fbpx
Wikipedia

Dimethylformamide

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 samples with an inert gas such as argon or by sonicating the samples under reduced pressure. As its name indicates, it is structurally related to formamide, having two methyl groups in the place of the two hydrogens. DMF is a polar (hydrophilic) aprotic solvent with a high boiling point. It facilitates reactions that follow polar mechanisms, such as SN2 reactions.

Dimethylformamide
Names
Preferred IUPAC name
N,N-Dimethylformamide[2]
Other names
Dimethylformamide
N,N-Dimethylmethanamide[1]
DMF
Identifiers
  • 68-12-2 Y
3D model (JSmol)
  • Interactive image
3DMet
  • B00545
605365
ChEBI
  • CHEBI:17741 Y
ChEMBL
  • ChEMBL268291 Y
ChemSpider
  • 5993 Y
DrugBank
  • DB01844 Y
ECHA InfoCard 100.000.617
EC Number
  • 200-679-5
KEGG
  • C03134 Y
MeSH Dimethylformamide
  • 6228
RTECS number
  • LQ2100000
UNII
  • 8696NH0Y2X Y
UN number 2265
  • DTXSID6020515
  • InChI=1S/C3H7NO/c1-4(2)3-5/h3H,1-2H3 Y
    Key: ZMXDDKWLCZADIW-UHFFFAOYSA-N Y
  • CN(C)C=O
Properties
C3H7NO
Molar mass 73.095 g·mol−1
Appearance Colourless liquid
Odor fishy, ammoniacal
Density 0.948 g/mL
Melting point −61 °C (−78 °F; 212 K)
Boiling point 153 °C (307 °F; 426 K)
Miscible
log P −0.829
Vapor pressure 516 Pa
Acidity (pKa) -0.3 (for the conjugate acid) (H2O)[3]
UV-vismax) 270 nm
Absorbance 1.00
1.4305 (at 20 °C)
Viscosity 0.92 mPa s (at 20 °C)
Structure
3.86 D
Thermochemistry
146.05 J/(K·mol)
−239.4 ± 1.2 kJ/mol
−1.9416 ± 0.0012 MJ/mol
Hazards
GHS labelling:
Danger
H226, H312, H319, H332, H360
P280, P305+P351+P338, P308+P313
NFPA 704 (fire diamond)
2
2
0
Flash point 58 °C (136 °F; 331 K)
445 °C (833 °F; 718 K)
Explosive limits 2.2–15.2%
30 mg/m (TWA)
Lethal dose or concentration (LD, LC):
  • 1.5 g/kg (dermal, rabbit)
  • 2.8 g/kg (oral, rat)
  • 3.7 g/kg (mouse, oral)
  • 3.5 g/kg (rat, oral)
3092 ppm (mouse, 2 h)[5]
5000 ppm (rat, 6 h)[5]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 10 ppm (30 mg/m3) [skin][4]
REL (Recommended)
TWA 10 ppm (30 mg/m3) [skin][4]
IDLH (Immediate danger)
500 ppm[4]
Related compounds
Related alkanamides
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)

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.[6]

DMF is a classic example of a fluxional molecule.[7]

 

The ambient temperature 1H NMR spectrum shows two methyl signals, indicative of hindered rotation about the (O)C-N bond.[6] 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.[8] The vapour pressure at 20 °C is 3.5 hPa.[9] 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.[10] The partition coefficient log POW is measured to −0.85.[11] Since the density of DMF (0.95 g cm−3 at 20 °C[8]) is similar to that of water, significant flotation or stratification in surface waters in case of accidental losses is not expected.

 
Left: two resonance structures of DMF. Right: illustration highlighting delocalization.

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.[12]

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.[13][14] The process involves initial conversion of DMF to a chloroiminium ion, [(CH3)2N=CH(Cl)]+, known as a Vilsmeier reagent,[15] which attacks arenes.

Organolithium compounds and Grignard reagents react with DMF to give aldehydes after hydrolysis in a reaction named after Bouveault.[16]

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.[18][19]

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.[20]

DMF is prepared by combining methyl formate and dimethylamine or by reaction of dimethylamine with carbon monoxide.[21]

Although currently impractical, DMF can be prepared from supercritical carbon dioxide using ruthenium-based catalysts.[22]

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.[8]

 
  • 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.

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.[29]
  • 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.

