10342-97-9Relevant academic research and scientific papers
RAPID REDUCTIVE-CARBOXYLATION OF SECONDARY AMINES. ONE POT SYNTHESIS OF TERTIARY N-METHYLATED AMINES
Ram, Siya,Ehrenkaufer, Richard E.
, p. 5367 - 5370 (1985)
Various tertiary N-methylated amines were synthesized by using a new reductive-carboxylation approach.Secondary amines, on carboxylation with carbon dioxide under moderate reaction conditions, afforded their corresponding carbamate esters, which, on in situ lithium aluminum hydride reduction, gave desired tertiary N-methylated amines in high yield.
N-Methylation of amines with methanol in a hydrogen free system on a combined Al2O3-mordenite catalyst
Su, Jiahui,Li, Xungang,Chen, Yunbin,Cui, Yuancun,Xu, Jingwei,Qian, Chao,Chen, Xinzhi
, p. 55643 - 55649 (2016)
N-Methyl amines play a major role in the production of medicines, pesticides, surfactants and dyes. N-Methylation of primary or second amines with methanol is considered to be a green path for the synthesis of N-methyl amines and the catalyst is key. In this article, the combined Al2O3-mordenite catalyst (mass fraction of alumina is 40%) with good activity, selectivity, lifetime and stability was prepared for N-methylation of various amines with methanol in a hydrogen free system in a fixed bed reactor, and characterized by XRD, N2 adsorption and NH3-TPD. Furthermore, the methanol adsorption was investigated by in situ FTIR, and the result indicated that methoxyl species may be the active species for the N-methylation of amines.
Ruthenium-Catalyzed Methylation of Amines with Paraformaldehyde in Water under Mild Conditions
van der Waals, Dominic,Heim, Leo. E.,Gedig, Christian,Herbrik, Fabian,Vallazza, Simona,Prechtl, Martin H. G.
, p. 2343 - 2347 (2016)
Methylated amines are highly important for a variety of pharmaceutical and agrochemical applications. Existing routes for their formation result in the production of large amounts of waste or require high reaction temperatures, both of which impact the ecological and economical footprint of the methodologies. Herein, we report the ruthenium-catalyzed reductive methylation of a range of aliphatic amines, using paraformaldehyde as both substrate and hydrogen source, in combination with water. This reaction proceeds under mild aqueous reaction conditions. Additionally the use of a secondary phase for catalyst retention and recycling has been investigated with promising results.
RANEY nickel-catalyzed reductive N-methylation of amines with paraformaldehyde: Theoretical and experimental study
Ge, Xin,Luo, Chenxi,Qian, Chao,Yu, Zhiping,Chen, Xinzhi
, p. 43195 - 43203 (2014)
RANEY Ni-catalyzed reductive N-methylation of amines with paraformaldehyde has been investigated. This reaction proceeds in high yield with water as a byproduct. RANEY Ni can be easily recovered and reused with a slight decrease of the yield. Using density functional theory (DFT), the mechanism of RANEY Ni-catalyzed reductive N-methylation is discussed in detail. The reaction pathway involves the addition of amine with formaldehyde, dehydration to form the imine and hydrogenation. In the transition state of hemiaminal dehydration, the C-O bond cleavage of the aromatic amine is more difficult than that of the aliphatic amine. For the aromatic amine, a higher energy barrier must be overcome, which results in a relatively low yield. After addition of amine with formaldehyde and dehydration, imine is obtained and preferred to adsorb on the bridge site of the Ni(111) surface. The preferential pathways of imine hydrogenation involve the pre-adsorbed hydrogen atom attacking the nitrogen atom of the imine. The energy barrier of hydrogenation is much lower than that of addition and dehydration. Thus, the hydrogenation of imine is a relatively rapid reaction step. In the reductive N-methylation of secondary amine, the possible dehydration pathway is different from the one of the primary amine. In the dehydration of the secondary amine, the intermediate hemiaminal is initially adsorbed on the bridge site of the Ni(111) surface, then undergoes C-O bond cleavage, and eventually the hydroxyl is located in the bridge site. With the final hydrogenation, the product is obtained by adsorption on the top site of the Ni(111) surface.
Towards the Development of Frustrated Lewis Pair (FLP) Catalyzed Hydrogenations of Tertiary and Secondary Carboxylic Amides
K?ring, Laura,Paradies, Jan,Sitte, Nikolai A.
supporting information, p. 1287 - 1300 (2022/01/20)
The development of the frustrated Lewis pair catalyzed hydrogenation of tertiary and secondary amides is reviewed. Detailed insight into our strategies in order to overcome challenges during the reaction development process is provided. Furthermore, the d
Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst
Benaissa, Idir,Cantat, Thibault,Genre, Caroline,Godou, Timothé,Pinault, Mathieu
, p. 57 - 61 (2022/01/19)
Formic acid is used as the sole carbon and hydrogen source in the methylation of aromatic and aliphatic amines to methylamines. The reaction proceeds via a formylation/transfer hydrogenation pathway over a solid Pd/In2O3 catalyst without the need for any additive.
