- Reductive amination of bio-based 2-hydroxytetrahydropyran to 5-Amino-1-pentanol over nano-Ni-Al2O3catalysts
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The synthesis of useful amines from bio-based carbonyl compounds is highly desired owing to their mild reaction conditions and green sustainability. The reductive amination of bio-furfural-derived 2-hydroxytetrahydropyran (2-HTHP) to high-value-added 5-Amino-1-pentanol (5-AP) was carried out over efficient Ni-Al2O3catalysts prepared by a co-precipitation method. Among the Ni-Al2O3catalysts with different Ni loadings (0-100 wt%) tested, the 50Ni-Al2O3catalyst exhibited the highest5-APyield of 91.3% under mild conditions of 60 °C and 2 MPa H2. This catalyst also presented good stability during a 150 h time-on-stream without appreciable deactivation. Characterization results showed that the 50Ni-Al2O3catalyst exhibited small Ni0nanoparticles (5.5 nm), a high reduction degree (up to 95%), and a large amount of strong Lewis acid sites. The cooperative catalysis of the strong Lewis acid sites and highly dispersed metallic Ni sites is suggested to play an important role in achieving high efficiency in2-HTHPreductive amination.
- Zhang, Jia,Yang, Jian,Tian, Junying,Liu, Hailong,Li, Xuemei,Fang, Weiguo,Hu, Xun,Xia, Chungu,Chen, Jing,Huang, Zhiwei
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p. 4236 - 4245
(2021/03/15)
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- Effective synthesis of 5-amino-1-pentanol by reductive amination of biomass-derived 2-hydroxytetrahydropyran over supported Ni catalysts
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A highly efficient and green process was developed for the synthesis of useful 5-amino-1-pentanol (5-AP) from biomass-derived dihydropyran by coupling the in situ generation of 5-hydroxypentanal (5-HP, via the ring-opening tautomerization of 2-hydroxytetrahydropyran (2-HTHP)) and its reductive amination over supported Ni catalysts. The catalytic performances of the supported Ni catalysts on different oxides including SiO2, TiO2, ZrO2, γ-Al2O3, and MgO as well as several commercial hydrogenation catalysts were investigated. The Ni/ZrO2 catalyst presented the highest 5-AP yield. The characterization results of the oxide-supported Ni catalysts showed that the Ni/ZrO2 catalyst possessed high reducibility and a high surface acid density, which lead to the enhanced activity and selectivity of the catalyst. The effect of reaction parameters on the catalytic performance of the Ni/ZrO2 catalyst was studied, and a high 5-AP yield of 90.8% was achieved in the reductive amination of 2-HTHP aqueous solution under mild conditions of 80 °C and 2 MPa H2. The stability of the Ni/ZrO2 catalyst was studied using a continuous flow reactor, and only a slight decrease in the 5-AP yield was observed after a 90-h time-on-stream. Additionally, the reaction pathways for the reductive amination of 2-HTHP to synthesize 5-AP were proposed.
- Li, Xuemei,Tian, Junying,Liu, Hailong,Tang, Congkui,Xia, Chungu,Chen, Jing,Huang, Zhiwei
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p. 631 - 641
(2020/01/28)
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- Method for preparing aliphatic amine compound
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The invention discloses a method for preparing an aliphatic amine compound, comprising the following steps: using furfuryl amine or a furfuryl amine derivative as a raw material, and carrying out hydrogenolysis in the presence of a supported metal catalyst to obtain the aliphatic amine compound. According to the method disclosed by the invention, the aliphatic amine compound is prepared by catalyzing hydrogenolysis of the biomass-based furfuryl amine and the derivative thereof for the first time. The catalyst has high activity and high product selectivity. According to the method, a biomass-based compound is used as a raw material to prepare the aliphatic amine compound, and the requirements of sustainable development and green chemistry are met. The aliphatic amine compound prepared by the method has high selectivity, and is convenient for separation and purification of products. After the reaction of the method is finished, the catalyst is easy to separate and can be recycled, so that the method has a good application prospect.
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Paragraph 0059-0061; 0083-0085
(2020/05/14)
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- Synthetic method of 5-amion-1-pentanol
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The invention discloses a synthetic method of 5-amion-1-pentanol. The synthetic method comprises the following step: carrying out a hydration reaction and a reductive amination reaction on 3,4-dihydro-2H-furan under the condition that the temperature is smaller than or equal to 120 DEG C and the pressure is smaller than or equal to 3PMa to prepare the 5-amion-1-pentanol. By taking 3,4-dihydro-2H-furan as a raw material, the 5-amion-1-pentanol is prepared through the hydration reaction and the reductive amination reaction under mild conditions, the reaction process is green and efficient, the yield of 5-amion-1-pentanol can reach 93%, the method is simple and safe to operate, the investment and production cost of a production device are lowered obviously, and scaled industrial production isachieved conveniently.
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Paragraph 0047; 0052; 0056; 0060; 0064; 0068; 0071
(2019/01/08)
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- Heterogeneously catalyzed selective hydrogenation of amides to alcohols and amines
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We report the heterogeneously catalyzed hydrogenation of amides to form alcohols and amines. This C-N bond cleavage reaction is catalyzed by silver on γ-alumina, proceeds smoothly in high yields and 100% selectivity, and is effective for both benzamides and aliphatic amides. This is in contrast to amide hydrogenation catalyzed by heterogeneous catalysts, which generally proceeds via C-O bond cleavage. Recycling experiments show that the catalyst Ag/γ-Al2O3 can be easily recovered and regenerated without decrease in catalytic activity.
