- Switchable synthesis of furfurylamine and tetrahydrofurfurylamine from furfuryl alcohol over RANEY nickel
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RANEY Ni proved to be an effective heterogeneous catalyst for switchable reductive amination of furfuryl alcohol to tetrahydrofurfurylamine and furfurylamine with NH3 by simply adding or not adding 1.0 MPa H2 into the reaction bulk. After further optimization of the reaction conditions, we finally obtained 94.0% yield of tetrahydrofurfurylamine and 78.8% yield of furfurylamine with high selectivity. By extensively studying the catalytic pathways and mechanism of catalyst deactivation with XRD and XPS characterization, we have confirmed that an excess amount of H2 in the reaction bulk leads to the deep hydrogenation of the furan ring while an insufficient amount of H2 leads to the formation of Ni3N and the deactivation of the catalyst.
- Liu, Yingxin,Zhou, Kuo,Shu, Huimin,Liu, Haiyan,Lou, Jiongtao,Guo, Dechao,Wei, Zuojun,Li, Xiaonian
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Read Online
- Ru/HZSM-5 as an efficient and recyclable catalyst for reductive amination of furfural to furfurylamine
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Furfurylamine converted from biomass-based platform molecules furfural was proven a significant intermediate in the synthesis of different valuable compounds. The combination of Ruthenium with HZSM-5 was acted as an excellent selective and reusable catalyst for the reduction amination of furfural with environmentally friendly ammonia and hydrogen. Incorporation of Ru species into HZSM-5 had a significant enhancement to the acid sites of Ru/HZSM-5. The Ru/HZSM-5(46) catalyst with optimized acid sites and interaction of the Ru-O-Al bond displayed an excellent catalytic performance, producing 76 % yield of furfurylamine at only 15 min, and could be recycled five times without loss of performance. Synergistic effect between RuO2 and metallic Ru in the Ru/HZSM-5 catalyst facilitated the reduction amination of furfural.
- Dong, Chenglong,Wang, Hongtao,Du, Haochen,Peng, Jiebang,Cai, Yang,Guo, Shuai,Zhang, Jianli,Samart, Chanatip,Ding, Mingyue
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- Preparation method of chiral 2 - aminomethyltetrahydrofuran (by machine translation)
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The invention provides a preparation method of chiral 2 -aminomethyl tetrahydrofuran, which comprises the following steps: (1) reaction of chiral epichlorohydrin with 2 - chloroethyl magnesium bromide to generate chiral 1-chloro 5 -pentanol; (-2 -) chiral 2-benzamido 1-chloro 5 - pentanol to react under the action of a palladium catalyst to generate chiral -2 -benzamidomethyl tetrahydrofurane in the presence of a basic substance to form chiral 5 - 1 - dichloro -5 -1-pentanol and a 4 chiral 2 -2 - 1 -dichloro 3 pentanol in -2 - the presence of a basic substance to form -5 - an intramolecular ring-closing reaction in the presence of a 2 - basic substance to 2 - 2 - form chirality of 5 - chloro-5 -1 and 2 -methylene tetrahydrofurfuryl alcohol in the presence of a basic substance. The synthetic method is short in route, low in production cost, less in three wastes and suitable for industrial production. (by machine translation)
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- Facile synthesis of controllable graphene-co-shelled reusable Ni/NiO nanoparticles and their application in the synthesis of amines under mild conditions
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The primary objective of many researchers in chemical synthesis is the development of recyclable and easily accessible catalysts. These catalysts should preferably be made from Earth-abundant metals and have the ability to be utilised in the synthesis of pharmaceutically important compounds. Amines are classified as privileged compounds, and are used extensively in the fine and bulk chemical industries, as well as in pharmaceutical and materials research. In many laboratories and in industry, transition metal catalysed reductive amination of carbonyl compounds is performed using predominantly ammonia and H2. However, these reactions usually require precious metal-based catalysts or RANEY nickel, and require harsh reaction conditions and yield low selectivity for the desired products. Herein, we describe a simple and environmentally friendly method for the preparation of thin graphene spheres that encapsulate uniform Ni/NiO nanoalloy catalysts (Ni/NiO?C) using nickel citrate as the precursor. The resulting catalysts are stable and reusable and were successfully used for the synthesis of primary, secondary, tertiary, and N-methylamines (more than 62 examples). The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, and H2 under very mild industrially viable and scalable conditions (80 °C and 1 MPa H2 pressure, 4 h), offering cost-effective access to numerous functionalized, structurally diverse linear and branched benzylic, heterocyclic, and aliphatic amines including drugs and steroid derivatives. We have also demonstrated the scale-up of the heterogeneous amination protocol to gram-scale synthesis. Furthermore, the catalyst can be immobilized on a magnetic stirring bar and be conveniently recycled up to five times without any significant loss of catalytic activity and selectivity for the product.
