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DIMETHYL FORMAMIDE
Dimethylformamide is an organic solvent for vinyl res ins and acetylene, butadiene and acid gases. It caused contact dermatitis in a technician at an epoxy resin manufacturers, and can provoke alcohol-induced flushing in exposed subjects.
Dimethylformamide is an organic compound with the formula (CH3)2NC(O)H. Commonly abbreviated as 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. DMF is a common solvent for chemical reactions. Dimethylformamide is odorless, but technical-grade or degraded samples often have a fishy smell due to impurity of dimethylamine. Dimethylamine degradation impurities can be removed by sparging degraded samples with an inert gas such as argon or by sonicating the samples under reduced pressure. 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.
Applications/uses:
• Agricultural chemical processing
• Fibers
• HTF - pharmaceutical processing
• Oil or gas processing
• Polymer processing
• Process solvents
• Refining
• Textile
INCI: Dimethyl Formamide
Chemical Formula: C3H7NO
CAS No.: 68-12-2
EC No.: 200-679-5
SYNONYMS:
KS-00000UCQ;CTK2F2910;D.M.F.;KSC352S1B;Tox21_300039;ANW-13584;N,N-Dimethylformamide, ACS grade;CHEMBL268291;WLN: VHN1&1;KSC352S1B;Dynasolve 100 (Salt/Mix);STL264197;s6192;UN 2265;NCGC00090785-01;191-EP1441224A2;Q409298;bmse000709;AKOS000121096;FT-0629532;FT-0629533;FT-0639029;FT-0696040;D0939;D0722;Dwumetyloformamid;EINECS 200-679-5;EPA Pesticide Chemical Code 366200;AI3-03311
TRADE NAMES:
Dimethylformamide;Formamide, N,N-dimethyl- (8CI, 9CI);N,N-Dimethylformamide;DMFA;DMF (amide);DMF;Formamide, N,N-dimethyl- (8CI, 9CI);N,N-Dimethylformamide;N-Formyldimethylamine
IUPAC NAMES:
Dimethylformamid;N,N-Dimethylformamide;N,N-dimethylformamide, DMF, Formic acid dimethylamide;N,N-dimetilformamida;DMF, Formic acid dimethylamide
OTHER IDENTIFIERS:
114057-15-7;15175-63-0;15175-77-6;33513-42-7;616-001-00-X;33513-42-7
Dimethyl Formamide:
Primarily used in the cleaning industry as a solvent, it has found extensive use as an additive, or an intermediate. It is also used in the production of adhesives, synthetic leathers, fibers, films and surface coatings.
Dimethylformamide is a colorless or slightly yellow liquid with a boiling point of 153°C and a vapor pressure of 380 Pa at 20°C. It is freely soluble in water and soluble in alcohols, acetone and benzene. Dimethylformamide is used as solvent, catalyst and gas absorbent. React violently with concentrated sulfuric acid, fuming nitric acid and can even explode. Pure Dimethylformamide is odorless, but industrial grade or modified Dimethylformamide has a fishy smell because it contains impurities of Dimethylamine. Dimethylformamide 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.
Clear, colorless to light yellow, hygroscopic, mobile liquid with a faint, characteristic, ammonialike odor. An experimentally determined odor threshold concentration of 100 ppmv was reported by Leonardos et al. (1969).
Molar Weight: 73.095g/mol
Specific Gravity: 0.9445
Melting Point: -61 °C
Boiling Point: 153 °C
Flash Point: 57.7 °C
Product description:
A clear, toxic liquid that is considered a universal Solvent since it is miscible in both water and organic solvents. Dimethylformamide (DMF) dissolves most natural and synthetic resins, and, with heat and time, DMF will even soften Epoxy. It is often used in liquid chromatographic systems as a gradient intermediate between polar and nonpolar solvents. DMF is also used in some commercial paint stripping formulations.
Dimethylformamide (DMF) is a clear, colorless, hygroscopic liquid with a slight amine odor. The solvent properties of DMF are particularly attractive because of the high dielectric constant, the aprotic nature of the solvent, its wide liquid range and low volatility. It is frequently used for chemical reactions and other applications, which require a high solvency power. The product is known as a universal solvent.
