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The reactions of N,N-dimethyl-p-anisidine (1a), N,N-dimethylaniline (1b), and N,N-dimethyl-p-fluoroaniline (1c) toward secondary anilines 2(a- d)-H in the presence of thallium triacetate sesquihydrate have been studied as representative of a novel oxidatively activated aromatic substitution affording 1,4-benzenediamine derivatives 3a-d. All of the substrates considered gave substitution with diphenylamine (2d-H). However, with anilines 2b,c-H, only 1a underwent substitution, and substrates 1b,c were practically unreactive. The observed differences in reactivity are well accounted for within a mechanistic framework wherein oxidative activation of both the substrate and the secondary aniline is regarded as alternatively (or simultaneously) possible, depending on the redox characteristics of the reactants. For instance, it can be stated, beyond any reasonable doubt, that reactions of 1a with 2b,c-H proceed via nucleophilic attack of the latter on 1a+., and that the reaction of 1a-c with 2d-H must involve the diphenylamino radical 2d·.

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The iron-catalyzed alpha-C-H alkylation of N-methylanilines without any directing group by cross-dehydrogenative coupling between unactivated C(sp3)-H and C(sp3)-H bonds has been established for the first time, which provides a good complement to C(sp3)-H activation reactions and expands the field of Fe-catalyzed C-H functionalizations. Many different C(sp3)-H bonds in cyclic alkanes, cyclic ethers, and toluene derivatives can be used as coupling partners. Mechanistic investigations including the radical reaction process, the main role of various reagents, and the kinetic isotope effect experiment were also described.

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A new, efficient route for the enantioselective construction of bispirotetrahydrofuran oxindoles is described via the cooperative dinuclear zinc-AzePhenol catalyst. Under mild conditions, a broad range of bispirotetrahydrofuran oxindoles have been synthesized with excellent stereoselectivities through the cascade Michael/hemiketalization/Friedel-Crafts reaction of beta,gamma-unsaturated alpha-ketoamide and 2-hydroxy-1-indanone. The reaction can be performed on a gram scale with low catalyst loading (2 mol %) without impacting its efficiency.

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The present account surveys the results of the plethora of works on N-methylation of nitrogen-containing substrates, mainly amines. The countless reports in the literature on this issue reveal the emergence of a set of methylating agents, which include: methanol, dimethyl carbonate, formaldehyde/formic acid, carbon dioxide/reductant, methyl iodide, dimethylsulfate, peroxides, dimethylsulfoxide, tetramethylammonium salts, and other unusual ones. Types of the methylating agents including, catalyst, solvent, base, ligand, reducing agent and other reaction conditions such as temperature and time would greatly affect the extent of selectivity of N-monomethylation vis-a-vis N,N-dimethylation. The degree of acidity or alkalinity of catalysts such as the solid catalysts (i.e. zeolites) showed a substantial impact on the selectivity and the course of methylation, leading to design adequate catalysts or to bring suitable modifications to the existing ones. Although this account takes into consideration all types of methylating agents, it is worthwhile to mention that the relatively recent works have been focused on the utilization of eco-friendly methylating agents, including carbon dioxide/reductant, methanol, and dimethylcarbonate. N-Methyl-containing drugs were successfully synthesized with some methylating agents under specified conditions. In some instances, unexpected products and events from the planned N-methylation of some nitrogen-containing molecules occurred. N-Formylation occurred as an intermediate or concomitant reaction when amines were subjected to catalyze methylation with methanol, formaldehyde/formic acid, and carbon dioxide/reductant. The occasionally depicted mechanisms would elucidate the carbon and hydrogen sources of the affixing methyl group on the nitrogen site. Peculiarly, methylation involving methanol as a methylating agent and transition metal catalysis called for borrowing hydrogen process as a new mechanistic approach.

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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 33282-15-4, name is 5-(4-Hydroxyphenyl)isoxazole-3-carboxylic acid, introducing its new discovery. HPLC of Formula: C10H7NO4

(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 (rho+ = -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 alpha-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/DeltaG 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 alpha-methyl carbon in the polar transition state for the hydrogen transfer process.

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Catalytic fixation of CO2 to produce valuable fine chemicals is of great significance to develop a green and sustainable circulation of excessive carbon in the environment. Herein, a series of non-toxic, biodegradable and recyclable acetylcholine-carboxylate bio-ionic liquids with different cations and anions were simply synthesized for producing formamides and methylamines using atmospheric CO2 as a carbon source, and phenylsilane as a hydrogen donor. The selectivity toward products was tuned by altering the reaction temperature under solvent or solvent-free conditions. N-Methylamines (ca. 96% yield) were obtained in acetonitrile at 50 C, while N-formamides (ca. 99% yield) were attained without a solvent at 30 C. The established bio-ionic liquid catalytic system found a wide range of applicability in substrates and possessed a high potentiality in scale-up to gram-grade production. The developed catalytic system was fairly stable, which could be easily reused without an apparent loss of reactivity, possibly due to the strong electrostatic interactions between the cation and anion. The combination of experimental and computational results explicitly elucidated the reaction mechanism: PhSiH3 activated by a bio-IL was favorable for the formation of silyl formate from hydrosilylation of CO2, followed by a reaction with an amine to give an N-formamide, while an N-methylamine was formed by further hydrosilylation of the N-formamide.

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A fuel composition is provided that contains a major amount of a mixture of hydrocarbons in the gasoline boiling range and a minor amount of a certain aniline additive compound. Use of such aniline additive compound in a combustion engine is also provided.

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A novel catalytic reaction has been designed to utilize, for the first time, CO2 as a C1 feedstock in the synthesis of N-methylamines. Simple zinc catalysts, based on commercially available zinc salts and ligands, prove highly efficient in promoting both a 6 electron reduction of carbon dioxide and the formation of a C-N bond, using hydrosilanes and amines.

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An expedient one-pot procedure for the atom-efficient production of a variety of sulfonylguanidines and sulfamoylguanidines under mild conditions is described. The route constitutes an important alternative to current methods.

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An efficient protocol for the preparation of alpha-aminoamides was developed via the Ru(II)-dm-Pheox catalyzed N-H insertion reaction of various diazoacetamides with several amines, including aniline. This catalytic N-H insertion reaction was also applied to the synthesis of 2-(2-methylquinolin-4- ylamino)-N-phenylacetamide, a potential antileishmanial agent.

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Reference:
Isoxazole – Wikipedia,
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