4430-09-5Relevant academic research and scientific papers
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.
Method for preparing N,N-Dimethylaniline compound through alkylation of alkyl tosylate
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Paragraph 0076; 0078, (2019/07/11)
The invention provides a method for preparing a N,N-Dimethylaniline compound through alkylation of alkyl tosylate, and belongs to the technical field of organic synthesis. According to the method, paratoluensulfonyl chloride and fatty alcohol serve as raw materials, pyridine serves as an acid-binding agent, and the alkyl tosylate is generated; the alkyl tosylate as an alkylation reagent and an aniline compound are alkylated under the alkaline condition to obtain the N,N-Dimethylaniline compound. The method is implemented at normal pressure, the operation is simple, no waste acid is generated,the yield and the purity are high, and the method is suitable for industrial and scaled production.
Iridium-Catalyzed Alkylation of Amine and Nitrobenzene with Alcohol to Tertiary Amine under Base- and Solvent-Free Conditions
Li, Chao,Wan, Ke-Feng,Guo, Fu-Ya,Wu, Qian-Hui,Yuan, Mao-Lin,Li, Rui-Xiang,Fu, Hai-Yan,Zheng, Xue-Li,Chen, Hua
, p. 2158 - 2168 (2019/05/16)
Herein, an efficient and green method for the selective synthesis of tertiary amines has been developed that involves iridium-catalyzed alkylation of various primary amines with aromatic or aliphatic alcohols. Notably, the catalytic protocol enables this transformation in the absence of additional base and solvent. Furthermore, the alkylation of nitrobenzene with primary alcohol to tertiary amine has also been achieved by the same catalytic system. Deuterium-labeling experiments and a series of control experiments were conducted, and the results suggested that an intermolecular borrowing hydrogen pathway might exist in the alkylation process.
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.
Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids
Fu, Ming-Chen,Shang, Rui,Cheng, Wan-Min,Fu, Yao
, p. 9042 - 9046 (2015/08/03)
A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts.
C-N bond formation between alcohols and amines using an iron cyclopentadienone catalyst
Rawlings, Andrew J.,Diorazio, Louis J.,Wills, Martin
supporting information, p. 1086 - 1089 (2015/03/14)
An iron-tetraphenylcyclopentadienone tricarbonyl complex is demonstrated to act as a precursor of a catalyst for the formation of C-N bonds through a "hydrogen-borrowing" reaction between amines and alcohols.
Iron-catalysed tandem isomerisation/hydrosilylation reaction of allylic alcohols with amines
Li, Haoquan,Achard, Mathieu,Bruneau, Christian,Sortais, Jean-Baptiste,Darcel, Christophe
, p. 25892 - 25897 (2014/07/07)
An iron(0)-catalysed cascade synthesis of N-alkylated anilines from allylic or homoallylic alcohols and primary and secondary anilines under hydrosilylation conditions has been developed. Notably, a simple Fe(cod)(CO)3 complex (cod = cycloocta-
BippyPhos: A single ligand with unprecedented scope in the Buchwald-Hartwig amination of (hetero)aryl chlorides
Crawford, Sarah M.,Lavery, Christopher B.,Stradiotto, Mark
supporting information, p. 16760 - 16771 (2014/01/06)
Over the past two decades, considerable attention has been given to the development of new ligands for the palladium-catalyzed arylation of amines and related NH-containing substrates (i.e., Buchwald-Hartwig amination). The generation of structurally diverse ligands, by research groups in both academia and industry, has facilitated the accommodation of sterically and electronically divergent substrates including ammonia, hydrazine, amines, amides, and NH heterocycles. Despite these achievements, problems with catalyst generality persist and access to multiple ligands is necessary to accommodate all of these NH-containing substrates. In our quest to address this significant limitation we identified the BippyPhos/[Pd(cinnamyl)Cl]2 catalyst system as being capable of catalyzing the amination of a variety of functionalized (hetero)aryl chlorides, as well as bromides and tosylates, at moderate to low catalyst loadings. The successful transformations described herein include primary and secondary amines, NH heterocycles, amides, ammonia and hydrazine, thus demonstrating the largest scope in the NH-containing coupling partner reported for a single Pd/ligand catalyst system. We also established BippyPhos/ [Pd(cinnamyl)Cl]2 as exhibiting the broadest demonstrated substrate scope for metal-catalyzed cross-coupling of (hetero)aryl chlorides with NH indoles. Furthermore, the remarkable ability of BippyPhos/[Pd(cinnamyl)Cl] 2 to catalyze both the selective monoarylation of ammonia and the N-arylation of indoles was exploited in the development of a new one-pot, two-step synthesis of N-aryl heterocycles from ammonia, ortho- alkynylhalo(hetero)arenes and (hetero) aryl halides through tandem N-arylation/hydroamination reactions. Although the scope in the NH-containing coupling partner is broad, BippyPhos/[Pd(cinnamyl)Cl]2 also displays a marked selectivity profile that was exploited in the chemoselective monoarylation of substrates featuring two chemically distinct NH-containing moieties.
Alkyl substituent effects on J- or H-aggregate formation of bisazomethine dyes
Kinashi, Kenji,Lee, Kyun-Phyo,Matsumoto, Shinya,Ishida, Kenji,Ueda, Yasukiyo
experimental part, p. 783 - 788 (2012/02/05)
Bisazomethine dyes with terminal alkyl substituents of different chain lengths (BAR: R = 1, 2, 3, 4, 5 and 6) were synthesized and deposited on a glass substrate to investigate the effect of the alkyl chain length on aggregate formation. Methyl- and ethyl-substituted bisazomethine dyes (BA1 and BA2) formed J-aggregates in thin films (ca. 50 nm), whereas, propyl-, butyl-, pentyl- and hexyl-substituted derivatives (BA3, BA4, BA5 and BA6) formed H-aggregates in thin films (ca. 50 nm). The aggregate formation of the BARs changed drastically between ethyl- and propyl-substituents (BA2/BA3). However, no remarkable changes were observed in the surface morphologies of BA2 and BA3 films. It is suggested that the critical determinant of aggregate formation of BAR is the molecular packing in the film, which depends on the chain length of the terminal alkyl substituent.
