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N,N-Dimethylformamide (DMF) is an organic compound with the chemical formula HCON(CH3)2.
N,N-Dimethylformamide (DMF)'s structure is HC(=O)−N(−CH3)2.
Commonly abbreviated as N,N-Dimethylformamide (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.
N,N-Dimethylformamide (DMF) is a common solvent for chemical reactions.
CAS: 68-12-2
MF: C3H7NO
MW: 73.09
EINECS: 200-679-5
Synonyms
Gadobutrol Impurity 48;C12727000 N,N-Dimethylformamide;N,N-Dimethylformamide in Methanol;N,N-Dimethylformamide in Water;HCL/KCL BUFFER PH2.2 1000ML;DMF (dimethylformamide);Dimethylamid kyseliny mravenci;dimethylamidkyselinymravenci
N,N-Dimethylformamide (DMF) is odorless, but technical-grade or degraded samples often have a fishy smell due to impurity of dimethylamine.
N,N-Dimethylformamide (DMF) degradation impurities can be removed by sparging samples with an inert gas such as argon or by sonicating the samples under reduced pressure.
As N,N-Dimethylformamide (DMF)'s name indicates, it is structurally related to formamide, having two methyl groups in the place of the two hydrogens.
N,N-Dimethylformamide (DMF) is a polar (hydrophilic) aprotic solvent with a high boiling point.
N,N-Dimethylformamide (DMF) facilitates reactions that follow polar mechanisms, such as SN2 reactions.
N,N-Dimethylformamide (DMF) is a flammable, colorlessliquid with a fishy, unpleasant, amine-like odor at relativelylow concentrations.
The odor threshold is 0.47100 ppm.Molecular weight= 73.11; Specific gravity (H2O:1)= 0.95;Boiling point = 153℃; Freezing/Melting point = 261℃;Vapor pressure= 3 mmHg at 20℃; Flash point = 58℃;Autoignition temperature= 444.5℃. Explosive limits are:LEL = 2.2%; UEL= 15.2% at 100℃. Hazard Identification(based on NFPA-704 M Rating System): Health 2,Flammability 2, Reactivity 0.
Soluble in water.Potential Exposure: Tumorigen,Mutagen; Reproductive Effector; Human Data; Hormone,Primary Irritant.
N,N-Dimethylformamide (DMF) is used as a solvent for liquids,gases, and as a gasoline additive.
N,N-Dimethylformamide (DMF) haspowerful solvent properties for a wide range of organiccompounds.
Because of its physical properties, this chemical has been used when solvents with a slow rate of evaporation are required.
N,N-Dimethylformamide (DMF) finds particular usage in themanufacture of polyacrylic fibers, butadiene, purified acetylene, pharmaceuticals, dyes, petroleum products, and otherorganic chemicals.
N,N-Dimethylformamide (DMF) is a member of the class of formamides that is formamide in which the amino hydrogens are replaced by methyl groups.
N,N-Dimethylformamide (DMF) has a role as a polar aprotic solvent, a hepatotoxic agent and a geroprotector.
N,N-Dimethylformamide (DMF) is a volatile organic compound and a member of formamides.
N,N-Dimethylformamide (DMF) is functionally related to a formamide.
N,N-Dimethylformamide (DMF) Chemical Properties
Melting point: -61 °C (lit.)
alpha: 0.94 º
Boiling point: 153 °C (lit.)
density: 0.944 g/mL (lit.)
vapor density: 2.5 (vs air)
vapor pressure: 2.7 mm Hg ( 20 °C)
refractive index: n20/D 1.430(lit.)
Fp: 136 °F
storage temp.: Store at +5°C to +30°C.
solubility water: miscible
form: liquid
pka: -0.44±0.70(Predicted)
color: APHA: ≤15
Odor: Faint, ammonia-like odor detectable at 100 ppm
Appearance: colorless liquid
Relative polarity: 0.386
PH: 7 (200g/l, H2O, 20℃)
explosive limit: 2.2-16%(V)
Odor Threshold: 1.8ppm
Water Solubility: soluble
Thermal Conductivity: 0.184 W/(m·K) at 25 ℃
Specific Heat Capacity: Cp(liquid): 2.06 J/(g·K), at 25℃
λmax λ: 270 nm Amax: 1.00
λ: 275 nm Amax: 0.30
λ: 295 nm Amax: 0.10
λ: 310 nm Amax: 0.05
λ: 340-400 nm Amax: 0.01
Sensitive: Hygroscopic
Merck: 14,3243
BRN: 605365
Henry's Law Constant: 1.3×102 mol/(m3Pa) at 25℃, Burkholder et al. (2019)
Exposure limits: ACGIH:TLV-TWA 5 ppm (15 mg/m3)
OSHA:PEL-TWA 10 ppm (30 mg/m3)
NIOSH:REL-TWA 10 ppm
Dielectric constant: 36.710000000000001
InChI: 1S/C3H7NO/c1-4(2)3-5/h3H,1-2H3
InChIKey: ZMXDDKWLCZADIW-UHFFFAOYSA-N
LogP: -1.010
Surface tension: 35.20mN/m at 298.15K
Surface tension: 37.1mN/m at 20°C
CAS DataBase Reference: 68-12-2(CAS DataBase Reference)
NIST Chemistry Reference: Formamide, N,N-dimethyl-(68-12-2)
IARC: 2A (Vol. 47, 71, 115) 2018
EPA Substance Registry System: N,N-Dimethylformamide (68-12-2)
Chemical Properties
N,N-Dimethylformamide (DMF) is a colorless or slightly yellow liquid with a boiling point of 153°C and a vapor pressure of 380 Pa at 20°C.