Electroactivated alkylation of amines with alcohols: Via both direct and indirect borrowing hydrogen mechanisms
Appiagyei, Benjamin,Bhatia, Souful,Keeney, Gabriela L.,Dolmetsch, Troy,Jackson, James E.
supporting information, p. 860 - 869 (2020/02/21)
A green, efficient N-alkylation of amines with simple alcohols has been achieved in aqueous solution via an electrochemical version of the so-called "borrowing hydrogen methodology". Catalyzed by Ru on activated carbon cloth (Ru/ACC), the reaction works well with methanol, and with primary and secondary alcohols. Alkylation can be accomplished by either of two different electrocatalytic processes: (1) in an undivided cell, alcohol (present in excess) is oxidized at the Ru/ACC anode; the aldehyde or ketone product condenses with the amine; and the resulting imine is reduced at an ACC cathode, combining with protons released by the oxidation. This process consumes stoichiometric quantities of current. (2) In a membrane-divided cell, the current-activated Ru/ACC cathode effects direct C-H activation of the alcohol; the resulting carbonyl species, either free or still surface-adsorbed, condenses with amine to form imine and is reduced as in (1). These alcohol activation processes can alkylate primary and secondary aliphatic amines, as well as ammonia itself at 25-70 °C and ambient pressure.
Selective reduction of formamides to O-silylated hemiaminals or methylamines with HSiMe2Ph catalyzed by iridium complexes
Guzmán, Jefferson,Bernal, Ana M.,García-Ordu?a, Pilar,Lahoz, Fernando J.,Oro, Luis A.,Fernández-Alvarez, Francisco J.
, p. 4255 - 4262 (2019/04/01)
The reaction of (4-methyl-pyridin-2-iloxy)ditertbutylsilane (NSitBu-H, 1) with [IrCl(coe)2]2 affords the iridium(iii) complex [Ir(H)(Cl)(κ2-NSitBu)(coe)] (2), which has been fully characterized including X-ray diffraction studies. The reaction of 2 with AgCF3SO3 leads to the formation of species [Ir(H)(CF3SO3)(κ2-NSitBu)(coe)] (3). The iridium complexes 2 and 3 are effective catalysts for the reduction of formamides with HSiMe2Ph. The selectivity of the reduction process depends on the catalyst. Thus, by using complex 2, with a chloride ancillary ligand, it has been possible to selectively obtain the corresponding O-silylated hemiaminal by reaction of formamides with one equivalent of HSiMe2Ph, while complex 3, with a triflate ligand instead of chloride, catalyzed the selective reduction of formamides to the corresponding methylamine.
Mild Hydrogenation of Amides to Amines over a Platinum-Vanadium Bimetallic Catalyst
Mitsudome, Takato,Miyagawa, Kazuya,Maeno, Zen,Mizugaki, Tomoo,Jitsukawa, Koichiro,Yamasaki, Jun,Kitagawa, Yasutaka,Kaneda, Kiyotomi
supporting information, p. 9381 - 9385 (2017/08/01)
Hydrogenation of amides to amines is an important reaction, but the need for high temperatures and H2 pressures is a problem. Catalysts that are effective under mild reaction conditions, that is, lower than 30 bar H2 and 70 °C, have not yet been reported. Here, the mild hydrogenation of amides was achieved for the first time by using a Pt-V bimetallic catalyst. Amide hydrogenation, at either 1 bar H2 at 70 °C or 5 bar H2 at room temperature was achieved using the bimetallic catalyst. The mild reaction conditions enable highly selective hydrogenation of various amides to the corresponding amines, while inhibiting arene hydrogenation. Catalyst characterization showed that the origin of the catalytic activity for the bimetallic catalyst is the oxophilic V-decorated Pt nanoparticles, which are 2 nm in diameter.
Method For Preparing Methylated Amines
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Paragraph 0161-0172, (2015/06/10)
The present invention relates to a method for preparing methylated amines using carbon dioxide and to the use of the method for manufacturing vitamins, pharmaceutical products, glues, acrylic fibres and synthetic leathers, pesticides and fertilizers. The invention also relates to a method for manufacturing vitamins, pharmaceutical products, glues, acrylic fibres, synthetic leathers, pesticides and fertilizers, including a step of preparing methylated amines by the method according to the invention. The present invention also relates to a method for preparing marked methylated amines and to the uses thereof.
