Dimethylformamide

Dimethylformamide

Names
IUPAC name N,N-Dimethylformamide
Other names N,N-Dimethylmethanamide, DMF
Identifiers
CAS Number	68-12-2 Y
3DMet	B00545
Beilstein Reference	605365
ChEBI	CHEBI:17741 Y
ChEMBL	ChEMBL268291 Y
ChemSpider	5993 Y
DrugBank	DB01844 Y
EC Number	200-679-5
Jmol 3D model	Interactive image Interactive image
KEGG	C03134 Y
MeSH	Dimethylformamide
PubChem	6228
RTECS number	LQ2100000
UNII	8696NH0Y2X Y
UN number	2265
InChI InChI=1S/C3H7NO/c1-4(2)3-5/h3H,1-2H3 Y Key: ZMXDDKWLCZADIW-UHFFFAOYSA-N Y
SMILES C[n](C):c:[o] CN(C)C=O
Properties
Chemical formula	C3H7NO
Molar mass	73.10 g·mol−1
Appearance	Colourless liquid
Odor	fishy, ammoniacal
Density	0.948 g mL−1
Melting point	−60.5 °C; −76.8 °F; 212.7 K
Boiling point	152 to 154 °C; 305 to 309 °F; 425 to 427 K
Solubility in water	Miscible
log P	−0.829
Vapor pressure	516 Pa
UV-vis (λmax)	270 nm
Absorbance	1.00
Refractive index (nD)	1.4305 (at 20 °C)
Viscosity	0.92 mPa s (at 20 °C)
Structure
Dipole moment	3.86 D
Thermochemistry
Specific heat capacity (C)	146.05 J K−1 mol−1
Std enthalpy of formation (ΔfHo298)	−240.6–−238.2 kJ mol−1
Std enthalpy of combustion (ΔcHo298)	−1.9428–−1.9404 MJ mol−1
Vapor pressure	{{{value}}}
Related compounds
Related alkanamides	N-Methylformamide Deuterated DMF
Related compounds	N-Nitroso-N-methylurea ENU
Supplementary data page
Structure and properties	Refractive index (n), Dielectric constant (εr), etc.
Thermodynamic data	Phase behaviour solid–liquid–gas
Spectral data	UV, IR, NMR, MS
Y verify (what is YN ?)
Infobox references

Dimethylformamide is an organic compound with the formula (CH₃)₂NC(O)H. Commonly abbreviated as DMF (although this acronym is sometimes used for dimethylfuran), this colourless liquid is miscible with water and the majority of organic liquids. DMF is a common solvent for chemical reactions. Dimethylformamide is odorless whereas technical grade or degraded samples often have a fishy smell due to impurity of dimethylamine. As its name indicates, it is a derivative of formamide, the amide of formic acid. DMF is a polar (hydrophilic) aprotic solvent with a high boiling point. It facilitates reactions that follow polar mechanisms, such as S_N2 reactions.

Structure and properties

As for most amides, the spectroscopic evidence indicates partial double bond character for the C-N and C-O bonds. Thus, the infrared spectrum shows a C=O stretching frequency at only 1675 cm⁻¹, whereas a ketone would absorb near 1700 cm^-1. The methyl groups are inequivalent on the NMR time scale, giving rise to two singlets of 3 protons each at δ 2.97 and 2.88 in the proton NMR spectrum.

DMF is miscible with water. The vapour pressure at 20 °C is 3.5hPa. A Henry's law constant of 7.47×10⁻⁵ hPa·m³/mol can be deduced from an experimentally determined equilibrium constant at 25 °C. The partition coefficient logPOW is measured to −0.85. Since the density of DMF (0.95 g/cm³ at 20 °C) is very similar to that of water, significant flotation or stratification in surface waters in case of accidental losses is not expected.

The two resonance forms of DMF

DMF is hydrolyzed by strong acids and bases, especially at elevated temperatures. With sodium hydroxide, DMF converts to formate and dimethylamine.

Production

DMF is prepared by combining methyl formate and dimethylamine or by reaction of dimethylamine with carbon monoxide.

Academic research

DMF can also be prepared from supercritical carbon dioxide using ruthenium-based catalysts.

Applications

The primary use of DMF is as a solvent with low evaporation rate. DMF is used in the production of acrylic fibers and plastics. It is also used as a solvent in peptide coupling for pharmaceuticals, in the development and production of pesticides, and in the manufacture of adhesives, synthetic leathers, fibers, films, and surface coatings.

• It is used as a reagent in the Bouveault aldehyde synthesis and in the Vilsmeier-Haack reaction, another useful method of forming aldehydes.
• It is a common solvent in the Heck reaction.
• It is also a common catalyst used in the synthesis of acyl halides, in particular the synthesis of acyl chlorides from carboxylic acids using oxalyl or thionyl chloride. The catalytic mechanism entails reversible formation of an imidoyl chloride.
• DMF penetrates most plastics and makes them swell. Because of this property DMF is suitable for solid phase peptide synthesis and as a component of paint strippers.
• DMF is used as a solvent to recover olefins such as 1,3-butadiene via extractive distillation.
• It is also used in the manufacturing of solvent dyes as an important raw material. It is consumed during reaction.
• Pure acetylene gas cannot be compressed and stored without the danger of explosion. Industrial acetylene gas is, therefore, dissolved in dimethylformamide and stored in metal cylinders or bottles. The casing is also filled with agamassan, which renders it safe to transport and use.

Niche uses

As a common and cheap reagent, DMF has many uses in the research laboratory.

• DMF is effective at separating and suspending carbon nanotubes, and is recommended by the NIST for use in near infrared spectroscopy of such.
• DMF can be utilized as a standard in proton NMR allowing for a quantitative determination of an unknown compound.
• In the synthesis of organometallic compounds, it is used as a source of carbon monoxide ligands.
• DMF is a common solvent used in electrospinning.
• DMF is a solvent commonly used in the solvothermal synthesis of Metal Organic Frameworks.

Safety

Reactions including the use of sodium hydride in DMF as a solvent are somewhat hazardous; exothermic decompositions have been reported at temperatures as low as 26 °C. On a laboratory scale any thermal runaway is (usually) quickly noticed and brought under control with an ice bath and this remains a popular combination of reagents. On a pilot plant scale, on the other hand, several accidents have been reported.

Toxicity

The potential toxicity DMF has received considerable attention. It is not classifiable as human carcinogen (A4), but it is thought to cause birth defects. In some sectors of industry, women are banned from working with DMF. For many reactions, it can be replaced with dimethyl sulfoxide. Most manufacturers of DMF list 'Life' or 'Chronic' as a health hazard in their MSDS since DMF is not readily disposed of by the body. According to IARC, DMF is not classifiable as to its carcinogenicity to humans, and the United States Environmental Protection Agency does not consider it a cancer risk.

External links

• International Chemical Safety Card 0457
• Dimethylformamide usage on Organic Syntheses
• Concise International Chemical Assessment Document 31: N,N-Dimethylformamide
• Material Safety Data Sheet for DMF
• DMF Chronic Toxicity Summary (PDF)
• Dimethylformamide Technical Specs from BASF(pdf)
• DMF GHS MSDS from NuGenTec (PDF)