N,N-Dimethylformamide (DMF) is freely soluble in water and soluble in alcohols, acetone and benzene.
N,N-Dimethylformamide (DMF) is used as solvent, catalyst and gas absorbent.
React violently with concentrated sulfuric acid, fuming nitric acid and can even explode.
Pure N,N-Dimethylformamide (DMF) is odorless, but industrial grade or modified Dimethylformamide has a fishy smell because it contains impurities of Dimethylamine.
N,N-Dimethylformamide (DMF) is unstable (especially at high temperatures) in the presence of a strong base such as sodium hydroxide or a strong acid such as hydrochloric acid or sulfuric acid, and is hydrolyzed to formic acid and dimethylamine.
Uses
N,N-Dimethylformamide (DMF) is a clear liquid that has been widely used in industries as a solvent, an additive, or an intermediate because of its extensive miscibility with water and most common organic solvents.
N,N-Dimethylformamide (DMF) solutions are used toprocess polymer fibers, films, and surface coatings; to permit easy spinning of acrylic fibers; to produce wire enamels, and as a crystallization medium in the pharmaceutical industry.
N,N-Dimethylformamide (DMF) can also be used for formylation with alkyllithium or Grignard reagents.
N,N-Dimethylformamide (DMF) is used as a reagent in Bouveault aldehyde synthesis and also in Vilsmeier-Haack reaction.
N,N-Dimethylformamide (DMF) acts as a catalyst in the synthesis of acyl chlorides.
N,N-Dimethylformamide (DMF) is used for separating and refining crude from olefin gas.
N,N-Dimethylformamide (DMF) along with methylene chloride acts as a remover of varnish or lacquers.
N,N-Dimethylformamide (DMF) is also used in the manufacture of adhesives, fibers and films.
The principal applications of N,N-Dimethylformamide (DMF) are as a solvent and as an extractant, particularly for salts and compounds with high molecular mass.
This role is consistent with its interesting combination of physical and chemical properties: low molecular mass, high dielectric constant, electron-donor characteristics, and ability to form complexes.
The use of N,N-Dimethylformamide (DMF) as a component in synthesis is of relatively minor significance, at least commercially.
N,N-Dimethylformamide (DMF) has been used as solvent for the synthesis of cytotoxic luteinizing hormone-releasing hormone (LH-RH) conjugate AN-152 (a chemotherapeutic drug) and fluorophore C625 [4-(N,N-diphenylamino)-4′-(6-O-hemiglutarate)hexylsulfinyl stilbene].
N,N-Dimethylformamide (DMF) may be employed as solvent medium for the various organic reduction reactions.
The primary use of N,N-Dimethylformamide (DMF) is as a solvent with low evaporation rate.
N,N-Dimethylformamide (DMF) is used in the production of acrylic fibers and plastics.
N,N-Dimethylformamide (DMF) 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.
N,N-Dimethylformamide (DMF) is used as a reagent in the Bouveault aldehyde synthesis and in the Vilsmeier-Haack reaction, another useful method of forming aldehydes.
N,N-Dimethylformamide (DMF) is a common solvent in the Heck reaction.
N,N-Dimethylformamide (DMF) 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.
N,N-Dimethylformamide (DMF) penetrates most plastics and makes them swell.
Because of this property N,N-Dimethylformamide (DMF) is suitable for solid phase peptide synthesis and as a component of paint strippers.
N,N-Dimethylformamide (DMF) is used as a solvent to recover olefins such as 1,3-butadiene via extractive distillation.
N,N-Dimethylformamide (DMF) is used in the manufacturing of solvent dyes as an important raw material.
N,N-Dimethylformamide (DMF) 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 N,N-Dimethylformamide (DMF) safe to transport and use.
