116057-81-9Relevant articles and documents
Ru-catalyzed direct amidation of carboxylic acids with N-substituted formamides
Bi, Xiaojing,Li, Junchen,Shi, Enxue,Wang, Hongmei,Gao, Runli,Xiao, Junhua
, p. 8210 - 8214 (2016)
The direct amidation of carboxylic acids with N-substituted formamides has been accomplished via ruthenium catalysis. In the presence of ruthenium catalyst, a versatile range of carboxylic acids and N-substituted formamides undergoes amidation reaction to produce synthetically useful amides in good yields. C[dbnd]O in amide product came from benzoic acid but not N-substituted formamides, and which was confirmed by Isotope experiment.
Palladium-catalyzed unstrained C(sp3) - N bond activation: The synthesis of N,N-dimethylacetamide by carbonylation of trimethylamine
Mei, Hui,Han, Wenjia,Hu, Jianglin,Xiao, Se,Lei, Yizhu,Zhang, Rui,Mo, Wanlin,Li, Guangxing
, p. 177 - 183 (2013)
This work describes a highly efficient unstrained C(sp3) - N bond activation approach for synthesis of N,N-dimethylacetamide (DMAc) via catalytic carbonylation of trimethylamine using a PdCl2/bipy (bipy = 2,2′-bipyridine)/Me4NI catalyst system. A low Pd catalyst dosage (1.0 mol%) is sufficient for high selectivity (98.1%) and yield (90.8%), with a turnover number (TON) of 90.0 mmol of DMAc obtained per mmol of PdCl 2 employed under mild reaction conditions. The influence of reaction parameters such as catalyst precursor dosage, ligand type and promoter on activity is investigated. This work also discusses in detail the halide promoter's role in the reaction, and provides a plausible mechanism based on the intermediates methyl iodide and acetyl iodide. Analyses indicate that the carbonylation of trimethylamine may proceed through an active intermediate acetyl iodide formed by carbonylation of methyl iodide generated from the decomposition of the promoter Me4NI under reaction conditions. The formation of acetyl iodide favors the cleaving efficiency of the inert unstrained C(sp3) - N bond of trimethylamine. Copyright
Jones,Gessner
, p. 1873 (1971)
Bagnall, K. W.,Brown, D.,Jones, P. J.
, (1966)
Chisholm, M. H.,Chiu, H. T.,Huffman, J. C.
, p. 759 - 760 (1984)
Carstens, P. A. B.,Knoetze, T. P.,Vuuren, C. P. J. van
, p. 237 - 250 (1988)
Formation and stability of enolates of acetamide and acetate anion: An eigen plot for proton transfer at α-carbonyl carbon
Richard, John P.,Williams, Glenn,O'Donoghue, AnnMarie C.,Amyes, Tina L.
, p. 2957 - 2968 (2002)
Second-order rate constants were determined in D2O for deprotonation of acetamide, N,N-dimethylacetamide, and acetate anion by deuterioxide ion and for deprotonation of acetamide by quinuclidine. The values of kB = 4.8 × 10-8 M-1 s-1 for deprotonation of acetamide by quinuclidine (pKBH = 11.5) and kBH = 2-5 × 109 M-1 s-1 for the encounter-limited reverse protonation of the enolate by protonated quinuclidine give pKac = 28.4 for ionization of acetamide as a carbon acid. The limiting value of kHOH = 1 × 1011 s-1 for protonation of the enolate of acetate anion by solvent water and kHO = 3.5 × 10-9 M-1 s-1 for deprotonation of acetate anion by HO- give pKac ≈ 33.5 for acetate anion. The change in the rate-limiting step from chemical proton transfer to solvent reorganization results in a downward break in the slope of the plot of log kHO against carbon acid pKa for deprotonation of a wide range of neutral α-carbonyl carbon acids by hydroxide ion, from -0.40 to -1.0. Good estimates are reported for the stabilization of the carbonyl group relative to the enol tautomer by electron donation from α-SEt, α-OMe, α-NH2, and (αO- substituents. The α-NH2 and α-OMe groups show similar stabilizing interactions with the carbonyl group, while the interaction of α-O- is only 3.4 kcal/mol more stabilizing than for α-OH. We propose that destabilization of the enolate intermediates of enzymatic reactions results in an increasing recruitment of metal ions by the enzyme to provide electrophilic catalysis of enolate formation.
Beste,Houtz
, p. 395,396 (1952)
A scalable continuous photochemical process for the generation of aminopropylsulfones
Baumann, Marcus,Bonciolini, Stefano,Di Filippo, Mara
, p. 9428 - 9432 (2020)
An efficient continuous photochemical process is presented that delivers a series of novel γ-aminopropylsulfones via a tetrabutylammonium decatungstate (TBADT) catalysed HAT-process. Crucial to this success is the exploitation of a new high-power LED emitting at 365 nm that was found to be superior to an alternative medium-pressure Hg lamp. The resulting flow process enabled the scale-up of this transformation reaching throughputs of 20 mmol h-1 at substrate concentrations up to 500 mM. Additionally, the substrate scope of this transformation was evaluated demonstrating the straightforward incorporation of different amine substituents as well as alkyl appendages next to the sulfone moiety. It is anticipated that this methodology will allow for further exploitations of these underrepresented γ-aminopropylsulfone scaffolds in the future. This journal is
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Tamagaki et al.
, p. 3421 (1977)
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Craig,Davidson
, p. 13,17 (1951)
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Pelter,A.,Levitt,T.E.
, p. 1899 - 1908 (1970)
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Lewis Acidic Boranes, Lewis Bases, and Equilibrium Constants: A Reliable Scaffold for a Quantitative Lewis Acidity/Basicity Scale
Mayer, Robert J.,Hampel, Nathalie,Ofial, Armin R.
supporting information, p. 4070 - 4080 (2021/01/29)
A quantitative Lewis acidity/basicity scale toward boron-centered Lewis acids has been developed based on a set of 90 experimental equilibrium constants for the reactions of triarylboranes with various O-, N-, S-, and P-centered Lewis bases in dichloromethane at 20 °C. Analysis with the linear free energy relationship log KB=LAB+LBB allows equilibrium constants, KB, to be calculated for any type of borane/Lewis base combination through the sum of two descriptors, one for Lewis acidity (LAB) and one for Lewis basicity (LBB). The resulting Lewis acidity/basicity scale is independent of fixed reference acids/bases and valid for various types of trivalent boron-centered Lewis acids. It is demonstrated that the newly developed Lewis acidity/basicity scale is easily extendable through linear relationships with quantum-chemically calculated or common physical–organic descriptors and known thermodynamic data (ΔH (Formula presented.)). Furthermore, this experimental platform can be utilized for the rational development of borane-catalyzed reactions.
METHOD FOR PRODUCING N,N-DISUBSTITUTED AMIDE AND CATALYST FOR PRODUCING N,N-DISUBSTITUTED AMIDE
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Page/Page column 0055-0079, (2020/04/01)
To provide a method for producing an N, N-disubstituted amide in which an N,N-disubstituted amide can be obtained by a reaction of a nitrile and an alcohol even by a liquid phase reaction and a gas phase reaction and the object product obtained after the reaction and a catalyst can be easily separated.SOLUTION: There is provided a method for producing an N,N-disubstituted amide by reacting a nitrile and an alcohol in the presence of a catalyst, wherein the catalyst is a heterogeneous catalyst composed of a carrier and a metal oxide carried on the carrier, the carrier is at least one selected from zeolite, silica and alumina and a metal included in the metal oxide includes at least one selected from copper and molybdenum.SELECTED DRAWING: None
