Dimethylformamide
Dimethylformamide, DMF is an organic compound with the chemical formula Template:Chem2. Its structure is Template:Chem2. 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.
Structure and propertiesEdit
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.<ref name=SDBS>{{#invoke:citation/CS1|citation |CitationClass=web }}Template:Dead link</ref>
DMF is a classic example of a fluxional molecule.<ref>Template:Cite journal</ref>
The ambient temperature 1H NMR spectrum shows two methyl signals, indicative of hindered rotation about the (O)C−N bond.<ref name=SDBS/> At temperatures near 100 °C, the 500 MHz NMR spectrum of this compound shows only one signal for the methyl groups.
DMF is miscible with water.<ref name=bipp>Template:Ullmann</ref> The vapour pressure at 20 °C is 3.5 hPa.<ref>IPCS (International Programme on Chemical Safety) (1991). Environmental Health Criteria 114 "Dimethylformamide" United Nations Environment Programme, International Labour Organisation, World Health Organization; 1–124.</ref> 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.<ref>Template:Cite journal</ref> The partition coefficient log POW is measured to −0.85.<ref>(BASF AG, department of analytical, unpublished data, J-No. 124659/08, 27.11.1987)</ref> Since the density of DMF (0.95 g·cm−3 at 20 °C<ref name=bipp/>) is similar to that of water, significant flotation or stratification in surface waters in case of accidental losses is not expected.
ReactionsEdit
DMF is hydrolyzed by strong acids and bases, especially at elevated temperatures. With sodium hydroxide, DMF converts to formate and dimethylamine. DMF undergoes decarbonylation near its boiling point to give dimethylamine. Distillation is therefore conducted under reduced pressure at lower temperatures.<ref>Template:Cite encyclopedia</ref>
In one of its main uses in organic synthesis, DMF is a reagent in the Vilsmeier–Haack reaction, which is used to formylate aromatic compounds.<ref name = VH1>Template:Cite journal</ref><ref name = VH2>Template:Cite book</ref> The process involves initial conversion of DMF to a chloroiminium ion, [(CH3)2N=CH(Cl)]+, known as a Vilsmeier reagent,<ref>Template:Cite journal</ref> which attacks arenes.
Organolithium compounds and Grignard reagents react with DMF to give aldehydes after hydrolysis in a reaction called Bouveault aldehyde synthesis.<ref name="Wang-2009">Template:Cite book</ref>
Dimethylformamide forms 1:1 adducts with a variety of Lewis acids such as the soft acid I2, and the hard acid phenol. It is classified as a hard Lewis base and its ECW model base parameters are EB = 2.19 and CB = 1.31.<ref>Template:Cite journal</ref> Its relative donor strength toward a series of acids, versus other Lewis bases, can be illustrated by C-B plots.<ref>Laurence, C. and Gal, J-F. Lewis Basicity and Affinity Scales, Data and Measurement, (Wiley 2010) pp 50-51 ISBN 978-0-470-74957-9</ref><ref>Template:Cite journal The plots shown in this paper used older parameters. Improved E&C parameters are listed in ECW model. </ref>
History and synthesisEdit
DMF was first obtained in 1893 by the French chemist Albert Verley (1867–1959), by distilling a mixture of dimethylamine hydrochloride and potassium formate.<ref>Template:Cite journal On p. 692, Verley states that DMF is prepared by a procedure analogous to that for the preparation of dimethylacetamide (see p. 691), which would be by distilling dimethylamine hydrochloride and potassium formate.</ref>
It is now industrially manufactured by combining methyl formate and dimethylamine or by reaction of dimethylamine with carbon monoxide.<ref name="indchem">Template:Cite book</ref>
Although currently impractical, DMF can be prepared from supercritical carbon dioxide using ruthenium-based catalysts.<ref>Template:Cite book</ref>
ApplicationsEdit
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.<ref name=bipp/>
- It is used as a reagent in the Bouveault aldehyde synthesis<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref><ref>Template:Cite book</ref> and in the Vilsmeier-Haack reaction,<ref name = VH1 /><ref name = VH2 /> another useful method of forming aldehydes.
- It is a common solvent in the Heck reaction.<ref>Template:Cite book</ref>
- It is 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 (also known as the 'Vilsmeier reagent'):<ref name = clayden>Template:Cite book</ref><ref>Ansell, M. F. in "The Chemistry of Acyl Halides"; S. Patai, Ed.; John Wiley and Sons: London, 1972; pp 35–68.</ref>
- 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 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 is safely compressed in the presence of dimethylformamide, which forms a safe, concentrated solution. The casing is also filled with agamassan, which renders it safe to transport and use.
As a cheap and common reagent, DMF has many uses in a 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.<ref name=miiswcn>Template:Cite book</ref>
- DMF can be utilized as a standard in proton NMR spectroscopy 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 commonly used in the solvothermal synthesis of metal–organic frameworks.
- DMF-d7 in the presence of a catalytic amount of potassium tert-butoxide under microwave heating is a reagent for deuteration of polyaromatic hydrocarbons.
SafetyEdit
Dimethylformamide vapor exposure has shown reduced alcohol tolerance and skin irritation in some cases.<ref>Template:Cite journal</ref>
On 20 June 2018, the Danish Environmental Protective Agency published an article about DMF's use in squishies. The density of the compound in the toy resulted in all squishies being removed from the Danish market. All squishies were recommended to be thrown out as household waste. <ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>
ToxicityEdit
The acute LD50 (oral, rats and mice) is 2.2–7.55 g/kg.<ref name=bipp/> Hazards of DMF have been examined.<ref name=dmf-uses>Template:Cite journal</ref>