33513-42-7

Basic information

• Product Name: N,N-dimethyl-formamide
• CAS NO: 33513-42-7
• Molecular Weight: 73.0947
• Mol File: 33513-42-7.mol
• Article Data: 205

Chemical Properties

• CAS DataBase Reference: N,N-dimethyl-formamide(CAS DataBase Reference)
• NIST Chemistry Reference: N,N-dimethyl-formamide(33513-42-7)
• EPA Substance Registry System: N,N-dimethyl-formamide(33513-42-7)

Safety Data

• Hazardous Substances Data: 33513-42-7(Hazardous Substances Data)

Upstream product

• 75-87-6 chloral 
• 124-40-3 dimethyl amine 
• 64-18-6 formic acid 
• 5815-08-7 tert-Butoxybis(dimethylamino)methane 
• 6343-54-0 N-benzylformamide 
• 125074-98-8 C₁₃₁H₁₁₂O₂₂*C₃H₇NO 
• 92446-10-1 [(E)-3-(4-Hydroxy-3-methoxy-phenyl)-acryloyloxymethylene]-dimethyl-ammonium; chloride 
• 618-36-0 rac-methylbenzylamine 
• 88-88-0 2,4,6-trinitrochlorobenzene 
• 15364-56-4 dimethylaminoacetone 
• 124-38-9 carbon dioxide 
• 19449-26-4 N,N-dimethylformamide ethylene acetal 
• 2206-27-1 dimethylsulfoxide-d6 
• 2802-08-6 (E)-4-(dimethylamino)but-3-en-2-one 

Downstream Products

• 42499-41-2 1-Nitro-piperazin 
• 98-01-1 furfural 
• 98-03-3 thiophene-2-carbaldehyde 
• 498-62-4 3-thiophene carboxaldehyde 
• 930-96-1 3-bromo-2-thiophenecarboxaldehyde 
• 23074-10-4 5-ethylfurfural 
• 2199-58-8 3,5-dimethylpyrrole-2-carbaldehyde 
• 2199-61-3 3,5-dimethyl-pyrrole-2,4-dicarbaldehyde 
• 85895-83-6 3,5-dimethyl-2-thiophenecarboxaldehyde 
• 24445-35-0 5-(methylthio)thiophene-2-carboxaldehyde 
• 2564-95-6 N,N-dimethylsuccinamic acid 
• 2199-59-9 ethyl (5-formyl-2,4-dimethyl-1H-pyrrole)-3-carboxylate 
• 21154-18-7 N,N-dimethylquinolin-2-amine 
• 31401-47-5 N,N-dimethyl-4-quinolylamine 

Relevant articles and documents

Bulk gold-catalyzed oxidations of amines and benzyl alcohol using amine N-oxides as oxidants

Bulk gold powder (～50 μm) catalyzes the oxidative dehydrogenation of amines to give imines using amine N-oxides (R3N-O) as the oxidant. The reaction of dibenzylamine (PhCH2-NH-CH2Ph) with N-methylmorpholine N-oxide (NMMO) in the presence of gold powder at 60 °C produced N-benzylidenebenzylamine (PhCH=N-CH2Ph) in 96% yield within 24 h. Benzyl alcohol was oxidized by NMMO to benzaldehyde in >60% yield in the presence of gold powder. Although O2 was previously shown to oxidize amines in the presence of bulk gold, it is surprising that gold is also capable of catalyzing the oxidation of amines using amine oxides, which are chemically so different from O2. Graphical Abstract: [Figure not available: see fulltext.]

Catalytic Formylation of Primary and Secondary Amines with CO2 and H2 Using Abundant-Metal Catalysts

Catalytic hydrogenation of CO2 is an efficient and selective way to prepare formic acid derivatives, but most of the highly active catalysts used for this purpose require precious metals. In this study, in situ abundant-metal complexes have been evaluated as potential catalysts for CO2 hydrogenation to prepare formamides, including N-formylmorpholine, 2-ethylhexylformamide, and dimethylformamide, from the corresponding amines. From these initial screening results, the most active catalysts for these reactions were found to be MX2/dmpe in situ catalysts (M = Fe(II), Ni(II); X = Cl-, CH3CO2-, acac- dmpe = 1,2-bis(dimethylphosphino)ethane) in DMSO. The optimal reaction conditions were found to be 100-135 °C and a total pressure of 100 bar. Morpholine was formylated with a TON value of up to 18000, which is the highest TON for the hydrogenation of CO2 to formamides using any abundant-metal-phosphine complex. With an appropriate selection of catalyst and reaction conditions, >90-98% conversion of amine to formamide could be achieved.

