Beyond a solvent:triple roles of dimethylformamide in organic chemistry-part 1

Introduction

N,N-Dimethylformamide (DMF) is an extraordinary organic compound with the formula (CH₃)₂NC(O)H. It generally abbreviated and literally always called, DMF (should not be mistaken with dimethylfuran or dimethyl fumarate). It is a colourless liquid with a high boiling point which is miscible with water and also with a majority of common organic solvents. DMF should be naturally odorless, however in its technical grade or degraded samples every so often it has a fishy smell due to some impurity of dimethylamine

As its name implies, it is a formamide derivative. Although, among most chemists, DMF is known as an inexpensive commercially available solvent which is widely used in synthetic organic chemistry, by a second look and further consideration, it is actually more than a solvent, showing multipurpose applications. It is a polar aprotic, but hydrophilic, solvent that dissolves most organic compounds. Thus, it is especially useful in organic reactions when their mechanisms involve polar species, such as SN₂ reactions. Therefore, DMF is mostly used as an excellent polar solvent with a relatively low evaporation rate, useful for a wide variety of organic transformations. Its usefulness and superiority as a solvent is due to its favored dissolution actually provided by favorited interactions with a substrate.

This uniquely versatile and powerful chemical is frequently used as a solvent for preparation of colloids, synthesis of block-copolymers, and also many other types of organic reactions like solvent-free hydrolysis, allylation, decarboxylation, polymerization, etc. It is also found as a perfect solvent for peptide coupling in the pharmaceuticals industry, in development and production of pesticides and in the manufacture of adhesives, synthetic leathers,fibers, films, and surface coatings. It also is used in the manufacturing of dyes as an important raw material which is consumed during a reaction. DMF also is a common solvent utilized in electrospinning

DMF as reagent

Beyond being used as an useful solvent, DMF is employed as a reagent in some important organic reactions, such as the Vilsmeier–Haack reaction, which results in the formylation of aromatic, non-aromatic, and heteroaromatic compounds. DMF can also be used as a reagent in two other important organic name reactions such as the Friedel–Crafts reaction and Beckmann rearrangement.

DMF can react as either an electrophilic or a nucleophilic agent, thus, can be considered as the source of various key intermediates mediating a plethora of important reactions. More significantly, because of its structure, DMF can participate in many reactions by serving as a multipurpose building block for various units, such as HCO₂, O, CO, H, NMe₂, CONMe₂, Me, CHO, etc

DMF as catalyst

It is also a common catalyst used in the synthesis of acyl halides, in particular, and in the synthesis of acyl chloride from carboxylic acids using oxalyl or thionyl chloride. The catalytic mechanism entails reversible formation of an imidoyl chloride. It acts as a catalyst in preparing the corresponding azepine, for the cycloaddition reaction of CO₂ to propylene oxide, synthesis of cyclic carbonates, condensation reactions of alkylisocyanides (or arylisocyanides) with barbituric acid derivatives, reductive ring-cleavage of isoxazole, allylation of aldehydes, conversion of both primary and secondary alcohols to bromides, and acylation of aromatic compounds.