- Xie, Yinjun,Hu, Peng,Bendikov, Tatyana,Milstein, David
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p. 2784 - 2788
(2018/06/18)
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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; 0103
(2016/10/27)
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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; 0113
(2016/10/09)
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- Hydrogenation of amides catalyzed by a combined catalytic system of a Ru complex with a zinc salt
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Addition of catalytic amounts of zinc salts facilitated the hydrogenation of amides catalyzed by a ruthenium complex bearing 2-(diphenylphosphino) ethanamine (L1). The combined catalytic system of the ruthenium complex [RuCl2(L1)2] with a zinc salt such as Zn(OCOCF 3)2 mediated hydrogenation of various amides under mild conditions to afford the corresponding primary alcohols.
- Kita, Yusuke,Higuchi, Takafumi,Mashima, Kazushi
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supporting information
p. 11211 - 11213
(2014/09/30)
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- Highly chemoselective reduction of amides (primary, secondary, tertiary) to alcohols using SmI2/amine/H2O under mild conditions
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Highly chemoselective direct reduction of primary, secondary, and tertiary amides to alcohols using SmI2/amine/H2O is reported. The reaction proceeds with C-N bond cleavage in the carbinolamine intermediate, shows excellent functional group tolerance, and delivers the alcohol products in very high yields. The expected C-O cleavage products are not formed under the reaction conditions. The observed reactivity is opposite to the electrophilicity of polar carbonyl groups resulting from the nX → πC=O (X = O, N) conjugation. Mechanistic studies suggest that coordination of Sm to the carbonyl and then to Lewis basic nitrogen in the tetrahedral intermediate facilitate electron transfer and control the selectivity of the C-N/C-O cleavage. Notably, the method provides direct access to acyl-type radicals from unactivated amides under mild electron transfer conditions.
- Szostak, Michal,Spain, Malcolm,Eberhart, Andrew J.,Procter, David J.
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supporting information
p. 2268 - 2271
(2014/03/21)
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- PROCESS FOR PREPARING ALKANOLAMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION
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Process for preparing alkanolamines which have a primary amino group (—NH2) and a hydroxyl group (—OH) by alcohol amination of diols having two hydroxyl groups (—OH) 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 13-14; 19
(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; 16
(2012/09/22)
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- Boiling water-catalyzed neutral and selective N-Boc deprotection
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A general protocol for removing Boc groups from various types of nitrogen is reported and a preliminary investigation of the reaction mechanism indicates that water acts as a dual acid/base catalyst at elevated temperature. The Royal Society of Chemistry 2009.
- Wang, Jia,Liang, Yan-Liang,Qu, Jin
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supporting information; experimental part
p. 5144 - 5146
(2009/12/08)
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- Amine-directed hydroboration: Scope and limitations
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Iodine activation induces intramolecular hydroboration of homoallylic and bis-homoallylic amine boranes with good to excellent control of regiochemistry compared to control experiments using excess THF?BH3. Deuterium labeling and other evidence confirm that the iodine-induced hydroboration reaction of homoallylic amine boranes occurs via an intramolecular mechanism equivalent to the classical 4-center process and without competing retro-hydroboration. Longer carbon chain tethers result in lower regioselectivity, whereas the shorter tether in allylic amines results in a switch to dominant intermolecular hydroboration. Regioselectivity in THF?BH3 control experiments is higher for the allylic amine boranes compared to the iodine activation experiments, whereas the reverse is true for homoallylic amine borane activation.
- Scheideman, Matthew,Wang, Guoqiang,Vedejs, Edwin
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supporting information; experimental part
p. 8669 - 8676
(2009/02/03)
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- N,N-Dibenzyl formamidine as a new protective group for primary amines
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Primary amines can be converted in high yield into N,N-dibenzyl formamidines under mild conditions. The N,N-dibenzyl formamidine group was found to be effective as a protective group for primary amines as it is stable to a variety of conditions and can be removed by catalytic hydrogenation.
- Vincent, Stephane,Mons, Stephane,Lebeau, Luc,Mioskowski, Charles
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p. 7527 - 7530
(2007/10/03)
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- Stoffwechselprodukte von Mikroorganismen Danoxamin, der eisenbindende Teil des Sideromycin-Antibioticums Danomycin
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The antibiotic danomycin was separated into its components, danomycin A and B (1 and 2, resp.), by various methods.Danomycin A is a carbamate of danomycin B and can be transformed to the latter by boiling with H2O.Both danomycins can be hydrolyzed by alkali to the Fe-containing moiety, danoxamine (3).The structure of the latter was determined by spectroscopy and chemical degradation as the Fe(III) complex of 5,16,27,32-tetrahydroxy-4,12,15,23,26-pentaoxo-5,11,16,22,27-pentaaza-dotriacontanoic acid.It belongs thus to the ferrioxamine family of siderophores.In the danomycins, this moiety is linked by an ester bond to a disaccharide moiety of unknown structure.One of the sugars is belived to be an aminohexane methyl ether.Chromatographically homogenous danomycins A and B are still mixtures of isomers, a neutral sugar being glucose or mannose.
- Huber, Peter,Leuenberger, Heinz,Keller-Schierlein, Walter
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p. 236 - 245
(2007/10/02)
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- Preparation of primary amines
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Primary aliphatic amines are prepared by reacting a corresponding aliphatic oxime with hydrazine in the presence of Raney nickel.
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