As a cheap and common reagent, N,N-Dimethylformamide (DMF) has many uses in a research laboratory.
N,N-Dimethylformamide (DMF) is effective at separating and suspending carbon nanotubes, and is recommended by the NIST for use in near infrared spectroscopy of such.
N,N-Dimethylformamide (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.
N,N-Dimethylformamide (DMF) is a common solvent used in electrospinning.
N,N-Dimethylformamide (DMF) is commonly used in the solvothermal synthesis of metal–organic frameworks.
N,N-Dimethylformamide (DMF)-d7 in the presence of a catalytic amount of potassium tert-butoxide under microwave heating is a reagent for deuteration of polyaromatic hydrocarbons.
Preparation
Two processes are used commercially to produce dimethylformamide.
In the direct or one-step process, dimethylamine and carbon monoxide react at 100°C and 200 psia in the presence of a sodium methoxide catalyst to make dimethylformamide.
The homogenous catalyst is separated from the crude N,N-Dimethylformamide (DMF), which is then refined to the final product.
In the indirect process, N,N-Dimethylformamide (DMF) is isolated, and then reacted with dimethylamine to form DMF.
To obtain methyl formate, two methods may be used - dehydrogenation of methanol and esterification of formic acid.
The two-step process for the synthesis of N,N-Dimethylformamide (DMF) differs from direct synthesis because methyl formate is prepared separately and introduced in the form of ca. 96% pure (commercialgrade) material.
Equimolar amounts of methyl formate and N,N-Dimethylformamide (DMF) are subjected to a continuous reaction at 60-100°C and 0.1 – 0.3 MPa.
The resulting product is a mixture of N,N-Dimethylformamide (DMF) and methanol.
The purification process involves distillation and is analogous to that described for direct synthesis.
However, no separation of salts is required because no catalysts are involved in the process.
According to the corrosive properties of both starting materials and products, stainless steel has to be used as material of construction for production facilities.
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.
DMF is a classic example of a fluxional molecule.
The ambient temperature 1H NMR spectrum shows two methyl signals, indicative of hindered rotation about the (O)C−N bond.
At temperatures near 100 °C, the 500 MHz NMR spectrum of this compound shows only one signal for the methyl groups.
N,N-Dimethylformamide (DMF) is miscible with water.
The vapour pressure at 20 °C is 3.5 hPa.
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.
The partition coefficient log POW is measured to −0.85.
Since the density of N,N-Dimethylformamide (DMF) (0.95 g·cm−3 at 20 °C) is similar to that of water, significant flotation or stratification in surface waters in case of accidental losses is not expected.
Reactions
N,N-Dimethylformamide (DMF) is hydrolyzed by strong acids and bases, especially at elevated temperatures.
With sodium hydroxide, N,N-Dimethylformamide (DMF) converts to formate and dimethylamine.
N,N-Dimethylformamide (DMF) undergoes decarbonylation near its boiling point to give dimethylamine and carbon monoxide.
Distillation is therefore conducted under reduced pressure at lower temperatures.
In one of its main uses in organic synthesis, N,N-Dimethylformamide (DMF) is a reagent in the Vilsmeier–Haack reaction, which is used to formylate aromatic compounds.
The process involves initial conversion of N,N-Dimethylformamide (DMF) to a chloroiminium ion, [(CH3)2N=CH(Cl)]+, known as a Vilsmeier reagent, which attacks arenes.
Organolithium compounds and Grignard reagents react with DMF to give aldehydes after hydrolysis in a reaction called Bouveault aldehyde synthesis.
N,N-Dimethylformamide (DMF) forms 1:1 adducts with a variety of Lewis acids such as the soft acid I2, and the hard acid phenol.
N,N-Dimethylformamide (DMF) is classified as a hard Lewis base and its ECW model base parameters are EB = 2.19 and CB = 1.31.
N,N-Dimethylformamide (DMF)'s relative donor strength toward a series of acids, versus other Lewis bases, can be illustrated by C-B plots.
Production Methods
Industrial production of N,N-Dimethylformamide (DMF) is via three separate processes (Eberling 1980).
N,N-Dimethylformamide (DMF) in methanol is reacted with carbon monoxide in the presence of sodium methoxide or metal carbonyls at 110-150°C and high pressure.
Alternately, methyl formate is produced from carbon monoxide and methanol under high pressure at 60-100°C in the presence of sodium methoxide.
The resulting methyl formate is distilled and then reacted with dimethylamine at 80-100°C and low pressure.
The third process involves reaction of carbon dioxide, hydrogen and dimethylamine in the presence of halogen-containing transition metal compounds to yield DMF.
