68-12-2 Usage
Uses
Used in Polymer Processing:
N,N-Dimethylformamide is used as a solvent for processing polymer fibers, films, and surface coatings, enabling efficient manufacturing processes.
Used in Textile Industry:
In the textile industry, N,N-Dimethylformamide is used as a solvent to facilitate the easy spinning of acrylic fibers, contributing to the production of quality textiles.
Used in Pharmaceutical Industry:
N,N-Dimethylformamide serves as a crystallization medium in the pharmaceutical industry, playing a crucial role in the development and production of various medications.
Used in Chemical Synthesis:
N,N-Dimethylformamide is used as a reagent in Bouveault aldehyde synthesis and the Vilsmeier-Haack reaction, supporting the creation of a range of chemical compounds.
Used as a Catalyst:
In the synthesis of acyl chlorides, N,N-Dimethylformamide acts as a catalyst, enhancing the efficiency of chemical reactions.
Used in Petroleum Industry:
N,N-Dimethylformamide is employed for separating and refining crude from olefin gas, contributing to the petroleum industry's processes.
Used in Paint and Varnish Removal:
Combined with methylene chloride, N,N-Dimethylformamide acts as an effective remover of varnish or lacquers, offering a solution for cleaning and surface preparation.
Used in Adhesive, Fiber, and Film Manufacturing:
N,N-Dimethylformamide is utilized in the production of adhesives, fibers, and films, playing a significant role in the manufacturing processes of these materials.
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 two-step process for the synthesis of N,N-dimethylformamide 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-dimethylamine 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 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.
Reactivity Profile
N,N-Dimethylformamide may react violently with a broad range of chemicals, e.g.: alkaline metals (sodium, potassium), azides, hydrides (sodium borohydride, lithium aluminum hydride), bromine, chlorine, carbon tetrachloride, hexachlorocyclohexane, phosphorus pentaoxide, triethylaluminum, magnesium nitrate, organic nitrates. Forms explosive mixtures with lithium azide [Bretherick, 5th ed., 1995, p. 453]. Oxidation by chromium trioxide or potassium permanganate may lead to explosion [Pal B. C. et al., Chem. Eng. News, 1981, 59, p. 47].
Health Hazard
The acute toxicity of DMF is low by inhalation, ingestion, and skin contact. Contact
with liquid DMF may cause eye and skin irritation. DMF 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 DMF may lead
to liver damage and other systemic effects.
Dimethylformamide 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 DMF may result in damage to the liver, kidneys,
and cardiovascular system
Flammability and Explosibility
DMF 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 DMF fires.
Contact allergens
This is an organic solvent for vinyl resins and acetylene, butadiene, and acid gases. It caused contact dermatitis in a technician at an epoxy resin factory and can provoke alcohol-induced flushing in exposed subjects.
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.
Carcinogenicity
DMF is not carcinogenic to
animals except under very high inhalation exposure conditions.
No increase in tumors was seen in rats that
inhaled 25, 100, or 400 ppm for 6 h/day, 5 days/week for
2 years. Similarly, no tumors were produced
in mice under the same conditions for 18 months. In
that chronic experiment, rats and mice were exposed by
inhalation (6 h/day, 5 days/week) to 0, 25, 100, or 400 ppm
DMF for 18 months (mice) or 2 years (rats). Body weights
of rats exposed to 100 (males only) and 400 ppm were
reduced and, conversely, body weights were increased in
400 ppm mice. Serum sorbitol dehydrogenase activity was
increased in rats exposed to 100 or 400 ppm. DMF-related
morphological changes in rats were observed only in the
liver and consisted of increased relative liver weights,
centrilobular hepatocellular hypertrophy, lipofuscin/hemosiderin
accumulation in Kupffer cells, and centrilobular
single cell necrosis (400 ppm only). The same liver effects
were seen in all groups of mice, although the response at
25 ppm was judged as minimal.
Environmental fate
Biological. Incubation of [14C]N,N-dimethylformamide (0.1–100 μg/L) in natural seawater
resulted in the compound mineralizing to carbon dioxide. The rate of carbon dioxide formation
was inversely proportional to the initial concentration (Ursin, 1985).
