31309-58-7

Upstream product

• 36602-08-1 (N-methylanilino)acetonitrile 
• 74-86-2 acetylene 
• 4377-33-7 2-chloromethylpyridine 
• 100-61-8 N-methylaniline 
• 1121-60-4 pyridine-2-carbaldehyde 
• 62-53-3 aniline 
• 7032-25-9 2-(phenyliminomethyl)pyridine 
• 4329-81-1 N-phenylpyridine-2-methylamine 
• 74-88-4 methyl iodide 
• 142-08-5 2-hydroxypyridin 
• 57785-86-1 pyridin-2-yl tosylate 
• 50-00-0 formaldehyd 
• 6959-47-3 2-chloromethylpyridine hydrochloride 
• 586-98-1 2-Hydroxymethylpyridine 

Relevant academic research and scientific papers

Synthesis, structural characterization and MMA polymerization studies of dimeric 5-coordinate copper(II), cadmium(II), and monomeric 4-coordinate zinc(II) complexes supported by N-methyl-N-((pyridine-2-yl)methyl)benzeneamine

Copper(II), cadmium(II) and zinc(II) complexes containing N-methyl-N-((pyridine-2-yl)methyl)benzeneamine (npmb) ligand have been synthesized and characterized by X-ray crystallography. Molecular structures of Cu(II) and Cd(II) complexes revealed dimeric structures with square pyramidal and distorted trigonal bipyramidal geometries, respectively, involving two nitrogen atoms, two bridged and one terminal halogen ligands. However, the monomeric Zn(II) complex showed a distorted tetrahedral geometry around the Zn centre. [(npmb)ZnCl2] exhibited the higher catalytic activity (2.88 × 104 g PMMA/molZn·h) for the polymerization of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO) at 60 °C and yielded high molecular weight (11.1 g/mol × 105) syndiotactic-enriched poly(methylmethacrylate) (PMMA) compared to its Cu(II) and Cd(II) analogues.

Phosphine-Free Well-Defined Mn(I) Complex-Catalyzed Synthesis of Amine, Imine, and 2,3-Dihydro-1 H-perimidine via Hydrogen Autotransfer or Acceptorless Dehydrogenative Coupling of Amine and Alcohol

The application of nontoxic, earth-abundant transition metals in place of costly noble metals is a paramount goal in catalysis and is especially interesting if the air- and moisture-stable ligand scaffold is used. Herein, we report the synthesis of amines/imines directly from alcohol and amines via hydrogen autotransfer or acceptorless dehydrogenation catalyzed by well-defined phosphine-free Mn complexes. Both imines and amines can be obtained from the same set of alcohols and amines using the same catalyst, only by tuning the reaction conditions. The amount and nature of the base are found to be a highly important aspect for the observed selectivity. Both the primary and secondary amines have been employed as substrates for the N-alkylation reaction. As a highlight, we showed the chemoselective synthesis of resveratrol derivatives. Furthermore, the Mn-catalyzed dehydrogenative synthesis of structurally important 2,3-dihydro-1H-perimidines has also been demonstrated. Density functional theory calculations were also carried out to model the reaction path and to calculate the reaction profile.

Experimental and mechanistic insights into copper(ii)-dioxygen catalyzed oxidative: N -dealkylation of N -(2-pyridylmethyl)phenylamine and its derivatives

A di-(2-pyridylmethyl)phenylamine ((PyCH2)2NPh) supported Cu(ii)/O2 catalytic system was explored with the synthesis of pyridylmethyl-based compounds of carboxylate (PyCOOH), amide (PyC(O)NHPh), and imine (PyCHNPh) from the oxidative N-dealkylation of N-(2-pyridylmethyl)phenylamine (PyCH2NHPh) and its derivatives, by means of controlling the addition of a base and/or water to the reaction system under a dioxygen atmosphere at room temperature. Experimental studies showed that the imine and amide species could be precursors in succession in the way to the final oxidation state of carboxylates. A cyclic catalytic mechanism was proposed including the base triggered C-H bond activation of the 2-pyridylmethyl group (PyCH2-) and the intermolecular Cu-OOH α-hydrogen atom abstraction from the coordinated imine substrate (PyCHNPh).

Coupling of C(sp3)-H bonds with C(sp2)-O electrophiles: mild, general and selective

Herein is reported the mild and general coupling of amine/ether C(sp3)-H bonds with various kinds of C(sp2)-O electrophiles with high selectivity and efficiency. Valuable allylic/benzylic amines are generated in moderate to excellent yields. The utility of this transformation is demonstrated by a broad substrate scope (>50 examples), good functional group tolerance and facile product modification.

