871-78-3Relevant articles and documents
Near-Ambient-Temperature Dehydrogenative Synthesis of the Amide Bond: Mechanistic Insight and Applications
Kar, Sayan,Xie, Yinjun,Zhou, Quan Quan,Diskin-Posner, Yael,Ben-David, Yehoshoa,Milstein, David
, p. 7383 - 7393 (2021/06/30)
The current existing methods for the amide bond synthesis via acceptorless dehydrogenative coupling of amines and alcohols all require high reaction temperatures for effective catalysis, typically involving reflux in toluene, limiting their potential practical applications. Herein, we report a system for this reaction that proceeds under mild conditions (reflux in diethyl ether, boiling point 34.6 °C) using ruthenium PNNH complexes. The low-temperature activity stems from the ability of Ru-PNNH complexes to activate alcohol and hemiaminals at near-ambient temperatures through the assistance of the terminal N-H proton. Mechanistic studies reveal the presence of an unexpected aldehyde-bound ruthenium species during the reaction, which is also the catalytic resting state. We further utilize the low-temperature activity to synthesize several simple amide bond-containing commercially available pharmaceutical drugs from the corresponding amines and alcohols via the dehydrogenative coupling method.
Rational design of bifunctional catalyst from KF and ZnO combination on alumina for cyclic urea synthesis from CO2 and diamine
John, Crowny,Kulal, Nagendra,Shanbhag, Ganapati V.
, (2020/04/22)
This study is mainly focused on the design of stable, active and selective catalyst for direct synthesis of 2-imidazolidinone (cyclic urea) from ethylenediamine and CO2. Based on the rationale for the catalyst properties needed for this reaction, KF, ZnO and Al2O3 combination was selected to design the catalyst. ZnO/KF/Al2O3 catalyst was prepared by stepwise wet-impregnation followed by the removal of physisorbed KF from the surface. High product yield could be achieved by tuning acid-base sites by varying the composition and calcination temperature. The catalysts were characterized by various techniques like XRD, N2-sorption, NH3-TPD, CO2-TPD, TEM, XPS and FT-IR measurements. It is shown that acidic and basic properties of the solvent can influence the activity and product selectivity for this reaction. Under optimized condition; 180 °C, 10 bar and 10 wt.% catalyst in batch mode, 96.3 % conversion and 89.6 % selectivity towards the 2-imidazolidinone were achieved.
Method for catalytic synthesis of tetraacetylethylenediamine by utilizing supported lithium chloride
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Paragraph 0015; 0017; 0018; 0020; 0022; 0023, (2019/08/20)
The invention provides a method for catalytic synthesis of tetraacetylethylenediamine by utilizing supported lithium chloride. Specifically, the method comprises the following steps: (1) sufficientlymixing a lithium chloride solution, a grinding aid dispersant and a carrier under stirring at room temperature, performing high-temperature drying, and performing grinding to obtain the supported lithium chloride solid acid catalyst; (2) quickly adding anhydrous acetic acid dropwise into ethylenediamine and a conventional catalyst; performing heating, performing a heat preservation reaction, and separating water; and adding acetic anhydride and the lithium chloride catalyst, continuing heating, and performing a reaction; and (3) performing cooling, performing crystallization, performing washing, and performing drying to obtain the tetraacetylethylenediamine. The method provided by the invention utilizes the supported lithium chloride solid acid to catalyze the synthesis of the tetraacetylethylenediamine by the ethylenediamine and an acylating reagent, and the catalyst is beneficial for recovering and can be recycled and has less pollution to the environment; the catalytic efficiency ishigh, the reaction time is effectively shortened, and the product yield can reach 90% or more; and the preparation method of the catalyst is simple, has low costs, and facilitates realizing industrial production and application of the tetraacetylethylenediamine.
Fe3O4@PEG core/shell nanoparticles as magnetic nanocatalyst for acetylation of amines and alcohols using ultrasound irradiations under solvent-free conditions
Veisi, Hojat,Nikseresht, Ahmad,Rostami, Afsaneh,Hemmati, Saba
, p. 507 - 520 (2018/10/24)
Abstract: Ultrasound irradiation was used to prepare one-pot Fe3O4@PEG core/shell nanostructure for the first time. The morphology, structure, and physicochemical properties were specified by different analytical techniques including field emission scanning electron microscopy, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray powder diffraction, and vibrating sample magnetometer. For acetylation of phenols, alcohols, and amines, the synthesized Fe3O4@PEG core/shell nanoparticles were used as an efficient heterogeneous and green catalyst with acetic anhydride under sonication applying mild reaction conditions. Different electron-withdrawing and electron-donating substrates indicate a prominent yield of desired products with the merit of reusability of Fe3O4@PEG nanocatalyst and magnetic separation. Graphical Abstract: [Figure not available: see fulltext.].
