698-69-1

Usage

InChI:InChI=1/C8H8FN/c9-7-1-3-8(4-2-7)10-5-6-10/h1-4H,5-6H2

Upstream product

• 512-56-1 trimethyl phosphite 
• 106-47-8 4-chloro-aniline 
• 50-00-0 formaldehyd 
• 64-18-6 formic acid 
• 77-78-1 dimethyl sulfate 
• 74-88-4 methyl iodide 
• 121-69-7 N,N-dimethyl-aniline 
• 99-98-9 4-amino-N,N-dimethylaniline 
• 874-52-2 N,N-dimethylaniline N-oxide 
• 20126-93-6 N-Isopropylacetonitrilium hexachloroantimonate 
• 876-00-6 p-chloro-N,N-dimethylaniline-N-oxide 
• 151-50-8 potassium cyanide 
• 67-56-1 methanol 
• 104745-41-7 4-chlorophenyl-1-phenylethyldimethylammonium bromide 

Downstream Products

• 1007-19-8 4-chloro-N-methyl-N-nitrosoaniline 
• 87066-91-9 5-chloro-2-dimethylamino-benzyl alcohol 
• 77265-65-7 5-chloro-2-dimethylamio-benzoic acid 
• 10219-10-0 N-(4-chloro-phenyl)-N-methylacetamide 
• 2442-15-1 4-Chloro-N,N,N-trimethylanilinium iodide 
• 62533-40-8 2-Chloro-5-dimethylamino-benzenesulfonyl chloride 
• 932-96-7 N-methyl(p-chloroaniline) 
• 26772-93-0 N-(4-chlorophenyl)-N-methylformamide 
• 39217-12-4 2-[(4-chlorophenyl)(methyl)amino]acetonitrile 
• 366-29-0 N,N,N',N'-tetramethylbenzidine 
• 1591-30-6 (1,1'-biphenyl)-4,4'-dicarbonitrile 
• 27104-69-4 4-(N,N-dimethylamino)-4'-carbonitrile-1,1'-biphenyl 
• 121-69-7 N,N-dimethyl-aniline 
• 90702-07-1 N-methyl-N-succinimidomethyl-o-bromo-p-chloroaniline 

Relevant academic research and scientific papers

Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst

Formic acid is used as the sole carbon and hydrogen source in the methylation of aromatic and aliphatic amines to methylamines. The reaction proceeds via a formylation/transfer hydrogenation pathway over a solid Pd/In2O3 catalyst without the need for any additive.

Borane-Trimethylamine Complex as a Reducing Agent for Selective Methylation and Formylation of Amines with CO2

We report herein that a borane-trimethylamine complex worked as an efficient reducing agent for the selective methylation and formylation of amines with 1 atm CO2 under metal-free conditions. 6-Amino-2-picoline serves as a highly efficient catalyst for the methylation of various secondary amines, whereas in its absence, the formylation of primary and secondary amines was achieved in high yield with high chemoselectivity. Mechanistic studies suggest that the 6-amino-2-picoline-borane catalytic system operates like an intramolecular frustrated Lewis pair to activate CO2.

Mesoionic N-heterocyclic olefin catalysed reductive functionalization of CO2for consecutiveN-methylation of amines

A mesoionic N-heterocyclic olefin (mNHO) was introduced as a metal-free catalyst for the reductive functionalization of CO2leading to consecutive doubleN-methylation of primary amines in the presence of 9-borabicyclo[3.3.1]nonane (9-BBN). A wide range of secondary amines and primary amines were successfully methylated under mild conditions. The catalyst sustained over six successive cycles ofN-methylation of secondary amines without compromising its activity, which encouraged us to check its efficacy towards doubleN-methylation of primary amines. Moreover, this method was utilized for the synthesis of two commercially available drug molecules. A detailed mechanistic cycle was proposed by performing a series of control reactions along with the successful characterisation of active catalytic intermediates either by single-crystal X-ray study or by NMR spectroscopic studies in association with DFT calculations.