Dimethylformamide (DMF) is a excellent polar aprotic solvent that is miscible with water and with most other organic solvents. It is used in a variety of industrial applications.
DMF is a clear liquid with high boiling point. DMF is considered to be biodegradable, but is toxic by inhalation or skin adsorption. DMF is produced by reaction of dimethylamine and carbon monoxide (single step process).
Uses and applications for dimethyl formamide industries:
• Pharma
• Water Treatment
• Oil & Gas
• Cleaning
• Coatings & Construction
• Food and Nutrition
• Cosmetics
• Polymers
• Rubber
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.
1. Dimethylformamide is primarily used as an industrial solvent. Dimethylformamide 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.
2. DMF can also be used for formylation with alkyllithium or Grignard reagents.
3. It is used as a reagent in Bouveault aldehyde synthesis and also in Vilsmeier-Haack reaction. It acts as a catalyst in the synthesis of acyl chlorides. It is used for separating and refining crude from olefin gas. DMF along with methylene chloride acts as a remover of varnish or lacquers. It is also used in the manufacture of adhesives, fibers and films.
4. N,N-Dimethylformamide (DMF) is a solvent with a low evaporation rate, useful for preparing solutions with a variety of hydrophobic organic compounds used in molecular biology applications.
5. N,N-Dimethylformamide was used to solubilize MTT crystals in cell viability assays.It was also used in feruloyl esterase activity assay in molds exhibiting high activity of the enzyme.
6. The world-wide consumption of DMF in 2001 was approximately 285, 000 metric tonnes and most of that was used as an industrial solvent.
Production Methods:
Industrial production of N,N-Dimethylformamide (DMF) is via three separate processes (Eberling 1980). Dimethylamine 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.
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 DMF, which is then refined to the final product. In the indirect process, methyl formate 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 high solubility of polyacrylonitrile in DMF, together with the good miscibility of DMF in water makes DMF the preferred solvent for the production of acrylic fibers. Also the spinning of polyurethane based elastomers is performed from DMF based solutions.
Another significant application is the use of DMF as a solvent for polyurethane-based coatings on leather and artificial leather fabrics.
Polymers like polyvinylchloride, vinylchloride- vinylacetate copolymers and some polyamides are also readily dissolved in DMF. DMF is also used in epoxy based formulations.
The pharmaceutical industry uses DMF as a reaction and crystallization solvent because of its exceptional solvency parameters.
In the petrochemical industry DMF is used for the purification of acetylene from ethylene and butadiene from C4 streams. Also for the separation of aromatics, which can be easily dissolved by DMF from aliphatic hydrocarbons. Those aliphatics are used in lube oils.
Due to the high solubility of SO2 in DMF, exhaust combustion streams from high sulfur containing fuels can be purified with CO2 being recovered.
Inorganic and organic based residual fluxes are highly soluble in DMF; therefore this solvent is used as a cleaner, for instance to clean hot-dip tinned parts. DMF is also used as industrial paint stripper.
This high solubility of inorganic substances also leads to the application of DMF in the production of high voltage capacitors.
DMF is also used as carrier for inks and dyes in various printing and fiber-dying applications.
DMF is widely used as a solvent, reagent and catalyst in the synthetic organic chemistry.
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.
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−1 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 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:
DMF is hydrolyzed by strong acids and bases, especially at elevated temperatures. With sodium hydroxide, DMF converts to formate and dimethylamine. DMF undergoes decarbonylation near its boiling point to give dimethylamine. Distillation is therefore conducted under reduced pressure at lower temperatures.
In one of its main uses in organic synthesis, DMF was a reagent in the Vilsmeier–Haack reaction, which is used to formylate aromatic compounds. The process involves initial conversion of 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 named after Bouveault.
Dimethylformamide forms 1:1 adducts with a variety of Lewis acids such as the soft acid I2, and the hard acid phenol. It is classified as a hard Lewis base and its ECW model base parameters are EB= 2.19 and CB= 1.31.[17] Its relative donor strength toward a series of acids, versus other Lewis bases, can be illustrated by C-B plots.