Chemical. Reacts with acids or bases forming formic acid and dimethylamine (BASF, 1999)
Metabolic pathway
Three urinary metabolites are identified in humans and
rodents, and the metabolites quantified are N-
(hydroxymethyl)-N-methylformamide (HMMF), resulting
in N-methylformamide (NMF) and N-acetyl-S-(N-
methylcarbamoyl)cysteine (AMCC). Ten volunteers
who absorb between 28 and 60 mmol/kg DMF during
an 8 h exposure to DMF in air at 6 mg=m3 excrete in
the urine within 72 h between 16.1 and 48.7% of the
dose as HMMF, between 8.3 and 23.9% as
formamide, and between 9.7 and 22.8% as AMCC.
AMCC together with HMMF is also detected in the
urine of workers after occupational exposure to DMF.
There is a quantitative difference between the
metabolic pathway of DMF to AMCC in humans and
rodents.
storage
DMF should be used only in areas free of ignition sources, and quantities greater than 1 liter should be stored in tightly sealed metal containers in areas separate from oxidizers.
Purification Methods
DMF decomposes slightly at its normal boiling point to give small amounts of dimethylamine and carbon monoxide. The decomposition is catalysed by acidic or basic materials, so that even at room temperature DMF is appreciably decomposed if allowed to stand for several hours with solid KOH, NaOH or CaH2. If these reagents are used as dehydrating agents, therefore, they should not be refluxed with the DMF. Use of CaSO4, MgSO4, silica gel or Linde type 4A molecular sieves is preferable, followed by distillation under reduced pressure. This procedure is adequate for most laboratory purposes. Larger amounts of water can be removed by azeotropic distillation with *benzene (10% v/v, previously dried over CaH2), at atmospheric pressure: water and *benzene distil below 80o. The liquid remaining in the distillation flask is further dried by adding MgSO4 (previously ignited overnight at 300-400o) to give 25g/L. After shaking for one day, a further quantity of MgSO4 is added, and the DMF is distillied at 15-20mm pressure through a 3-ft vacuum-jacketed column packed with steel helices. However, MgSO4 is an inefficient drying agent, leaving about 0.01M water in the final DMF. More efficient drying (to around 0.001-0.007M water) is achieved by standing with powdered BaO, followed by decanting before distillation, then with alumina powder (50g/L, previously heated overnight to 500-600o), and distilling from more of the alumina, or by refluxing at 120-140o for 24hours with triphenylchlorosilane (5-10g/L), then distilling at ca 5mm pressure [Thomas & Rochow J Am Chem Soc 79 1843 1957]. Free amine in DMF can be detected by the colour reaction with 1-fluoro-2,4-dinitrobenzene. It has also been purified by drying overnight over KOH pellets and then distilling from BaO through a 10 cm Vigreux column (p 11) [Jasiewicz et al. Exp Cell Res 100 213 1976]. [For efficiency of desiccants in drying dimethylformamide see Burfield & Smithers J Org Chem 43 3966 1978, and for a review on purification, tests of purity and physical properties, see Juillard Pure Appl Chem 49 885 1977.] It has been purified by distilling from K2CO3 under high vacuum and fractionated in an all-glass apparatus. The middle fraction is collected, degassed (seven or eight freeze-thaw cycles) and redistilled under as high a vacuum as possible [Mohammad & Kosower J Am Chem Soc 93 2713 1971]. [Beilstein 4 IV 171.] Rapid purification: Stir over CaH2 (5% w/v) overnight, filter, then distil at 20mmHg. Store the distilled DMF over 3A or 4A molecular sieves. For solid phase synthesis, the DMF used must be of high quality and free from amines.
Incompatibilities
Though stable at normal temperatures and storage conditions, DMF may react violently with halogens, acyl halides, strong oxidizers, and polyhalogenated compounds in the presence of iron. Decomposition products include toxic gases and vapors such as dimethylamine and carbon monoxide. DMF will attack some forms of plastics, rubber, and coatings.
Waste Disposal
Excess DMF and waste material containing this substance should be placed in an appropriate container, clearly labeled, and handled according to your institution's waste disposal guidelines.
Check Digit Verification of cas no
The CAS Registry Mumber 68-12-2 includes 5 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 2 digits, 6 and 8 respectively; the second part has 2 digits, 1 and 2 respectively.
Calculate Digit Verification of CAS Registry Number 68-12:
(4*6)+(3*8)+(2*1)+(1*2)=52
52 % 10 = 2
So 68-12-2 is a valid CAS Registry Number.