The interaction of N,N,N′,N′-tetramethylphosphoric triamide with chloral: Phosphorus-nitrogen fission products and the X-ray crystal structure of N,N,N′,N′-tetramethyl-n″-(2,2,2-trichloro-1- dimethylaminoethyl)phosphoric triamide

The interaction of N,N,N′,N′-tetramethylphosphoric triamide with chloral gives dimethylformamide, chloroform, and a complex mixture of phosphorus-containing products, amongst which N,N,N′,N′-tetramethyl-N″-(2,2,2-trichloro-1- dimethylaminoethyl)phosphoric triamide was characterized by single crystal X-ray diffraction. Dimethylamino(imino)oxophosphorane is postulated as a tricoordinate phosphorus (V) by-product, which undergoes oligomerization or reaction with other components of the reaction system.

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Synthesis of N,N-dimethylformamide from carbon dioxide in aqueous biphasic solvent systems

This paper presents the homogeneous catalyzed hydrogenation of carbon dioxide to N,N-dimethylformamide (DMF) with an in-situ generated ruthenium catalyst based on RuCl3?×?H2O and the phosphine ligand 2,2′-bis(diphenylphosphinomethyl)-1,1′-biphenyl (BISBI). Investigations showed that the complex formation of an active species requires the presence of an amine. The catalyst was recycled by immobilization in a nonpolar alcoholic solvent while the formed product was extracted in-situ into the aqueous phase. The self-assembling reaction system showed stability for 10 recycling runs without a significant loss of activity resulting in an average yield of 31% DMF at 40?bar and 140?°C without the occurrence of any byproducts. Furthermore, a combination of the developed reaction system with ternary amines enables the application of wash amine solutions as carbon dioxide carrier.

Thermodynamic Analysis of Metal-Ligand Cooperativity of PNP Ru Complexes: Implications for CO2 Hydrogenation to Methanol and Catalyst Inhibition

The hydrogenation of CO2 in the presence of amines to formate, formamides, and methanol (MeOH) is a promising approach to streamlining carbon capture and recycling. To achieve this, understanding how catalyst design impacts selectivity and performance is critical. Herein we describe a thorough thermochemical analysis of the (de)hydrogenation catalyst, (PNP)Ru-Cl (PNP = 2,6-bis(di-tert-butylphosphinomethyl)pyridine; Ru = Ru(CO)(H)) and correlate our findings to catalyst performance. Although this catalyst is known to hydrogenate CO2 to formate with a mild base, we show that MeOH is produced when using a strong base. Consistent with pKa measurements, the requirement for a strong base suggests that the deprotonation of a six-coordinate Ru species is integral to the catalytic cycle that produces MeOH. Our studies also indicate that the concentration of MeOH produced is independent of catalyst concentration, consistent with a deactivation pathway that is dependent on methanol concentration, not equivalency. Our temperature-dependent equilibrium studies of the dearomatized congener, (*PNP)Ru, with various H-X species (to give (PNP)Ru-X; X = H, OH, OMe, OCHO, OC(O)NMe2) reveal that formic acid equilibrium is approximately temperature-independent; relative to H2, it is more favored at elevated temperatures. We also measure the hydricity of (PNP)Ru-H in THF and show how subsequent coordination of the substrate can impact the apparent hydricity. The implications of this work are broadly applicable to hydrogenation and dehydrogenation catalysis and, in particular, to those that can undergo metal-ligand cooperativity (MLC) at the catalyst. These results serve to benchmark future studies by allowing comparisons to be made among catalysts and will positively impact rational catalyst design.

