Dimethylformamide
Overview
 
Dimethylformamide is an organic compound
Organic compound
An organic compound is any member of a large class of gaseous, liquid, or solid chemical compounds whose molecules contain carbon. For historical reasons discussed below, a few types of carbon-containing compounds such as carbides, carbonates, simple oxides of carbon, and cyanides, as well as the...

 with the formula
Chemical formula
A chemical formula or molecular formula is a way of expressing information about the atoms that constitute a particular chemical compound....

 (CH3)2NC(O)H. Commonly abbreviated as DMF (though this acronym is sometimes used for dimethylfuran
2,5-Dimethylfuran
2,5-Dimethylfuran is a heterocyclic compound with the formula 2C4H2O. Although often abbreviated DMF, it should not be confused with dimethylformamide. A derivative of furan, this simple compound is a potential biofuel, being derivable from cellulose.-Production:Fructose can be converted into...

), this colourless liquid is miscible with water and the majority of organic liquids. DMF is a common solvent
Solvent
A solvent is a liquid, solid, or gas that dissolves another solid, liquid, or gaseous solute, resulting in a solution that is soluble in a certain volume of solvent at a specified temperature...

 for chemical reactions. Pure dimethylformamide is odorless whereas technical grade or degraded dimethylformamide often has a fishy smell due to impurity of dimethylamine
Dimethylamine
Dimethylamine is an organic compound with the formula 2NH. This secondary amine is a colorless, flammable liquified gas with an ammonia-like odor. Dimethylamine is generally encountered as a solution in water at concentrations up to around 40%...

.
Encyclopedia
Dimethylformamide is an organic compound
Organic compound
An organic compound is any member of a large class of gaseous, liquid, or solid chemical compounds whose molecules contain carbon. For historical reasons discussed below, a few types of carbon-containing compounds such as carbides, carbonates, simple oxides of carbon, and cyanides, as well as the...

 with the formula
Chemical formula
A chemical formula or molecular formula is a way of expressing information about the atoms that constitute a particular chemical compound....

 (CH3)2NC(O)H. Commonly abbreviated as DMF (though this acronym is sometimes used for dimethylfuran
2,5-Dimethylfuran
2,5-Dimethylfuran is a heterocyclic compound with the formula 2C4H2O. Although often abbreviated DMF, it should not be confused with dimethylformamide. A derivative of furan, this simple compound is a potential biofuel, being derivable from cellulose.-Production:Fructose can be converted into...

), this colourless liquid is miscible with water and the majority of organic liquids. DMF is a common solvent
Solvent
A solvent is a liquid, solid, or gas that dissolves another solid, liquid, or gaseous solute, resulting in a solution that is soluble in a certain volume of solvent at a specified temperature...

 for chemical reactions. Pure dimethylformamide is odorless whereas technical grade or degraded dimethylformamide often has a fishy smell due to impurity of dimethylamine
Dimethylamine
Dimethylamine is an organic compound with the formula 2NH. This secondary amine is a colorless, flammable liquified gas with an ammonia-like odor. Dimethylamine is generally encountered as a solution in water at concentrations up to around 40%...

. Its name is derived from the fact that it is a derivative of formamide
Formamide
Formamide, also known as methanamide, is an amide derived from formic acid. It is a clear liquid which is miscible with water and has an ammonia-like odor. It is used primarily for manufacturing sulfa drugs and synthesizing vitamins and as a softener for paper and fiber...

, the amide
Amide
In chemistry, an amide is an organic compound that contains the functional group consisting of a carbonyl group linked to a nitrogen atom . The term refers both to a class of compounds and a functional group within those compounds. The term amide also refers to deprotonated form of ammonia or an...

 of formic acid
Formic acid
Formic acid is the simplest carboxylic acid. Its chemical formula is HCOOH or HCO2H. It is an important intermediate in chemical synthesis and occurs naturally, most notably in the venom of bee and ant stings. In fact, its name comes from the Latin word for ant, formica, referring to its early...

.

Dimethylformamide is a polar (hydrophilic) aprotic solvent with a high boiling point
Boiling point
The boiling point of an element or a substance is the temperature at which the vapor pressure of the liquid equals the environmental pressure surrounding the liquid....

. It facilitates reactions that follow polar mechanisms, such as SN2 reactions. Dimethylformamide can be synthesized from methyl formate
Methyl formate
Methyl formate, also called methyl methanoate, is the methyl ester of formic acid. The simplest example of an ester, it is a clear liquid with an ethereal odor, high vapor pressure, and low surface tension.-Production:...

 and dimethylamine
Dimethylamine
Dimethylamine is an organic compound with the formula 2NH. This secondary amine is a colorless, flammable liquified gas with an ammonia-like odor. Dimethylamine is generally encountered as a solution in water at concentrations up to around 40%...

 or by reaction of dimethylamine with carbon monoxide
Carbon monoxide
Carbon monoxide , also called carbonous oxide, is a colorless, odorless, and tasteless gas that is slightly lighter than air. It is highly toxic to humans and animals in higher quantities, although it is also produced in normal animal metabolism in low quantities, and is thought to have some normal...

