22699-63-4

Upstream product

• 108-94-1 cyclohexanone 
• 77287-34-4 formamide 
• 64-18-6 formic acid 
• 101-83-7 N-cyclohexyl-cyclohexanamine 
• 107-31-3 Methyl formate 
• 68-12-2 N,N-dimethyl-formamide 
• 540-69-2 ammonium formate 
• 3261-33-4 N¹,N¹,N²,N²-tetracyclohexylethane-1,2-diamine 
• 96-26-4 dihydroxyacetone 
• 124-38-9 carbon dioxide 
• 67-56-1 methanol 
• 27942-54-7 N,N-dicyclohexyl-n-butylamine 
• 67-66-3 chloroform 
• 201230-82-2 carbon monoxide 

Downstream Products

• 40683-91-8 N,N-dicyclohexylcyanamide 
• 63640-95-9 N-(Chlormethylen)-N-cyclohexyl-cyclohexanaminium-chlorid 
• 99678-84-9 N,N-Dicyclohexyldiphenylmethylamin 
• 99678-83-8 1-Butyl-N,N-dicyclohexylpentylamin 
• 99678-82-7 N,N-Dicyclohexyl-1-propylbutylamin 
• 99678-81-6 N,N-Dicyclohexyl-1-ethylpropylamin 
• 99679-21-7 N,N-Dicyclohexyl-N-(diphenylmethyl)ammonium-fluorsulfonat 
• 6030-36-0 4-methylthiophene-2-carbaldehyde 
• 5834-16-2 3-methyl-2-thiophenecarboxaldehdye 

Relevant academic research and scientific papers

Microwave assisted amine formylation by a heterogeneous HCO 2H/SiO2 system

A simple, fast and efficient procedure has been developed for the synthesis of formamides by treating a silica gel/formic acid mixture with amines under microwave irradiation.

Insertion of Carbon Monoxide into Lithium-Nitrogen Bonds. One-Pot Synthesis of Dialkylformamides and Dialkylglyoxylamides

Lithium dialkylamides react with CO to afford dialkylformamides 2, tetraalkylhydroxymalonamides 3, and dialkylglyoxylamides 4.Reaction conditions are described to produce 2 or 4 in good yields.

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.

Germyliumylidene: A Versatile Low Valent Group 14 Catalyst

Bis-NHC stabilized germyliumylidenes [RGe(NHC)2]+ are typically Lewis basic (LB) in nature, owing to their lone pair and coordination of two NHCs to the vacant p-orbitals of the germanium center. However, they can also show Lewis acidity (LA) via Ge?CNHC σ* orbital. Utilizing this unique electronic feature, we report the first example of bis-NHC-stabilized germyliumylidene [MesTerGe(NHC)2]Cl (1), (MesTer=2,6-(2,4,6-Me3C6H2)2C6H3; NHC= IMe4=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO2 with amines and arylsilane, which proceeds via its Lewis basic nature. In contrast, the Lewis acid nature of 1 is utilized in the catalyzed hydroboration and cyanosilylation of carbonyls, thus highlighting the versatile ambiphilic nature of bis-NHC stabilized germyliumylidenes.

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.

Zinc Powder Catalysed Formylation and Urealation of Amines Using CO2 as a C1 Building Block?

Transformation of CO2 into valuable organic compounds catalysed by cheap and biocompatible metal catalysts is one of important topics of current organic synthesis and catalysis. Herein, we report the zinc powder catalysed formylation and urealation of amines with CO2 and (EtO)3SiH under solvent free condition. Using 2 molpercent zinc powder as the catalyst, a series of secondary amines, both the aromatic ones and the aliphatic ones, can be formylated into formamides. When primary aromatic amines were used as the substrates, the reactions produce urea derivatives. The electronic and steric effects from the substrates on the formylation and urealation reactions were observed and discussed. The recovery and reusability of zinc powder were investigated, showing the zinc powder can be reused in the formylation reaction without loss of catalytic activity. The analysis on the reactants/products mixture after filtering out the zinc powder showed the zinc concentration in the mixture is low to 1 ppm. The pathways for the formylation and urealation of amines with this catalytic system were also investigated, and related to the different substrates.