Production:
DMF was first prepared in 1893 by the French chemist Albert Verley (8 January 1867 – 27 November 1959), by distilling a mixture of dimethylamine hydrochloride and potassium formate.
DMF is prepared by combining methyl formate and dimethylamine or by reaction of dimethylamine with carbon monoxide.
Although currently impractical, DMF can be prepared from supercritical carbon dioxide using ruthenium-based catalysts.
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.
• 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:
Me2NC(O)H + (COCl)2 → CO + CO2 + [Me2N=CHCl]Cl
• The iminium intermediate reacts with the carboxylic acid, abstracting an oxide, and regenerating the DMF catalyst.
• 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 is safely compressed in the presence of dimethylformamide, which forms a safe, concentrated solution. The casing is also filled with agamassan, which renders it safe to transport and use.
Proper uses:
As a cheap and common reagent, DMF has many uses in a 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.
• 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.
• DMF is a common solvent used in electrospinning.
• DMF is commonly used in the solvothermal synthesis of Metal–Organic Frameworks.
• DMF-d7 in the presence of a catalytic amount of KOt-Bu under microwave heating is a reagent for deuteration of polyaromatic hydrocarbons.
Industrial uses:
World production capacity of DMF is about 225 x 103 tons per year. The main application of DMF is as solvent in industrial processes, especially for polar polymers such as Polyvinylchloride, polyacrylonitrile and polyurethanes. DMF solutions of high molecular weight polymers are processed to fibers, films, surface coatings and synthetic leathers. Since salts can be dissolved and dissociated in DMF, the solutions are used in electrolytic capacitors and certain electrolytic processes.
Chemical Synthesis:
N,N-Dimethylformamide is predominantly produced in a single-step reaction between dimethylamine and carbon monoxide under pressure at high temperatures and in the presence of basic catalysts such as sodium methoxide. The crude product contains methanol and N,N-dimethylformamide with increased purity (up to 99.9%) is obtained by multiple distillations. Alternatively, it can be produced by a two-step process in which methyl formate is prepared separately and, in a second step, reacts with dimethylamine under similar conditions as those described for the single-step reaction. No catalysts are involved in the process.
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.
On the 20 of June 2018, the Danish Environmental Protective Agency published an article about the DMF's use in squishies. The density of the compound in the toy resulted in all squishes being removed from the Danish market. All squishies were recommended to be thrown out as household waste.
Toxicity:
The acute LD50 (oral, rats and mice) is 2.2–7.55 g/kg.
Dimethylformamide (DMF) is a clear, colorless, hygroscopic liquid with a slight amine odor. The solvent properties of dimethyl formamide are particularly attractive because of the high dielectric constant, the aprotic nature of the solvent, its wide liquid range and low volatility. It is frequently used for chemical reactions and other applications, which require a high solvency power. The product is known as a universal solvent.The high solubility of polyacrylonitrile in dimethyl formamide, together with the good miscibility of dimethyl formamide in water makes dimethyl formamide the preferred solvent for the production of acrylic fibers. Also the spinning of polyurethane based elastomers is performed from dimethyl formamide based solutions.Another significant application is the use of dimethyl formamide as a solvent for polyurethane-based coatings on leather and artificial leather fabrics.Polymers like polyvinylchloride, vinylchloride- vinylacetate copolymers and some polyamides are also readily dissolved in dimethyl formamide.Dimethyl formamide is also used in epoxy based formulations.
The pharmaceutical industry uses dimethyl formamide as a reaction and crystallization solvent because of its exceptional solvency parameters.In the petrochemical industry dimethyl formamide is used for the purification of acetylene from ethylene and butadiene from C4 streams. Also for the separation of aromatics, which can be easily dissolved by dimethyl formamide from aliphatic hydrocarbons. Those aliphatics are used in lube oils.Due to the high solubility of SO2 in dimethyl formamide, exhaust combustion streams from high sulfur containing fuels can be purified with CO2 being recovered.Inorganic and organic based residual fluxes are highly soluble in dimethyl formamide; therefore this solvent is used as a cleaner, for instance to clean hot-dip tinned parts.Dimethyl formamide is also used as industrial paint stripper.This high solubility of inorganic substances also leads to the application of dimethyl formamide in the production of high voltage capacitors.Dimethyl formamide is also used as carrier for inks d dyes in various printing and fiber-dying applications.Dimethyl formamide is widely used as a solvent, reagent and catalyst in the synthetic organic chemistry.
