15429-21-7Relevant academic research and scientific papers
BNAH-mediated free radical addition to aromatic imines
Jin,Zhang,Yang,Liu,Liu
, p. 7357 - 7360 (2000)
Benzyl radical is added regioselectively to the carbon-nitrogen double bond of aromatic imines by UV irradiation (λ > 300 nm) of a ternary mixture of benzyl bromide/aromatic imines/1-benzyl-1,4-dihydronicotinamide (BNAH) in acetonitrile via a BNAH-mediated photoinduced electron transfer mechanism. (C) 2000 Elsevier Science Ltd.
DYNAMIC NMR AS A NONDESTRUCTIVE METHOD FOR THE DETERMINATION OF RATES OF DISSOCIATION. V. PROTON AFFINITIES OF p-SUBSTITUTED N,N-DIBENZYLANILINES IN APROTIC SOLVENTS.
Oki,Ohira,Yoshioka,Morita,Kihara,Nakamura
, p. 2224 - 2229 (1984)
Rates of proton exchange between p-substituted N,N-dibenzylanilinium ion and chloride ion in chloroform-d and acetonitrile-d//3 were determined by the dynamic NMR technique. Comparison of the kinetic proton affinity of the anilines in the aprotic solvents with the proton affinity of anilines in the gas phase and the basicity in water revealed that they could be linearly correlated. The feature of the kinetic data was a large positive entropy of activation which can be ascribed to the change from an ionic ground state to a covalent transition state. The entropy of activation was somewhat smaller in acetonitrile-d//3 than in chloroform-d. This was attributed to the change in the stage of the transition state for the exchange.
Regioselective Synthesis of 2° Amides Using Visible-Light-Induced Photoredox-Catalyzed Nonaqueous Oxidative C-N Cleavage of N, N-Dibenzylanilines
Neerathilingam, Nalladhambi,Bhargava Reddy, Mandapati,Anandhan, Ramasamy
supporting information, p. 15117 - 15127 (2021/10/25)
A visible-light-driven photoredox-catalyzed nonaqueous oxidative C-N cleavage of N,N-dibenzylanilines to 2° amides is reported. Further, we have applied this protocol on 2-(dibenzylamino)benzamide to afford quinazolinones with (NH4)2S2O8 as an additive. Mechanistic studies imply that the reaction might undergo in situ generation of α-amino radical to imine by C-N bond cleavage followed by the addition of superoxide ion to form amides.
N-Benzylation of primary amines using magnetic Fe3O4 nanoparticles functionalized with hexamethylenetetramine as an efficient and recyclable heterogeneous catalyst
Ghorbani-Vaghei, Ramin,Mirzaei-Mosbat, Maryam,Noori, Samira
, (2020/06/22)
Herein we report, a new, simple and mild procedure for N-benzylation and N,N-dibenzylation of anilines through the reaction of aniline derivatives and benzyl bromide at 60 °C in EtOH in the presence of catalytic amounts of magnetic Fe3O4 nanoparticles functionalized with hexamethylenetetramine (Fe3O4?SiO2?Propyl-HMTA). The title compounds were formed in high purity and their structures characterized by spectral analysis. The results also showed that the magnetic nanoparticle catalyst had significant advantages including, simplicity of preparation, heterogeneity, stability and recyclability. Moreover, the catalyst was characterized by various methods, such as FT-IR, SEM, VSM, TEM, TGA and XRD, after the reaction to compare with its structure before reaction.
Direct reductive coupling of nitroarenes and alcohols catalysed by Co-N-C/CNT@AC
Liu, Di,Yang, Ping,Zhang, Hao,Liu, Minjie,Zhang, Wenfei,Xu, Dongmei,Gao, Jun
, p. 2129 - 2137 (2019/04/27)
A non-noble heterogeneous catalyst-a Co, N and C composite encapsulated carbon nanotube grown in situ on the surface of activated carbon (Co-N-C/CNT@AC)-was fabricated via the pyrolysis-reduction process. Co-N-C/CNT@AC catalyzed the reductive coupling of structurally diverse nitroarenes and alcohols to imines and secondary amines under exogenous base- and solvent-free conditions. BET, TEM, SEM, XRD and XPS characterization showed that the exceptional catalytic property of Co-N-C/CNT@AC could be explained by its nanostructure, Co-N and basic N species. Our protocol had advantages of low cost, environment-friendliness, and good applicability. Furthermore, a reaction route of nitroarenes, amines and alcohols as the starting materials was proposed to improve the atom economy of the reductive coupling of nitroarenes with alcohols.
