- Hydrogenation of Aliphatic Nitriles to Primary Amines over a Bimetallic Catalyst Ni25.38Co18.21/MgO–0.75Al2O3 Under Atmospheric Pressure
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Abstract: A mixed oxide supported bimetallic catalyst Ni25.38Co18.21/MgO–0.75Al2O3 was readily prepared and found to be efficient in the hydrogenation of valeronitrile (VN) to amylamine (AA) under atmospheric pressure. Under the optimal conditions: H2 to VN molar ratio of 4:1, NH3 to VN molar ratio of 3:1, reaction temperature of 130?°C and residence time of 5?s, the conversion of VN reached 100% with a AA yield of 70.8%, and a diamylamine (DAA) yield of 25.9%. This catalyst was also active in the hydrogenation of other low carbon aliphatic nitriles to their corresponding primary amines. The characterization results revealed that the catalyst had the properties of large surface area, uniform and fine dispersion of metal particles in the form of Ni/Co alloy with synergy effect between the two metals, which endowed the catalyst with good catalytic performances in the hydrogenation reaction of aliphatic nitriles. Graphic Abstract: [Figure not available: see fulltext.]
- Shi, Dongxu,Zhu, He,Han, Yaping,Zhang, Yuecheng,Zhao, Jiquan
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p. 2784 - 2794
(2021/02/03)
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- Selective Synthesis of Primary Amines from Nitriles under Hydrogenation Conditions
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The hydrogenation of aliphatic nitriles over Pd/C, Pd/Al2O3, and Pd?Au/Al2O3 catalysts were evaluated for the selective hydrogenation of aliphatic nitriles to the corresponding primary amines. The highest selectivity (>99%) toward primary amines was achieved when the reaction was carried out in acetic acid using 10 mol% of 25% Pd-5% Au/Al2O3 under relatively low hydrogen pressure (0.8 MPa). Characterization of the catalysts by XRD, CO adsorption experiments, and EXAFS revealed that the excellent selectivity of 25% Pd-5% Au/Al2O3 toward the synthesis of primary amines is determined by the electronic properties and/or the surface structure resulting from alloying Pd with Au. (Figure presented.).
- Yoshimura, Masatoshi,Komatsu, Akira,Niimura, Masaru,Takagi, Yukio,Takahashi, Tohru,Ueda, Shun,Ichikawa, Tomohiro,Kobayashi, Yutaka,Okami, Hiroki,Hattori, Tomohiro,Sawama, Yoshinari,Monguchi, Yasunari,Sajiki, Hironao
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p. 1726 - 1732
(2018/03/21)
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- Hydrogenolysis of Amide Acetals and Iminium Esters
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Amide acetals and iminium esters were hydrogenated into amines under very mild reaction conditions over common hydrogenation catalysts. This finding provides a new strategy for the selective reduction of amides. The synthetic utility of this approach was demonstrated by the selective reduction of amides bearing ester and nitrile groups.
- Kadyrov, Renat
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p. 170 - 172
(2017/12/26)
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- Continuous Production of Dialkylamines by Selective Hydrogenation of Nitriles on a Nickel-Zeolite Catalyst
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Hydrogenation of aliphatic nitriles in the presence of nickel supported by NaX zeolite was studied. The data obtained were used to develop a continuous method for obtaining dialkylamines with the yield of the target product of up to 98%.
- Popov, Yu. V.,Mokhov,Latyshova,Panov,Pletneva, M. Yu.
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p. 1778 - 1782
(2018/03/21)
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- Colloid and nanosized catalysts in organic synthesis: XVI.1 Continuous hydrogenation of carbonitriles catalyzed by nickel nanoparticles applied on a support
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Conversion of the starting nitriles and selectivity of the products formation during continuous hydrogenation of various nitriles catalyzed by Ni0/Ceokar-2 have been studied as functions of temperature. Performing the process at temperature 120–260°С has led to the formation of a mixture of products containing di- and trialkylamines as well as the corresponding imines and enamines.
- Popov, Yu. V.,Mokhov,Latyshova,Nebykov,Panov,Pletneva, M. Yu.
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p. 2276 - 2281
(2017/11/24)
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- Catalyst-Dependent Selective Hydrogenation of Nitriles: Selective Synthesis of Tertiary and Secondary Amines
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In the presence of palladium on carbon (Pd/C) as a catalyst, hydrogenation of aliphatic nitriles in cyclohexane efficiently proceeded at 25-60 °C under ordinary hydrogen gas pressure to afford the corresponding tertiary amines. However, the use of rhodium on carbon (Rh/C) led to the highly selective generation of secondary amines. Hydrogenation of aromatic nitriles and cyclohexanecarbonitrile selectively produced secondary amines in the presence of either Pd/C or Rh/C.
