97860-68-9

Upstream product

• 498-66-8 norborn-2-ene 
• 62820-00-2 4-cyano-N,N-dimethylaniline-N-oxide 
• 64-18-6 formic acid 
• 4714-62-9 4-cyano-N-methylaniline 
• 931-88-4 cis-Cyclooctene 
• 563-79-1 2,3-Dimethyl-2-butene 
• 142-29-0 cyclopentene 
• 110-83-8 cyclohexene 
• 873-74-5 4-Aminobenzonitrile 
• 79121-27-0 N-Methylene-p-cyanoaniline 
• 1197-19-9 4-cyano-N,N-dimethylaniline 
• 298-12-4 Glyoxilic acid 
• 667-27-6 Ethyl bromodifluoroacetate 

Downstream Products

• 1643531-65-0 (E)-tert-butyl 3-[N-(4-cyanophenyl)-N-(methyl)amino]acrylate 
• 4714-62-9 4-cyano-N-methylaniline 
• 1197-19-9 4-cyano-N,N-dimethylaniline 
• 909132-78-1 (E)-β-(4-cyano-N-methylanilino)acrylic acid ethyl ester 
• 909132-79-2 (E)-3-(4-cyano-N-methylanilino)acrylonitrile 

Relevant academic research and scientific papers

Highly Efficient Binuclear Copper-catalyzed Oxidation of N,N-Dimethylanilines with O2

A binuclear copper-salicylate complex, [Cu(Sal)2(NCMe)]2 (Sal=salicylate), was found to be an active catalyst for the oxidation of N,N-dimethylanilines by O2, affording the corresponding N-methyl-N-phenylformamides as major products. The reactions were carried out with a O2 balloon and the S/C (substrate/catalyst ratio) of the model reaction could be up to 1×105, providing a practical and highly efficient catalytic protocol for accessing N-methyl-N-phenylformamides.

An efficient method for the N-formylation of amines under catalyst- and additive-free conditions

A simple catalyst- and additive-free method for the N-formylation of amines has been developed. The advantages of this protocol include a wide range of functional group tolerance, high efficiency and a lack of required extra promoters under mild conditions. This convenient strategy will provide a facile synthesis towards N-formamide natural products and pharmaceutical derivatives. A mechanism that involves difluorocarbene is proposed for this reaction.

Catalytic and stoichiometric oxidation of N,N-dimethylanilines mediated by nonheme oxoiron(IV) complex with tetrapyridyl ligand

Nonheme iron(II) complex, [(N4Py*)FeII(CH3CN)](ClO4)2 (1) with pentadentate tetrapyridyl ligand (N4Py* = N,N-bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine) has been shown to catalyze the oxidation of N,N-dimethylaniline (DMA) with H2O2, tert-butyl hydroperoxide (TBHP), peracetic acid (PAA), meta-chloroperoxybenzoic acid (mCPBA) and PhIO resulting N-methylaniline (MA) as the predominant product with N-methylformanilide (MFA) as a result of a free-radical chain process. The product composition (MA/MFA) is remarkably influenced by the electron density on the substrate, especially in the 1/mCPBA system, and by the co-oxidants used. No formation of MFA occurred when the oxidation of DMA was carried out in the presence of 1 with PhIO as co-oxidants under argon. Based on spectral investigation (UV–Vis) of reaction systems above, oxoiron(IV) intermediate, [FeIV(N4Py*)(O)]2+ (2) has been suggested to be the key active species of the N-dealkylation reaction in all catalytic systems. The shift in the λmax value of the oxoiron(IV) species in the presence of DMA from 705 to 750 nm, and the new intense absorption in the range of 5–600 nm indicates a complexation and charge-transfer (CT) type interactions between the oxidant and substrate. The stoichiometric oxidation of various N,N-dimethylaniline derivatives with 2 provided clear evidence (Hammett correlation with ρ = ?1.99, and the large negative slope (?4.1) from the logkobs versus Eoox (DMAs) plot) for the rate-determining electron transfer (ET) followed by a proton transfer (PT) process.

