35452-54-1

Upstream product

• 93-61-8 N-methyl-N-phenylformamide 
• 586-77-6 4-bromo-N,N-dimethylaniline 
• 124-38-9 carbon dioxide 
• 6911-87-1 4-bromo-N-methylaniline 
• 667-27-6 Ethyl bromodifluoroacetate 
• 32328-81-7 4-bromo-N-methylen-aniline 
• 64-18-6 formic acid 
• 106-40-1 4-bromo-aniline 
• 2617-78-9 N-(4-bromophenyl)formamide 
• 74-88-4 methyl iodide 
• 85462-16-4 N-Methyl-O-p-nitrophenylsulphonylhydroxylamine 
• 1122-91-4 4-bromo-benzaldehyde 

Downstream Products

• 2058-72-2 5-bromo-1-methyl-1H-indole-2,3-dione 
• 180140-09-4 (E)-N,N'-Bis-(4-bromo-phenyl)-1,2-dichloro-N,N'-dimethyl-ethene-1,2-diamine 
• 1643531-64-9 (E)-tert-butyl 3-[N-(4-bromophenyl)-N-(methyl)amino]acrylate 
• 157671-45-9 2-[(4-bromophenyl)(methyl)amino]acetonitrile 
• 6911-87-1 4-bromo-N-methylaniline 
• 586-77-6 4-bromo-N,N-dimethylaniline 
• 180140-18-5 5,5'-Dibromo-N³,N^3'-bis-(4-bromo-phenyl)-1,1',N³,N^3'-tetramethyl-1H,1'H-[2,2']biindolyl-3,3'-diamine 
• 653605-07-3 8,8'-bis(5,11-dimethyl-5,6,11,12-tetrahydro-2-bromodibenzo[b,f][1,5]diazocine) 
• 535920-92-4 7-bromo-4-(4-bromophenyl)-1-methylbenzo[f][1,4]-diazepine-2,3-dicarboxylic anhydride 

Relevant academic research and scientific papers

Method for preparing formamide compound by using MCOF to catalyze CO2 as carbon source at normal temperature and pressure

The invention provides a method for preparing a formamide compound by using MCOF to catalyze CO2 as a carbon source at normal temperature and pressure, and belongs to the technical field of chemistry and chemical engineering. Under the conditions of normal temperature and normal pressure, CO2 is used as a carbon source to realize N-formylation reaction of various amine substrates. The method has the advantages that the reaction system uses the metal ion-doped two-dimensional covalent organic framework MCOF as the catalyst, CO2 is reduced at normal temperature and normal pressure to provide acyl, high-pressure hydrogen and toxic CO are prevented from being used, and the reaction conditions are mild (normal temperature and normal pressure). According to the method for preparing the formamide, the greenhouse gas carbon dioxide serves as a carbon source, the cost is low, operation is easy, reaction conditions are mild (normal temperature and normal pressure), the yield of the prepared formamide product is excellent (99%), and a green synthesis method is provided for N-acylation reaction.

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.

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.

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.

Catalyst-free selective: N -formylation and N -methylation of amines using CO2 as a sustainable C1 source

We herein describe catalyst-free selective N-formylation and N-methylation of amines using CO2 as a sustainable C1 source. By tuning the reaction solvent and temperature, the selective synthesis of formamides and methylamines is achieved in good to excellent yields using sodium borohydride (NaBH4) as a sustainable reductant.

Alkyl-substituted ethyl acetate-based guanidine ionic liquid as well as preparation and application thereof

The invention discloses alkyl-substituted ethyl acetate-based guanidine ionic liquid as well as preparation and application thereof, which are characterized in that tetramethylguanidine and 2-bromo ester are ionized to obtain alkyl-substituted ethyl acetate-based guanidine ionic liquid, and the alkyl-substituted ethyl acetate-based guanidine ionic liquid is applied as a catalyst to formylation and methylation reactions of carbon dioxide, N-methylaniline and derivatives of the N-methylaniline to selectively generate N-methylformylaniline or N, N-dimethylaniline and derivatives thereof. Compared with the prior art, the alkyl-substituted ethyl acetate-based guanidine ionic liquid has the advantages of good catalytic performance, mild reaction conditions, simple post-treatment, simple synthesis, low cost, greenness and high efficiency, avoids the use of a large amount of organic solvents when being used as a solvent and a catalyst at the same time, and has important meanings in the research of medicinal chemistry and medical intermediate compounds.

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.

Unexpected Macrocyclic Multinuclear Zinc and Nickel Complexes that Function as Multitasking Catalysts for CO2 Fixations

Unique self-assembled macrocyclic multinuclear ZnII and NiII complexes with binaphthyl-bipyridyl ligands (L) were synthesized. X-ray analysis revealed that these complexes consisted of an outer ring (Zn3L3 or Ni3L3) and an inner core (Zn2 or Ni). In the ZnII complex, the inner Zn2 part rotated rapidly inside the outer ring in solution on an NMR timescale. These complexes exhibited dual catalytic activities for CO2 fixations: synthesis of cyclic carbonates from epoxides and CO2 and temperature-switched N-formylation/N-methylation of amines with CO2 and hydrosilane.

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.