- Monguchi, Yasunari,Mizuno, Masahiro,Ichikawa, Tomohiro,Fujita, Yuki,Murakami, Eri,Hattori, Tomohiro,Maegawa, Tomohiro,Sawama, Yoshinari,Sajiki, Hironao
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p. 10939 - 10944
(2017/10/27)
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- Catalytic Hydrogenation for the Preparation of Amines from Amide Acetals, Ketene N,O-Acetals or Ester Imides
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The present invention relates to a process for the preparation of amines, comprising the following steps: Reaction of a (i) amide acetal of the general formula (I), or (ii) ketene N,O-acetal of the general formula (II), or (iii) ester imide of the general formula (III) with H2 in the presence of a hydrogenation catalyst, where catalyst and amide acetal or ketene N,O-acetal or ester imide are used in a molar ratio of from 1:10 to 1:100 000 and where a hydrogen pressure of from 0.1 bar to 200 bar is established and where a temperature in the range of from 0° C. to 250° C. is established.
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Paragraph 0153; 0154
(2016/10/04)
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- Cobalt-Catalyzed Synthesis of Aromatic, Aliphatic, and Cyclic Secondary Amines via a "hydrogen-Borrowing" Strategy
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The replacement of precious metals with inexpensive, less toxic, and earth-abundant elements in typical noble-metal-mediated organic transformations is a major goal in current synthetic chemistry and industries. The metal-catalyzed N-alkylation of amines with other amines through a "hydrogen-borrowing" principle represents a green and atom-economical reaction for the synthesis of secondary amines. However, catalysts developed thus far that are effective for this process remain quite scarce and are only limited to a few ruthenium and iridium complexes. In this work, we present a cobalt-catalyzed selective alkylation of amines with amines to synthesize a large variety of secondary amines. A range of amine substrates have been converted to the corresponding products through hetero- or homocoupling between amines. Cyclic sec-amines are also achieved from diamine precursors as rare examples.
- Yin, Zhiwei,Zeng, Haisu,Wu, Jing,Zheng, Shengping,Zhang, Guoqi
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p. 6546 - 6550
(2016/10/14)
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- Iron-catalyzed Cα-H oxidation of tertiary, aliphatic amines to amides under mild conditions
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De novo syntheses of amides often generate stoichiometric amounts of waste. Thus, recent progress in the field has focused on precious metal catalyzed, oxidative protocols to generate such functionalities. However, simple tertiary alkyl amines cannot be used as starting materials in these protocols. The research described herein enables the oxidative synthesis of amides from simple, noncyclic tertiary alkyl amines under synthetically useful, mild conditions through a biologically inspired approach: Fe-catalyzed Cα-H functionalization. Mechanistic investigations provide insight into reaction intermediates and allow the development of a mild Cα-H cyanation method using the same catalyst system. The protocol was further applied to oxidize the drug Lidocaine, demonstrating the potential utility of the developed chemistry for metabolite synthesis. Let′s iron it out! The title reaction enables the oxidative synthesis of amides directly from tertiary, noncyclic alkyl amines under synthetically useful, mild conditions through a biologically inspired approach employing oxidative iron catalysis. Mechanistic studies suggest that hemiaminals are likely intermediates in this reaction and that the catalytic system can be employed for other Cα-H oxidations of amines.
- Legacy, Christopher J.,Wang, Anqi,O'Day, Brian J.,Emmert, Marion H.
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supporting information
p. 14907 - 14910
(2016/02/05)
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- PROCESS FOR PREPARING AMINES FROM ALCOHOLS AND AMMONIA
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The present invention provides novel ruthenium based catalysts, and a process for preparing amines, by reacting a primary alcohol and ammonia in the presence of such catalysts, to generate the amine and water. According to the process of the invention, primary alcohols react directly with ammonia to produce primary amines and water in high yields and high turnover numbers. This reaction is catalyzed by novel ruthenium complexes, which are preferably composed of quinolinyl or acridinyl based pincer ligands.
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Page/Page column 24; 31; 32
(2010/04/03)
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- Selective synthesis of primary amines directly from alcohols and ammonia
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(Chemical Equation Presented) Air stable and waterproof: Selective and efficient synthesis of primary amines directly from alcohols and ammonia is achieved under mild conditions (see scheme). The reaction is homogenously catalyzed by a novel air-stable ruthenium pincer complex and can proceed in toluene or even in the absence of solvent or "on water".
- Gunanathan, Chidambaram,Milstein, David
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supporting information; experimental part
p. 8661 - 8664
(2009/05/15)
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- Reaction of primary amines with Pt/C catalyst in water under microwave irradiation: A convenient synthesis of secondary amines from primary amines
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Upon microwave irradiation in water, Pt/C converts primary amines into secondary amines in good yield via retro-reductive and reductive amination.
