1124-53-4Relevant academic research and scientific papers
Furan-based acetylating agent for the chemical modification of proteins
De, Sudipta,Kumar, Tarun,Bohre, Ashish,Singh, Laishram R.,Saha, Basudeb
, p. 791 - 796 (2015)
We have synthesized a furan-based acetylating agent, 2,5-bisacetoxymethylfuran (BAMF) from carbohydrate derived 5-hydroxymethylfurfural (HMF) and studied its acetylation activity with amines and cytochrome c. The results show that BAMF can modify proteins in biological conditions without affecting their structure and function. The modification of cytochrome c with BAMF occurred through the reduction of heme center, but there was no change in the coordination property of iron and the tertiary structure of cytochrome c. Further analysis using MALDI-TOF-MS spectrometer suggests that BAMF selectively targeted lysine amino acid of cytochrome c under our experimental conditions. Kinetics study revealed that the modification of cytochrome c with BAMF took place at faster rates than aspirin.
Ruthenium-supported catalysts for the stereoselective hydrogenation of paracetamol to 4-trans-acetamidocyclohexanol: Effect of support, metal precursor, and solvent
Bachiller-Baeza,Guerrero-Ruiz,Rodriguez-Ramos
, p. 439 - 445 (2005)
The influence of the support, the metal precursor, and the solvent on the selective hydrogenation of paracetamol (4-acetamidophenol) was studied over supported ruthenium catalysts. The catalysts supported on the oxidic supports Al2O3 and SiO2 gave the best results in terms of activity, selectivity for the acetamidocyclohexanols (99%), and stereoselectivity for the trans isomer (53 and 46%, respectively). Carbon-supported catalysts produced larger amounts of secondary compounds, mainly N-cyclohexylacetamide, which was derived from the hydrogenolysis reaction of the OH group. The use of a chloride precursor resulted in the enhancement of the formation of N-cyclohexylacetamide and partially hydrogenated products; the stereoselectivity also increased. Moreover, because of the acidity caused by residual Cl, condensation led to oligomers of paracetamol. In spite of the decrease in the selectivity for cyclohexanol derivatives when the more polar solvent ethanol was used instead of isopropanol or tetrahydrofuran the stereoselectivity for the trans isomer increased from 30 to 38%. The results confirm that the factors studied affect the mode of adsorption of the molecule of paracetamol on the catalyst in different ways. These effects determine the product distribution and the selectivity of the reaction.
Colloid and nano-sized catalysts in organic synthesis: X. Synthesis of carboxamides by direct amidation of carboxylic acids and transamidation catalyzed by colloid copper
Mokhov,Popov, Yu. V.,Budko
, p. 820 - 826 (2015)
Abstract It was found that in the presence of colloid copper the direct amidation of some carboxylic acids with primary and secondary amines in benzene with azeotropic distillation of water became possible. The catalyst was proven to be suitable also for transamidation reaction of a number of carboxylic acid amides under mild conditions in solvent-free conditions.
Amidomercuration; a New and Regiospecific Addition of Amides to Olefins
Barluenga, Jose,Jimenez, Carmen,Najera, Carmen,Yus, Miguel
, p. 670 - 671 (1981)
The reaction of olefins with anhydrous mercury(II) nitrate in the presence of primary amides leads, after in situ alkaline sodium borohydride reduction, to the corresponding N-substituted amides; this procedure provides a new, convenient method for the Markovnikov amidation of carbon-carbon double bonds.
A Study on the Activation of Carboxylic Acids by Means of 2-Chloro-4,6-dimethoxy-1,3,5-triazine and 2-Chloro-4,6-diphenoxy-1,3,5-triazine
Kaminski,Paneth,Rudzinski
, p. 4248 - 4255 (1998)
Activation of carboxylic function by means of 2-chloro-4,6-disubstituted-1,3,5-triazines 1 and 2 leading to triazine esters was found to be a multistep process with participation of quarternary triazinylammonium salts 3-6 as the intermediates, with the rate of reaction strongly dependent on the structure of the tertiary amine. The studies on alkylation of tertiary amines with CDMT revealed the two-step process AN + DN, and zwitterionic addition product 9 was identified by 1H NMR spectroscopy. Semiempirical modeling of the reaction as well as measured nitrogen and chlorine isotope effects also support this mechanism.
