27208-38-4Relevant academic research and scientific papers
Kinetics and mechanism of hydrolysis of N-amidomethylsulfonamides
Iley, Jim,Lopes, Francisca,Moreira, Rui
, p. 749 - 753 (2001)
The kinetics of the hydrolyses of secondary and tertiary N-amidomethylsulfonamides were studied at 50 °C. Both types of N-amidomethylsulfonamide hydrolyse through acid- and base-catalysed processes, as indicated by the pH-rate profiles. The order of reactivity for the acid-catalysed pathway implies a mechanism involving protonation of the amide followed by expulsion of a neutral amide and formation of a sulfonyliminium ion. In the base-catalysed region, compound 5c, which is substituted at both amide and sulfonamide nitrogen atoms, hydrolyses by nucleophilic attack of hydroxide ion at the amide carbonyl carbon atom to form benzoic acid and a sulfonamide. In contrast, compound 5b, which contains a sulfonamide NH group, hydrolyses to benzamide and sulfonamide products by an E1cbrev mechanism involving ionisation of the sulfonamide. Compound 5a, which contains an amide NH, also hydrolyses to sulfonamide and amide products, probably by an E2 mechanism.
Cu/SBA-15 is an efficient solvent-free and acid-free catalyst for the rearrangement of benzaldoxime into benzamide
Saidulu, Ganji,Anand, Narani,Rao, Kamaraju Seetha Rama,Burri, Abhishek,Park, Sang-Eon,Burri, David Raju
, p. 1865 - 1871 (2011)
Cu/SBA-15 catalysts with various Cu loadings in the range of 5-20 wt% were prepared by an impregnation method and characterized by N2 adsorption, X-ray diffraction, temperature programmed reduction and X-Ray photoelectron spectroscopic techniques. Cu/SBA-15 catalysts are found to be highly active and selective for the Beckmann rearrangement of benzaldoxime into benzamide under solvent-free and acid-free conditions. Graphical Abstract: [Figure not available: see fulltext.]
Sulfenamides as prodrugs of NH-acidic compounds: A new prodrug option for the amide bond
Guarino, Victor R.,Karunaratne, Veranja,Stella, Valentino J.
, p. 4910 - 4913 (2007)
The objective of this report is to introduce the novel concept of utilizing sulfenamides as prodrugs for compounds containing an NH-acidic functionality, particularly weakly acidic amide-type functionalities (amides, ureas, carbamates, etc.). Included are the syntheses and physicochemical characterizations of some model sulfenamides to illustrate the promise of this new prodrug technology.
Synthesis, structure, redox behavior, catalytic activity and DFT study of a new family of ruthenium(III)1-(arylazo)naphtholate complexes
Ramesh, Madhan,Kalidass, Mani,Jaccob, Madhavan,Kaleeswaran, Dhananjayan,Venkatachalam, Galmari
, p. 33 - 41 (2017)
Treatment of [RuCl2(DMSO)4] with 1-(arylazo)naphthol ligands in benzene under reflux afford the air-stable new ruthenium(III) complexes with general composition [Ru(L-R)3] (L = bidentate O, N donor; R = H, CH3, OCH3, Br, NO2) in good yield. The 1-(arylazo)naphthol ligands behave as tris-bidentate O, N donors via naphtholic proton and azo nitrogen. The molecular and electronic structure of the complexes have been established by elemental analysis and spectral (FT-IR, UV–vis & EPR) methods. DFT calculations were also carried out on the complexes 1 and 3 along with X-ray crystallized geometry of complex 5. These complexes in dichloromethane solution show intense ligand-to-metal charge transfer (LMCT) transitions in the visible region. The absorption and g-tensor value of these complexes (1, 3 & 5) were also computed and compared along with the available experimental results. The redox behavior of the complexes has been investigated by cyclic voltammetry and the potentials are observed with respect to the electronic nature of substituents (R) in the 1-(arylazo)naphthol ligands. These complexes have shown great promise as catalysts for the conversion of aldehydes to primary amides in good yield.
A simple Ru catalyst for the conversion of aldehydes or oximes to primary amides
Hull, Jonathan F.,Hilton, Sheena T.,Crabtree, Robert H.
, p. 1243 - 1245 (2010)
Ru(DMSO)4Cl2 is catalytically active for converting aldehydes to primary amides via oxime intermediates. This catalyst is readily available, and requires no additional ligands, a great simplification compared to previous work. A Ru(II)/(IV) mechanism is proposed.
Superoxide-mediated regioselective deblocking of the tosyl group from N-tosylcarboxamides
Raghuvanshi,Singh
, p. 3075 - 3078 (2006)
In situ-generated tetraethylammonium superoxide brings about an easy and selective cleavage of the N-S bond of N-tosylcarboxamides, providing a new method for the deblocking of the tosyl group from such substrates. Copyright Taylor & Francis Group, LLC.
