1116-76-3Relevant articles and documents
A multifaceted role of a mobile bismuth promoter in alcohol amination over cobalt catalysts
Bahri, Mounib,Ersen, Ovidiu,Khodakov, Andrei Y.,Kusema, Bright T.,Niu, Feng,Ordomsky, Vitaly V.,Yan, Zhen
, p. 4270 - 4278 (2020)
Promotion with small amounts of different elements is an efficient strategy for the enhancement of the performance of many heterogeneous catalysts. Supported cobalt catalysts exhibit significant activity in the synthesis of primary amines via alcohol amination with ammonia, which is an economically efficient and environmentally friendly process. Insufficient selectivity to primary amines, low activity and fast cobalt catalyst deactivation remain serious issues restricting the application of alcohol amination in the industry. In this work, we have discovered the multifaceted role of the bismuth promoter, which is highly mobile under reaction conditions, in 1-octanol amination over supported cobalt catalysts. First, the overall reaction rate was enhanced more than twice on promotion with bismuth. Second, the selectivity to primary amines increased 6 times in the presence of Bi at high alcohol conversion. Finally, the bismuth promotion resulted in extremely high stability of the cobalt catalyst. Characterization by XRD, temperature programmed reduction, STEM, CO chemisorption, BET, TGA and FTIR has showed that the enhancement of the catalytic performance on promotion with bismuth is due to better cobalt reducibility, easy removal of strongly adsorbed intermediates and products by the mobile promoter and suppression of amine coupling reactions resulting in secondary and tertiary amines.
Ru(II)-triphos catalyzed amination of alcohols with ammonia via ionic species
Derrah, Eric J.,Hanauer, Matthias,Plessow, Philipp N.,Schelwies, Mathias,Da Silva, Marion K.,Schaub, Thomas
, p. 1872 - 1881 (2015)
An active and selective system for the amination of primary alcohols to primary amines with ammonia based on ruthenium and triphos as the tridentate phosphine ligand was developed. On the basis of detailed mechanistic studies, we propose that the active catalyst is, unlike the previously reported systems on this reaction, a cationic ruthenium complex. The experimental findings are supported by detailed density functional theory (DFT) calculations on the catalytic cycle. Because of the cationic nature of the active catalyst, strong anion and solvent effects were observed in the catalytic amination reaction when using the ruthenium triphos complexes. Therefore, a higher activity could be achieved when the nonpolar solvent toluene is used in this amination instead of tetrahydrofuran. Our findings can help to develop and optimize the system systematically for an application to relevant target molecules.
Catalytic amination of octanol for synthesis of trioctylamine and catalyst characterization
Li, Yunling,Li, Qiuxiao,Zhi, Lifei,Zhang, Minghui
, p. 1635 - 1642 (2011)
Synthesis of trioctylamine by the amination of octanol and ammonia under atmospheric pressure over an excellent Ni-Cu catalyst supported on diatomite is studied in this article. The key factor for the synthesis is the preparation of catalyst with a high activity and selectivity. The activity and selectivity can be adjusted by varying the Ni to Cu ratios. The optimum molar ratio of Ni to Cu was 1.25:1. For the catalyst with a Ni/Cu ratio of 1.25:1, the conversion of octanol and the selectivity of trioctylamine reached 100 and 97.3%, respectively, at 5 h. The reaction of dioctylamine with octanol was the rate-determining step for the formation of trioctylamine. The Physical properties of catalysts, such as particle size, Brunauer-Emmett-Teller (BET) surface area, valence state of catalyst elements, morphology and reduction properties of catalysts were investigated by using X-ray diffraction, nitrogen adsorption-desorption isotherms (BET), X-ray photoelectron spectroscopy, Transmission electron microscopy, and temperature programmed reduction, respectively. The reaction scheme of catalytic amination of octanol with ammonia was discussed. Graphical Abstract: [Figure not available: see fulltext.][Figure not available: see fulltext.]
Rapid Multialkylation of Aqueous Ammonia with Alcohols by Heterogeneous Iridium Catalyst under Simple Conditions
Yu, Han,Ma, Lin,Wada, Kenji,Kurihara, Ryohsuke,Feng, Qi,Uemura, Shinobu,Isoda, Kyosuke
, p. 3588 - 3593 (2021)
This paper reports the synthesis of tertiary and secondary amines from aqueous ammonia and benzylic alcohols by titania-supported iridium catalyst. It is a successful example of heterogeneous systems at moderate temperature without either additional solvent or high pressure. The catalytic system showed good tolerance to the atmosphere condition and performed rapidly to give tribenzylamine a yield of over 99 % within 6 hours in argon. The crystal structure of titania supports for iridium catalysts strongly affected their activity. The catalysis smoothly proceeded on larger scales. The catalyst could be easily reused and run at least for 5 cycles without significant loss of activity. The highly-dispersed iridium species of less than 2 nm in diameter would be responsible for the excellent catalytic activity. This catalyst is well applicable in multialkylation of aqueous ammonia with various primary and secondary benzylic alcohols.
