347-39-7

Upstream product

• 462-06-6 fluorobenzene 
• 109-89-7 diethylamine 
• 459-60-9 1-fluoro-4-methoxybenzene 
• 372-18-9 1,3-Difluorobenzene 
• 540-36-3 para-difluorobenzene 
• 67-66-3 chloroform 
• 7664-39-3 hydrogen fluoride 
• 91-66-7 N,N-diethylaniline 
• 388078-36-2 N-ethyl-N-(4-fluoro)acetamide 
• 75-03-6 ethyl iodide 
• 371-40-4 4-fluoroaniline 
• 75-05-8 acetonitrile 
• 460-00-4 1-Bromo-4-fluorobenzene 
• 5775-33-7 N-chlorodiethylamine 

Downstream Products

• 1169841-37-5 N-ethyl-N-(4-fluorophenyl)-N'-tosylformimidamide 

Relevant academic research and scientific papers

A highly efficient Co-based catalyst fabricated by coordination-assisted impregnation strategy towards tandem catalytic functionalization of nitroarenes with various alcohols

A well-defined hexamethylenetetramine (abbreviated as HMTA) based two-dimensional (2D) MOFs metalloligand (termed Zn-HMTA), with free uncoordinated tertiary amine groups, has been synthesized via solution diffusion method for the first time. The crystal structure of 2D Zn-HMTA metalloligand was determined by the single crystal X-ray diffraction (SCXRD). The SCXRD and X-ray photoelectron spectroscopy (XPS) analyses have revealed that the 2D Zn-HMTA metalloligand is rich in- free tertiary amine groups, which are of strong coordination ability to transition metal ions (e.g. Ni2+, Co2+, Zn2+, Cu2+). As a result, a 2D bimetallic Co@Zn-HMTA MOFs was synthesized via coordination-assisted impregnation (CAI) strategy attributed to the unique feature of strong coordinated ability of free tertiary amine groups. Furthermore, a series of self-supported Co-ZnO-CN nanocatalysts were afforded upon the as-synthesized Co@Zn-HMTA MOFs served as a self-sacrificial template for pyrolysis at different temperatures. The optimized catalyst (termed as Co-ZnO@CN-CAI) demonstrated the excellent catalytic performance for hydrogenation-alkylation tandem reaction in comparison with the classic ZnO@CN composite (derived from Zn-HMTA MOFs) supported metallic Co catalyst (Co-ZnO@CN-IWI) prepared by incipient wetness impregnation method. Moreover, the kinetic study was also performed to confirm that the alkylation is the rate-determining step in the hydrogenation-alkylation tandem reaction. The origin of enhanced catalytic performance of Co-ZnO@CN-CAI and the role of Co@Zn-HMTA MOFs precursor have been explored by way of various characterizations, e.g. HADDF-STEM-EDS, SEM-EDS, 13C MAS NMR, XRD, Raman and XPS, etc. It is anticipated that the prepared low-cost and easily prepared 2D Zn-HMTA metalloligand will become a general template for synthesis of highly self-supported catalysts with coordination-assisted impregnation strategy (CAI) for various catalytic reactions.

A strategy of two-step tandem catalysis towards direct N-alkylation of nitroarenes with ethanol via facile fabricated novel Co-based catalysts derived from coordination polymers

Three novel N-doped carbon supported Co/Co3O4 catalysts, namely, Co@CN-hmta, Co@CN-larg and Co-Co3O4@CN-bipy, with sheet-, worm-, honeycomb-like morphologies respectively, have been fabricated by the pyrolysis of well-defined coordination polymers (CPs). Upon the as-prepared catalysts were applied for the reaction of N-alkylation of nitroarenes with ethanol, a direct two-step tandem reaction is realized, in which the Co@CN-hmta delivers 100% conversion/selectivity of N-ethylaniline/N,N-diethylaniline from the direct N-alkylation of nitroarenes with ethanol. The kinetic studies were conducted to confirm that the N-alkylation of aniline with ethanol is the rate-determining step in the two-step tandem reaction. The SEM/EDX, XRD, Raman, TEM, XPS, and CO2-TPD characterization results have revealed that sizes and dispersion of metallic Co, amount of structural defects and surface Lewis basicity towards three catalysts can be tuned by changing the structures of Co-based CPs designed by different organic linkers, which may also help to understand the preparation of industrial catalysts on a molecular level. The optimized Co@CN-hmta catalyst is easily recycled by using the external magnet for successive reuses without any loss in both activity and selectivity. To the best of our knowledge, this is the first carbon-nitrogen species supported Co/Co3O4 catalysts derived from the CPs, which could effectively catalyzed the N-alkylation of nitroarenes with ethanol to produce the secondary amines and/or tertiary amines. This low-cost, recyclable and easy scale-up N-doped carbon supported catalyst may be of potential application in various heterogeneous catalytic reactions.