. Dimethylformamide is not stable in the presence of strong bases like sodium hydroxide or strong acids such as hydrochloric acid
Hydrochloric acid
Hydrochloric acid is a solution of hydrogen chloride in water, that is a highly corrosive, strong mineral acid with many industrial uses. It is found naturally in gastric acid....

 or sulfuric acid
Sulfuric acid
Sulfuric acid is a strong mineral acid with the molecular formula . Its historical name is oil of vitriol. Pure sulfuric acid is a highly corrosive, colorless, viscous liquid. The salts of sulfuric acid are called sulfates...

 and is hydrolyzed
Hydrolysis
Hydrolysis is a chemical reaction during which molecules of water are split into hydrogen cations and hydroxide anions in the process of a chemical mechanism. It is the type of reaction that is used to break down certain polymers, especially those made by condensation polymerization...

 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
Carbonyl
In organic chemistry, a carbonyl group is a functional group composed of a carbon atom double-bonded to an oxygen atom: C=O. It is common to several classes of organic compounds, as part of many larger functional groups....

 C=O bond is reduced, while that of the carbon-nitrogen bond
Carbon-nitrogen bond
A carbon–nitrogen bond is a covalent bond between carbon and nitrogen and is one of the most abundant bonds in organic chemistry and biochemistry....

 is increased. Thus the infrared spectrum
Infrared spectroscopy
Infrared spectroscopy is the spectroscopy that deals with the infrared region of the electromagnetic spectrum, that is light with a longer wavelength and lower frequency than visible light. It covers a range of techniques, mostly based on absorption spectroscopy. As with all spectroscopic...

 of DMF shows a lower C=O stretching frequency at 1675 cm−1 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
Nuclear magnetic resonance
Nuclear magnetic resonance is a physical phenomenon in which magnetic nuclei in a magnetic field absorb and re-emit electromagnetic radiation...

 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
Proton NMR
Proton NMR is the application of nuclear magnetic resonance in NMR spectroscopy with respect to hydrogen-1 nuclei within the molecules of a substance, in order to determine the structure of its molecules. In samples where natural hydrogen is used, practically all of the hydrogen consists of the...

 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
Henry's law
In physics, Henry's law is one of the gas laws formulated by William Henry in 1803. It states that:An equivalent way of stating the law is that the solubility of a gas in a liquid at a particular temperature is proportional to the pressure of that gas above the liquid...

 constant of 7.47×10−5 hPa·m3/mol can be deduced from an experimentally determined equilibrium constant at 25 °C. The partition coefficient
Partition coefficient
In chemistry and the pharmaceutical sciences, a partition- or distribution coefficient is the ratio of concentrations of a compound in the two phases of a mixture of two immiscible solvents at equilibrium. The terms "gas/liquid partition coefficient" and "air/water partition coefficient" are...

 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.

Production

Dimethyl formamide is produced either via catalyzed reaction of dimethylamine
Dimethylamine
Dimethylamine is an organic compound with the formula 2NH. This secondary amine is a colorless, flammable liquified gas with an ammonia-like odor. Dimethylamine is generally encountered as a solution in water at concentrations up to around 40%...

 and carbon monoxide
Carbon monoxide
Carbon monoxide , also called carbonous oxide, is a colorless, odorless, and tasteless gas that is slightly lighter than air. It is highly toxic to humans and animals in higher quantities, although it is also produced in normal animal metabolism in low quantities, and is thought to have some normal...

 in methanol or via the reaction of methyl formate
Methyl formate
Methyl formate, also called methyl methanoate, is the methyl ester of formic acid. The simplest example of an ester, it is a clear liquid with an ethereal odor, high vapor pressure, and low surface tension.-Production:...

 with dimethylamine. It may also be prepared on a laboratory scale by reacting dimethylamine with formic acid
Formic acid
Formic acid is the simplest carboxylic acid. Its chemical formula is HCOOH or HCO2H. It is an important intermediate in chemical synthesis and occurs naturally, most notably in the venom of bee and ant stings. In fact, its name comes from the Latin word for ant, formica, referring to its early...

.