InChI:InChI=1/C3H7NO/c1-4(2)3-5/h3H,1-2H3
68-12-2Relevant articles and documents
N-formylation of amines using phenylsilane and CO2 over ZnO catalyst under mild condition
Cheng, Yujie,Gan, Tao,He, Qian,He, Xiaohui,Ji, Hongbing,Sun, Qingdi,Wang, Pengbo,Zhang, Hao
, (2020/10/27)
Several research studies have been conducted on N-formylation of amines using phenylsilane and CO2. However, most of these studies involved tedious processes of catalyst preparation or complex procedures. In the present study, we describe the use of a simple and commercially available ZnO catalyst for selective N-formylation of amines under mild condition. High-yielding N-formylation products with good recyclability and wide substrate scope were obtained, which can promote fine chemical synthesis and CO2 capture.
Mesoporous Sn(IV) Doping DFNS Supported BaMnO3 Nanoparticles for Formylation of Amines Using Carbon Dioxide
Yang, Jie,Wang, Liujie,Sun, Aili,Zhiani, Rahele
, p. 573 - 581 (2020/07/27)
Abstract: In the present paper, Sn(IV) doping DFNS (SnD) supported nanoparticles of BaMnO3 (BaMnO3/SnD) and using as a catalyst for the N-formylation of amines by CO2 hydrogenation. In this catalyst, the SnD with the ratios of Si/Sn in the range of from 6 to 50 were obtained with method of direct hydrothermal synthesis (DHS) as well as the nanoparticles of BaMnO3 were on the surfaces of SnD in situ reduced. Scanning electron microscope (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray energy dispersive spectroscopy (EDS), and transmission electron microscopy (TEM) were utilized for characterizing the nanostructures BaMnO3/SnD. It is found that the nanostructures of BaMnO3/SnD can be a nominate due to its effective and novel catalytic behavior in N-formylation of amines through hydrogenation of CO2. Graphic Abstract: [Figure not available: see fulltext.]
Bifunctional Ru-loaded Porous Organic Polymers with Pyridine Functionality: Recyclable Catalysts for N-Formylation of Amines with CO2 and H2
Zhang, Kai,Zong, Lingbo,Jia, Xiaofei
, p. 1335 - 1340 (2021/02/05)
A series of pyridine functionalized porous organic polymers (POPs-Py&PPh3) have been synthesized by polymerizing tris(4-vinylphenyl)phosphane and 4-vinylpyridine. The pyridine moieties in the copolymer materials contribute to CO2 adsorption and promote the subsequent conversion of CO2. The POP supported Ru catalyst (Ru/POP3-Py&PPh3) shows a high catalytic activity (TON up to 710) in the N-formylation of various primary and secondary amines with CO2/H2, affording the corresponding formamides in good yields (55–95%) under mild reaction conditions. The heterogeneous catalyst can be easily separated from the reaction system and reused for at least eight cycles in the N-formylation of morpholine. (Figure presented.).
Highly Efficient and Selective N-Formylation of Amines with CO2 and H2 Catalyzed by Porous Organometallic Polymers
Shen, Yajing,Zheng, Qingshu,Chen, Zhe-Ning,Wen, Daheng,Clark, James H.,Xu, Xin,Tu, Tao
supporting information, p. 4125 - 4132 (2021/01/12)
The valorization of carbon dioxide (CO2) to fine chemicals is one of the most promising approaches for CO2 capture and utilization. Herein we demonstrated a series of porous organometallic polymers could be employed as highly efficient and recyclable catalysts for this purpose. Synergetic effects of specific surface area, iridium content, and CO2 adsorption capability are crucial to achieve excellent selectivity and yields towards N-formylation of diverse amines with CO2 and H2 under mild reaction conditions even at 20 ppm catalyst loading. Density functional theory calculations revealed not only a redox-neutral catalytic pathway but also a new plausible mechanism with the incorporation of the key intermediate formic acid via a proton-relay process. Remarkably, a record turnover number (TON=1.58×106) was achieved in the synthesis of N,N-dimethylformamide (DMF), and the solid catalysts can be reused up to 12 runs, highlighting their practical potential in industry.
Method for preparing N, N-dimethylformamide
-
Paragraph 0009-0052, (2021/06/06)
The invention relates to a method for preparing N, N-dimethylformamide (DMF). According to the method, dimethylamine and carbon monoxide (CO) are used as reactants, and the DMF is prepared through CO-inserted carbonylation reaction under the catalytic action, wherein the reaction conditions are as follows: the reaction is carried out in a fixed bed reactor, the reaction pressure is 1.0-8.0 MPa, the reaction temperature is 150-250 DEG C, the feeding volume space velocity of dimethylamine is 50-800 h, and the volume space velocity of CO is 50-800 h. The method is characterized in that (1) the reaction has 100% atom economy and no by-product is generated, and (2) the oxide A-metal-oxide B composite material is used as the catalyst, the catalyst catalyzes the reaction with high selectivity, the selectivity of DMF reaches 99% or above, and the catalyst is high in stability and can be continuously operated for 500 h.
