Dimethylformamide
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| Names | |||
|---|---|---|---|
| IUPAC name
N,N-Dimethylformamide[1] | |||
| Other names
N,N-Dimethylmethanamide,[2] DMF | |||
| Identifiers | |||
| 3DMet | B00545 | ||
| 605365 | |||
68-12-2  | |||
| ChEBI | CHEBI:17741 | ||
| ChEMBL | ChEMBL268291 | ||
| ChemSpider | 5993 | ||
| DrugBank | DB01844 | ||
| EC number | 200-679-5 | ||
| |||
| Jmol-3D images | Image Image | ||
| KEGG | C03134 | ||
| MeSH | Dimethylformamide | ||
| PubChem | 6228 | ||
| RTECS number | LQ2100000 | ||
| |||
| UNII | 8696NH0Y2X | ||
| UN number | 2265 | ||
| Properties | |||
| Molecular formula |
C3H7NO | ||
| Molar mass | 73.09 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 °C; 305 °F; 425 K | ||
| 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 (ΔfH |
−240.6–−238.2 kJ mol−1 | ||
| Std enthalpy of combustion (ΔcH |
−1.9428–−1.9404 MJ mol−1 | ||
| Hazards | |||
| MSDS | External MSDS | ||
| GHS pictograms |    | ||
| GHS signal word | DANGER | ||
| H226, H312, H319, H332, H360 | |||
| P280, P305+351+338, P308+313 | |||
| EU Index | 616-001-00-X | ||
| EU classification |  T | ||
| R-phrases | R61, R20/21, R36 | ||
| S-phrases | S53, S45 | ||
| NFPA 704 | |||
| Flash point | 58 °C (136 °F; 331 K) | ||
| 445 °C (833 °F; 718 K) | |||
| Explosive limits | 2.2–15.2% | ||
| Threshold Limit Value |
30 mg m−3 (TWA) | ||
| LD50 (Median lethal dose) |
| ||
| US health exposure limits (NIOSH): | |||
| PEL (Permissible) |
TWA 10 ppm (30 mg/m3) [skin][3] | ||
| REL (Recommended) |
TWA 10 ppm (30 mg/m3) [skin][3] | ||
| IDLH (Immediate danger) |
500 ppm[3] | ||
| Related compounds | |||
| Related alkanamides |
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| Related compounds |
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| 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 | ||
| Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa) | |||
verify (what is: / ?) | |||
| 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.
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.[4] Dimethylformamide is reactive toward strong bases such as 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 major resonance structures of an amide, the bond order of the carbonyl C=O bond is reduced and that of the carbon–nitrogen bond is increased. Thus the infrared spectrum of DMF shows a lower C=O stretching frequency at 1675 cm−1[5] 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,[5] instead of one singlet of 6 protons in the proton NMR spectrum.
DMF is miscible with water in all proportions.[6] The vapour pressure at 20 °C is 3.5hPa.[7] 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.[8] The partition coefficient logPOW is measured to −0.85.[9] Since the density of DMF (0.95 g/cm3 at 20 °C[6]) 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 a catalyzed reaction of dimethylamine and carbon monoxide in methanol or via the reaction of methyl formate with dimethylamine.[4]
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.[10]
- 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. The catalytic mechanism entails reversible formation of an imidoyl chloride.[11][12]
- 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.[13]
- 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.[14]
Toxicity
DMF has been linked to cancer in humans, and it is thought to cause birth defects.[15] 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.,[16] and the United States Environmental Protection Agency does not consider it a cancer risk.
References
- ↑ "Dimethylformamide – Compound Summary". PubChem Compound. USA: National Center for Biotechnology Information. September 2004. Identification. Retrieved 2012-06-28.
- ↑ N,N-Dimethylmethanamide, NIST web thermo tables
- ↑ 3.0 3.1 3.2 "NIOSH Pocket Guide to Chemical Hazards #0226". National Institute for Occupational Safety and Health (NIOSH).
- ↑ 4.0 4.1 Weissermel, K.; Arpe, H.-J. Industrial Organic Chemistry: Important Raw Materials and Intermediates. Wiley-VCH. pp. 45–46. ISBN 3-527-30578-5.
- ↑ 5.0 5.1 "Dimethylformamide". Spectral Database for Organic Compounds. Japan: AIST. Retrieved 2012-06-28.
- ↑ 6.0 6.1 Bipp, H.; Kieczka, H. (2005), "Formamides", Ullmann's Encyclopedia of Industrial Chemistry, Weinheim: Wiley-VCH, doi:10.1002/14356007.a12_001.pub2
- ↑ 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.; Abraham, M. H.; Doherty, R. M.; Kamlet, M. J. (1985). "The molecular properties governing solubilities of organic nonelectrolytes in water". Nature 313 (6001): 384–386. doi:10.1038/313384a0.
- ↑ (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. (1988). "Liver disease associated with occupational exposure to the solvent dimethylformamide". Annals of Internal Medicine 108 (5): 680–686. doi:10.7326/0003-4819-108-5-680. PMID 3358569.
- ↑ Clayden, J. (2001). Organic Chemistry. Oxford: Oxford University Press. pp. 276–296. ISBN 0-19-850346-6.
- ↑ Ansell, M. F. in "The Chemistry of Acyl Halides"; S. Patai, Ed.; John Wiley and Sons: London, 1972; pp 35–68.
- ↑ Haddon, R.; Itkis, M. (March 2008). "3. Near-Infrared (NIR) Spectroscopy". In Freiman, S.; Hooker, S.; Migler; K.; Arepalli, S. Publication 960-19 Measurement Issues in Single Wall Carbon Nanotubes (PDF). NIST. p. 20. Retrieved 2012-06-28.
- ↑ 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)