Catalytic N-Alkylation of Amines Using Carboxylic Acids and Molecular Hydrogen

A convenient, practical and green N-alkylation of amines has been accomplished by applying readily available carboxylic acids in the presence of molecular hydrogen. Applying an in situ formed ruthenium/triphos complex and an organic acid as cocatalyst, a broad range of alkylated secondary and tertiary amines are obtained in good to excellent yields. This novel method is also successfully applied for the synthesis of unsymmetrically substituted N-methyl/alkyl anilines through a direct three-component coupling reaction of the corresponding amines, carboxylic acids, and CO2 as a C1 source.

Homogeneous catalytic hydrogenation of amides to amines

Hydrogenation of amides in the presence of [Ru(acac)3] (acacH=2,4-pentanedione), triphos [1,1,1-tris- (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from prepared from [Ru(acac) 3], triphos and MSA, or from reactions of [RuX-(OAc)(triphos)] (X=H or OAc) or [RuH2(CO)(triphos)] with MSA. Crys-tallographically characterised complexes include: [Ru(OAc-κ1O) 2(H2O)-(triphos)], [Ru(OAc-κ2O,O') (CH3SO3-κ1O)(triphos)], [Ru(CH 3SO3-κ1O)2-(H 2O)(triphos)] and [Ru2(μ-CH3SO 3)3-(triphos)2][CH3SO3], whereas other complexes, such as [Ru(OAc-κ1O)(OAc- κ2O,O')(triphos)],[Ru(CH3SO3- κ1O)(CH3SO3-κ2O,O')- (triphos)], H[Ru(CH3SO3-κ1O) 3-(triphos)], [RuH(CH3SO3-κ1O) (CO)-(triphos)] and [RuH(CH3SO3-k2O,O')- (triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.

Cobalt-catalyzed electrophilic amination of arylzincs with N-chloroamines

Roles reversed: An efficient cobalt-catalyzed electrophilic amination of arylzinc reagents has been achieved. A variety of functionalized arylzincs and N-chloroamines were coupled under mild conditions (see scheme). Both secondary and tertiary arylamines were obtained in moderate to excellent yields. Copyright

Selective N-alkylation of amines using nitriles under hydrogenation conditions: Facile synthesis of secondary and tertiary amines

Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH4OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.

Bis(triarylmethylium)-mediated diaryl ether synthesis: Oxidative arylation of phenols with N,N-dialkyl-4-phenylthioanilines

Various aryl 4-dialkylaminophenyl ethers were readily synthesized without heating in good yield from phenols and N,N-dialkyl-4-phenylthioanilines. This oxidative arylation of phenols was successfully promoted by a bis(diphenylmethylium)naphthalenediyl dication via ipso-substitution of the phenylthio group in the anilines through a radical process. Copyright

4-Fluoroanilines: Synthesis and decomposition

Fourteen N- and/or 2-substituted 4-fluoroanilines were prepared (the series includes N-C2-bridged compounds). Some of them were found to be thermally unstable when dissolved in chloroform. Both 19F NMR spectra and comparison of GIAO-DFT calculated and experimental 13C chemical shifts were used to suggest decomposition products of 4-fluoroanilines.

Amination of aryl bromides catalysed by supported palladium

Palladium particles immobilised onto a metal oxide support or Pd(0), Pd(II) and [Pd(NH3)4]2+ in NaY zeolite have been prepared and characterised. They exhibit a good activity towards the amination of aryl bromides using secondary amines such as piperidine and diethyl amine with a good regio-selectivity for these reactions. Low Pd concentrations (1 mol%) are required to observe a reasonable regio-selectivity. The catalysts can easily be separated from the reaction mixture (filtration) and reused without loss of activity and selectivity. The electronic nature of the aryl halides plays an important role for both the reaction yields and the regio-control of the reaction. It depends on the relation of the direct amination via a benzyne intermediate versus the Pd-catalysed route.

Photochemical Reactions of Substituted Benzenes with Aliphatic Amines

The products arising from the irradiation of diethylamine and t-butylamine with toluene, chlorobenzene, anisole, benzonitrile, benzyl fluoride, benzotrifluoride (α,α,α-trifluorotoluene), m-fluorobenzotrifluoride (α,α,α,m-tetrafluorotoluene), p-fluorotoluene, m-fluorotoluene, p-fluoroanisole, m-fluoroanisole, and 1,3-bis(trifluoromethyl)benzene, and of triethylamine with toluene, benzotrifluoride and 1,3-bis(trifluoromethyl)benzene, all at 254 nm, are described.Reaction pathways involving both substitution and 1,2- and 1,4-acyclic addition processes are observed and which predominates depends upon the arene substituent.The novel acyclic adduct, Me2C=CH-CH=CH-CH=NBut, is obtained from toluene and t-butylamine and, contrary to previous reports, chlorobenzene yields arene-amine 1:1 adducts as well as the amine α-substitution product (16); benzonitrile gives aniline derivatives with the primary and secondary amines.