''N''-Methylformamide (NMF) is a colorless, nearly odorless,

organic compound In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. The ...

and secondary amide with molecular formula CH₃NHCHO, which is a liquid at room temperature. NMF is mainly used as a reagent in various organic syntheses with limited applications as a highly

polar solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for p ...

. NMF is closely related to other formamides, notably

formamide Formamide is an amide derived from formic acid. It is a colorless liquid which is miscible with water and has an ammonia-like odor. It is chemical feedstock for the manufacture of sulfa drugs and other pharmaceuticals, herbicides and pesticide ...

and

dimethylformamide Dimethylformamide is an organic compound with the formula ( CH3)2NC(O)H. Commonly abbreviated as DMF (although this initialism is sometimes used for dimethylfuran, or dimethyl fumarate), this colourless liquid is miscible with water and the majo ...

(DMF). However, industrial use and production of NMF are far less than for either of these other formamides. DMF is favored over NMF as a

solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...

due to its greater stability. Annual production of NMF can be assumed to be significantly less than the production of either formamide (100,000 tons) or DMF (500,000 tons).

Structure and properties

Like DMF and formamide, each of the two

rotamer In chemistry, conformational isomerism is a form of stereoisomerism in which the isomers can be interconverted just by rotations about formally single bonds (refer to figure on single bond rotation). While any two arrangements of atoms in a molec ...

s of NMF are described by two principal

resonance structure In chemistry, resonance, also called mesomerism, is a way of describing Chemical bond, bonding in certain molecules or polyatomic ions by the combination of several contributing structures (or ''forms'', also variously known as ''resonance stru ...

s: :: This description highlights the partial

double bond In chemistry, a double bond is a covalent bond between two atoms involving four bonding electrons as opposed to two in a single bond. Double bonds occur most commonly between two carbon atoms, for example in alkenes. Many double bonds exist betw ...

that exists between the carbonyl carbon and nitrogen, which gives rise to a high

rotational barrier In chemistry, conformational isomerism is a form of stereoisomerism in which the isomers can be interconverted just by rotations about formally single bonds (refer to figure on single bond rotation). While any two arrangements of atoms in a mo ...

. Thus, the molecule is not able to freely rotate around its main axis and the (''E'')-configuration is preferred due to

steric repulsion Steric effects arise from the spatial arrangement of atoms. When atoms come close together there is a rise in the energy of the molecule. Steric effects are nonbonding interactions that influence the shape ( conformation) and reactivity of ions ...

of the larger substituents. This molecule has been tentatively identified in

interstellar space Outer space, commonly shortened to space, is the expanse that exists beyond Earth and its atmosphere and between celestial bodies. Outer space is not completely empty—it is a near-perfect vacuum containing a low density of particles, predo ...

by the

ALMA Alma or ALMA may refer to: Arts and entertainment * ''Alma'' (film), a 2009 Spanish short animated film * ''Alma'' (Oswald de Andrade novel), 1922 * ''Alma'' (Le Clézio novel), 2017 * ''Alma'' (play), a 1996 drama by Joshua Sobol about Alma ...

radio telescope. It may have formed on dust grains. This could prove to be a key molecule for interstellar pre-biotic chemistry due to its

peptide bond In organic chemistry, a peptide bond is an amide type of covalent chemical bond linking two consecutive alpha-amino acids from C1 (carbon number one) of one alpha-amino acid and N2 (nitrogen number two) of another, along a peptide or protein cha ...

Preparation

NMF is typically prepared by allowing

methylamine Methylamine is an organic compound with a formula of . This colorless gas is a derivative of ammonia, but with one hydrogen atom being replaced by a methyl group. It is the simplest primary amine. Methylamine is sold as a solution in methanol, ...

to react with

methyl formate Methyl formate, also called methyl methanoate, is the methyl ester of formic acid. The simplest example of an ester, it is a colorless liquid with an ethereal odour, high vapor pressure, and low surface tension. It is a precursor to many other co ...

: :CH₃NH₂ + HCOOCH₃ → CH₃NHCHO + CH₃OH A less common alternative to this process is

transamidation Transamidation is a chemical reaction in which an amide reacts with an amine to generate a new amide: :RC(O)NR'2 + HNR"2 → RC(O)NR"2 + HNR'2 The reaction is typically very slow, but it can be accelerated with Lewis acid and organometallic ...

involving

: :HCONH₂ + CH₃NH₂ → CH₃NHCHO + NH₃

Uses

NMF is a specialized solvent in oil refineries. It is a precursor in specialized amidation reactions where formamide would not be suitable. These reactions can generally be categorized by the following equation: :R-Lg + CH₃NHCHO → R-NCH₃CHO + H-Lg (where Lg is a

leaving group In chemistry, a leaving group is defined by the IUPAC as an atom or group of atoms that detaches from the main or residual part of a substrate during a reaction or elementary step of a reaction. However, in common usage, the term is often limited t ...

Laboratory uses

NMF is the precursor to

methyl isocyanide Methyl isocyanide or isocyanomethane is an organic compound and a member of the isocyanide family. This colorless liquid is isomeric to methyl cyanide (acetonitrile), but its reactivity is very different. In contrast to the faintly sweet, ethereal ...

, a ligand in

coordination chemistry A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many ...

. NMF is used as a solvent in Aluminum Electrolytic Capacitors.

References

{{DEFAULTSORT:Methylformamide, N- Formamides Amide solvents Solvents