Industrial production of Dimethyl formamide is via three separate processes. Dimethyl 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 dimethyl formamide.
Two processes are used commercially to produce dimethyl formamide. 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 dimethyl formamide. The homogenous catalyst is separated from the crude Dimethyl formamide, which is then refined to the final product. In the indirect process, methyl formate is isolated, and then reacted with dimethylamine to form dimethyl formamide.To obtain methyl formate, two methods may be used - dehydrogenation of methanol and esterification of formic acid.
Dimethyl formamide is predominantly produced in a single-step reaction between dimethylamine and carbon monoxide under pressure at high temperatures and in the presence of basic catalysts such as sodium methoxide. The crude product contains methanol and dimethyl formamide with increased purity (up to 99.9%) is obtained by multiple distillations. Alternatively, it can be produced by a two-step process in which methyl formate is prepared separately and, in a second step, reacts with dimethylamine under similar conditions as those described for the single-step reaction. No catalysts are involved in the process.World production capacity of dimethyl formamide is about 225 x 103 tons per year. The main application of dimethyl formamide is as solvent in industrial processes, especially for polar polymers such as polyvinylchloride, polyacrylonitrile and polyurethanes.Dimethyl formamide solutions of high molecular weight polymers are processed to fibers, films, surface coatings and synthetic leathers.Since salts can be dissolved and dissociated in dimethyl formamide, the solutions are used in electrolytic capacitors and certain electrolytic processes.
The acute toxicity of dimethyl formamide is low by inhalation, ingestion, and skin contact.Contact with liquid dimethyl formamide may cause eye and skin irritation.Dimethyl formamide is an excellent solvent for many toxic materials that are not ordinarily absorbed and can increase the hazard of these substances by skin contact. Exposure to high concentrations of dimethyl formamide may lead to liver damage and other systemic effects.Dimethyl formamide is listed by IARC in Group 2B ("possible human carcinogen"). It is not classified as a "select carcinogen" according to the criteria of the OSHA Laboratory Standard.No significant reproductive effects have been observed in animal tests. Repeated exposure to dimethyl formamide may result in damage to the liver, kidneys, and cardiovascular system.Dimethyl formamide is a combustible liquid (NFPA rating = 2). Vapors are heavier than air and may travel to source of ignition and flash back. DMF vapor forms explosive mixtures with air at concentrations of 2.2 to 15.2% (by volume).Carbon dioxide or dry chemical extinguishers should be used to fight dimethyl formamide fires.
Chronic occupational exposure to dimethyl formamide by inhalation has resulted in effects on the liver and digestive disturbances in workers.Liver effects have also been reported in animals exposed by inhalation. The Reference Concentration (RfC) for dimethylformamide is 0.03 milligrams per cubic meter (mg/m3) based on digestive disturbances and minimal hepatic changes suggestive of liver abnormalities in humans.The RfC is an estimate (with uncertainty spanning perhaps an order of magnitude) of a continuousinhalation exposure to the human population (including sensitive subgroups), that is likely to be withoutappreciable risk of deleterious noncancer effects during a lifetime. It is not a direct estimator of risk butrather a reference point to gauge the potential effects. At exposures increasingly greater than the RfC, thepotential for adverse health effects increases. Lifetime exposure above the RfC does not imply that anadverse health effect would necessarily occur.EPA has medium confidence in the study on ich the RfC was based because, although it is a human studywith the lowest LOAEL, the exposed population was large, well-defined, and compared with the controls,concentrations are not well characterized and the exposure duration is relatively short; medium confidence in the database because, although there are several inhalation developmental toxicity studies, there are no reproductive toxicity data; and, consequently, medium confidence in the RfC. EPA has calculated a provisional Reference Dose (RfD) of 0.1 milligrams per kilogram body weight per day (mg/kg/d) for dimethylformamide based on liver effects in rats.The provisional RfD is a value that has had some form of Agency review, but it does not appear on IRIS.