Safety

Reactions including the use of sodium hydride in DMF as a solvent are somewhat hazardous;[30] 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.[31]

Dimethylformamide vapor exposure has shown reduced alcohol tolerance and skin irritation in some cases.[32]

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 squishies being removed from the Danish market. All squishies were recommended to be thrown out as household waste. [33]

Toxicity

The acute LD50 (oral, rats and mice) is 2.2–7.55 g/kg.[8] Hazards of DMF have been examined.[34]

References

  1. ^ N,N-Dimethylmethanamide, NIST web thermo tables
  2. ^ Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. pp. 841, 844. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4. The traditional name 'formamide' is retained for HCO-NH2 and is the preferred IUPAC name. Substitution is permitted on the –NH2 group.
  3. ^ "Hazardous Substances Data Bank (HSDB) - N,N-DIMETHYLFORMAMIDE".
  4. ^ a b c NIOSH Pocket Guide to Chemical Hazards. "#0226". National Institute for Occupational Safety and Health (NIOSH).
  5. ^ a b "Dimethylformamide". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  6. ^ a b "Dimethylformamide". Spectral Database for Organic Compounds. Japan: AIST. Retrieved 2012-06-28.[permanent dead link]
  7. ^ H. S. Gutowsky; C. H. Holm (1956). "Rate Processes and Nuclear Magnetic Resonance Spectra. II. Hindered Internal Rotation of Amides". J. Chem. Phys. 25 (6): 1228–1234. Bibcode:1956JChPh..25.1228G. doi:10.1063/1.1743184.
  8. ^ a b c d Bipp, H.; Kieczka, H. "Formamides". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a12_001.pub2.
  9. ^ IPCS (International Programme on Chemical Safety) (1991). Environmental Health Criteria 114 “Dimethylformamide” United Nations Environment Programme, International Labour Organisation, World Health Organization; 1–124.
  10. ^ Taft, R. W.; Abraham, M. H.; Doherty, R. M.; Kamlet, M. J. (1985). "The molecular properties governing solubilities of organic nonelectrolytes in water". Nature. 313 (6001): 384–386. Bibcode:1985Natur.313..384T. doi:10.1038/313384a0. S2CID 36740734.
  11. ^ (BASF AG, department of analytical, unpublished data, J-No. 124659/08, 27.11.1987)
  12. ^ Comins, Daniel L.; Joseph, Sajan P. (2001). "N,N-Dimethylformamide". N,N-Dimethylformamide. Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. doi:10.1002/047084289x.rd335. ISBN 9780470842898.
  13. ^ a b Vilsmeier, Anton; Haack, Albrecht (1927). "Über die Einwirkung von Halogenphosphor auf Alkyl-formanilide. Eine neue Methode zur Darstellung sekundärer und tertiärer p-Alkylamino-benzaldehyde" [On the reaction of phosphorus halides with alkyl formanilides. A new method for the preparation of secondary and tertiary p-alkylamino-benzaldehyde]. Ber. Dtsch. Chem. Ges. A/B (in German). 60 (1): 119–122. doi:10.1002/cber.19270600118.
  14. ^ a b Meth-Cohn, Otto; Stanforth, Stephen P. (1993). "The Vilsmeier-Haack Reaction". In Trost, Barry M.; Heathcock, Clayton H. (eds.). Additions to CX π-Bonds, Part 2. Comprehensive Organic Synthesis: Selectivity, Strategy and Efficiency in Modern Organic Chemistry. Vol. 2. Elsevier. pp. 777–794. doi:10.1016/B978-0-08-052349-1.00049-4. ISBN 9780080405933.
  15. ^ Jones, Gurnos; Stanforth, Stephen P. (2000). "The Vilsmeier Reaction of Non-Aromatic Compounds". Org. React. 56 (2): 355–686. doi:10.1002/0471264180.or056.02.
  16. ^ Wang, Zerong (2009). Comprehensive organic name reactions and reagents. Hoboken, N.J.: John Wiley. pp. 490–492. ISBN 9780471704508.
  17. ^ Vogel G. C.; Drago, R. S. (1996). "The ECW Model". Journal of Chemical Education. 73 (8): 701–707. Bibcode:1996JChEd..73..701V. doi:10.1021/ed073p701.