Highly Selective Hydrogenative Conversion of Nitriles into Tertiary, Secondary, and Primary Amines under Flow Reaction Conditions
Furugen, Chikara,Ito, Naoya,Jiang, Jing,Park, Kwihwan,Sajiki, Hironao,Shimizu, Eisho,Yamada, Tsuyoshi
, (2021/12/13)
Flow reaction methods have been developed to selectively synthesize tertiary, secondary, and primary amines depending on heterogeneous platinum-group metal species under catalytic hydrogenation conditions using nitriles as starting materials. A 10 % Pd/C-packed catalyst cartridge affords symmetrically substituted tertiary amines in good to excellent yields. A 10 % Rh/C-packed catalyst cartridge enables the divergent synthesis of secondary and primary amines, with either cyclohexane or acetic acid as a solvent, respectively. Reaction parameters, such as the metal catalyst, solvent, and reaction temperature, and continuous-flow conditions, such as flow direction and second support of the catalyst in a catalyst cartridge, are quite important for controlling the reaction between the hydrogenation of nitriles and nucleophilic attack of in situ-generated amines to imine intermediates. A wide variety of aliphatic and aromatic nitriles could be highly selectively transformed into the corresponding tertiary, secondary, and primary amines by simply changing the metal species of the catalyst or flow parameters. Furthermore, the selective continuous-flow methodologies are applied over at least 72 h to afford three different types of amines in 80–99 % yield without decrease in catalytic activities.
Nanoceria-promoted low Pd-Ni catalyst for the synthesis of secondary amines from aliphatic alcohols and ammonia
Fang,Yan,Vits,Southward,Pera-Titus
, p. 1215 - 1230 (2019/03/12)
This paper describes the preparation of a series of bimetallic Pd-Ni catalysts supported over nanoceria with very low Ni and Pd loading (2-TPR, H2-TPD, STEM-EDS-SDD and XPS. The sequence of impregnation of both metals and the Pd loading affected to an important extent the catalytic activity by conditioning the crystallite size and the Pd and Ni speciation, as well as the reducibility and reversible H2 storage properties. By optimizing the preparation protocols, a 0.5wt% Pd-0.5wt% Ni-Pd/CeO2 formulation prepared by sequential impregnation of the nickel and palladium precursors afforded 80% yield of dioctylamine at almost full conversion [TON = 1160 mmol per mmol (Ni + Pd)surface] in the direct amination reaction of 1-octanol with ammonia at 180 °C for 2 h. Metal leaching during the reaction could be completely avoided. The high catalytic performance of Pd-Ni induced by nanoceria places this catalyst among the best ever reported catalysts for the synthesis of secondary amines.
Conversion of Primary Amines to Symmetrical Secondary and Tertiary Amines using a Co-Rh Heterobimetallic Nanocatalyst
Chung, Hyunho,Han, Seulgi,Chung, Young Keun,Park, Ji Hoon
supporting information, p. 1267 - 1272 (2018/02/12)
Symmetrical tertiary amines have been efficiently realized from amine and secondary amines via deaminated homocoupling with heterogeneous bimetallic Co2Rh2/C as catalyst (molar ratio Co:Rh=2:2). Unsymmetric secondary anilines were produced from the reaction of anilines with symmetric tertiary amines. The Co2Rh2/C catalyst exhibited very high catalytic activity towards a wide range of amines and could be conveniently recycled ten times without considerable leaching. (Figure presented.).
Direct Synthesis of Lactams from Keto Acids, Nitriles, and H2 by Heterogeneous Pt Catalysts
Siddiki,Touchy, Abeda S.,Bhosale, Ashvini,Toyao, Takashi,Mahara, Yuji,Ohyama, Junya,Satsuma, Atsushi,Shimizu, Ken-Ichi
, p. 789 - 795 (2018/02/27)
We report herein the first general catalytic system for the direct synthesis of N-substituted γ- and δ-lactams by reductive amination/cyclization of keto acids (including levulinic acid) with nitriles and H2 under mild conditions (7 bar H2, 110 °C, solvent free). The most effective catalyst, Pt and MoOx co-loaded TiO2 (Pt-MoOx/TiO2), shows a wide substrate scope, high turnover number (TON), and good reusability.
Colloid and Nanosized Catalysts in Organic Synthesis: XVIII.1 Disproportionation and Cross-Coupling of Amines During Catalysis with Immobilized Nickel Nanoparticles
Popov, Yu. V.,Mokhov,Latyshova,Nebykov,Panov,Davydova
, p. 2757 - 2761 (2018/02/21)
It has been stated that immobilized nickel nanoparticles catalyze disproportionation and cross-coupling of amines. The influence of the support on the catalysis of these properties in the in plug-flow reactor has been studied. The use of active carbon as the support has been found advantageous for the cross-coupling of amines, whereas alumina was a better support for the disproportionation reaction.
Ruthenium-Catalyzed Deaminative Hydrogenation of Aliphatic and Aromatic Nitriles to Primary Alcohols
Molnár, István Gábor,Calleja, Pilar,Ernst, Martin,Hashmi, A. Stephen K.,Schaub, Thomas
, p. 4175 - 4178 (2017/10/09)
The deaminative hydrogenation of nitriles towards alcohols is a useful reaction to transform nitriles into alcohols with NH3 as the sole byproduct. Using the simple and robust RuHCl(CO)(PPh3)3 complex as a catalyst, at low H2 pressures a series of aliphatic and aromatic nitriles could be transformed into the corresponding alcohols. Suitable solvent systems for these reactions were 1,4-dioxane/water and EtOH/water mixtures. In most cases, the selectivity for the alcohols was excellent, and the corresponding amines were formed only in trace amounts.