- Cui, Zhibing,Liu, Jianguo,Liu, Qiying,Ma, Longlong,Singh, Thishana,Wang, Chenguang,Wang, Nan,Zhu, Yuting
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supporting information
p. 7387 - 7397
(2020/11/19)
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- One-pot reductive amination of carboxylic acids: a sustainable method for primary amine synthesis
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The reductive amination of carboxylic acids is a very green, efficient and sustainable method for the production of (bio-based) amines. However, with current technology, this reaction requires two to three reaction steps. Here, we report the first (heterogeneous) catalytic system for the one-pot reductive amination of carboxylic acids to amines, with solely H2 and NH3 as the reactants. This reaction can be performed with relatively cheap ruthenium-tungsten bimetallic catalysts in the green and benign solvent cyclopentyl methyl ether (CPME). Selectivities of up to 99% for the primary amine could be achieved at high conversions. Additionally, the catalyst is recyclable and tolerant for common impurities such as water and cations (e.g. sodium carboxylate).
- Coeck, Robin,De Vos, Dirk E.
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supporting information
p. 5105 - 5114
(2020/08/25)
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- A Comprehensive Study on the Reductive Amination of 5-Hydroxymethylfurfural into 2,5-Bisaminomethylfuran over Raney Ni Through DFT Calculations
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Reductive amination of furfuryl alcohol, furfural and 5-hydroxymethylfurfural (5-HMF) were carried out on various metal catalysts. Over Raney Ni catalyst, we obtained the highest furfurylamine yields of 81.8 % and 94.0 % from furfuryl alcohol in absence and presence of H2, respectively. While furfural was used as the substrate, 100 % yield of furfurylamine could be achieved over Raney Ni under rather moderate conditions. Although 5-HMF was completely converted over all catalysts used, the highest yield of 2,5-bisaminomethylfuran (60.7 %) was obtained over Raney Ni at 160 °C in 12 h. The DFT calculations on the adsorption behavior of NH3 and H2 on different metal surfaces showed that the difference of the adsorption energy between NH3 and H2 on Ni is lower than those of other metals, indicating that less metal active sites on Ni surface is occupied by NH3, which leaves more active sites for dehydrogenation/hydrogenation reactions and in the end promotes the reductive amination reactions.
- Zhou, Kuo,Liu, Haiyan,Shu, Huimin,Xiao, Shuwen,Guo, Dechao,Liu, Yingxin,Wei, Zuojun,Li, Xiaonian
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p. 2649 - 2656
(2019/05/17)
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- Selective Synthesis of Furfurylamine by Reductive Amination of Furfural over Raney Cobalt
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Effect of metal nature on reductive amination was investigated with biomass-based furfural as a typical substrate. Among the tested heterogeneous metal catalysts, cobalt proved to be the most effective metal for the synthesis of the corresponding primary amine. Under a relatively mild reaction condition, 98.9 % yield of furfurylamine was obtained over Raney Co and it can be reused more than eight times without a significant decrease in the catalytic performance. By extensively studying the catalytic pathways and reaction mechanism, it is found that the selectivity to primary amine and secondary amine was governed by the relative rate of hydrogenolysis and hydrogenation of the Schiff base intermediate. The superiority of Raney Co in furfurylamine synthesis can be ascribed to its high efficiency on hydrogenolysis of the Schiff base intermediate and its low performance in the hydrogenation of the Schiff base, carbonyl group and furan ring. Furthermore, ammonia greatly promoted the catalytic hydrogenolysis of the Schiff base intermediate over Raney Co without clear deactivation of the metal active sites.
- Zhou, Kuo,Chen, Bixian,Zhou, Xiaoting,Kang, Shimin,Xu, Yongjun,Wei, Jinjia
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p. 5562 - 5569
(2019/11/03)
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- Method for selectively preparing furfuryl amine or tetrahydrofurfuryl amine
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The invention discloses a method for selectively preparing furfuryl amine or tetrahydrofurfuryl amine. The method comprises the following steps: taking furfuryl alcohol as a raw material and taking metal nickel as a catalyst; carrying out reductive amination reaction under a hydrogen-free condition to prepare the furfuryl amine; carrying out reductive amination reaction under a hydrogen condition to prepare the tetrahydrofurfuryl amine. According to the method for selectively preparing the furfuryl amine or the tetrahydrofurfuryl amine, disclosed by the invention, the furfuryl alcohol is used as the raw material and the heterogeneous catalyst is adopted; the selectivity of products is changed through introducing hydrogen by utilizing the same raw material and the same catalysis system under basically the same technological conditions.
