51657-89-7Relevant academic research and scientific papers
A general method for N-methylation of amines and nitro compounds with dimethylsulfoxide
Jiang, Xue,Wang, Chao,Wei, Yawen,Xue, Dong,Liu, Zhaotie,Xiao, Jianliang
, p. 58 - 63 (2014/01/17)
DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst. Not just a solvent: DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst. Copyright
Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 CH bond and lewis acid catalysis
Wang, Ming-Zhong,Zhou, Cong-Ying,Wong, Man-Kin,Che, Chi-Ming
supporting information; experimental part, p. 5723 - 5735 (2010/08/20)
Ruthenium porphyrins (particularly [Ru(2,6-Cl2tpp)CO]; tpp = tetraphenylporphinato) and RuCl3 can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82
N-Demethylation of N,N-Dimethylanilines by the benzotriazole N-Oxyl radical: Evidence for a two-step electron transfer-proton transfer mechanism
Baciocchi, Enrico,Bietti, Massimo,Lanzalunga, Osvaldo,Lapi, Andrea,Raponi, Daniele
supporting information; experimental part, p. 1378 - 1385 (2010/06/11)
"Chemical Equation Presented" The reaction of the benzotriazole N-oxyl radical (BTNO) with a series of 4-X-N,N-dimethylanilines (X = CN, CF 3, CO2CH2CH3, CH3, OC6H5, OCH3) has been investigated in CH 3CN. Product analysis shows that the radical, 4-X-C6H 4N(CH3)CH2·, is first formed, which can lead to the N-demethylated product or the product of coupling with BTNO. Reaction rates were found to increase significantly by increasing the electron-donating power of the aryl substituents (p+ = -3.8). With electron-donating substituents (X = CH3, OC6H5, OCH3), no intermolecular deuterium kinetic isotope effect (DKIE) and a substantial intramolecular DKIE are observed. With electron-withdrawing substituents (X = CN, CF3, CO2CH2CH 3), substantial values of both intermolecular and intramolecular DKIEs are observed. These results can be interpreted on the basis of an electron-transfer mechanism from the N,N-dimethylanilines to the BTNO radical followed by deprotonation of the anilinium radical cation (ET-PT mechanism). By applying the Marcus equation to the kinetic data for X = CH3, OC 6H5, OCH3 (rate-determining ET), a reorganization energy for the ET reaction was determined (λ BTNO/DMA= 32.1 kcal mol- 1). From the self-exchange reorganization energy for the BTNO/BTNO- couple, a self-exchange reorganization energy value of 31.9 kcal mol-1 was calculated for the DMA·+/DMA couple.
A kinetic study of the reaction of N,N-dimethylanilines with 2,2-diphenyl-1-picrylhydrazyl Radical: A Concerted Proton-Electron Transfer?
Baciocchi, Enrico,Calcagni, Alessandra,Lanzalunga, Osvaldo
, p. 4110 - 4115 (2008/09/21)
(Chemical Equation Presented) The reactivity of the 2,2-diphenyl-1- picrylhydrazyl radical (dpph?) toward the N-methyl C-H bond of a number of 4-X-substituted-N,N-dimethylanilines (X = OMe, OPh, CH3, H) has been investigated in MeCN, in the absence and in the presence of Mg(ClO4)2, by product, and kinetic analysis. The reaction was found to lead to the N-demethylation of the N,N-dimethylaniline with a rate quite sensitive to the electron donating power of the substituent (ρ+ = -2.03). With appropriately deuterated N,N-dimethylanilines, the intermolecular and intramolecular deuterium kinetic isotope effects (DKIEs) were measured with the following results. Intramolecular DKIE [(k H/kD)intra] was found to always be similar to intermolecular DKIE [(kH/kD)inter]. These results suggest a single-step hydrogen transfer mechanism from the N-C-H bond to dpph? which might take the form of a concerted proton-electron transfer (CPET). An electron transfer (ET) step from the aniline to dpph ? leading to an anilinium radical cation, followed by a proton transfer step that produces an α-amino carbon radical, appears very unlikely. Accordingly, a rate-determining ET step would require no DKIE or at least different inter and intramolecular isotope effects. On the other hand, an equilibrium-controlled ET is not compatible with the small slope value (-0.22 kcal-1 K-1) of the log kH/ΔG° plot. Furthermore, the reactivity increases by changing the solvent to the less polar toluene whereas the reverse would be expected for an ET mechanism. In the presence of Mg2+, a strong rate acceleration was observed, but the pattern of the results remained substantially unchanged: inter and intramolecular DKIEs were again very similar as well as the substituent effects. This suggests that the same mechanism (CPET) is operating in the presence and in the absence of Mg2+. The significant rate accelerating effect by Mg2+ is likely due to a favorable interaction of the Mg2+ ion with the partial negatively charged α-methyl carbon in the polar transition state for the hydrogen transfer process.