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
    Bouveault aldehyde synthesis
    The Bouveault aldehyde synthesis is a one-pot chemical reaction that converts a primary alkyl halide to an aldehyde one carbon longer.-Reaction mechanism:The first step of the Bouveault aldehyde synthesis is the formation of the Grignard reagent...

     and in the Vilsmeier-Haack reaction
    Vilsmeier-Haack reaction
    The Vilsmeier–Haack reaction is the chemical reaction of a substituted amide with phosphorus oxychloride and an electron-rich arene to produce an aryl aldehyde or ketone . The reaction is named after Anton Vilsmeier and Albrecht Haack...

    , 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
    Oxalyl chloride
    Oxalyl chloride or ethanedioyl dichloride is a chemical compound with the formula 2. This colourless, sharp-smelling liquid, the diacid chloride of oxalic acid, is a useful reagent in organic synthesis...

     or thionyl chloride
    Thionyl chloride
    Thionyl chloride is an inorganic compound with the formula SOCl2. It is a reactive chemical reagent used in chlorination reactions. It is a colorless, distillable liquid at room temperature and pressure that decomposes above 140 °C. Thionyl chloride is sometimes confused with sulfuryl...

    .
  • DMF penetrates most plastics and makes them swell
    Swelling (medical)
    In medical parlance, swelling is the transient enlargement or protuberance in the body and may include tumors. According to cause, it may be congenital, traumatic, inflammatory, neoplastic or miscellaneous....

    . 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
    National Institute of Standards and Technology
    The National Institute of Standards and Technology , known between 1901 and 1988 as the National Bureau of Standards , is a measurement standards laboratory, otherwise known as a National Metrological Institute , which is a non-regulatory agency of the United States Department of Commerce...

     for use in near infrared spectroscopy
    Near infrared spectroscopy
    Near-infrared spectroscopy is a spectroscopic method that uses the near-infrared region of the electromagnetic spectrum...

     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
    1,3-Butadiene
    1,3-Butadiene is a simple conjugated diene with the formula C4H6. It is an important industrial chemical used as a monomer in the production of synthetic rubber. When the word butadiene is used, most of the time it refers to 1,3-butadiene....

     via extractive distillation
    Extractive distillation
    Extractive distillation is defined as distillation in the presence of a miscible, high boiling, relatively non-volatile component, the solvent, that forms no azeotrope with the other components in the mixture. The method is used for mixtures having a low value of relative volatility, nearing unity...

    .
  • It is also used in the manufacturing of solvent dyes as an important raw material. It is consumed during reaction.
  • Pure acetylene
    Acetylene
    Acetylene is the chemical compound with the formula C2H2. It is a hydrocarbon and the simplest alkyne. This colorless gas is widely used as a fuel and a chemical building block. It is unstable in pure form and thus is usually handled as a solution.As an alkyne, acetylene is unsaturated because...

     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
    Agamassan
    Agamassan is a porous substrate used to safely absorb acetylene and thus allow the transport, storage and commercial exploitation of the otherwise unstable gas. It was developed and patented by the Swedish Nobel Laureate and industrialist Gustaf Dalén...

    , which renders it safe to transport and use.

Safety

Reactions including the use of sodium hydride
Sodium hydride
Sodium hydride is the chemical compound with the empirical formula NaH. It is primarily used as a strong base in organic synthesis. NaH is representative of the saline hydrides, meaning it is a salt-like hydride, composed of Na+ and H− ions, in contrast to the more molecular hydrides such as...

 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
Pilot plant
A pilot plant is a small chemical processing system which is operated to generate information about the behavior of the system for use in design of larger facilities....

 scale, on the other hand, several accidents have been reported.

Toxicity

DMF has been linked to cancer
Cancer
Cancer , known medically as a malignant neoplasm, is a large group of different diseases, all involving unregulated cell growth. In cancer, cells divide and grow uncontrollably, forming malignant tumors, and invade nearby parts of the body. The cancer may also spread to more distant parts of the...

 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
Dimethyl sulfoxide
Dimethyl sulfoxide is an organosulfur compound with the formula 2SO. This colorless liquid is an important polar aprotic solvent that dissolves both polar and nonpolar compounds and is miscible in a wide range of organic solvents as well as water...

. 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
International Agency for Research on Cancer
The International Agency for Research on Cancer is an intergovernmental agency forming part of the World Health Organisation of the United Nations....

, DMF is a possible carcinogen
Carcinogen
A carcinogen is any substance, radionuclide, or radiation that is an agent directly involved in causing cancer. This may be due to the ability to damage the genome or to the disruption of cellular metabolic processes...

, although EPA
United States Environmental Protection Agency
The U.S. Environmental Protection Agency is an agency of the federal government of the United States charged with protecting human health and the environment, by writing and enforcing regulations based on laws passed by Congress...

 does not consider it a cancer risk.

External links

The source of this article is wikipedia, the free encyclopedia.  The text of this article is licensed under the GFDL.
 
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