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Paragraph 0040; 0041; 0045; 0046; 0050-0057; 0061-0067
(2017/10/28)
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- Electronic Effect of Ruthenium Nanoparticles on Efficient Reductive Amination of Carbonyl Compounds
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Highly selective synthesis of primary amines over heterogeneous catalysts is still a challenge for the chemical industry. Ruthenium nanoparticles supported on Nb2O5 act as a highly selective and reusable heterogeneous catalyst for the low-temperature reductive amination of various carbonyl compounds that contain reduction-sensitive functional groups such as heterocycles and halogens with NH3 and H2 and prevent the formation of secondary amines and undesired hydrogenated byproducts. The selective catalysis of these materials is likely attributable to the weak electron-donating capability of Ru particles on the Nb2O5 surface. The combination of this catalyst and homogeneous Ru systems was used to synthesize 2,5-bis(aminomethyl)furan, a monomer for aramid production, from 5-(hydroxymethyl)furfural without a complex mixture of imine byproducts.
- Komanoya, Tasuku,Kinemura, Takashi,Kita, Yusuke,Kamata, Keigo,Hara, Michikazu
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p. 11493 - 11499
(2017/08/30)
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- MANUFACTURING METHOD OF AROMATIC COMPOUND AND FURAN DERIVATIVE HAVING METHYLAMINO GROUP
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PROBLEM TO BE SOLVED: To provide a method for manufacturing an aromatic compound or a furan derivative where only aldehyde group is converted to an aminomethyl group while maintaining a structure of aromatic or furan ring from an aromatic compound or a furan derivative having an aldehyde group, capable of being conducted in a water solvent containing no organic solvent and relatively low in by-product. SOLUTION: Amine or ammonia is added in water at first to convert to imine, then a reaction is conducted by using compressive hydrogen with a pressure of 0.1 MPa to 4 MPa in the presence of a metal carried solid catalyst carrying one or more kind of metal selected from rhodium, palladium and platinum or an alloy containing these metal elements. SELECTED DRAWING: Figure 2 COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0028
(2017/10/26)
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- Reductive amination of furfural to furfurylamine using aqueous ammonia solution and molecular hydrogen: An environmentally friendly approach
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A simple and highly efficient method was developed for the transformation of furfural (a biomass derived aldehyde) to furfurylamine by reductive amination using an aqueous solution of ammonia and molecular hydrogen as an amine source and a reducing agent, respectively. By choosing a suitable catalyst, such as Rh/Al2O3, and reaction conditions, a very high selectivity of furfurylamine (～92%) can be achieved within the reaction time of 2 h at 80 °C. A detailed analysis of the reaction system sheds some light on the reaction pathway and provides an understanding about each elementary step. The reaction was believed to proceed via an imine pathway although no such intermediate was detected because of the highly reactive nature. Optimization of different reaction parameters such as hydrogen pressure, temperature and substrate/ammonia mole ratio is shown to be critical to achieve high selectivity of furfurylamine. Time-dependent reaction profiles suggested that a Schiff base type intermediate was in the detectable range, which offers indirect evidence of the formation of imine. Competitive hydrogenation and amination of an aldehyde group were strongly dictated by the nature of the metal used. The studied protocol represents an environmentally benign process for amine synthesis, which can be effectively extended to the other aldehydes also. The studied catalyst could be recycled successfully without any significant loss of catalytic activity.
- Chatterjee, Maya,Ishizaka, Takayuki,Kawanami, Hajime
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supporting information
p. 487 - 496
(2016/01/30)
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- HIV INTEGRASE INHIBITORS
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The present invention features compounds that are HIV integrase inhibitors and therefore are useful in the inhibition of HIV replication, the prevention and/or treatment of infection by HIV, and in the treatment of AIDS and/or ARC.
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- Photorelease of primary aliphatic and aromatic amines by visible-light-induced electron transfer
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Visible-light-absorbing tris(bipyridyl)ruthenium(II) has been used to mediate electron transfer to N-methylpicolinium carbamates that undergo C-O bond fragmentation followed by spontaneous carbon dioxide release to give free amines. Release of several aliphatic and aromatic primary amines has been demonstrated under mild conditions using visible light.
- Edson, Joseph B.,Spencer, Liam P.,Boncella, James M.
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supporting information; experimental part
p. 6156 - 6159
(2012/01/05)
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- Preparative separation of tetrahydrofurfurylamine enantiomers
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Tetrahydrofurfurylamine enantiomers were separated on a preparative scale by fractional crystallization of diastereoisomeric salts with natural L-tartaric acid. (R)-Tetrahydrofurfurylamine was isolated in 68% yield with an optical purity of more than 98.5% according to the HPLC data.