  18. ^ Laurence, C. and Gal, J-F. Lewis Basicity and Affinity Scales, Data and Measurement, (Wiley 2010) pp 50-51 ISBN 978-0-470-74957-9
  19. ^ Cramer, R. E.; Bopp, T. T. (1977). "Graphical display of the enthalpies of adduct formation for Lewis acids and bases". Journal of Chemical Education. 54: 612–613. doi:10.1021/ed054p612. The plots shown in this paper used older parameters. Improved E&C parameters are listed in ECW model.
  20. ^ Verley, A. (1893). "Sur la préparation des amides en général" [On the preparation of amides in general]. Bulletin de la Société Chimique de Paris. 3rd series (in French). 9: 690–692. On p. 692, Verley states that DMF is prepared by a procedure analogous to that for the preparation of dimethylacetamide (see p. 691), which would be by distilling dimethylamine hydrochloride and potassium formate.
  21. ^ Weissermel, K.; Arpe, H.-J. (2003). Industrial Organic Chemistry: Important Raw Materials and Intermediates. Wiley-VCH. pp. 45–46. ISBN 3-527-30578-5.
  22. ^ Walter Leitner; Philip G. Jessop (1999). Chemical synthesis using supercritical fluids. Wiley-VCH. pp. 408–. ISBN 978-3-527-29605-7. Retrieved 27 June 2011.
  23. ^ Bouveault, Louis (1904). "Modes de formation et de préparation des aldéhydes saturées de la série grasse" [Methods of preparation of saturated aldehydes of the aliphatic series]. Bulletin de la Société Chimique de Paris. 3rd series (in French). 31: 1306–1322.
  24. ^ Bouveault, Louis (1904). "Nouvelle méthode générale synthétique de préparation des aldéhydes" [Novel general synthetic method for preparing aldehydes]. Bulletin de la Société Chimique de Paris. 3rd series (in French). 31: 1322–1327.
  25. ^ Li, Jie Jack (2014). "Bouveault aldehyde synthesis". Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications (5th ed.). Springer Science & Business Media. pp. 72–73. ISBN 978-3-319-03979-4.
  26. ^ Oestreich, Martin, ed. (2009). The Mizoroki–Heck Reaction. John Wiley & Sons. ISBN 9780470716069.
  27. ^ Clayden, J. (2001). Organic Chemistry. Oxford: Oxford University Press. pp. 276–296. ISBN 0-19-850346-6.
  28. ^ Ansell, M. F. in "The Chemistry of Acyl Halides"; S. Patai, Ed.; John Wiley and Sons: London, 1972; pp 35–68.
  29. ^ Haddon, R.; Itkis, M. (March 2008). "3. Near-Infrared (NIR) Spectroscopy" (pdf). In Freiman, S.; Hooker, S.; Migler; K.; Arepalli, S. (eds.). Publication 960-19 Measurement Issues in Single Wall Carbon Nanotubes. NIST. p. 20. Retrieved 2012-06-28.
  30. ^ Explosion Hazards of Sodium Hydride in Dimethyl Sulfoxide, N,N-Dimethylformamide, and N,N-Dimethylacetamide Qiang Yang, Min Sheng, James J. Henkelis, Siyu Tu, Eric Wiensch, Honglu Zhang, Yiqun Zhang, Craig Tucker, and David E. Ejeh Organic Process Research & Development 2019 23 (10), 2210-2217 DOI: 10.1021/acs.oprd.9b00276 https://pubs.acs.org/doi/10.1021/acs.oprd.9b00276
  31. ^ UK Chemical Reaction Hazards Forum 2011-10-06 at the Wayback Machine and references cited therein
  32. ^ Lyle, W. H.; Spence, T. W.; McKinneley, W. M.; Duckers, K. (1979). "Dimethylformamide and alcohol intolerance". British Journal of Industrial Medicine. 36 (1): 63–66. doi:10.1136/oem.36.1.63. PMC 1008494. PMID 444443.
  33. ^ Magnus Løfstedt. . Archived from the original on 2021-09-03. Retrieved 2019-06-13.
  34. ^ Redlich, C.; Beckett, W. S.; Sparer, J.; Barwick, K. W.; Riely, C. A.; Miller, H.; Sigal, S. L.; Shalat, S. L.; Cullen, M. R. (1988). "Liver disease associated with occupational exposure to the solvent dimethylformamide". Annals of Internal Medicine. 108 (5): 680–686. doi:10.7326/0003-4819-108-5-680. PMID 3358569.

