18364-47-1

Usage

Chemical Properties

Liquid

InChI:InChI=1/C6H8N2/c1-7-6-3-2-4-8-5-6/h2-5,7H,1H3

Upstream product

• 626-60-8 3-Chloropyridine 
• 22236-96-0 3-N-formylaminopyridine 
• 462-08-8 pyridin-3-ylamine 
• 74-88-4 methyl iodide 
• 124-38-9 carbon dioxide 
• 74-89-5 methylamine 
• 115-10-6 Dimethyl ether 
• 616-38-6 carbonic acid dimethyl ester 
• 201230-82-2 carbon monoxide 
• 75-52-5 nitromethane 
• 131534-65-1 pyridine-3-boronic acid 1,3-propanediol cyclic ester 
• 68-12-2 N,N-dimethyl-formamide 
• 67-56-1 methanol 
• 2530-26-9 3-nitropyridine 

Downstream Products

• 65442-07-1 N-methyl-N-pyridin-3-yl-benzamide 
• 69658-91-9 3-nitrosomethylaminopyridine 
• 84539-50-4 (2,6-dibromo-[3]pyridyl)-methyl-amine 
• 56291-51-1 2-amino-3-methylaminopyridine 
• 500-22-1 3-pyridinecarboxaldehyde 
• 152438-43-2 Boc-Tra-Phe-nicotinylaminomethyl ketone 
• 1221277-39-9 2-hydroxy-N-methyl-N-pyridin-3-yl-benzamide 

Relevant academic research and scientific papers

Electronically tuneable orthometalated RuII–NHC complexes as efficient catalysts for C–C and C–N bond formations via borrowing hydrogen strategy

The catalytic activities of a series of simple and electronically tuneable cyclometalated RuII–NHC complexes (2a–d) were explored in various C–C/N bond formations following the borrowing hydrogen process. Slight modifications in the ligand backbone were noted to tune the activities of these complexes. Among them, the complex 2d featuring a 1,2,4-triazolylidene donor with a 4-NO2–phenyl substituent displayed the highest activity for the coupling of diverse secondary and primary alcohols with a low catalyst loading of 0.01 mol% and a sub-stoichiometric amount of inexpensive KOH base. The efficacy of this simple system was further showcased in the challenging one-pot unsymmetrical double alkylation of secondary alcohols using different primary alcohols. Moreover, the complex 2d also effectively catalyses the selective mono-N-methylation of various aromatic and aliphatic primary amines using methanol to deliver a range of N-methyl amines. Mechanistically, the β-alkylation reaction follows a borrowing hydrogen pathway which was established by the deuterium labelling experiment in combination with various control experiments. Intriguingly, in situ1H NMR and ESI-MS analyses evidently suggested the involvement of a Ru–H species in the catalytic cycle and further, the kinetic studies revealed a first order dependence of the reaction rate on the catalyst as well as the alcohol concentrations.

Preparation method of 3-methylaminopyridine and derivative or salt thereof

The invention discloses a preparation method of 3-methylaminopyridine and derivatives thereof, such as 3-methylaminopiperidine or salts thereof. The method comprises the following steps: taking carbon dioxide or carbon monoxide as a carbon source; and directly forming and efficiently combining carbonyl groups at the stage of forming a methanol precursor from carbon dioxide or carbon monoxide and hydrogen under the action of a catalyst with 3-aminopyridine, and generating 3-methylaminopyridine under the action of hydrogen. Therefore, the preparation method disclosed by the invention has high activity and selectivity, is simple to operate and low in raw material and catalyst price, does not need other reaction steps, and is beneficial to large-scale industrial production. Compared with previous reports, precious metal does not need to be used, continuous operation can be achieved, no other organic solvent or reducing agent is used in the process, generation of a large amount of organic waste liquid and solid waste is avoided, and collection operation of process products is easy.

Method for catalyzing N-alkylation of aminopyridine

The invention discloses a method for catalyzing N-alkylation of aminopyridine. The method comprises the step of reacting an aminopyridine compound with an alkylation raw material in the presence of a heterogeneous catalyst to obtain an N-alkylated aminopyridine compound. The alkylation reaction has high activity and selectivity, is simple to operate and low in catalyst price, does not need other reaction steps, is beneficial to large-scale industrial production, and compared with previous reports, does not need to use a large amount of noble metals, can be continuously carried out, and does not use other expensive organic raw materials or reducing agents in the process. Generation of a large amount of organic waste liquid and solid waste is avoided, and collection operation of process products is simple.

Ruthenium(ii) complexes with N-heterocyclic carbene-phosphine ligands for theN-alkylation of amines with alcohols

Metal hydride complexes are key intermediates forN-alkylation of amines with alcohols by the borrowing hydrogen/hydrogen autotransfer (BH/HA) strategy. Reactivity tuning of metal hydride complexes could adjust the dehydrogenation of alcohols and the hydrogenation of imines. Herein we report ruthenium(ii) complexes with hetero-bidentate N-heterocyclic carbene (NHC)-phosphine ligands, which realize smart pathway selection in theN-alkylated reactionviareactivity tuning of [Ru-H] species by hetero-bidentate ligands. In particular, complex6cbwith a phenyl wingtip group and BArF?counter anion, is shown to be one of the most efficient pre-catalysts for this transformation (temperature is as low as 70 °C, neat conditions and catalyst loading is as low as 0.25 mol%). A large variety of (hetero)aromatic amines and primary alcohols were efficiently converted into mono-N-alkylated amines in good to excellent isolated yields. Notably, aliphatic amines, challenging methanol and diamines could also be transformed into the desired products. Detailed control experiments and density functional theory (DFT) calculations provide insights to understand the mechanism and the smart pathway selectionvia[Ru-H] species in this process.