Unexpected Rearrangement of 2-Bromoaniline under Biphasic Alkylation Conditions
Barraza, Scott J.,Denmark, Scott E.
, p. 2891 - 2895 (2017/10/06)
Alkylation of 2-bromoaniline with benzyl bromide under ostensibly basic N-alkylation conditions resulted in migration of bromine from the 2- to the 4-aryl position. Herein we report our studies to elucidate the mechanism of this rearrangement with the objective of suppressing this unexpected outcome. We find that careful choice of reagents is critical, and that this behavior may be extrapolated to alkylation reactions of electron-rich bromo- and iodoanilines in general.
A by a process for preparing amine derivatives of green method (by machine translation)
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Paragraph 0124 - 0127, (2017/08/14)
The invention discloses a by a process for preparing amine derivatives of green method, dumping with amine compound in a non-transition metal catalyst under solvent-free conditions and through the controllable high selection dehydration alkylation reaction different amine derivatives, a non-transition metal catalyst is a halogenated hydrocarbon, halogenated hydrocarbon in an amount of 1 - 50 μM %, under the catalysis of the mellow and amine in halogenated hydrocarbon can be directly performed by the amine derivative dehydration reaction, the reaction temperature is 100 - 180 °C, the reaction time is 12 - 48 hours, the by-product is water, the reaction needs to be carried out under the protection of inert gas, simple conditions, easy to operate, the by-product is water, the reaction selectivity is controllable, the target high selectivity. Requirements for reaction condition of relatively low, primary and secondary alcohol can be used for the alkylation reagent, is suitable for the dehydration of the primary and secondary amines single alkylation reaction, is also suitable for the dehydration of the double alkylation reaction of a primary amine, with wider scope, should also has certain research and industrial application prospect. (by machine translation)
Selective catalytic Hofmann: N -alkylation of poor nucleophilic amines and amides with catalytic amounts of alkyl halides
Xu, Qing,Xie, Huamei,Zhang, Er-Lei,Ma, Xiantao,Chen, Jianhui,Yu, Xiao-Chun,Li, Huan
supporting information, p. 3940 - 3944 (2016/07/21)
Using only catalytic amounts of alkyl halides in the reactions of poor nucleophilic amines/amides and alcohols led to a selective Hofmann N-alkylation reaction catalytic in alkyl halides, providing a practical and efficient method for the practical synthesis of mono- or di-alkylated amines/amides in high selectivities. This new method avoids the use of large amounts of bases, alkyl halides, and solvents, and generates water as the only byproduct. Preliminary mechanistic studies showed that alkyl halides are key intermediates/catalysts regeneratable in the reaction cycle.
Deuterodechlorination of Aryl/Heteroaryl Chlorides Catalyzed by a Palladium/Unsymmetrical NHC System
Kuriyama, Masami,Hamaguchi, Norihisa,Yano, Gemba,Tsukuda, Kotaro,Sato, Kanako,Onomura, Osamu
, p. 8934 - 8946 (2016/10/14)
The catalytic deuterodechlorination of aryl/heteroaryl chlorides was developed with a palladium/unsymmetrical NHC system, and the precisely controlled introduction of deuterium into a variety of aryl/heteroaryl compounds was achieved with a high level of efficiency, selectivity, and deuteration degree. This method was also successfully applied to the transformation of bioactive agents even in a gram-scale synthesis. The crystal structure analysis of Pd-NHC complexes led to the observation of Pd-arene interaction.
Metal-free reductive amination of aldehydes for the synthesis of secondary and tertiary amines
Ambica,Khajuria, Rajni,Saini, Yeshwinder,Kapoor, Kamal K
, p. 1252 - 1259 (2015/11/25)
Reductive amination of aldehydes to produce secondary amines at room-temperature by in situ generated benzimidazoline is discussed. The bonus of the reaction is the formation of pharmaceutically important benzimidazole as a by-product in good yield, which can be recovered from the reaction mixture by simple filtration. The product, secondary amine, is transformed to tertiary amine in the same pot.