Only one study is available on the reproductive effects of dimethylformamide in humans.This study reported an increased rate of spontaneous abortion among pregnant women occupationally exposed to dimethylformamide. However, these results cannot be attributed solely to dimethylformamide, as these women were exposed to a number of additional chemicals.Dimethylformamide is embryotoxic in animals; reduced implantation efficiency, decreased mean fetal weight, and increased abortions have been reported in rats exposed by inhalation. In rabbits exposed to dimethyl formamide by gavage (experimentally placing the chemical in the stomach), decreased mean fetal weight and increased percentage of malformed live fetuses per litter and increased percentage of litters with malformed fetuses were observed in the high-dose group. Human studies suggested a possible association between dimethylformamide exposure and testicular cancer, but further studies failed to confirm this relationship.Animal studies have not reported an increase in tumors from inhalation exposure to dimethylformamide.EPA has not classified dimethylformamide with respect to its carcinogenicity dimethylformamide(DMF) is an organic solvent extensively used in industries such as synthetic leather, fibers and films, and induces liver toxicity and carcinogenesis.Despite a series of experimental and clinical reports on dimethyl formamide-induced liver failure, the mechanism of toxicity is yet unclear. This study investigated whether dimethyl formamide in combination with a low dose of hepatotoxicant enhances hepatotoxicity, and if so, on what mechanistic basis.
Treatment of rats with either dimethyl formamide (50-500 mg/kg/day, for 3 days) or a single low dose of CCl(4) (0.2mL/kg) alone caused small increases in plasma transaminases and lactate dehydrogenase activities. However, combinatorial treatment of dimethyl formamide with CCl(4) markedly increased blood biochemical changes.Histopathology confirmed the synergism in hepatotoxicity.Moreover, DMF+CCl(4) caused PARP cleavage and caspase-3 activation, but decreased the level of Bcl-xL, all of which confirmed apoptosis of hepatocytes. Consistently, DMF+CCl(4) treatment markedly increased lipid peroxidation. By contrast, treatment of dimethyl formamide in combination with lipopolysaccharide, acetaminophen or d-galactosamine caused no enhanced hepatotoxicity. Given the link between endoplasmic reticulum (ER) dysfunction and cell death, ER stress response was monitored after dimethyl formamide and/or CCl(4) treatment. Whereas either dimethyl formamide or CCl(4) treatment alone marginally changed the expression levels of glucose-regulated protein 78 and 94 and phosphorylated PKR-like ER-localized eIF2alpha kinase, concomitant treatment with dimethyl formamide and CCl(4) synergistically induced them with increases in glucose-regulated protein 78 and C/EBP homologous protein mRNAs.These results demonstrate that dimethyl formamide treatment in combination with CCl(4) synergistically increases hepatocyte death, which may be associated with the induction of severe ER stress.
Dimethyl formamide reached an average level of 2.8 ug/L in the blood of subjects exposed to 21 ppm of the vapor for 4 hr, and was undetectable at 4 hr after the exposure; the metabolite, methyl formamide, averaged between 1 and 2 mg/L in the blood and this level was maintained for at least 4 hr after exposure. Maximal blood levels of about 14 and 8 ug/L were observed for dimethyl formamide and methylformamide, respectively, at 0 and 3 hr, after a 4 hr exposure to 87 ppm of the vapor. Repeated daily exposures to 21 ppm of dimethylformamide did not result in accumulation of the chemical or its metabolite in blood. Dimethyl formamide and methyl formamide
Eight healthy male subjects were exposed to dimethyl formamide (DMF) vapor at a concn of 8.79 + or - 0.33 ppm for 6 hr daily for 5 consecutive days. All urine voided by the subjects was collected from the beginning of the first exposure to 24 hr past the end of the last exposure and each sample was analyzed for monomethylformamide. Monomethylformamide was rapidly eliminated from the body with urine values peaking within a few hours following the end of each exposure period. The mean for the 7 hr (end of exposure) sample was 4.74 mg/mL.The amount of N-methylformamide recovered in the urine represents only 2-6% of the dose of dimethylformamide inhaled. A substantial portion of an absorbed dose of DMF is excreted unchanged in the expired breath.
