This is an old revision of this page, as edited by Beetstra (talk | contribs) at 11:48, 1 November 2011 (Script assisted update of identifiers for the Chem/Drugbox validation project (updated: 'ChEBI', 'StdInChI', 'StdInChIKey').). The present address (URL) is a permanent link to this revision, which may differ significantly from the current revision.
Revision as of 11:48, 1 November 2011 by Beetstra (talk | contribs) (Script assisted update of identifiers for the Chem/Drugbox validation project (updated: 'ChEBI', 'StdInChI', 'StdInChIKey').)(diff) ← Previous revision | Latest revision (diff) | Newer revision → (diff)
| |||
| Names | |||
|---|---|---|---|
| IUPAC name N,N-Dimethylmethanamide | |||
| Other names DMF; Dimethylformamide; N,N-Dimethylformamide; DMFA | |||
| Identifiers | |||
| CAS Number | |||
| 3D model (JSmol) | |||
| ChEBI | |||
| ChEMBL | |||
| ChemSpider | |||
| DrugBank | |||
| ECHA InfoCard | 100.000.617 
| ||
| KEGG | |||
| PubChem CID | |||
| RTECS number |
| ||
| UNII | |||
| CompTox Dashboard (EPA) | |||
InChI
| |||
SMILES
| |||
| Properties | |||
| Chemical formula | C3H7NO | ||
| Molar mass | 73.09 g/mol | ||
| Appearance | Clear liquid | ||
| Density | 0.944 g/cm, liquid | ||
| Melting point | −61 °C (−78 °F; 212 K) | ||
| Boiling point | 153 °C (307 °F; 426 K) | ||
| Solubility in water | Miscible | ||
| Vapor pressure | 0.3 kPa (@ 20°C) | ||
| Refractive index (nD) | 1.4305 (20 °C), εr = 36.71 (25°C) | ||
| Viscosity | 0.92 cP at 20 °C | ||
| Structure | |||
| Dipole moment | 3.86 D (25 °C) | ||
| Hazards | |||
| Occupational safety and health (OHS/OSH): | |||
| Main hazards | flammable | ||
| NFPA 704 (fire diamond) |
 | ||
| Flash point | 58 °C | ||
| Threshold limit value (TLV) | 10 ppm (TWA) | ||
| Related compounds | |||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa).
 Y verify (what is ?)
Infobox references
| |||
Dimethylformamide is an organic compound with the formula (CH3)2NC(O)H. Commonly abbreviated DMF (though 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. Pure dimethylformamide is odorless whereas technical grade or degraded dimethylformamide often has a fishy smell due to impurity of dimethylamine. Its name is derived from the fact that it is a derivative of formamide, the amide of formic acid.
Dimethylformamide is a polar (hydrophilic) aprotic solvent with a high boiling point. It facilitates reactions that follow polar mechanisms, such as SN2 reactions. Dimethylformamide can be synthesized from methyl formate and dimethylamine or by reaction of dimethylamine with carbon monoxide. Dimethylformamide is not stable in the presence of strong bases like sodium hydroxide or strong acids such as hydrochloric acid or sulfuric acid and is hydrolyzed back into formic acid and dimethylamine, especially at elevated temperatures.
Structure and properties
Due to the contribution of the two possible resonance structures of an amide, the bond order of the carbonyl C=O bond is reduced, while that of the carbon-nitrogen bond is increased. Thus the infrared spectrum of DMF shows a lower C=O stretching frequency at 1675 cm than an unsubstituted C=O bond. Also, because of the partial double bond character, the rotation about the C-N axis is slow at room temperature, making the two methyl groups inequivalent on the NMR time scale, giving rise to two singlets of 3 protons each at δ 2.97 and 2.88, instead of one singlet of 6 protons in the proton NMR spectrum.
N,N-Dimethylformamide (DMF) is miscible with water in all proportions. The vapour pressure at 20°C is 3.5hPa. A Henry's law constant of 7.47×10 hPa·m/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/cm 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.
Production
Dimethyl formamide is produced either via catalyzed reaction of dimethylamine and carbon monoxide in methanol or via the reaction of methyl formate with dimethylamine. It may also be prepared on a laboratory scale by reacting dimethylamine with formic acid.
Applications
The primary use of dimethylformamide 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 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.
- DMF penetrates most plastics and makes them swell. This property makes it very suitable for solid phase peptide synthesis. It also frequently occurs as a component of paint strippers for this purpose.
- DMF is very 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 chemical.
- 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.
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
DMF has been linked to cancer in humans, and 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 a possible carcinogen, although EPA does not consider it a cancer risk.
References
- ScienceLab.com MSDS
- ^ Klaus Weissermel, Hans-Jürgen Arpe. Industrial Organic Chemistry: Important Raw Materials and Intermediates. Wiley-VCH. pp. 45–46. ISBN 3527305785.
- ^ Spectral Database for Organic Compounds, Dimethylformamide, accessed 27 Jan 2007.
- ^ Bipp, H. and Kieczka, H. (1989). Ullmann’s Encyclopedia of Industrial Chemistry. Vol. A12 (5 ed.). Weinheim: VCH Verlagsgesellschaft. pp. 1–12.
{{cite book}}: CS1 maint: multiple names: authors list (link) - IPCS (International Programme on Chemical Safety) (1991). Environmental Health Criteria 114 “Dimethylformamide” United Nations Environment Programme, International Labour Organisation, World Health Organization; 1-124.
- Taft, R.W.; et al. (1985). "The molecular properties governing solubilities of organic nonelectrolytes in water". Nature. 313 (6001): 384–386. doi:10.1038/313384a0.
{{cite journal}}: Explicit use of et al. in:|author=(help) - (BASF AG, department of analytical, unpublished data, J-No. 124659/08, 27.11.1987)
- Redlich, C; Beckett, W. S.; Sparer, J.; Barwick, K. W.; Riely, C. A.; Miller, H.; Sigal, S. L.; Shalat, S. L.; Cullen, M. R.; et al. (1988). "Liver disease associated with occupational exposure to the solvent dimethylformamide". Ann. Intern. Med. 108 (5): 680–686. PMID 3358569.
{{cite journal}}: Explicit use of et al. in:|first9=(help) - Clayden, Jonathan (2001). Organic chemistry. Oxford: Oxford University Press. pp. 276–296. ISBN 0-19-850346-6.
- Haddon, Robert (March, 2008). "Measurement Issues in Single Wall Carbon Nanotubes" (PDF). NIST: 20. Retrieved 2008-08-15.
{{cite journal}}: Check date values in:|date=(help); Cite journal requires|journal=(help); Unknown parameter|coauthors=ignored (|author=suggested) (help) - UK Chemical Reaction Hazards Forum and references cited therein
- Hazardous substance fact sheet for Dimethylformamide
External links
- International Chemical Safety Card 0457
- NIOSH Pocket Guide to Chemical Hazards. "#0226". National Institute for Occupational Safety and Health (NIOSH).
- 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)