- Musatov,Kublitskii,Malyshev,Kurilov,Vinogradov
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experimental part
p. 1813 - 1814
(2009/09/25)
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- Pyrazolopyrimidines as therapeutic agents
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The present invention is directed to pyrazolopyrimidine derivatives of formula (I) wherein the substituents are defined herein, which are useful as kinase inhibitors and as such are useful for affecting angiogenesis and diseases and conditions associated with angiogenesis.
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- Amine compounds, resist compositions and patterning process
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Amine compounds having a cyano group are useful in resist compositions for preventing a resist film from thinning and also for enhancing the resolution and focus margin of resist.
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- Oligomeric aminodiol-containing compounds, libraries thereof, and process of preparing the same
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Oligomeric compounds comprising a plurality of aminodiol monomer subunits joined by linking groups are provided, as well as libraries of such compounds and processes for preparing the oligomeric compounds and libraries.
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- Tetracyclic benzimidazole derivatives and combinatorial libraries thereof
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The present invention relates to novel tetracyclic benzimidazole derivative compounds of the following formula: wherein R1to R10have the meanings described in here. The invention further relates to combinatorial libraries containing two or more such compounds, as well as methods of preparing tetracyclic benzimidazole derivative compounds.
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- Pyrazolopyrimidines as therapeutic agents
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The present invention provides compounds of Formula I, including pharmaceutically acceptable salts and/or prodrugs thereof, where G, R2, and R3 are defined as described herein.
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- 2-aminobenzoxazole derivatives and combinatorial libraries thereof
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The present invention relates to novel 2-aminobenzoxazole derivative compounds of the following formula: wherein R1 to R4 and Z have the meanings provided herein. The invention further relates to combinatorial libraries containing two or more such compounds, as well as methods of preparing 2-aminobenzoxazole derivative compounds.
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- 2-aminopyridine derivatives and combinatorial libraries thereof
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The present invention relates to novel 2-aminopyridine derivative compounds of the following formula: wherein R1to R5have the meanings provided herein. The invention further relates to combinatorial libraries containing two or more such compounds, as well as methods of preparing 2-aminopyridine derivative compounds.
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- Scavenger assisted combinatorial process for preparing libaries of secondary amine compounds
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This invention relates to a novel solution phase process for the preparation of secondary amine combinatorial libraries. These libraries have use for drug discovery and are used to form wellplate components of novel assay kits.
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- Reaction of tetrahydrofurfuryl alcohol with ammonia and hydrogen on heterogeneous catalysts
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A study has been made of the vapour-phase reaction of tetrahydrofurfuryl alcohol with ammonia and hydrogen on Cu-, Ni-, Co- and Fe-containing bifunctional catalysts at a temperature of 180-240°C. It has been established that, irrespective of the type of catalyst, the main reaction products are piperidine, tetrahydrofurfurylamine and their derivatives. Copyright
- Glebov,Kliger,Shuikin,Zaikin
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p. 346 - 352
(2007/10/03)
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- Process for producing furfurylamine and/or tetrahydrofurfurylamine
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A process for producing furfurylamine and/or tetrahydrofurfurylamine in a high yield is disclosed, which comprises subjecting a mixture of furfural and a primary amine to a liquid-phase catalytic hydrogenation using a hydrogenation catalyst in the presence of ammonia, wherein the primary amine is furfurylamine and/or tetrahydrofurfurylamine and the hydrogenation catalyst is selected from the group consisting of cobalt-based catalysts and nickel-based catalysts.
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- Syntheses of optically active 2-tetrahydrofuran derivatives
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The resolution of 2-tetrahydrofuran-carboxylic acid and assignment of configuration to the enantiomers are reported.New syntheses of the enantiomers of 2-tetrahydofurancarboxaldehyde are also described.
- Belanger, Patrice C.,Williams, Haydn W. R.
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p. 1383 - 1386
(2007/10/02)
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- Treatment of atherosclerosis with khellin-related furochromones
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The present specification relates to the antiatherosclerotic use of khellin and related furochromones, and further provides novel antiatherogenic furochromones.
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- Antiatherosclerotic furochromones
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The present specification relates to the antiatherosclerotic use of khellin and related furochromones, and further provides novel antiatherogenic furochromones.
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- Resolution of certain asymmetric primary amines using lasalocid
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Racemic modifications of optically active primary or tertiary amines are treated with lasalocid to form diastereomeric salts. The so-formed diastereomeric salts are separated and, subsequently, can be chemically decomposed to give the desired enantiomers of the amine. The resolving agent, lasalocid, is recovered in this process by precipitation or evaporation from organic solvents.
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