External links

dimethylformamide, organic, compound, with, formula, commonly, abbreviated, although, this, initialism, sometimes, used, dimethylfuran, dimethyl, fumarate, this, colourless, liquid, miscible, with, water, majority, organic, liquids, common, solvent, chemical, . 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 samples with an inert gas such as argon or by sonicating the samples under reduced pressure As its name indicates it is structurally related to formamide having two methyl groups in the place of the two hydrogens DMF is a polar hydrophilic aprotic solvent with a high boiling point It facilitates reactions that follow polar mechanisms such as SN2 reactions Dimethylformamide NamesPreferred IUPAC name N N Dimethylformamide 2 Other names DimethylformamideN N Dimethylmethanamide 1 DMFIdentifiersCAS Number 68 12 2 Y3D model JSmol Interactive image3DMet B00545Beilstein Reference 605365ChEBI CHEBI 17741 YChEMBL ChEMBL268291 YChemSpider 5993 YDrugBank DB01844 YECHA InfoCard 100 000 617EC Number 200 679 5KEGG C03134 YMeSH DimethylformamidePubChem CID 6228RTECS number LQ2100000UNII 8696NH0Y2X YUN number 2265CompTox Dashboard EPA DTXSID6020515InChI InChI 1S C3H7NO c1 4 2 3 5 h3H 1 2H3 YKey ZMXDDKWLCZADIW UHFFFAOYSA N YSMILES CN C C OPropertiesChemical formula C 3H 7N OMolar mass 73 095 g mol 1Appearance Colourless liquidOdor fishy ammoniacalDensity 0 948 g mLMelting point 61 C 78 F 212 K Boiling point 153 C 307 F 426 K Solubility in water Misciblelog P 0 829Vapor pressure 516 PaAcidity pKa 0 3 for the conjugate acid H2O 3 UV vis lmax 270 nmAbsorbance 1 00Refractive index nD 1 4305 at 20 C Viscosity 0 92 mPa s at 20 C StructureDipole moment 3 86 DThermochemistryHeat capacity C 146 05 J K mol Std enthalpy offormation DfH 298 239 4 1 2 kJ molStd enthalpy ofcombustion DcH 298 1 9416 0 0012 MJ molHazardsGHS labelling PictogramsSignal word DangerHazard statements H226 H312 H319 H332 H360Precautionary statements P280 P305 P351 P338 P308 P313NFPA 704 fire diamond 220Flash point 58 C 136 F 331 K Autoignitiontemperature 445 C 833 F 718 K Explosive limits 2 2 15 2 Threshold limit value TLV 30 mg m TWA Lethal dose or concentration LD LC LD50 median dose 1 5 g kg dermal rabbit 2 8 g kg oral rat 3 7 g kg mouse oral 3 5 g kg rat oral LC50 median concentration 3092 ppm mouse 2 h 5 LCLo lowest published 5000 ppm rat 6 h 5 NIOSH US health exposure limits PEL Permissible TWA 10 ppm 30 mg m3 skin 4 REL Recommended TWA 10 ppm 30 mg m3 skin 4 IDLH Immediate danger 500 ppm 4 Related compoundsRelated alkanamides N MethylformamideDeuterated DMFRelated compounds N Nitroso N methylureaENUExcept where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Y verify what is Y N Infobox references Contents 1 Structure and properties 2 Reactions 3 Production 4 Applications 5 Safety 6 Toxicity 7 References 8 External linksStructure and properties EditAs 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 6 DMF is a classic example of a fluxional molecule 7 The ambient temperature 1H NMR spectrum shows two methyl signals indicative of hindered rotation about the O C N bond 6 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 8 The vapour pressure at 20 C is 3 5 hPa 9 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 10 The partition coefficient log POW is measured to 0 85 11 Since the density of DMF 0 95 g cm 3 at 20 C 8 is similar to that of water significant flotation or stratification in surface waters in case of accidental losses is not expected Left two resonance structures of DMF Right illustration highlighting delocalization Reactions EditDMF 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 12 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 13 14 The process involves initial conversion of DMF to a chloroiminium ion CH3 2N CH Cl known as a Vilsmeier reagent 15 which attacks arenes Organolithium compounds and Grignard reagents react with DMF to give aldehydes after hydrolysis in a reaction named after Bouveault 16 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 18 19 Production EditDMF 