N-Methylformamide

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]

N-Methylformamide
Skeletal formula of N-methylformamide
Ball and stick model of N-methylformamide
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
EC Number
  • 204-624-6
KEGG
MeSH methylformamide
RTECS number
  • LQ3000000
UNII
  • InChI=1S/C2H5NO/c1-3-2-4/h2H,1H3,(H,3,4) checkY
    Key: ATHHXGZTWNVVOU-UHFFFAOYSA-N checkY
  • CNC=O
Properties
C2H5NO
Molar mass 59.068 g·mol−1
Appearance Colourless 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:
GHS07: Exclamation mark GHS08: Health hazard
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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Infobox references

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:

Principal resonance structures for one rotamer of NMF

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.

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.

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.

References
  1. 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
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