4430-09-5Relevant articles and documents
Reductive Alkylation of Azides and Nitroarenes with Alcohols: A Selective Route to Mono- And Dialkylated Amines
Borthakur, Ishani,Maji, Milan,Joshi, Abhisek,Kundu, Sabuj
, p. 628 - 643 (2021/12/27)
Herein, we demonstrated an efficient protocol for reductive alkylation of azides/nitro compounds via a borrowing hydrogen (BH) method. By following this protocol, selective mono- and dialkylated amines were obtained under mild and solvent-free conditions. A series of control experiments and deuterium-labeling experiments were performed to understand this catalytic process. Mechanistic studies suggested that the Ir(III)-H was the active intermediate in this reaction. KIE study revealed that the breaking of the C-H bond of alcohol might be the rate-limiting step. Notably, this solvent-free strategy disclosed a high TON of around 5600. Based on kinetic studies and control experiments, a metal-ligand cooperative mechanism was proposed.
Plasma-Made (Ni0.5Cu0.5)Fe2O4 Nanoparticles for Alcohol Amination under Microwave Heating
Li, Alain You,Dumaresq, Nicolas,Segalla, Andréanne,Braidy, Nadi,Moores, Audrey
, p. 3959 - 3972 (2019/08/12)
Amine N-alkylation is a process involved in the production of a wide range of chemicals. Here we describe the synthesis of well-defined (Ni0.5Cu0.5)Fe2O4 magnetic nanoparticles by plasma induction, and their successful application to amine N-alkylation using alcohols as coupling agents through a borrowing hydrogen pathway. Plasma induction allows precise morphology and size control over nanoparticle synthesis, while allowing the one-pot production of decagram quantities of material. Up to date, such nanoparticles have never been applied for organic reactions. By coupling high-end characterization techniques with catalytic optimization, we showed that small Cu(0) satellite nanoparticles played an essential role in alcohol oxidation, whereas both Ni and Cu were required for the last step of the reaction. Using elemental mapping, we demonstrated that catalyst deactivation occurred through a leaching/re-deposition mechanism of Cu and Ni. The reactions were conducted under microwave conditions, which exerted a positive effect on catalytic activity. Finally, the catalyst was active at low metal loadings (2 mol%) even on the gram-scale, and affording unprecedented TON for this reaction catalyzed by Ni/Cu bimetallic systems (19).
Substituent modification of electro-optic chromophores with 4-cyano-5-dicyanomethylene-2,5-dihydro-1H-pyrrol-2-one as an acceptor
Inada, Shunsuke,Araki, Tatsunori,Sato, Yukichi,Tatewaki, Yoko,Okada, Shuji
, p. 24 - 29 (2016/11/11)
Electro-optic chromophores with 4-cyano-5-dicyanomethylene-2,5-dihydro-1H-pyrrol-2-one (CDCOP) and aniline moieties as an acceptor and a donor, respectively, were synthesized with modification of three substituents, among which two were attached to the aniline moiety (R) and one was introduced to the CDCOP ring (R′). Butyl and hexyl groups were introduced as R and R′, and higher melting points were observed when R and R′ were the same. For the chromophore fixation, thermal crosslinking based on cyanate trimerization was performed. The chromophore with cyanate moiety in R′ was combined with bisphenol A dicyanate, and the thermal chromophore fixation was confirmed with almost no chromophore degradation.