General-buffer catalysis of the reaction of N-(hydroxymethyl)benzamide: A new pathway for the aqueous reaction of carbinolamides
Mennenga, Amanda G.,Johnson, Amy L.,Nagorski, Richard W.
, p. 3079 - 3083 (2005)
The second-order rate constants for the general-buffer catalyzed breakdown of N-(hydroxymethyl)benzamide (1) in water at 25°C, I = 1.0 (KCl) by pivalic, acetic, chloroacetic, and dichloroacetic acid were determined by initial rates. The observed rate increased with increasing amounts of the acidic form of the buffer and a Br?nsted correlation of α = 0.35 was determined. The results presented here, represent the first evidence for a general-buffer catalytic mechanism for the aqueous reaction of 1 and for carbinolamides in general.
The use of an electrophile carrier to determine the number of intermediates in the chlorination of 1-methylpyrrole
De Rosa, Michael,Marquez, Manuel
, p. 2125 - 2129 (2003)
A kinetic and product study of the dichloroacetic acid catalyzed chlorination of 1-methylpyrrole with 3- and 4-substituted N-chlorobenzamides was carried out. Protonated N-chlorobenzamides served as carriers of CI+. A Hammett correlation was obtained with ρ=-0.68 (r=0.98, n=8). General acid catalysis was observed with α=0.48 (r=0.99 and n=7). The yields of 2-chlorination (84±0.7%) and 3-chlorination (2.6±0.4%) were essentially constant (constant intramolecular selectivity) as the substituent on the N-chlorobenzamide was varied. Observation of constant intramolecular selectivity indicated that two intermediates were formed during the acid catalyzed chlorination of 1-methylpyrrole with N-chlorobenzamides. The carrier method is applicable to all types of aromatic systems and limited only by the availability of suitable carrier molecules.
Decomposition of N′-benzoyl-N-nitrosoureas in aqueous media
Faustino, Celia,Garcia-Rio, Luis,Leis, Jose Ramon,Norberto, Fatima
, p. 154 - 161 (2005)
The decomposition of N′-benzoyl-N-methyl-N-nitrosourea (BMNU) in aqueous media over the 0-14 pH range has been studied. In basic and neutral media (6 a = 7.8) and subsequent decomposition of the conjugate base of the thus formed nitrosourea, via an intermediate benzoyl isocyanate. Support for this mechanism is provided by the presence of N,N′-dibenzoylurea in the final reaction mixtures, as the result of the trapping of benzoyl isocyanate with benzamide generated from hydrolysis of the former. The hydrolysis of BMNU takes place through three competitive pathways: spontaneous decomposition of the conjugate base of BMNU, and buffer-catalyzed and hydroxide ion catalyzed water addition to the carbonyl group of the deprotonated nitrosourea. N′-Benzoyl-N,N′-dimethyl-N-nitrosourea (BDMNU), a benzoyl nitrosourea lacking the acidic proton of BMNU, is hydrolyzed in basic media by attack of hydroxide ion on the carbonyl group of the urea. In acid media (0 pH 6), BMNU gives only deamination products, differing from the reported behavior of other N-nitroso compounds and of the isoster nitrosoguanidine, in which denitrosation is almost quantitative. The reaction is acid-catalyzed in the 0-2.5 pH range and pH-independent in the 3-5 pH range. The presence of general acid catalysis (a = 0.60), the absence of nucleophilic catalysis, and the thermodynamic activation parameters for the reaction support the mechanism proposed in the literature for the deamination of N-nitrosoureas in acidic media. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
Exfoliation effect of PEG-type surfactant on Pd supported GO (SE-Pd(nanoparticle)/GO) in cascade synthesis of amides: A comparison with Pd(nanoparticle)/rGO
Rostamnia, Sadegh,Doustkhah, Esmail,Zeynizadeh, Behzad
, p. 88 - 95 (2016)
In the presence investigation, a cascade method for the synthesis of primary amides is discussed by the catalysis of Pd supported onto graphene oxide (Pd/GO) nanosheets. Also, the effect of different polyethyleneglycol-type (PEG-type) polyethers including PEG-300, P123 and F127 on the catalytic activity of Pd/rGO is studied in the the reaction of aldehyde and hydroxylamine hydrochloride to give benzamide. Addition of PEG-type polyethers played an important role in raising the catalytic power of Pd(nanoparticle)/GO by exfoliation of GO sheets. The present paper introduces Pd(nanoparticle)/GO as first Pd supported GO for the synthesis of primary amides through this method. This catalyst was highly active, efficient, tolerant, and environmentally benign in one-pot conditions with recyclability at least for 8 runs. Also, this study suggests the prevailing catalytic activity of Pd(nanoparticle)/GO rather to Pd(nanoparticle)/rGO in a comparitive experiment.