N-Heterocyclic Carbene-Stabilized Germa-acylium Ion: Reactivity and Utility in Catalytic CO2Functionalizations

The first acceptor-free heavier germanium analogue of an acylium ion, [RGe(O)(NHC)2]X (R = MesTer = 2,6-(2,4,6-Me3C6H2)2C6H3; NHC = IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene; X = (Cl or BArF = {(3,5-(CF3)2C6H5)4B}), was isolated by reacting [RGe(NHC)2]X with N2O. Conversion of the germa-acylium ion to the first solely donor-stabilized germanium ester [(NHC)RGe(O)(OSiPh3)] and corresponding heavier analogues ([RGe(S)(NHC)2]X and [RGe(Se)(NHC)2]X) demonstrated its classical acylium-like behavior. The polarized terminal GeO bond in the germa-acylium ion was utilized to activate CO2 and silane, with the former found to be an example of reversible activation of CO2, thus mimicking the behavior of transition metal oxides. Furthermore, its transition-metal-like nature is demonstrated as it was found to be an active catalyst in both CO2 hydrosilylation and reductive N-functionalization of amines using CO2 as the C1 source. Mechanistic studies were undertaken both experimentally and computationally, which revealed that the reaction proceeds via an N-heterocyclic carbene (NHC) siloxygermylene [(NHC)RGe(OSiHPh2)].

Method for preparing N-formylated amine compounds

The invention discloses a method for preparation N-formylated amine compounds. In the method, the amine compounds and 1,3-dihydroxy acetone are taken as reaction raw materials reacting in a reactor for 2-48 hours at the reaction temperature of 0-100DEG C in a reaction medium in the presence of composite catalysts and oxidants, and the N-formylated amine compounds are obtained. The method is simpleand moderate in reaction conditions, cost can be reduced, target products can be obtained with high yield, and the catalysts used have high catalytic activity and are easy to be separated from a reaction system and reuses; the method is environment friendly during the whole process, the reaction raw materials are easy to be converted from biodiesel by-product propylene glycol, and use of glycerolis facilitated.

Ru@PsIL-Catalyzed Synthesis of N-Formamides and Benzimidazole by using Carbon Dioxide and Dimethylamine Borane

This work reports the synthesis and characterization of ruthenium nanoparticles (Ru NPs) supported on polymeric ionic liquids (PILs). This catalyst shows high catalytic activity towards the N-formylation of amines and synthesis of benzimidazoles from 1,2-diamines and carbon dioxide (CO2) by reductive dehydrogenation of dimethylamine borane. This methodology shows excellent functional group tolerance with broad substrate scope towards the synthesis of N-formamides and benzimidazoles. Interestingly, this protocol also provides the tandem reduction of 2-nitroamines and CO2 to synthesize benzimidazoles. It was proposed that the ionic liquid phase of the polymer plays pivotal roles such as assisting the stabilization of nanoparticles electrostatically, providing an ionic environment, and controlling the easy access of the substrates/reagents to the active sites. The developed methodology utilizes CO2 as a C1 source and water/ethanol as a green solvent system. Additionally, the catalyst was found to be recyclable in nature and shows five consecutive recycling runs without significant loss in its activity.

B(C6F5)3: a robust catalyst for the activation of CO2 and dimethylamine borane for the N-formylation reactions

In this work, B(C6F5)3 is utilized as an organocatalyst for the transition-metal-free N-formylation of amines using carbon dioxide (CO2) as a C1 source and dimethylamine borane (Me2NH·BH3) as a green hydrogen transfer source at 80 °C. Most reported works utilize silane and hydrogen for the N-formylation reactions using CO2 which have thus far been limited by low atom economy, high cost or the use of harsh reaction conditions. This catalytic protocol affords a broad range of formylated products in moderate to excellent yields under mild reaction conditions with a high TON and TOF. The bulky boron (B(C6F5)3) catalyst reacts with amines and forms a Frustrated Lewis Pair (FLP) and activates CO2 and Me2NH·BH3 molecules. Additionally, this boron catalyst shows high catalytic activity for the cyclization of o-phenylenediamines using CO2 and Me2NH·BH3 to synthesize benzimidazoles.