The urinary concn of N-methylformamide is probably the best index of worker exponent dimethylformamide.Dimethyl formamide is known that dimethylformamide is metabolized in man by sequential N-demethylation to methylformamide and formamide, which are largely eliminated in the urine.Dimethylformamide is primarily used as an industrial solvent. Dimethyl formamide solutions are used to process 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.Dimethyl formamide is used as an industrial solvent and in the production of fibers, films, and surface coatings. Acute (short-term) exposure to dimethylformamide has been observed to damage the liver in animals and in humans. Symptoms of acute exposure in humans include abdominal pain, nausea, vomiting, jaundice, alcohol intolerance, and rashes. Chronic (long-term) occupational exposure to dimethylformamide by inhalation has resulted in effects on the liver and digestive disturbances in workers. Human studies suggested a possible association between dimethylformamide exposure and testicular cancer, but further studies failed to confirm this relationship. EPA has not classified dimethylformamide with respect to its carcinogenicity.
This action promulgates standards of performance for equipment leaks of Volatile Organic Compounds (VOC) in the Synthetic Organic Chemical Manufacturing Industry (SOCMI). The intended effect of these standards is to require all newly constructed, modified, and reconstructed SOCMI process units to use the best demonstrated system of continuous emission reduction for equipment leaks of VOC, considering costs, non air quality health and environmental impact and energy requirements.
Dimethylformamide is produced, as an intermediate or a final product, by process units covered under this subpart.Pursuant to section 8(d) of TSCA, EPA promulgated a model Health and Safety Data Reporting Rule. The section 8(d) model rule requires manufacturers, importers, and processors of listed chemical substances and mixtures to submit to EPA copies and lists of unpublished health and safety studies.Dimethylformamide is included on this list. The determination of a dimethylformamide metabolite, dimethyl formamide, in the urine of exposed workers has been recommended as a guide to monitoring worker exposure. The fluctuation in the rate of excretion of this metabolite requires that methylformamide determinations be carried out on 24 hr urine specimens. The 24 hr urinary excretion of 50 mg or less of methylformamide is consistent with occupational exposure to 20 ppm of dimethyl formamide vapor.Dimethyl formamide exposure to air concn of 3500 ppm is considered immediately dangerous to life or health.Dimethy lformamide's production and use as a solvent, in pharmaceutical intermediate, in acrylic fibers and in plastics may result in its release to the environment through various waste streams. If released to air, a vapor pressure of 3.87 mm Hg at 25 °C indicates dimethyl formamide will exist solely as a vapor in the atmosphere. Vapor-phase dimethyl formamide will be degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 20 hours.Dimethyl formamide contains chromophores that absorb at wavelengths >290 nm and, therefore, may be susceptible to direct photolysis by sunlight. If released to soil, dimethyl formamide is expected to have very high mobility based upon an estimated Koc of 1. Volatilization from moist soil surfaces is expected to be an important fate process based upon a Henry's Law constant of 7.39X10-8 atm-cu m/mole.Dimethyl formamide may volatilize from dry soil surfaces based upon its vapor pressure.
Utilizing the Japanese MITI test, 4.4% of the theoretical BOD was reached in 2 weeks, however, 100% of dimethyl formamide was biodegraded in 9 days using a river die-away test. These results indicate that biodegradation may be an important environmental fate process. If released into water,dimethyl formamide is not expected to adsorb to suspended solids and sediment based upon the estimated Koc. Volatilization from water surfaces is not expected to be an important fate process based upon this compound's Henry's Law constant. BCFs of 0.3 to 1.2, in carp, suggests bioconcentration in aquatic organisms is low. Hydrolysis is not expected to be an important environmental fate process since neutral hydrolysis rate constants for amides are <10-9/sec under environmental conditions (pH 5 to 9). Occupational exposure to dimethy lformamide may occur through inhalation and dermal contact with this compound at workplaces where dimethyl formamide is produced or used.Monitoring data indicate that the general population may be exposed to dimethyl formamide via inhalation of ambient air and dermal contact with consumer products containing dimethyl formamide. Dimethyl formamide's production and use as a solvent, in pharmaceuticals, in acrylic fibers and in plastics may result in its release to the environment through various waste streams(SRC).
