Dimethylformamide

About: Dimethylformamide is a research topic. Over the lifetime, 6793 publications have been published within this topic receiving 87752 citations. The topic is also known as: Dimethyl formamide & N,N-Dimethylformamide.

Tandem amine and ruthenium-catalyzed hydrogenation of CO2 to methanol.

Abstract: This Communication describes the hydrogenation of carbon dioxide to methanol via tandem catalysis with dimethylamine and a homogeneous ruthenium complex. Unlike previous examples with homogeneous catalysts, this CO2-to-CH3OH process proceeds under basic reaction conditions. The dimethylamine is proposed to play a dual role in this system. It reacts directly with CO2 to produce dimethylammonium dimethylcarbamate, and it also intercepts the intermediate formic acid to generate dimethylformamide. With the appropriate selection of catalyst and reaction conditions, >95% conversion of CO2 was achieved to form a mixture of CH3OH and dimethylformamide.

Role of solvent reorganization dynamics in electron-transfer processes. Theory-experiment comparisons for electrochemical and homogeneous electron exchange involving metallocene redox couples

Abstract: : Electrochemical Rate Constants and Activation Parameters are reported for the electron exchange of five metallocene couples and dibenzenechromium (I)/ (O) in eight solvents at mercury electrodes. The solvents (acetonitrile, acetone, methylene chloride, formamide, N-methylformamide, N,N'- dimethylformamide, dimethylsulfoxide, and benzonitrile) were chosen so to provide substantial variations in their dynamical as well as dielectric properties. The metallocene couples are of the form M(Cp)2(+/o), where M = Fe, Co, or Mn, and Cp = cyclopentadiene or pentamethylcyclopentadiene. The inner- shell (i.e., bond distortional) barriers are calculated for the metallocene and arene couples from bond-distance and vibrational data to be small (< or approx, 0.25 kcal/mol) yet metal-dependent. Detailed comparisons of the observed solvent-dependent kinetics are made with the rate parameters calculated from contemporary theoretical treatments of outer-sphere electron transfer. Considerably better agreement between the experimental and theoretical kinetic parameters was obtained when the latter take into account the influence of solvent friction upon the barrier-crossing frequency. These results indicate that the conventional transition-state theory may not apply to electron-transfer reactions where the free-energy barrier is due chiefly to solvent reorganization, at least in 'high friction' media where concerted solvent relaxation is slow.

Eine Methode zur katalysierten Herstellung von Carbonsäure- und Sulfosäure-chloriden mit Thionylchlorid†

Abstract: 1 Sulphonic acids and carboxylic acids which do not react with thionyl chloride under normal conditions give the corresponding acid chlorides with this reagent in excellent yields when dimethylformamide is present as a catalyst. 2 The reaction of thionylchloride with dimethylformamide yields the corresponding amide chloride which has not been isolated before in pure state. This amide chloride reacts with acids under formation of acid chlorides. The mechanism of these reactions is discussed.