N-aryl formamide prepared by using ethyl bromodifluoroacetate as formylating reagent

The invention discloses a compound of N-aryl formamide prepared by using ethyl bromodifluoroacetate as a formylating reagent. The compound is prepared by using N-alkyl arylamine as a raw material, ethyl bromodifluoroacetate as a formylating reagent and copper as a catalyst, adding different ligands, bases, etc., performing reaction under stirring in a reaction solvent at 100-120 DEG C for 10-14 hours; then filtering the reaction solution to obtain filtrate after reaction ending; concentrating the filtrate, removing the solvent by using a rotary evaporator to obtain a residue, treating the residue by silica gel column chromatography, eluting with an eluent, collecting the effluent according to the actual gradient; combining the effluent containing the product, concentrating the combined effluent to remove the solvent, and performing vacuum drying to obtain the target product. The compound has the advantages of simple and easily obtained raw materials, simple preparation process, less pollution, low energy consumption and high yield.

Copper-Catalyzed N-Formylation of Amines through Tandem Amination/Hydrolysis/Decarboxylation Reaction of Ethyl Bromodifluoroacetate

Ethyl bromodifluoroacetate (BrCF2COOEt) was first used as the N-formylating reagent in the copper-catalyzed N-formylation of amines. A range of primary, secondary, cyclic arylamines, and aliphatic amines underwent the N-formylation smoothly to furnish the N-formamides in moderate-to-excellent yields.

Electrochemical N -Formylation of Amines via Decarboxylation of Glyoxylic Acid

A new method for the synthesis of formamides has been developed through electrochemical decarboxylative N-formylation of amines with glyoxylic acid. This protocol provides an efficient approach to formamides with a broad range of functional group tolerance under ambient conditions.

Method for synthesizing N-aryl formamide compound

A method for synthesizing an N-aryl formamide compound comprises the following steps: putting an N, N-dimethylaniline compound, cuprous chloride, sodium tetrafluoroborate and salicylic acid in an organic solvent in an oxygen atmosphere, reacting for 0.5-4

Photoinduced Oxidative Formylation of N,N-Dimethylanilines with Molecular Oxygen without External Photocatalyst

A photoinduced oxidative formylation of N,N-dimethylanilines with molecular oxygen in the absence of an external photocatalyst was developed and provided the corresponding formamides in good yields under mild reaction conditions. Investigations indicated that both the starting material and product act as photosensitizers and that 1O2 coexists with O2?- during the reaction through energy transfer and single electron transfer process.

Redox inactive metal ion triggered N-dealkylation by an iron catalyst with dioxygen activation: A lesson from lipoxygenases

Utilization of dioxygen as the terminal oxidant at ambient temperature is always a challenge in redox chemistry, because it is hard to oxidize a stable redox metal ion like iron(iii) to its high oxidation state to initialize the catalytic cycle. Inspired by the dioxygenation and co-oxidase activity of lipoxygenases, herein, we introduce an alternative protocol to activate the sluggish iron(iii) species with non-redox metal ions, which can promote its oxidizing power to facilitate substrate oxidation with dioxygen, thus initializing the catalytic cycle. In oxidations of N,N-dimethylaniline and its analogues, adding Zn(OTf)2 to the [Fe(TPA)Cl2]Cl catalyst can trigger the amine oxidation with dioxygen, whereas [Fe(TPA)Cl2]Cl alone is very sluggish. In stoichiometric oxidations, it has also been confirmed that the presence of Zn(OTf)2 can apparently improve the electron transfer capability of the [Fe(TPA)Cl2]Cl complex. Experiments using different types of substrates as trapping reagents disclosed that the iron(iv) species does not occur in the catalytic cycle, suggesting that oxidation of amines is initialized by electron transfer rather than hydrogen abstraction. Combined experiments from UV-Vis, high resolution mass spectrometry, electrochemistry, EPR and oxidation kinetics support that the improved electron transfer ability of iron(iii) species originates from its interaction with added Lewis acids like Zn2+ through a plausible chloride or OTf- bridge, which has promoted the redox potential of iron(iii) species. The amine oxidation mechanism was also discussed based on the available data, which resembles the co-oxidase activity of lipoxygenases in oxidative dealkylation of xenobiotic metabolisms where an external electron donor is not essential for dioxygen activation.

Direct condensation of functionalized sp3 carbons with formanilides for enamine synthesis using an in situ generated HMDS amide catalyst

The efficient synthesis of functionalized enamines including β-enaminoesters was effectively accomplished by the direct condensation of functionalized sp3 carbanions such as acetates with formamides using in situ generated HMDS base from catalytic cesium fluoride and stoichiometric tristrimethylsilylamine. This journal is the Partner Organisations 2014.