Based on a classification scheme, an estimated Koc value of 1(SRC), determined from a structure estimation method(2), indicates that dimethyl formamide is expected to have very high mobility in soil(SRC). Volatilization of dimethyl formamide from moist soil surfaces is not expected to be an important fate process(SRC) given a Henry's Law constant of 7.39X10-8 atm-cu m/mole(3).Dimethyl formamide is expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 3.87 mm Hg at 25 °C(4).Dimethyl formamide may biodegrade in soil based upon river die-away tests (100% in 6 days)(5), however, utilizing the Japanese MITI test, only 4.4% of the theoretical BOD was reached in 2 weeks(6).Aerobic unacclimated and acclimated river die-away tests showed that dimethyl formamide at an initial concentration of 30 mg/L completely disappeared within 6 and 3 days, respectively. However, 24 to 48 hours was required before any degradation was observed among unacclimated samples.Dimethyl formamide, present at 100 mg/L, reached 4.4% of its theoretical BOD in 2 weeks using an activated sludge inoculum at 30 mg/L in the Japanese MITI test.
Aerobic grab sample data for dimethyl formamide in sea water showed a mineralization rate of <3% in 24 hours for initial concentration of 10 ug/L and 100 ug/L(3). However, 20% of dimethyl formamide at a concentration of 0.1 ug/L was mineralized in 24 hrs(3). All samples were adjusted to sterilized controls. Aqueous screening test data demonstrated that dimethyl formamide was easily removed by sewage treatment facilities upon acclimation(4). Wastewater from a polyimide synthesis operation at Kansas City, MO contained N,N-dimethylformamide at a concentration of 65,500 mg/L before entering a bench scale biological treatment system(5). At feed rates of 90 lb/day/1000 cu ft, effluent from the biological reactor contained N,N-dimethylformamide at a concentration of <10 mg/L(5). The concentration of dimethyl formamide in the reactor sludge was not documented.The rate constant for the vapor-phase reaction of dimethyl formamide with photochemically-produced hydroxyl radicals has been estimated as 1.8X10-11 cu cm/molecule-sec at 25 °C(SRC) using a structure estimation method(1). This corresponds to an atmospheric half-life of about 20 hours at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(1). Hydrolysis is not expected to be an important environmental fate process since neutral hydrolysis rate constants for amides are <10-9/sec under environmental conditions (pH 5 to 9)(2).Dimethyl formamide contains chromophores that absorb at wavelengths >290 nm(3) and, therefore, may be susceptible to direct photolysis by sunlight(SRC).
Dimethyl formamide is stable. Dimethyl formamide is hygroscopic and easily absorbs water form a humid atmosphere and should therefore be kept under dry nitrogen. High purity Dimethylformamide, required for acrylic fibers, is best stored in aluminum tanks. Dimethylformamide dose not change under light or oxygen and does not polymerize spontaneously. Temperatures >350 °C may cause decomposition to form dimethylamine and carbon dioxide, with pressure developing in closed containers.Dimethyl formamide is metabolized by the microsomal cytochrome p-450 into mainly dimethyl formamide, which further breaks down to dimethyl formamide . However, the detailed mechanism of its toxicity remains unclear. We investigated the metabolism and the toxicity of dimethyl formamide using the isolated perfused liver model. Dimethyl formamide was added to the recirculating perfusate of the isolated perfused rat liver at concentrations of 0, 10 and 25 mM. Samples were collected from the inferior vena cava at 0, 30, 45, 60, 75, and 90 minutes following addition of the Dimethylformamide. The metabolites of Dimethylformamide were analyzed using Gas-chromatography (GC).
