109-83-1Relevant articles and documents
CO2 Methanation via Amino Alcohol Relay Molecules Employing a Ruthenium Nanoparticle/Metal Organic Framework Catalyst
Chidambaram, Arunraj,Cui, Xinjiang,Dyson, Paul J.,Fei, Zhaofu,Nguyen, Tu N.,Shyshkanov, Serhii,Stylianou, Kyriakos C.
, p. 16371 - 16375 (2020)
Methanation of carbon dioxide (CO2) is attractive within the context of a renewable energy refinery. Herein, we report an indirect methanation method that harnesses amino alcohols as relay molecules in combination with a catalyst comprising ruthenium nanoparticles (NPs) immobilized on a Lewis acidic and robust metal–organic framework (MOF). The Ru NPs are well dispersed on the surface of the MOF crystals and have a narrow size distribution. The catalyst efficiently transforms amino alcohols to oxazolidinones (upon reaction with CO2) and then to methane (upon reaction with hydrogen), simultaneously regenerating the amino alcohol relay molecule. This protocol provides a sustainable, indirect way for CO2 methanation as the process can be repeated multiple times.
Combining Low-Pressure CO2 Capture and Hydrogenation to Form Methanol
Khusnutdinova, Julia R.,Garg, Jai Anand,Milstein, David
, p. 2416 - 2422 (2015)
This paper describes a novel approach to CO2 hydrogenation, in which CO2 capture with aminoethanols at low pressure is coupled with hydrogenation of the captured product, oxazolidinone, directly to MeOH. In particular, (2-methylamino)ethanol or valinol captures CO2 at 1-3 bar in the presence of catalytic Cs2CO3 to give the corresponding oxazolidinones in up to 65-70 and 90-95% yields, respectively. Efficient hydrogenation of oxazolidinones was achieved using PNN pincer Ru catalysts to give the corresponding aminoethanol (up to 95-100% yield) and MeOH (up to 78-92% yield). We also have shown that both CO2 capture and oxazolidinone hydrogenation can be performed in the same reaction mixture using a simple protocol that avoids intermediate isolation or purification steps. For example, CO2 can be captured by valinol at 1 bar with Cs2CO3 catalyst followed by 4-isopropyl-2-oxazolidinone hydrogenation in the presence of a bipy-based pincer Ru catalyst to produce MeOH in 50% yield after two steps.
Schiff's Bases as Intermediates in the Hydrolytic Decomposition of 2-Alkyl-3-methyl-1,3-oxazolidines in Aqueous Acid
Pihlaja, Kalevi,Parkkinen, Aija,Loennberg, Harri
, p. 1223 - 1226 (1983)
The kinetics for the hydrolysis of 2-alkyl-3-methyl-1,3-oxazolidines have been examined spectrophotometrically in acidic solutions.The decomposition of the substrates to 2-methylaminoethanol and the corresponding aldehydes have been shown to proceed via stable intermediates which are kinetically and u.v.-spectroscopically very similar to the acyclic cationic Schiff's base derived from isobutyraldehyde and 2-methoxyethylmethylamine.The mechanisms for the formation and breakdown of the Schiff's base intermediate are discussed on the basis of pH-rate profiles, activation parameters, salt effects, and solvent deuterium isotope effects.
A near-IR uncaging strategy based on cyanine photochemistry
Gorka, Alexander P.,Nani, Roger R.,Zhu, Jianjian,Mackem, Susan,Schnermann, Martin J.
, p. 14153 - 14159 (2014)
The development of photocaging groups activated by near-IR light would enable new approaches for basic research and allow for spatial and temporal control of drug delivery. Here we report a near-IR light-initiated uncaging reaction sequence based on readily synthesized C4'-dialkylamine-substituted heptamethine cyanines. Phenol-containing small molecules are uncaged through sequential release of the C4'-amine and intramolecular cyclization. The release sequence is initiated by a previously unexploited photochemical reaction of the cyanine fluorophore scaffold. The uncaging process is compatible with biological milieu and is initiated with low intensity 690 nm light. We show that cell viability can be inhibited through light-dependent release of the estrogen receptor antagonist, 4-hydroxycyclofen. In addition, through uncaging of the same compound, gene expression is controlled with near-IR light in a ligand-dependent CreERT/LoxP-reporter cell line derived from transgenic mice. These studies provide a chemical foundation that we expect will enable specific delivery of small molecules using cytocompatible, tissue penetrant near-IR light.
Electrochemical Reductive N-Methylation with CO2Enabled by a Molecular Catalyst
Rooney, Conor L.,Wu, Yueshen,Tao, Zixu,Wang, Hailiang
supporting information, p. 19983 - 19991 (2021/12/01)
The development of benign methylation reactions utilizing CO2 as a one-carbon building block would enable a more sustainable chemical industry. Electrochemical CO2 reduction has been extensively studied, but its application for reductive methylation reactions remains out of the scope of current electrocatalysis. Here, we report the first electrochemical reductive N-methylation reaction with CO2 and demonstrate its compatibility with amines, hydroxylamines, and hydrazine. Catalyzed by cobalt phthalocyanine molecules supported on carbon nanotubes, the N-methylation reaction proceeds in aqueous media via the chemical condensation of an electrophilic carbon intermediate, proposed to be adsorbed or near-electrode formaldehyde formed from the four-electron reduction of CO2, with nucleophilic nitrogenous reactants and subsequent reduction. By comparing various amines, we discover that the nucleophilicity of the amine reactant is a descriptor for the C-N coupling efficacy. We extend the scope of the reaction to be compatible with cheap and abundant nitro-compounds by developing a cascade reduction process in which CO2 and nitro-compounds are reduced concurrently to yield N-methylamines with high monomethylation selectivity via the overall transfer of 12 electrons and 12 protons.
