013/07/05)
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- Cyclization of monoethanolamine to aziridine over Cs2O-P 2O5/SiO2
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Several commercially available supports were examined for cyclization of monoethanolamine to aziridine, and SiO2 was found to yield the best results. The obtained results indicated that selectivity of aziridine was mainly influenced by support. The catalysts were characterized by NH3-TPD and XRD. It was found that SiO2 with lower acidity could inhibit the intermolecular condensations, and thus favored the formation of aziridine. The Cs4P2O7 phase was confirmed as the active site in the supported cesium phosphate catalyst. The reaction parameters were also optimized and a yield of 52% aziridine was obtained over 200 h. Thus, a continuous process for the cyclization of monoethanolamine to aziridine has been established. Springer Science+Business Media B.V. 2012.
- Kong, Xiangjin,Wang, Guangyuan,Li, Lei,Sun, Meng,Du, Xiaobao,Chen, Ligong
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p. 1743 - 1750
(2013/02/22)
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- REACTION OF GLYCOLALDEHYDE WITH AN AMINATING AGENT
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The present invention relates to a process for reacting glycolaldehyde with an aminating agent in the presence of hydrogen and of a catalyst, the catalyst being activated by reducing a catalyst precursor or by reducing a passivated catalyst, which comprises effecting the reaction in the presence of a solvent and contacting the glycolaldehyde with the activated catalyst.
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Page/Page column 7-9
(2012/11/07)
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- PROCESS FOR THE PREPARATION OF PRIMARY AMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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Preparing a primary amine by alcohol amination of alcohol with ammonia and elimination of water includes reacting, in a homogeneously catalyzed reaction, a mixture of alcohol, ammonia, nonpolar solvent, and catalyst, in a liquid phase, to obtain a product mixture. The process then includes phase separating the product mixture into a polar product phase and a nonpolar product phase, and separating off the nonpolar product phase. At least some of the nonpolar phase returns to the homogenously catalyzed reaction. The process further includes separating off amination product from the polar product phase. At least some of the catalyst is in the nonpolar phase, and the catalyst accumulates in the nonpolar phase.
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Page/Page column 14-15; 18
(2012/09/22)
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- PROCESS FOR PREPARING DI-, TRI- AND POLYAMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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Process for preparing primary amines which have at least one functional group of the formula (—CH2—NH2) and at least one further primary amino group by alcohol amination of starting materials having at least one functional group of the formula (—CH2—OH) and at least one further functional group (—X), where (—X) is selected from among hydroxyl groups and primary amino groups, by means of ammonia with elimination of water, wherein the reaction is carried out homogeneously catalyzed in the presence of at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one donor ligand.
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Page/Page column 12; 17
(2012/09/22)
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