The changes in the rate of oxygen consumption by the Dimethyl formamide were monitored during perfusion. The enzyme activities (aspartic aminotransferase:AST, alanine aminotransferase:ALT, and lactic dehydrogenase:LDH) in the perfusate were monitored to see if dimethyl formamide caused hepatotoxicity. As the perfusion progressed, the dimethyl formamide concentration in the perfusate decreased, but the level of dimethyl formamide increased to a maximum of 1.16 mM. The rate of oxygen consumption increased at Dimethylformamide concentrations of 10 mM and 25 mM. However, when a known inhibitor of cytochrome P-450, SKF 525A (300 uM), was used to pretreat the perfusate prior to the addition of the Dimethylformamide, the rate of oxygen consumption was significantly inhibited, indicating the cytochrome P-450 system was responsible for the conversion of Dimethylformamide to NMF. On addition of the Dimethylformamide, the activities of the enzymes AST, ALT and LDH were significantly increased a time and dose dependent manner. However, following pretreatment with SKF 525A, their releases were inhibited.
Dimethylformamide, DMF, is a clear, colorless, hygroscopic liquid with a slight amine odor. The solvent properties of DMF are particularly attractive because of the high dielectric constant, the aprotic nature of the solvent, its wide liquid range and low volatility. It is frequently used for chemical reactions and other applications, which require a high solvency power. The product is known as a universal solvent.
Storage and Handling:
Dimethylformamide has practically no corrosive effect on ordinary metals with the exception of copper and its alloys.
Dimethylformamide may be stored in stainless steel or aluminum tanks.
Seals should preferably be made of polytetrafluoro- ethylene (PTFE), polyethylene, or high-density polypropylene.
Dimethylformamide is hygroscopic and it is advisable to store it under nitrogen. Additional technical information may be obtained on request.
As dimethylformamide is very easily absorbed through the skin, it is advisable for personnel to wear masks and polyethylene gloves. Independent breathing apparatus should be worn inside tanks that have contained dimethylformamide.
People susceptible to skin disease or liver and stomach disorders should not be exposed to dimethylformamide.
In the event of accidental spillage of a small amount of the substance, it may be diluted with water and removed without any danger to purification plants.
If the amount spilt is large, the product should be recovered by pumping and then destroyed by incineration or by absorption in a suitable substance for subsequent removal in compliance with current legislation.
Principal chemical properties:
Formation of complexes:
Dimethylformamide complexes with a number of substances including the following: S03, P205, POCl3, HCI, BF3 metal salts: CoCl2, NiCl2, FeCl3, SnCl4
Stability:
Decomposition reactions, which may be violent with metallic sodium, some halogenated hydrocarbons, inorganic nitrates (particularly magnesium nitrate), triethylaluminum, bromine, and potassium permanganate.
Decomposition into dimethylamine and formaldehyde may occur as a result of UV irradiation.
Hydrolysis:
Slight tendency towards hydrolysis in aqueous solution and at elevated temperature. The rate of hydrolysis increases in the presence of acids or alkalis (formation of formic acid and dimethylamine).
Principal applications:
The high solubility of polyacrylonitrile in DMF, together with the good miscibility of DMF in water makes DMF the preferred solvent for the production of acrylic fibers. Also the spinning of polyurethane based elastomers is performed from DMF based solutions.
Another significant application is the use of DMF as a solvent for polyurethane-based coatings on leather and artificial leather fabrics.
Polymers like polyvinylchloride, vinylchloride- vinylacetate copolymers and some polyamides are also readily dissolved in DMF. DMF is also used in epoxy based formulations.
The pharmaceutical industry uses DMF as a reaction and crystallization solvent because of its exceptional solvency parameters.
In the petrochemical industry DMF is used for the purification of acetylene from ethylene and butadiene from C4 streams. Also for the separation of aromatics, which can be easily dissolved by DMF from aliphatic hydrocarbons. Those aliphatics are used in lube oils.
Due to the high solubility of SO2 in DMF, exhaust combustion streams from high sulfur containing fuels can be purified with CO2 being recovered.
Inorganic and organic based residual fluxes are highly soluble in DMF; therefor this solvent is used as a cleaner for instance hot-dip tinned parts. DMF is also used as industrial paint stripper.
This high solubility of inorganic substances also leads to the application of DMF in the production of high voltage capacitors.
DMF is also used as carrier for inks and dyes in various printing and fiber-dying applications.
DMF is widely used as a solvent, reagent and catalyst in the synthetic organic chemistry.