Preparation method of N-methylmonoethanolamine
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Paragraph 0047-0048; 0049-0050; 0063-0064; 0065-0066, (2021/11/03)
The invention provides a preparation method of N-methyl monoethanolamine. Under the action of a supported Cu catalyst, formaldehyde, ammonia gas and ethanol react, the product is separated through vacuum distillation, and the used supported Cu catalyst is prepared from a Cu-containing compound, a ligand and a carrier. According to the catalyst, amino acid is adopted as a ligand, N and O in the amino acid are complexed with copper, the activity of an active component is improved, complexation with formaldehyde and ammonia gas is avoided, an intermediate for an addition reaction of the ammonia gas and the formaldehyde is efficiently catalyzed to generate a coupling reaction with ethanol, and the supported Cu catalyst is not prone to loss. And a secondary addition reaction in an ethylene oxide method is avoided.
Discovery of benzimidazole analogs as a novel interleukin-5 inhibitors
Boggu, Pulla Reddy,Kim, Youngsoo,Jung, Sang-Hun
, (2019/08/12)
A series of novel hydroxyethylaminomethylbenzimidazole analogs 5a-y were synthesized and evaluated for their IL-5 inhibitory activity using pro-B Y16 cell line. Among them, 2-(((4-(cyclohexylmethoxy)-1H-benzo[d]imidazol-2-yl)methyl)amino)butan-1-ol (5e, 94.3% inhibition at 30 μM, IC50 = 3.5 μM, cLogP = 4.132) and 3-cyclohexyl-2-(((4-(cyclohexylmethoxy)-1H-benzo[d]imidazol-2-yl)methyl)amino) propan-1-ol (5k, 94.7% inhibition at 30 μM, IC50 = 5.0 μM, cLogP = 6.253) showed the most potent inhibitory activity. The essential feature of SAR (Fig. 5) indicated that the chromenone ring can be replaced by a benzimidazole ring to maintain the inhibitory activity. In addition, the hydroxyethylaminomethyl group was suitable for the IL-5 inhibitory activity. Moreover, the hydrophobic substituents on carbon play an important role in the IL-5 inhibitory activity of these analogs. However, N-substituted analogs did not improve inhibitory activity. In addition, MTT assay of 5e and 5k with normal B lymphoblasts revealed that they had no significant effects on cell viability.
MALDI-TOF MS investigation of the unconventional termination of living polyoxazoline with ammonia
Kosakowska, Karolina A.,Dimitrov, Philip,Panambur, Gangadhar,Grayson, Scott M.
, p. 1303 - 1312 (2017/03/15)
Poly(2-oxazoline) (POx) based materials have experienced renewed interest, due to their biocompatibility and broad functional diversity. Although research pertaining to cationic ring opening polymerization (CROP) of 2-oxazoline derivatives spans upwards of 5 decades, modern characterization techniques, specifically Matrix Assisted Laser-Desorption Ionization—Time of Flight Mass Spectrometry (MALDI-TOF MS), were not available during early studies to aid in identifying polymer end-groups. Through careful synthesis and analytical characterization, evidence supports an alternative mode of nucleophilic attack during ammonia termination, with nucleophilic attack occurring at a different site on the terminal oxazolinium than where polymer propagation occurs. Furthermore, investigations employing targeted end-group modification, in conjunction with MALDI and NMR analysis, determined the structure of the resultant terminal group was a hydroxyethylamino end group. Based on the observed data, a mechanistic explanation for the observed 2-oxazoline ring-opening termination is proposed.
N-Alkylation of Alkylolamines with Alcohols Over Mesoporous Solid Acid–Base Cs–B–Zr Catalyst
Chen, Aimin,Wang, Houyong,Liu, Rui,Bo, Yingying,Hu, Jun
, p. 1182 - 1193 (2016/07/06)
Abstract: The mesoporous solid acid–base Cs–B–Zr mixed oxides were synthesized using the co-precipitation method followed by a subsequent thermal treatment. The catalytic activity of solid Cs–B–Zr mixed oxide was tested for solvent free acid–base catalysed direct alkylolamines with alcohols as green alkylating agent. The effects of Cs/B/Zr ratio, calcination temperature, reaction conditions, and reaction substrate on the catalytic performance of the catalysts were investigated. The XRD, N2 adsorption–desorption, ICP-OES, FT-IR and NH3/CO2-TPD results showed that the mesoporous structure and acid–base properties of the catalysts play important roles in the reaction. A suitable number of acid and basic sites on the catalyst lead to a high activity for the N-alkylation reaction. Graphical Abstract: A direct N-alkylation of amino alcohol with alcohols has been developed using mixed oxide Cs–B–Zr as an acid–base bifunctionalized catalyst.[Figure not available: see fulltext.]
Preparation of ionic liquid-based vilsmier reagent from novel multi-purpose dimethyl formamide-like ionic liquid and its application
Hullio, Ahmed Ali,Mastoi
experimental part, p. 1647 - 1657 (2012/09/21)
In continuation of research to explore the applied potential of DMF-like ionic liquid, the ionic liquid version of N,N-dimethyliminiumchloride (Vilsmier reagent) has been synthesized from DMF-like ionic liquid and tested effectively for its capacity to achieve more useful organic transformations. The results show that DMF-like ionic liquid is world's first task specific ionic liquid which has catalyzed numerous diverse type of reaction and is multipurpose in its application. Thus a new term for this DMF-like ionic liquid has been coined that is DMF-like "multipurpose" ionic liquid. Copyright