- Miyazawa, Akira,Saitou, Kaori,Tanaka, Kan,G?dda, Thomas M.,Tashiro, Masashi,Prakash, G. K. Surya,Olah, George A.
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p. 1437 - 1439
(2007/10/03)
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- Process for producing bismuth dithiocarbamates and dithiophosphorates
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A process for producing a bismuth dithiocarbamate or dithiophosphorate by the reaction of a bismuth hydroxide, bismuth oxide or bismuth oxynitrate with a dithiocarbamate or a dithiophosphoric acid. The bismuth dithiocarbamates and dithiophosphorates exhibit very good EP and antiwear properties and are useful in lubricant formulations.
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- Push-pull mechanism of hydrodenitrogenation over silica-supported MoP, WP, and MoS2 hydroprocessing catalysts
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The mechanism of liquid-phase catalytic hydrodenitrogenation at 3.1 MPa on silica-supported molybdenum phosphide, MoP/SiO2, and tungsten phosphide, WP/SiO2, was studied using a series of pentylamines of different structures. The reactivity pattern suggested that removal of nitrogen occurred primarily by an E2 elimination mechanism involving acidic and base sites on the catalyst surfaces in a push-pull process. Infrared spectroscopy and temperature-programmed reaction studies of ethylamine indicated that alkyl ammonium species formed on Bronsted acid sites were intermediates in the reaction. Similar results were obtained with a reference MoS2/SiO2 sample tested at the same conditions. This suggested that sulfur was probably present on the active surface and assisted in the removal of sulfur.
- Clark,Wang,Deck,Oyama
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p. 116 - 126
(2007/10/03)
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- The first efficient hydroaminomethylation with ammonia: With dual metal catalysts and two-phase catalysis to primary amines
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Primary and unbranched secondary amines are obtained by the highly selective hydroaminomethylation of olefins with ammonia [Eq. (a)]. The selectivity is readily controlled with a new dual Rh/Ir catalyst in a two- phase system.
- Zimmermann, Burkhard,Herwig, Juergen,Beller, Matthias
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p. 2372 - 2375
(2007/10/03)
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- Catalytic hydrogenation of valeronitrile over Raney nickel. Part 2: Reactivity of intermediates
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Hydrogenation of valeronitrile on a Raney nickel catalyst, gives rise to primary, secondary and tertiary amines, the proportions of which depend on several factors.Synthesis of dipentylimine which is an intermediate in the formation of dipentylamine from valeronitrile was performed.The hydrogenation of this dipentylimine at different hydrogen pressures and in the presence or absence of ammonia, allowed us to explain the modifications of selectivity observed when we varied these two factors during the reduction of valeronitrile.Secondary products formed on the course of the hydrogenation of valeronitrile in the presence of added primary amines (hexylamine or pentylamine) have also been studied.Secondary amines were found consistent with the mechanism proposed and the reversibility of reaction was confirmed.
- Besson, M.,Bonnier, J. M.,Djaouadi, D.,Joucla, M.
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- Catalytic hydrogenation of valeronitrile over Raney nickel. Part 1: Influence of reaction parameters on activity and selectivity
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The liquid phase hydrogenation of valeronitrile in the presence of Raney nickel was studied under different experimental conditions in order to examinate the effect of the reaction parameters on the rate and selectivity of hydrogenation.The factors included stirring speed, catalyst concentration, temperature, hydrogen pressure, reactant concentration, added ammonia, nature of the solvent.The results were found to be independent of the catalyst loading.Decreasing the hydrogen pressure, lower temperatures, high concentrations of valeronitrile and large amounts of ammonia were found to be beneficial in obtaining primary amine.The effects of alcohol as solvent were attributed to the presence of the carbonyl compounds obtained by dehydrogenation of alcohols.
- Besson, M.,Bonnier, J. M.,Joucla, M.
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- The Chemistry of N-Substituted Benzotriazoles. Part 14. Novel Routes to Secondary and Tertiary Amines and to N,N-Disubstituted Hydroxylamines
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Tertiary amines of types R4R3CHNR1R2 (2), (R2CH2)2NR1 (10) and 11, or (R2CH2)3N (12), secondary amines of type (R2CH2)2NH (8), and N,N-disubstituted hydroxylamines of type (R2CH2)2NOH (9), are prepared in high yield by the action of Grignard reagents or sodium borohydride on easily available N,N-dialkyl-N-amines (1) or tris(benzotriazolylmethyl)amine (7), on bis(benzotriazolylmethyl)amines (3), (5), and (6), and on N,N-bis(benzotriazolylmethyl)hydroxylamine (4), respectively.