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 20 DMF is prepared by combining methyl formate and dimethylamine or by reaction of dimethylamine with carbon monoxide 21 Although currently impractical DMF can be prepared from supercritical carbon dioxide using ruthenium based catalysts 22 Applications EditThe 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 8 It is used as a reagent in the Bouveault aldehyde synthesis 23 24 25 and in the Vilsmeier Haack reaction 13 14 another useful method of forming aldehydes It is a common solvent in the Heck reaction 26 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 also known as the Vilsmeier reagent 27 28 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 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 29 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 Safety EditReactions including the use of sodium hydride in DMF as a solvent are somewhat hazardous 30 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 31 Dimethylformamide vapor exposure has shown reduced alcohol tolerance and skin irritation in some cases 32 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 squishies being removed from the Danish market All squishies were recommended to be thrown out as household waste 33 Toxicity EditThe acute LD50 oral rats and mice is 2 2 7 55 g kg 8 Hazards of DMF have been examined 34 References Edit N N Dimethylmethanamide NIST web thermo tables Nomenclature of Organic Chemistry IUPAC Recommendations and Preferred Names 2013 Blue Book Cambridge The Royal Society of Chemistry 2014 pp 841 844 doi 10 1039 9781849733069 FP001 ISBN 978 0 85404 182 4 The traditional name formamide is retained for HCO NH2 and is the preferred IUPAC name Substitution is permitted on the NH2 group Hazardous Substances Data Bank HSDB N N DIMETHYLFORMAMIDE a b c NIOSH Pocket Guide to Chemical Hazards 0226 National Institute for Occupational Safety and Health NIOSH a b Dimethylformamide Immediately Dangerous to Life or Health Concentrations IDLH National Institute for Occupational Safety and Health NIOSH a b Dimethylformamide Spectral Database for Organic Compounds Japan AIST Retrieved 2012 06 28 permanent dead link H S Gutowsky C H Holm 1956 Rate Processes and Nuclear Magnetic Resonance Spectra II Hindered Internal Rotation of Amides J Chem Phys 25 6 1228 1234 Bibcode 1956JChPh 25 1228G doi 10 1063 1 1743184 a b c d Bipp H Kieczka H Formamides Ullmann s Encyclopedia of Industrial Chemistry Weinheim Wiley VCH doi 10 1002 14356007 a12 001 pub2 IPCS International Programme on Chemical Safety 1991 Environmental Health Criteria 114 Dimethylformamide United Nations Environment Programme International Labour Organisation World Health Organization 1 124 Taft R W Abraham M H Doherty R M Kamlet M J 1985 The molecular properties governing solubilities of organic nonelectrolytes in water Nature 313 6001 384 386 Bibcode 1985Natur 313 384T doi 10 1038 313384a0 S2CID 36740734 BASF AG department of analytical unpublished data J No 124659 08 27 11 1987 Comins Daniel L Joseph Sajan P 2001 N N Dimethylformamide N N Dimethylformamide Encyclopedia of Reagents for Organic Synthesis John Wiley amp Sons doi 10 1002 047084289x rd335 ISBN 9780470842898 a b Vilsmeier Anton Haack Albrecht 1927 Uber die Einwirkung von Halogenphosphor auf Alkyl formanilide Eine neue Methode zur Darstellung sekundarer und tertiarer p Alkylamino benzaldehyde On the reaction of phosphorus halides with alkyl formanilides A new method for the preparation of secondary and tertiary p alkylamino benzaldehyde Ber Dtsch Chem Ges A B in German 60 1 119 122 doi 10 1002 cber 19270600118 a b Meth Cohn Otto Stanforth Stephen P 1993 The Vilsmeier Haack Reaction In Trost Barry M Heathcock Clayton H eds Additions to CX p Bonds Part 2 Comprehensive Organic Synthesis Selectivity Strategy and Efficiency in Modern Organic Chemistry Vol 2 Elsevier pp 777 794 doi 10 1016 B978 0 08 052349 1 00049 4 ISBN 9780080405933 Jones Gurnos Stanforth Stephen P 2000 The Vilsmeier Reaction of Non Aromatic Compounds Org React 56 2 355 686 doi 10 1002 