Alcohol promoted N -methylation of anilines with CO2/H2over a cobalt catalyst under mild conditions

N-Methylation of amines with CO2/H2 to N-methylamines over non-noble metal catalysts is very interesting but remains challenging. Herein, we present an alcohol (e.g., ethanol) promoted strategy for the N-methylation of anilines with CO2/H2 with high efficiency under mild conditions (e.g., 125 °C), which is achieved over a cobalt catalytic system composed of Co(OAc)2·4H2O, triphos and Sn(OTf)2. This catalytic system has a broad substrate scope and is tolerant toward a wide range of anilines and N-methyl anilines, and a series of N,N-dimethyl anilines were obtained in high yields. Mechanism investigation indicates that the alcohol solvent shifts the equilibrium of CO2 hydrogenation by forming an alkyl formate, which further reacts with the amine to produce N-formamide, and Sn(OTf)2 promotes the deoxygenative hydrogenation of N-formamides to afford N-methylamines. This is the first example of the N-methylation of amines with CO2/H2 over a cobalt catalytic system, which shows comparable performance to the reported Ru catalysts and may have promising applications.

Photochemical Reaction of N,N-Dimethylanilines with N-Substituted Maleimides Utilizing Benzaldehyde as the Photoinitiator

Photoorganocatalysis constitutes a powerful domain of photochemistry and organic synthesis. The scaffold of pyrrolo[3,4-c]quinolinoles exhibits interesting and potent inhibition against various enzymes, making them really promising pharmaceutical targets. Herein, we describe a photochemical methodology for the reaction of N,N-dimethylanilines with N-substituted maleimides, utilizing benzaldehyde as the photoinitiator. A variety of substituted N,N-dimethylanilines and N-substituted maleimides were converted into the corresponding adducts in moderate to high yields.

Aminomethylation of Aryl Bromides by Nickel-Catalyzed Electrochemical Redox Neutral Cross Coupling

We develop an electrochemical nickel-catalyzed aminomethylation of aryl bromides under mild conditions. The convergent paired electrolysis makes full use of anode and cathode processes, free of a terminal oxidant, a sacrificial anode, a metal reductant, and a prefunctionalized radical precursor. In addition, this method exhibits wide functional group tolerance (63 examples), including some sensitive substituents and aromatic heterocycles. This redox neutral cross coupling provides a more environmentally friendly and synthetic practical protocol for forging C(sp2)–C(sp3) bonds.

Preparation method of N-alkylated derivative of primary amine compound

The invention relates to a preparation method of an N-alkylated derivative of a primary amine compound. The method comprises the following steps: uniformly mixing a primary amine compound, an alcohol compound and a catalyst in a reactor, and heating to react for a period of time to generate an N-alkylated substituted tertiary amine compound; wherein the catalyst is a copper-cobalt bimetallic catalyst, and the carrier of the catalyst is Al2O3. According to the method, alcohol is adopted as an alkylating reagent and is low in price and easy to obtain, a byproduct is water, no pollution is caused to the environment, and the overall reaction atom economy is high; the catalyst is simple in preparation method, low in cost, high in reaction activity and good in structural stability; meanwhile, by using the copper-cobalt bimetallic catalyst, the use of strong base additives can be avoided, and the requirement on reaction equipment is low; and the reaction post-treatment is convenient, and the catalyst can be recycled and is environment-friendly.

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.

Dirhodium-Catalyzed Chemo-and Site-Selective C-H Amidation of N, N-Dialkylanilines

A method for dirhodium-catalyzed C(sp 3)-H amidation of N, N-dimethylanilines was developed. Chemoselective C(sp 3)-H amidation of N-methyl group proceeded exclusively in the presence of C(sp 2)-H bonds of the electron-rich aromatic ring. Site-selective C(sp 3)-H amidation proceeded exclusively at the N-methyl group of N-methyl-N-Alkylaniline derivatives with secondary, tertiary, and benzylic C(sp 3)-H bonds α to a nitrogen atom.

Fe(III)-catalyzed Oxidative Povarov Reaction with Molecular Oxygen Oxidant

The synthesis of tetrahydroquinoline derivatives from dimethyl anilines and enamides has been developed by Fe(III)-phenanthroline complex under aerobic condition. The oxidation of tertiary anilines involving a single electron transfer of Fe(phen)3(PF6)3 afforded the iminium ion intermediate, which reacted with electron-rich alkenes to build a six-membered N-heterocycles containing quaternary carbon center via the oxidative Povarov reaction process.