- Katritzky, Alan R.,Yannakopoulou, Konstantina,Lue, Ping,Rasala, Danuta,Urogdi, Laszlo
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p. 225 - 233
(2007/10/02)
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- Competing Hydride Transfer and Ene Reactions in the Aminoalkylation of 1-Alkenes with N,N-Dimethylmethyleniminium Ions. A Literature Correction
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A literature report that N,N-dimethylmethyleniminium ion (2) reacts with propylene and styrene to form unsaturated tertiary amines is shown to be incorrect.The major products are the secondary amines 1-(methylamino)butane and 1-(methylamino)-3-phenylpropane in which N-demethylation has occurred along with the saturation of the alkene.Analogous major products are formed with 1-butene, 1-hexene, 1-octene, 1-dodecene, 1-tetradecene, p-methylstyrene, and m-nitrostyrene as substrates.When the substrates are isobutylene, 2-ethyl-1-hexene, α-methylstyrene, and p-methoxystyrene, the major products are tertiary amines, but the secondary amines are also formed in smaller yields.The small yields of tertiary amines obtained in the cases of styrene and p-methylstyrene were increased by going from solvent acetic acid to acetonitrile and by increasing the branching of the alkyl groups on nitrogen.The internal olefins 5-decene and cyclohexene were far less reactive, giving only 3-4percent of amine products that were mainly tertiary in the former case and secondary in the latter.It is concluded that tertiary amine products are favored by an alkene structure and a solvent that favors the formation of a stable carbenium ion intermediate or a transition state with substantial carbenium ion character upon electrophilic attack of the iminium ion on the alkene.The secondary amine products are favored when a carbenium ion is of low stability and when the β-carbon atom of the olefin and/or the alkyl group attached to nitrogen is sterically unhindered; such hindrance decreases the rate of hydride ion transfer that is believed to occur in the production of secondary amines.
- Cohen, Theodore,Onopchenko, Anatoli
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p. 4531 - 4537
(2007/10/02)
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- FORMATION OF SULFUR COMPOUNDS IN THE HYDRODENITROGENATION OF PIPERIDINE, PYRIDINE, 1-PENTYLAMINE AND 1-PENT-4-ENYLAMINE ON A NICKEL-TUNGSTEN CATALYST IN THE PRESENCE OF HYDROGEN SULFIDE
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Hydrogenations of piperidine, pyridine, 1-pentylamine, and 1-pent-4-enylamine were carried out in an autoclave at 300 deg C on a sulfidized nickel-tungsten catalyst using either pure hydrogen or a mixture of hydrogen with hydrogen sulfide.Hydrogen sulfide was found to raise the degree of conversion of the starting substances and accelerate the hydrodenitrogenation by formation of sulfur compounds; 1-pentanethiol, di(1-pentyl)sulfide, 2-methylthiacyclopentane, thiacyclohexane and other sulfur compounds were detected in the reaction mixtures in the presence of hydrogensulfide.A reaction pathway is suggested of the hydrodenitrogenation of piperidine in the presence of hydrogen sulfide, accounting for the favourable effect of the latter on the hydrodenitrogenation of nitrogen compounds.
- Cerny, Mirko
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p. 928 - 935
(2007/10/02)
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- Hydrogenolysis of nitrogen-containing compounds on cobalt-molybdenium catalyst
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Hydrogenolysis of N-(1-hexyl)piperidine, N-(1-pentyl)piperidine and 1-pentyl-1-hexylamine on sulphidized CoO-MoO3 catalysts has been investigated.The primary reaction in the hydrogenolysis is the cleavage of the bond between the nitrogen atom and the methylene group of the alkyl substituent or of the methylene ring.Alkylation and transalkylation reactions on the nitrogen play also a role.
- Cerny, Mirko
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p. 2215 - 2218
(2007/10/02)
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- Turning the product selectivity of nitrile hydrogenation from primary to secondary amines by precise modification of Pd/SiC catalysts using NiO nanodots
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The selectivity of supported metal catalysts is mainly determined by the active metallic component, and thus turning the selectivity to a completely different product is rarely achieved by modification of the catalysts. Hydrogenation of nitriles is an efficient and environmentally benign route for the synthesis of valuable amines, but it usually produces mixtures of primary, secondary and even tertiary amines. Herein we report that the selectivity of Pd/SiC catalysts for the hydrogenation of nitriles with H2 can be turned from primary to secondary amines by modification of NiO nanodots. In the modified catalysts, the NiO nanodots act as reactive sites to consume hydrogen radicals on the Pd surface, and thus prolong the lifetime of an imine intermediate that determines the product selectivity. Under mild conditions (30 °C, atmospheric H2), Pd/SiC and NiO-Pd/SiC catalysts exhibit high selectivity to primary (94%) and secondary (99%) amines, respectively.
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