Titanocene-Catalyzed Radical Opening of N-Acylated Aziridines
Zhang, Yong-Qiang,Vogelsang, Elisabeth,Qu, Zheng-Wang,Grimme, Stefan,Gans?uer, Andreas
, p. 12654 - 12657 (2017)
Aziridines activated by N-acylation are opened to the higher substituted radical through electron transfer from titanocene(III) complexes in a novel catalytic reaction. This reaction is applicable in conjugate additions, reductions, and cyclizations and suited for the construction of quaternary carbon centers. The concerted mechanism of the ring opening is indicated by DFT calculations.
AN IMPROVED MODIFICATION OF RITTER REACTION
Martinez, A. Garcia,Alvarez, A. Martinez,Vilar, E. Teso,Fraile, A. Garcia,Hanack, M.,Subramanian, L. R.
, p. 581 - 582 (1989)
The reaction of alcohols 1 with trifluoromethane sulfonic anhydride (Tf2O) in dichloromethane in presence of a 2:1 excess of nitriles 3 affords the corresponding amides 5 in good yields.
Decarboxylative Ritter-Type Amination by Cooperative Iodine (I/III)─Boron Lewis Acid Catalysis
Narobe, Rok,Murugesan, Kathiravan,Schmid, Simon,K?nig, Burkhard
, p. 809 - 817 (2022/01/15)
Recent years have witnessed important progress in synthetic strategies exploiting the reactivity of carbocations via photochemical or electrochemical methods. Yet, most of the developed methods are limited in their scope to certain stabilized positions in molecules. Herein, we report a metal-free system based on the iodine (I/III) catalytic manifold, which gives access to carbenium ion intermediates also on electronically disfavored benzylic positions. The unusually high reactivity of the system stems from a complexation of iodine (III) intermediates with BF3. The synthetic utility of our decarboxylative Ritter-type amination protocol has been demonstrated by the functionalization of benzylic as well as aliphatic carboxylic acids, including late-stage modification of different pharmaceutical molecules. Notably, the amination of ketoprofen was performed on a gram scale. Detailed mechanistic investigations by kinetic analysis and control experiments suggest two mechanistic pathways.
A Metal-Free, Photocatalytic Method for Aerobic Alkane Iodination
Anna, Jessica M.,Goldberg, Karen I.,Hirscher, Nathanael A.,Ohri, Nidhi,Schelter, Eric J.,Yang, Qiaomu,Zhou, Jiawang
supporting information, p. 19262 - 19267 (2021/11/30)
Halogenation is an important alkane functionalization strategy, but O2 is widely considered the most desirable terminal oxidant. Here, the aerobic iodination of alkanes, including methane, was performed using catalytic [nBu4N]Cl and light irradiation (390 nm). Up to 10 turnovers of CH3I were obtained from CH4 and air, using a stop-flow microtubing system. Mechanistic studies using cyclohexane as the substrate revealed important details about the iodination reaction. Iodine (I2) serves multiple roles in the catalysis: (1) as the alkyl radical trap, (2) as a precursor for the light absorber, and (3) as a mediator of aerobic oxidation. The alkane activation is attributed to Cl? derived from photofragmentation of the electron donor-acceptor complex of I2 and Cl-. The kinetic profile of cyclohexane iodination showed that aerobic oxidation of I3- to produce I2 in CH3CN is turnover-limiting.
Preparation method of acetamide compound
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Paragraph 0035-0047; 0060-0063, (2021/05/19)
The invention discloses a preparation method of an acetamide compound, the preparation method comprises the following steps: reacting tetracarbonyl dichloride rhodium, 1, 3-bis (diphenylphosphine) propane, tungsten carbonyl, sodium phosphate, sodium iodide, water, a nitro compound and dimethyl carbonate at 120 DEG C for 24 hours, and after the reaction is completed, performing post-treatment to obtain the acetamide compound. According to the preparation method, dimethyl carbonate serves as a C1 source and also serves as a green solvent, operation is easy, reaction starting raw materials are low in price and easy to obtain, the tolerance range of substrate functional groups is wide, and reaction efficiency is high. Various acetamide compounds can be synthesized according to actual needs, so that the practicability of the method is widened while the operation is convenient.
