34495-87-9

Upstream product

• 589-09-3 N-allyl-N-phenylamine 
• 64-18-6 formic acid 
• 85021-15-4 Allyl-N-phenylformimidat 
• 103-70-8 Formanilid 
• 106-95-6 allyl bromide 
• 67-66-3 chloroform 
• 62-53-3 aniline 
• 124-38-9 carbon dioxide 
• 667-27-6 Ethyl bromodifluoroacetate 
• 201230-82-2 carbon monoxide 
• 6247-00-3 N,N-diallylaniline 
• 1314108-34-3 2-(allyl(phenyl)amino)-1-(4-methoxyphenyl)ethanone 

Downstream Products

• 909132-81-6 (E)-3-(N-allylanilino)acrylonitrile 
• 909132-80-5 (E)-β-(N-allylanilino)acrylic acid ethyl ester 
• 589-09-3 N-allyl-N-phenylamine 

Relevant academic research and scientific papers

Visible-light-induced oxidative formylation of N-alkyl-N-(prop-2-yn-1-yl)anilines with molecular oxygen in the absence of an external photosensitizer

Visible-light-induced oxidative formylation of N-alkyl-N-(prop-2-yn-1-yl)anilines with molecular oxygen in the absence of an external photosensitizer was developed and afforded the corresponding formamides in good yields under mild conditions. The investigation of the mechanism disclosed that both the starting material and the product act as photosensitizers, and 1O2 and O2- are generated through energy transfer and a single electron transfer pathway and play an important role in the reaction.

Preparation method of formamide compound

The invention belongs to CO. 2 The invention relates to the technical field of activation conversion and related chemistry, and provides a preparation method of a formamide compound, which uses carbon dioxide. The amide compound and phenylsilane are used as raw materials, and the formamide compound is synthesized under the action of the nano porous palladium catalyst. The invention mainly provides a novel simple catalytic system and utilizes CO. 2 C1 The catalytic system has the advantages of mild reaction conditions, simple experiment operation, good functional group compatibility and the like. Because carbon dioxide is abundant, cheap and easily available and renewable C1 , The invention has great application value and social economic benefits.

Design of Lewis base functionalized ionic liquids for the N-formylation of amines with CO2 and hydrosilane: The cation effects

A series of functionalized ionic liquids (ILs) were developed for the reductive functionalization of CO2 with amine and hydrosilane to afford formamides under mild conditions. It was found that 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)-based IL i.e. [DBUC12]Br showed high efficiency for the N-formylation reaction of amines without using any organic solvents or additives. Furthermore, control experiments suggested the cations with active hydrogen may weaken the nucleophilicity of anions through ion pairing interactions, thereby affecting the activation of hydrosilane. The reaction mechanism was then investigated by Density Functional Theory (DFT) calculations. This protocol represents a highly efficient and environmentally friendly example for catalytic conversion of CO2 into value-added chemicals such as formamide derivatives by employing DBU functionalized ILs.

Synthesis of silyl formates, formamides, and aldehydesviasolvent-free organocatalytic hydrosilylation of CO2

Carbon dioxide (CO2) was used as a C1 source to prepare silyl formates, formamides, and aldehydes. Tetrabutylammonium acetate (TBAA) catalyzed the solvent-freeN-formylation of amines with CO2and hydrosilane to give formamides including Weinreb formamide, Me(MeO)NCHO, which was successively converted into aldehydes by one-pot reactions with Grignard reagents.

Selective: N-formylation/N-methylation of amines and N-formylation of amides and carbamates with carbon dioxide and hydrosilanes: Promotion of the basic counter anions of the zinc catalyst

A catalyst composed of commercially available Zn(OAc)2 and 1,10-phenanthroline (phen) was effective in the N-formylation/N-methylation of amines using CO2 as the C1 source in the presence of hydrosilanes. An equimolar reaction of N-methylaniline with PhSiH3 under a CO2 atmosphere yielded the N-formylation product in 92% yield at 25 °C. Scale-up of the reaction using 10 mmol substrate was also successful in affording the desired product in 83% yield (1.1 g). This catalyst exhibits a high thermal stability and a turnover number (TON) of 385000 at 150 °C. In addition, the reaction of N-methylaniline in the presence of excess Ph2SiH2 produced N,N-dimethylaniline. Furthermore, our catalytic protocol was developed for the N-formylation of amides and carbamates, which have smaller pKa values and lower reactivities than the corresponding amines. The present Zn(OAc)2/phen catalyst was found to show versatility in the conversion of CO2 and amines into several functionalized organic chemicals under mild conditions. We propose that the basic counter anion (i.e., the acetate) of the catalyst activates both the Si-H and N-H bonds.

Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide

We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.

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.

Mn-Catalyzed Selective Double and Mono-N-Formylation and N-Methylation of Amines by using CO2

Functionalization of amines by using CO2 is of fundamental importance considering the abundance of amines and CO2. In this context, the catalytic formylation and methylation of amines represent convenient and successful protocols for selective CO2 utilization as a C1 building block. This study represents the first example of selective catalytic double N-formylation of aryl amines by using a dinuclear Mn complex in the presence of phenylsilane. This robust system also allows for selective formylation and methylation of amines under a range of conditions.

Iron-Catalyzed Selective N-Methylation and N-Formylation of Amines with CO2

We herein describe an efficient iron-catalyzed selective N-methylation and N-formylation of amines with CO2 and silane using mono-phosphine as ligand. With commercially available [CpFe(CO)2]2 as catalyst, Fe-catalyzed methylation of amines was achieved with triphenylphosphine as a ligand. Using tributylphosphine as a ligand, Fe-catalyzed formylation of amines was realized at a lower temperature. The method was successfully applied in the late-stage methylation and formylation of drug molecules containing amine moiety. (Figure presented.).

Eco-friendly acetylcholine-carboxylate bio-ionic liquids for controllable: N-methylation and N-formylation using ambient CO2 at low temperatures

Catalytic fixation of CO2 to produce valuable fine chemicals is of great significance to develop a green and sustainable circulation of excessive carbon in the environment. Herein, a series of non-toxic, biodegradable and recyclable acetylcholine-carboxylate bio-ionic liquids with different cations and anions were simply synthesized for producing formamides and methylamines using atmospheric CO2 as a carbon source, and phenylsilane as a hydrogen donor. The selectivity toward products was tuned by altering the reaction temperature under solvent or solvent-free conditions. N-Methylamines (ca. 96% yield) were obtained in acetonitrile at 50 °C, while N-formamides (ca. 99% yield) were attained without a solvent at 30 °C. The established bio-ionic liquid catalytic system found a wide range of applicability in substrates and possessed a high potentiality in scale-up to gram-grade production. The developed catalytic system was fairly stable, which could be easily reused without an apparent loss of reactivity, possibly due to the strong electrostatic interactions between the cation and anion. The combination of experimental and computational results explicitly elucidated the reaction mechanism: PhSiH3 activated by a bio-IL was favorable for the formation of silyl formate from hydrosilylation of CO2, followed by a reaction with an amine to give an N-formamide, while an N-methylamine was formed by further hydrosilylation of the N-formamide.