General Reductive Amination of Aldehydes and Ketones with Amines and Nitroaromatics under H2 by Recyclable Iridium Catalysts

Heterogeneous iridium catalysts were prepared and applied for the reductive amination of aldehydes and ketones with nitroaromatics and amines using H2. The iridium catalysts were prepared by pyrolysis of ionic liquid 1-methyl-3-cyanomethylimidazoulium chloride ([MCNI]Cl) with iridium chloride (IrCl3) in activated carbons. Iridium particles were well dispersed and stable in the N-doped carbon materials from [MCNI]Cl with activated carbon. The Ir@NC(600-2h) catalyst was found to be highly active and selective for the reductive amination of aldehydes and ketones using H2 and a variety of nitrobenzenes and amines were selectively converted into the corresponding secondary and tertiary amines. The Ir@NC(600-2h) catalyst can be reusable several times without evident deactivation.

Heterogeneous cobalt catalysts for reductive amination with H2: General synthesis of secondary and tertiary amines

Heterogeneous Co@NC catalysts were prepared, characterized and applied for the reductive amination of aldehydes and ketones with H2 gas. The Co catalyst Co@NC (800-2 h) was found to be active and selective for the reductive amination of aldehydes and ketones using H2 gas. Thus, general synthesis of secondary and tertiary amines was developed by the Co-catalyzed reductive amination with H2 gas, and various secondary and tertiary amines can be obtained in high yields. Moreover, a practical synthesis of N-substituted isoindolinones was also presented by a one step process with the Co@NC (800-2 h) catalyst. The Co@NC (800-2 h) catalyst is reusable at least five times without evident loss of activity.

Palladium(II) complexes with N,N′-bidentate N-methyl-N-(pyridin-2-ylmethyl)aniline and its derivatives: Synthesis, characterization, and methyl methacrylate polymerization

The N,N′-bidentate [(N,N′)PdCl2] complexes [i.e., [LnPdCl2] (Ln = L1-L5)] were synthesized by the reaction of [Pd(CH3CN)2Cl2] with N-methyl-N-(pyridin-2-ylmethyl)aniline (L1) and its derivatives (L2-L5) in ethanol. The molecular structures of [LnPdCl2] (Ln = L1-L3) were characterized using X-ray crystallography, which showed that the Pd atom in the Pd(II) complexes had a square planar geometry involving two nitrogen atoms of N,N′-bidentate and two chlorido ligands. The complexes [LnPdCl2] (Ln = L1-L5) were investigated for methyl methacrylate (MMA) polymerization in the presence of modified methylaluminoxane (MMAO) at 60°C. Specifically, complex [L1PdCl2] showed moderate catalytic activity toward MMA polymerization with an activity of 3.03 × 104 g poly(methylmethacrylate) (PMMA)/mol Pd·h and PMMA syndiotacticity (characterized by 1H NMR spectroscopy) of ～0.68.

Development of a solvent selection guide for aldehyde-based direct reductive amination processes

A range of alternative, more environmentally conservative solvents have been evaluated for use within the direct reductive amination reactions of aldehydes using borane-based reductants. The data generated has been used to develop a guide to facilitate replacement of less desirable chlorinated solvents, such as DCE, from these widely used synthetic processes.

Efficient and chemoselective direct reductive amination of aromatic aldehydes catalyzed by oxo-rhenium complexes containing heterocyclic ligands

This work describes the catalytic activity of 17 oxo-rhenium complexes containing heterocyclic ligands in the direct reductive amination of 4-nitrobenzaldehyde with 4-chloroaniline, using phenylsilane as reducing agent. In general, all of the catalysts tested gave excellent yields of the secondary amine, although, the best result was obtained with the catalytic system PhSiH3/ReOBr2(Hhmpbta)(PPh3) (2.5 mol %). This system was also applied to the synthesis of a large variety of secondary amines in good to excellent yields and tertiary amines in moderate yields, with tolerance of different functional groups.

SYNTHESIS OF 2-AMINOMETHYLPYRIDINES FROM AMINONITRILES AND ACETYLENE

2-Aminomethylpyridines were synthesized from α-aminonitriles containing various substitutents at the α-carbon atom and acetylene at elevated pressures and temperatures in the presence of η5-dicyclopentadienylcobalt (cobaltocene) as catalyst.The