0471264180 or056 02 Wang Zerong 2009 Comprehensive organic name reactions and reagents Hoboken N J John Wiley pp 490 492 ISBN 9780471704508 Vogel G C Drago R S 1996 The ECW Model Journal of Chemical Education 73 8 701 707 Bibcode 1996JChEd 73 701V doi 10 1021 ed073p701 Laurence C and Gal J F Lewis Basicity and Affinity Scales Data and Measurement Wiley 2010 pp 50 51 ISBN 978 0 470 74957 9 Cramer R E Bopp T T 1977 Graphical display of the enthalpies of adduct formation for Lewis acids and bases Journal of Chemical Education 54 612 613 doi 10 1021 ed054p612 The plots shown in this paper used older parameters Improved E amp C parameters are listed in ECW model Verley A 1893 Sur la preparation des amides en general On the preparation of amides in general Bulletin de la Societe Chimique de Paris 3rd series in French 9 690 692 On p 692 Verley states that DMF is prepared by a procedure analogous to that for the preparation of dimethylacetamide see p 691 which would be by distilling dimethylamine hydrochloride and potassium formate Weissermel K Arpe H J 2003 Industrial Organic Chemistry Important Raw Materials and Intermediates Wiley VCH pp 45 46 ISBN 3 527 30578 5 Walter Leitner Philip G Jessop 1999 Chemical synthesis using supercritical fluids Wiley VCH pp 408 ISBN 978 3 527 29605 7 Retrieved 27 June 2011 Bouveault Louis 1904 Modes de formation et de preparation des aldehydes saturees de la serie grasse Methods of preparation of saturated aldehydes of the aliphatic series Bulletin de la Societe Chimique de Paris 3rd series in French 31 1306 1322 Bouveault Louis 1904 Nouvelle methode generale synthetique de preparation des aldehydes Novel general synthetic method for preparing aldehydes Bulletin de la Societe Chimique de Paris 3rd series in French 31 1322 1327 Li Jie Jack 2014 Bouveault aldehyde synthesis Name Reactions A Collection of Detailed Mechanisms and Synthetic Applications 5th ed Springer Science amp Business Media pp 72 73 ISBN 978 3 319 03979 4 Oestreich Martin ed 2009 The Mizoroki Heck Reaction John Wiley amp Sons ISBN 9780470716069 Clayden J 2001 Organic Chemistry Oxford Oxford University Press pp 276 296 ISBN 0 19 850346 6 Ansell M F in The Chemistry of Acyl Halides S Patai Ed John Wiley and Sons London 1972 pp 35 68 Haddon R Itkis M March 2008 3 Near Infrared NIR Spectroscopy pdf In Freiman S Hooker S Migler K Arepalli S eds Publication 960 19 Measurement Issues in Single Wall Carbon Nanotubes NIST p 20 Retrieved 2012 06 28 Explosion Hazards of Sodium Hydride in Dimethyl Sulfoxide N N Dimethylformamide and N N Dimethylacetamide Qiang Yang Min Sheng James J Henkelis Siyu Tu Eric Wiensch Honglu Zhang Yiqun Zhang Craig Tucker and David E Ejeh Organic Process Research amp Development 2019 23 10 2210 2217 DOI 10 1021 acs oprd 9b00276 https pubs acs org doi 10 1021 acs oprd 9b00276 UK Chemical Reaction Hazards Forum Archived 2011 10 06 at the Wayback Machine and references cited therein Lyle W H Spence T W McKinneley W M Duckers K 1979 Dimethylformamide and alcohol intolerance British Journal of Industrial Medicine 36 1 63 66 doi 10 1136 oem 36 1 63 PMC 1008494 PMID 444443 Magnus Lofstedt Skumlegetoj afgiver farlige kemikalier in English Squishies giving dangerous chemicals Archived from the original on 2021 09 03 Retrieved 2019 06 13 Redlich C Beckett W S Sparer J Barwick K W Riely C A Miller H Sigal S L Shalat S L Cullen M R 1988 Liver disease associated with occupational exposure to the solvent dimethylformamide Annals of Internal Medicine 108 5 680 686 doi 10 7326 0003 4819 108 5 680 PMID 3358569 External links EditInternational Chemical Safety Card 0457 NIOSH Pocket Guide to Chemical Hazards 0226 National Institute for Occupational Safety and Health NIOSH Concise International Chemical Assessment Document 31 N N Dimethylformamide Retrieved from https en wikipedia org w index php title Dimethylformamide amp oldid 1127590408, wikipedia, wiki, book, books, library,

article

, read, download, free, free download, mp3, video, mp4, 3gp, jpg, jpeg, gif, png, picture, music, song, movie, book, game, games.