Preparation method of N, N-dimethylformamide
-
Paragraph 0011-0080, (2021/06/06)
The invention relates to a preparation method of N, N-dimethylformamide (DMF). According to the method, dimethylamine and carbon monoxide (CO) are adopted as reactants, and the DMF is prepared through CO-inserted carbonylation reaction under the catalytic action, wherein the reaction conditions are as follows: the reaction is carried out in a fixed bed reactor, the reaction pressure is 1.0-8.0 MPa, the reaction temperature is 150-250 DEG C, the feeding space velocity of dimethylamine is 50-800 h, and the flow velocity of the raw material CO is 5-25 mL.min. The method is characterized in that (1) the reaction has 100% atom economy and no by-product is generated, and (2) the Ru-loaded HAP is used as the catalyst, the catalyst is simple to prepare and efficiently catalyzes the reaction, the optimal yield of DMF can reach 95%, the catalyst is high in stability, and continuous operation can be performed for 500 h.
Catalysis of Positively Charged Ru Species Stabilized by Hydroxyapatite in Amine Formylation
Jiao, Dongxia,Wang, Yehong,Zhang, Zhixin,Zhang, Jian,Lei, Lijun,Wang, Feng
, p. 4159 - 4163 (2021/08/20)
Formamide is an important solvent and synthetic intermediate. Herein, we designed a hydroxyapatite (HAP)-stabilized, positively charged Ru-based catalysts which can efficiently catalyze the formylation reaction of amines with CO for the synthesis of formamide. The Ru-HAP showed excellent catalytic performance in N,N-Dimethylformamide (DMF) synthesis, with about 75 % dimethylamine conversion and >99 % DMF selectivity at 300 h of continuous reaction. The combination of characterization results and control experiments showed that positively charged Ru species, including hydrated RuOx and Ru3+ species, were catalytically active. In particular, the surface RuOx species were more active than the Ru3+ species located within the HAP framework.
Chromium-catalysed efficient: N -formylation of amines with a recyclable polyoxometalate-supported green catalyst
Dan, Demin,Chen, Fubo,Zhao, Whenshu,Yu, Han,Han, Sheng,Wei, Yongge
supporting information, p. 90 - 94 (2021/01/11)
A simple and efficient protocol for the formylation of amines with formic acid, catalyzed by a polyoxometalate-based chromium catalyst, is described. Notably, this method shows excellent activity and chemoselectivity for the formylation of primary amines; diamines have also been successfully employed. Importantly, the chromium catalyst is potentially non-toxic, environmentally benign and safer than the widely used high valence chromium catalysts such as CrO3 and K2Cr2O7. The catalyst can be recycled several times with a negligible impact on activity. Finally, a plausible mechanism is provided based on the observation of intermediate and control experiments.
Solvate sponge crystals of (DMF)3NaClO4: reversible pressure/temperature controlled juicing in a melt/press-castable sodium-ion conductor
Prakash, Prabhat,Ardhra, Shylendran,Fall, Birane,Zdilla, Michael J.,Wunder, Stephanie L.,Venkatnathan, Arun
, p. 5574 - 5581 (2021/04/30)
A new type of crystalline solid, termed “solvate sponge crystal”, is presented, and the chemical basis of its properties are explained for a melt- and press-castable solid sodium ion conductor. X-ray crystallography and atomistic simulations reveal details of atomic interactions and clustering in (DMF)3NaClO4and (DMF)2NaClO4(DMF =N-N′-dimethylformamide). External pressure or heating results in reversible expulsion of liquid DMF from (DMF)3NaClO4to generate (DMF)2NaClO4. The process reverses upon the release of pressure or cooling. Simulations reveal the mechanism of crystal “juicing,” as well as melting. In particular, cation-solvent clusters form a chain of octahedrally coordinated Na+-DMF networks, which have perchlorate ions present in a separate sublattice space in 3?:?1 stoichiometry. Upon heating and/or pressing, the Na+?DMF chains break and the replacement of a DMF molecule with a ClO4?anion per Na+ion leads to the conversion of the 3?:?1 stoichiometry to a 2?:?1 stoichiometry. The simulations reveal the anisotropic nature of pressure induced stoichiometric conversion. The results provide molecular level understanding of a solvate sponge crystal with novel and desirable physical castability properties for device fabrication.
