N-Methylformamide

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N-Methylformamide
Methylformamide skeletal.png
Methylformamide-3D-balls.png
Names
Preferred IUPAC name
N-Methylformamide
Other names
Methylformide
NMF
N-methylmethanamide
Identifiers
3D model (JSmol)
1098352
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.004.205 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 204-624-6
KEGG
MeSH methylformamide
PubChem CID
RTECS number
  • LQ3000000
UNII
  • InChI=1S/C2H5NO/c1-3-2-4/h2H,1H3,(H,3,4) Yes check.svgY
    Key: ATHHXGZTWNVVOU-UHFFFAOYSA-N Yes check.svgY
  • CNC=O
Properties
C2H5NO
Molar mass 59.068 g·mol−1
AppearanceColourless liquid
Odor fishy, ammoniacal
Density 1.011 g mL−1
Melting point −4 °C (25 °F; 269 K)
Boiling point 182.6 °C; 360.6 °F; 455.7 K
Miscible
1.432
Thermochemistry
125.2 J K−1 mol−1
Hazards
GHS labelling:
GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg
Danger
H312, H360
P280, P308+P313
Flash point 111 °C (232 °F; 384 K)
Lethal dose or concentration (LD, LC):
4 g kg−1(oral, rat)
Related compounds
Related alkanamides
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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N-Methylformamide (NMF) is a colorless, nearly odorless, organic compound 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. [1]

Contents

NMF is closely related to other formamides, notably formamide and dimethylformamide (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 due to its greater stability. [1] 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). [1]

Structure and properties

Like DMF and formamide, each of the two rotamers of NMF are described by two principal resonance structures:

NMFresonanceStr's.png

This description highlights the partial double bond that exists between the carbonyl carbon and nitrogen, which gives rise to a high rotational barrier. Thus, the molecule is not able to freely rotate around its main axis and the (E)-configuration is preferred due to steric repulsion of the larger substituents.[ citation needed ]

This molecule has been tentatively identified in interstellar space by the 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. [2]

Preparation

NMF is typically prepared by allowing methylamine to react with methyl formate: [1]

CH3NH2 + HCOOCH3 → CH3NHCHO + CH3OH

A less common alternative to this process is transamidation involving formamide: [1]

HCONH2 + CH3NH2 → HCONHCH3 + 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). [1]
Formothion is an insecticide prepared from N-methylformamide. Formothion.svg
Formothion is an insecticide prepared from N-methylformamide.

Laboratory uses

NMF is the precursor to methyl isocyanide, a ligand in coordination chemistry. [3] NMF is used as a solvent in Aluminum Electrolytic Capacitors.

Related Research Articles

In chemistry, amines are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group. Important amines include amino acids, biogenic amines, trimethylamine, and aniline. Inorganic derivatives of ammonia are also called amines, such as monochloramine.

<span class="mw-page-title-main">Amide</span> Organic compounds of the form RC(=O)NR′R″

In organic chemistry, an amide, also known as an organic amide or a carboxamide, is a compound with the general formula R−C(=O)−NR′R″, where R, R', and R″ represent any group, typically organyl groups or hydrogen atoms. The amide group is called a peptide bond when it is part of the main chain of a protein, and an isopeptide bond when it occurs in a side chain, such as in the amino acids asparagine and glutamine. It can be viewed as a derivative of a carboxylic acid with the hydroxyl group replaced by an amine group ; or, equivalently, an acyl (alkanoyl) group joined to an amine group.

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Ketone</span> Organic compounds of the form >C=O

In organic chemistry, a ketone is a functional group with the structure R−C(=O)−R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group −C(=O)−. The simplest ketone is acetone, with the formula (CH3)2CO. Many ketones are of great importance in biology and in industry. Examples include many sugars (ketoses), many steroids, and the solvent acetone.

<span class="mw-page-title-main">Organic chemistry</span> Subdiscipline of chemistry, with especial focus on carbon compounds

Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms. Study of structure determines their structural formula. Study of properties includes physical and chemical properties, and evaluation of chemical reactivity to understand their behavior. The study of organic reactions includes the chemical synthesis of natural products, drugs, and polymers, and study of individual organic molecules in the laboratory and via theoretical study.

<span class="mw-page-title-main">Aldehyde</span> Organic compound containing the functional group R−CH=O

In organic chemistry, an aldehyde is an organic compound containing a functional group with the structure R−CH=O. The functional group itself can be referred to as an aldehyde but can also be classified as a formyl group. Aldehydes are a common motif in many chemicals important in technology and biology.

<span class="mw-page-title-main">Methyl radical</span> Chemical compound

Methyl radical is an organic compound with the chemical formula CH
3
. It is a metastable colourless gas, which is mainly produced in situ as a precursor to other hydrocarbons in the petroleum cracking industry. It can act as either a strong oxidant or a strong reductant, and is quite corrosive to metals.

Benzonitrile is the chemical compound with the formula C6H5(CN), abbreviated PhCN. This aromatic organic compound is a colorless liquid with a sweet bitter almond odour. It is mainly used as a precursor to the resin benzoguanamine.