Electrochemical Reaction of CO2 with MeNH to Afford N,N-Dimethylformamide, Catalyzed by 2+ (bpy = 2,2'-bipyridine)

Electrochemical CO2 reduction catalyzed by 2+ in the presence of Me2NH and Me2NH*HCl in anhydrous acetonitrile catalytically produces HCOO- and N,N-dimethylformamide (DMF) with current efficiency 75.7 and 21.4percent, respectively, via the carbamoyl Ru(II) complex as an intermediate, whose formation was confirmed by FT-IR and 1H NMR spectra.

Nucleophilic Activation of CO for Reduction by Hydrogen

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Partially reduced iridium oxide clusters dispersed on titania as efficient catalysts for facile synthesis of dimethylformamide from CO2, H 2 and dimethylamine

A novel bifunctional catalyst based on partially reduced iridium oxide supported on TiO2 was found to be exceedingly efficient for the organic-solvent-free synthesis of dimethylformamide from CO2, H 2 and dimethylamine. This journal is the Partner Organisations 2014.

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Aqueous Biphasic Systems for the Synthesis of Formates by Catalytic CO2 Hydrogenation: Integrated Reaction and Catalyst Separation for CO2-Scrubbing Solutions

Aqueous biphasic systems were investigated for the production of formate–amine adducts by metal-catalyzed CO2 hydrogenation, including typical scrubbing solutions as feedstocks. Different hydrophobic organic solvents and ionic liquids could be employed as the stationary phase for cis-[Ru(dppm)2Cl2] (dppm=bis-diphenylphosphinomethane) as prototypical catalyst without any modification or tagging of the complex. The amines were found to partition between the two phases depending on their structure, whereas the formate–amine adducts were nearly quantitatively extracted into the aqueous phase, providing a favorable phase behavior for the envisaged integrated reaction/separation sequence. The solvent pair of methyl isobutyl carbinol (MIBC) and water led to the most practical and productive system and repeated use of the catalyst phase was demonstrated. The highest single batch activity with a TOFav of approximately 35 000 h?1 and an initial TOF of approximately 180 000 h?1 was achieved in the presence of NEt3. Owing to higher stability, the highest productivities were obtained with methyl diethanolamine (Aminosol CST 115) and monoethanolamine (MEA), which are used in commercial scale CO2-scrubbing processes. Saturated aqueous solutions (CO2 overpressure 5–10 bar) of MEA could be converted into the corresponding formate adducts with average turnover frequencies up to 14×103 h?1 with an overall yield of 70 % based on the amine, corresponding to a total turnover number of 150 000 over eleven recycling experiments. This opens the possibility for integrated approaches to carbon capture and utilization.

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PYRAZINE DERIVATIVE AND APPLICATION THEREOF IN INHIBITING SHP2

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Preparation method of N, N-dimethylformamide

The invention relates to a preparation method of N, N-dimethylformamide (DMF). According to the method, dimethylamine and carbon monoxide (CO) are adopted as reactants, and the DMF is prepared through CO-inserted carbonylation reaction under the catalytic action, wherein the reaction conditions are as follows: the reaction is carried out in a fixed bed reactor, the reaction pressure is 1.0-8.0 MPa, the reaction temperature is 150-250 DEG C, the feeding space velocity of dimethylamine is 50-800 h, and the flow velocity of the raw material CO is 5-25 mL.min. The method is characterized in that (1) the reaction has 100% atom economy and no by-product is generated, and (2) the Ru-loaded HAP is used as the catalyst, the catalyst is simple to prepare and efficiently catalyzes the reaction, the optimal yield of DMF can reach 95%, the catalyst is high in stability, and continuous operation can be performed for 500 h.

Chromium-catalysed efficient: N -formylation of amines with a recyclable polyoxometalate-supported green catalyst

A simple and efficient protocol for the formylation of amines with formic acid, catalyzed by a polyoxometalate-based chromium catalyst, is described. Notably, this method shows excellent activity and chemoselectivity for the formylation of primary amines; diamines have also been successfully employed. Importantly, the chromium catalyst is potentially non-toxic, environmentally benign and safer than the widely used high valence chromium catalysts such as CrO3 and K2Cr2O7. The catalyst can be recycled several times with a negligible impact on activity. Finally, a plausible mechanism is provided based on the observation of intermediate and control experiments.