Preparation of Polydopamine Sulfamic Acid-Functionalized Silica Gel as Heterogeneous and Recyclable Nanocatalyst for Acetylation of Alcohols and Amines Under Solvent-Free Conditions
Veisi, Hojat,Vafajoo, Saba,Bahrami, Kiumars,Mozafari, Bita
, p. 2734 - 2745 (2018/07/30)
To fabricate SiO2/PDA–SO3H nanocatalyst, a suitable method is designed for the loading of sulfonic acid groups on the surface of polydopamine (PDA)-encapsulated SiO2 nanoparticles. To bridge the gap between heterogeneous and homogeneous catalysis, surface functionalization of silica gel is an elegant procedure. The morphology, structure, and physicochemical features were specified using different analytical techniques including field emission scanning electron microscopy (FESEM), Fourier transformed infrared spectroscopy (FT-IR), high resolution-transmission electron microscopy (HR-TEM), energy dispersive X-ray spectroscopy (EDS), wavelength-dispersive X-ray spectroscopy (WDX), X-ray photoelectron spectroscopy (XPS), and back titration. The SiO2/PDA–SO3H nanoparticles are efficient nanocatalysts for the acetylation of many alcohols, phenols, and amines with acetic anhydride under solvent-free conditions in good to excellent yields. Moreover, the reuse and recovery of the catalyst was shown seven times without detectible loss in activity. Graphical Abstract: [Figure not available: see fulltext.]
Anodic oxidation of bisamides from diaminoalkanes by constant current electrolysis
Golub, Tatiana,Becker, James Y.
, p. 861 - 868 (2018/04/30)
In general, bisamides derived from diamines and involving 3 and 4 methylene groups as spacers between the two amide functionalities behave similar to monoamides upon anodic oxidation in methanol/LiClO4 because both types undergo majorly mono- and dimethoxylations at the α-position to the N atom. However, in cases where the spacer contains two methylene groups only the anodic process leads mostly to CH2-CH2 bond cleavage to afford products of type RCONHCH2OCH3. Moreover, upon replacing LiClO4 with Et4NBF4 an additional fragmentation type of product was generated from the latter amides, namely RCONHCHO. Also, the anodic process was found to be more efficient with C felt as the anode, and in a mixture of 1:1 methanol/acetonitrile co-solvents.
Simple and Versatile Laboratory Scale CSTR for Multiphasic Continuous-Flow Chemistry and Long Residence Times
Chapman, Michael R.,Kwan, Maria H. T.,King, Georgina,Jolley, Katherine E.,Hussain, Mariam,Hussain, Shahed,Salama, Ibrahim E.,González Nino, Carlos,Thompson, Lisa A.,Bayana, Mary E.,Clayton, Adam D.,Nguyen, Bao N.,Turner, Nicholas J.,Kapur, Nikil,Blacker, A. John
, p. 1294 - 1301 (2017/09/23)
A universal multistage cascade CSTR has been developed that is suitable for a wide range of continuous-flow processes. Coined by our group the "Freactor" (free-to-access reactor), the new reactor integrates the efficiency of pipe-flow processing with the advanced mixing of a CSTR, delivering a general "plug-and-play" reactor platform which is well-suited to multiphasic continuous-flow chemistry. Importantly, the reactor geometry is easily customized to accommodate reactions requiring long residence times (≥3 h tested).
Four b acyl radicals alkane diamine method for manufacturing
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Page/Page column 11, (2017/05/12)
The present invention relates to a preparation method for tetraacetyl alkylene diamine, characterized in that tetraacetyl alkylene diamine is prepared by carrying out an acylation reaction of a diacetyl alkylene diamine and a carboxylic anhydride under the catalysis of a solid acidic catalyst.
Amide exchange reaction: A simple and efficient CuO catalyst for diacetamide synthesis
Li, Qinghe,Wang, Peixue,Deng, Youquan
, p. 40890 - 40894 (2016/05/19)
A highly copper-catalysed amide exchange reaction of hexamethylenediamine (HDA) with CH3CN and H2O for the synthesis of hexamethylenebisacetamide (HMBA) without an organic solvent or gas protection was developed. 100% HDA conversion and >99% HMBA selectivity was obtained. X-ray diffraction, scanning emission microscopy, and temperature-programmed reduction of hydrogen were used to characterize the structural properties of the catalyst. The reaction mechanism was also investigated.
Colloid and nanosized catalysts in organic synthesis: XIII. Synthesis of 2-R-2-imidazolines catalyzed by copper and iron oxide nanoparticles
Popov,Mokhov,Kalitina
, p. 281 - 285 (2016/04/20)
The reaction of carboxylic acids with ethylenediamine catalyzed by copper or iron oxide nanoparticles proceeds at 80°C with azeotropic water distilling off during 2-8 h to form 2-R-2-imidazolines. Acyl and diacyl derivatives of ethylenediamine are formed in the reaction as side products.
