Dimethylformamide
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Names | |||
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IUPAC name
N,N-Dimethylformamide[2]
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Other names
N,N-Dimethylmethanamide,[1] DMF
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Identifiers | |||
68-12-2 ![]() |
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3DMet | B00545 | ||
605365 | |||
ChEBI | CHEBI:17741 ![]() |
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ChEMBL | ChEMBL268291 ![]() |
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ChemSpider | 5993 ![]() |
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DrugBank | DB01844 ![]() |
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EC Number | 200-679-5 | ||
Jmol 3D model | Interactive image Interactive image |
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KEGG | C03134 ![]() |
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MeSH | Dimethylformamide | ||
PubChem | 6228 | ||
RTECS number | LQ2100000 | ||
UNII | 8696NH0Y2X ![]() |
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UN number | 2265 | ||
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Properties | |||
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 | ||
Miscible | |||
log P | −0.829 | ||
Vapor pressure | 516 Pa | ||
UV-vis (λmax) | 270 nm | ||
Absorbance | 1.00 | ||
Refractive index (nD)
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1.4305 (at 20 °C) | ||
Viscosity | 0.92 mPa s (at 20 °C) | ||
Structure | |||
3.86 D | |||
Thermochemistry | |||
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 | ||
Vapor pressure | {{{value}}} | ||
Related compounds | |||
Related alkanamides
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Related compounds
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Supplementary data page | |||
Refractive index (n), Dielectric constant (εr), etc. |
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Thermodynamic
data |
Phase behaviour solid–liquid–gas |
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UV, IR, NMR, MS | |||
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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 SN2 reactions.
Contents
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.[3] 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.[3]
DMF is miscible with water.[4] The vapour pressure at 20 °C is 3.5hPa.[5] 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.[6] The partition coefficient logPOW is measured to −0.85.[7] Since the density of DMF (0.95 g/cm3 at 20 °C[4]) is very similar to that of water, significant flotation or stratification in surface waters in case of accidental losses is not expected.
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.[8]
Academic research
DMF can also be prepared from supercritical carbon dioxide using ruthenium-based catalysts.[9]
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.[4]
- 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.[10][11]
- 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.[12]
- 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.[13]
Toxicity
The potential toxicity DMF has received considerable attention.[14] It is not classifiable as human carcinogen (A4), but 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.[citation needed]
References
- ↑ N,N-Dimethylmethanamide, NIST web thermo tables
- ↑ Lua error in package.lua at line 80: module 'strict' not found.
- ↑ 3.0 3.1 Lua error in package.lua at line 80: module 'strict' not found.
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- ↑ IPCS (International Programme on Chemical Safety) (1991). Environmental Health Criteria 114 “Dimethylformamide” United Nations Environment Programme, International Labour Organisation, World Health Organization; 1–124.
- ↑ Lua error in package.lua at line 80: module 'strict' not found.
- ↑ (BASF AG, department of analytical, unpublished data, J-No. 124659/08, 27.11.1987)
- ↑ Lua error in package.lua at line 80: module 'strict' not found.
- ↑ Lua error in package.lua at line 80: module 'strict' not found.
- ↑ Lua error in package.lua at line 80: module 'strict' not found.
- ↑ Ansell, M. F. in "The Chemistry of Acyl Halides"; S. Patai, Ed.; John Wiley and Sons: London, 1972; pp 35–68.
- ↑ Lua error in package.lua at line 80: module 'strict' not found.
- ↑ UK Chemical Reaction Hazards Forum and references cited therein
- ↑ Lua error in package.lua at line 80: module 'strict' not found.
- ↑ Hazardous substance fact sheet for Dimethylformamide
- ↑ [1]
External links
- International Chemical Safety Card 0457
- Lua error in package.lua at line 80: module 'strict' not found.
- 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)