Effect of the ancillary ligand in N-heterocyclic carbene iridium(III) catalyzed N-alkylation of amines with alcohols

A series of air-stable N-heterocyclic carbene (NHC) Ir(III) complexes (Ir1-6), bearing various combinations of chlorine, pyridine and NHC ligands, were assayed for the N-alkylation of amines with alcohols. It was found that Ir3, with two monodentate 1,3-bis-methyl-imidazolylidene (IMe) ligands, emerged as the most active complex. A large variety of amines and primary alcohols were efficiently converted into mono-N-alkylated amines in 53–96% yields. As a special highlight, for the challenging MeOH, selective N-monomethylation could be achieved using KOH as a base under an air atmosphere. Moreover, this catalytic system was successfully applied to the gram-scale synthesis of some valuable compounds.

Additive-freeN-methylation of amines with methanol over supported iridium catalyst

An efficient and versatile zinc oxide-supported iridium (Ir/ZnO) catalyst was developed to catalyze the additive-freeN-methylation of amines with methanol. Mechanistic studies suggested that the high catalytic reactivity is rooted in the small sizes (1.4 nm) of Ir nanoparticles and the high ratio (93%) of oxidized iridium species (IrOx, Ir3+and Ir4+) on the catalyst. Moreover, the delicate cooperation between the IrOxand ZnO support also promoted its high reactivity. The selectivity of this catalyticN-methylation was controllable between dimethylation and monomethylation by carefully tuning the catalyst loading and reaction solvent. Specifically, neat methanol with high catalyst loading (2 mol% Ir) favored the formation ofN,N-dimethylated amine, while the mesitylene/methanol mixture with low catalyst loading (0.5 mol% Ir) was prone to producing mono-N-methylated amines. An environmentally benign continuous flow system with a recycled mode was also developed for the efficient production ofN-methylated amines. With optimal flow rates and amine concentrations, a variety ofN-methylamines were produced with good to excellent yields in this Ir/ZnO-based flow system, providing a starting point for the clean and efficient production ofN-methylamines with this cost-effective chemical process.

Selective Pd-catalyzed monoarylation of small primary alkyl amines through backbone-modification in ylide-functionalized phosphines (YPhos)

Ylide-substituted phosphines have been shown to be excellent ligands for C-N coupling reactions under mild reaction conditions. Here we report studies on the impact of the steric demand of the substituent in the ylide-backbone on the catalytic activity. Two new YPhos ligands with bulky ortho-tolyl (pinkYPhos) and mesityl (mesYPhos) substituents were synthesized, which are slightly more sterically demanding than their phenyl analogue but considerably less flexible. This change in the ligand design leads to higher selectivities and yields in the arylation of small primary amines compared to previously reported YPhos ligands. Even MeNH2 and EtNH2 could be coupled at room temperature with a series of aryl chlorides in high yields.

P(III)/P(V)-Catalyzed Methylamination of Arylboronic Acids and Esters: Reductive C-N Coupling with Nitromethane as a Methylamine Surrogate

The direct reductive N-arylation of nitromethane by organophosphorus-catalyzed reductive C-N coupling with arylboronic acid derivatives is reported. This method operates by the action of a small ring organophosphorus-based catalyst (1,2,2,3,4,4-hexamethylphosphetane P-oxide) together with a mild terminal reductant hydrosilane to drive the selective installation of the methylamino group to (hetero)aromatic boronic acids and esters. This method also provides for a unified synthetic approach to isotopically labeled N-methylanilines from various stable isotopologues of nitromethane (i.e., CD3NO2, CH315NO2, and 13CH3NO2), revealing this easy-to-handle compound as a versatile precursor for the direct installation of the methylamino group.

Selective N -monomethylation of primary anilines with the controllable installation of N -CH2D, N -CHD2, and N -CD3units

The selective N-monomethylation of primary anilines was realized by the use of the Me3N-BH3/N,N-dimethylformamide (DMF) system as the methyl source. This method also allows for the controllable introduction of N-CH2D, N-CHD2, and N-CD3 units with high lev

EffectiveN-methylation of nitroarenes with methanol catalyzed by a functionalized NHC-based iridium catalyst: a green approach toN-methyl amines

Compound [IrBr(CO)2(κC-tBuImCH2PyCH2OMe)] featuring a flexible pyridine/OMe functionalized NHC ligand κ1C coordinated efficiently catalyzes the selectiveN-monomethylation of nitroarenes using methanol as both the reducing agent and the C1 source. A range of functionalized nitroarenes including heterocyclic or sterically hindered derivatives have been efficiently converted to the correspondingN-monomethyl amines in good yields at low catalyst loadings using sub-stoichiometric amounts of Cs2CO3as a base. Mechanistic investigations support a borrowing-hydrogen mechanism in which methanol acts as the hydrogen source and methylating agent. Further, the hydrogen transfer reduction of nitrobenzene to aniline under optimized reaction conditions should proceed through a direct mechanism involving nitrosobenzene andN-phenylhydroxylamine intermediates.