Acetamide (systematic name: ethanamide) is an organic compound with the formula CH3CONH2. It is derived from acetic acid. It finds some use as a plasticizer and as an industrial solvent. The related compound N,N-dimethylacetamide (DMA) is more widely used, but it is not prepared from acetamide. Acetamide can be considered an intermediate between acetone, which has two methyl (CH3) groups either side of the carbonyl (CO), and urea which has two amide (NH2) groups in those locations. Acetamide is also a naturally occurring mineral with the IMA symbol: Ace.

Methylamine is an organic compound with a formula of CH3NH2. 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.

<span class="mw-page-title-main">Formamide</span> Chemical compound

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 pesticides, and in the manufacture of hydrocyanic acid. It has been used as a softener for paper and fiber. It is a solvent for many ionic compounds. It has also been used as a solvent for resins and plasticizers. Some astrobiologists suggest that it may be an alternative to water as the main solvent in other forms of life.

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 majority of organic liquids. DMF is a common solvent for chemical reactions. Dimethylformamide is odorless, but technical-grade or degraded samples often have a fishy smell due to impurity of dimethylamine. Dimethylamine degradation impurities can be removed by sparging samples with an inert gas such as argon or by sonicating the samples under reduced pressure. As its name indicates, it is structurally related to formamide, having two methyl groups in the place of the two hydrogens. DMF is a polar (hydrophilic) aprotic solvent with a high boiling point. It facilitates reactions that follow polar mechanisms, such as SN2 reactions.

An isocyanide is an organic compound with the functional group –N+≡C. It is the isomer of the related nitrile (–C≡N), hence the prefix is isocyano. The organic fragment is connected to the isocyanide group through the nitrogen atom, not via the carbon. They are used as building blocks for the synthesis of other compounds.

<span class="mw-page-title-main">Methyllithium</span> Chemical compound

Methyllithium is the simplest organolithium reagent with the empirical formula CH3Li. This s-block organometallic compound adopts an oligomeric structure both in solution and in the solid state. This highly reactive compound, invariably used in solution with an ether as the solvent, is a reagent in organic synthesis as well as organometallic chemistry. Operations involving methyllithium require anhydrous conditions, because the compound is highly reactive toward water. Oxygen and carbon dioxide are also incompatible with MeLi. Methyllithium is usually not prepared, but purchased as a solution in various ethers.

<span class="mw-page-title-main">TosMIC</span> Chemical compound

TosMIC (toluenesulfonylmethyl isocyanide) is an organic compound with the formula CH3C6H4SO2CH2NC. The molecule contains both sulfonyl and isocyanide groups. It is a colourless solid that, unlike many isocyanides, is odorless. It is prepared by dehydration of the related formamide derivative. It is used in the Van Leusen reaction which is used to convert aldehydes to nitriles or in the preparation of oxazoles and imidazoles. The versatility of TosMIC in organic synthesis has been documented. It is a fairly strong carbon acid, with an estimated pKa of 14 (compared to 29 for methyl tolyl sulfone), the isocyano group acting as an electron acceptor of strength comparable to an ester group.

<span class="mw-page-title-main">Organoindium chemistry</span> Chemistry of compounds with a carbon to indium bond

Organoindium chemistry is the chemistry of compounds containing In-C bonds. The main application of organoindium chemistry is in the preparation of semiconducting components for microelectronic applications. The area is also of some interest in organic synthesis. Most organoindium compounds feature the In(III) oxidation state, akin to its lighter congeners Ga(III) and B(III).

<span class="mw-page-title-main">Methyl azide</span> Chemical compound

Methyl azide is an organic compound with the formula CH3N3. It is a white solid and it is the simplest organic azide.

<span class="mw-page-title-main">Propionaldehyde</span> Chemical compound

Propionaldehyde or propanal is the organic compound with the formula CH3CH2CHO. It is the 3-carbon aldehyde. It is a colourless, flammable liquid with a slightly fruity odour. It is produced on a large scale industrially.

The Ritter reaction is a chemical reaction that transforms a nitrile into an N-alkyl amide using various electrophilic alkylating reagents. The original reaction formed the alkylating agent using an alkene in the presence of a strong acid.

Formamide-based prebiotic chemistry is a reconstruction of the beginnings of life on Earth, assuming that formamide could accumulate in sufficiently high amounts to serve as the building block and reaction medium for the synthesis of the first biogenic molecules.

References

  1. 1 2 3 4 5 6 Bipp, H.; Kieczka, H. "Formamides". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a12_001.
  2. Belloche, A.; et al. (May 2017). "Rotational spectroscopy, tentative interstellar detection, and chemical modeling of N-methylformamide". Astronomy & Astrophysics. 601: 41. arXiv: 1701.04640 . Bibcode:2017A&A...601A..49B. doi:10.1051/0004-6361/201629724. A49.
  3. Schuster, R. E.; Scott, J. E.; Casanova, J. Jr. (1966). "Methyl Isocyanide". Organic Syntheses . 46: 75.; Collective Volume, vol. 5, p. 772