Formamide

Formamide
Names
IUPAC name
Methanamide
Other names
Carbamaldehyde
Formamide
Identifiers
75-12-7 Yes
ChEBI CHEBI:48431 Yes
ChEMBL ChEMBL266160 Yes
ChemSpider 693 Yes
Jmol-3D images Image
KEGG C00488 Yes
PubChem 713
Properties
CH3NO
Molar mass 45.04 g/mol
Appearance Colorless, oily liquid[1]
Density 1.133 g/cm3
Melting point 2 °C (36 °F; 275 K)
Boiling point 210 °C (410 °F; 483 K)
Miscible
Vapor pressure 0.08 mmHg at 20 °C
Acidity (pKa) 23.5 (in DMSO)[2]
Hazards
NFPA 704
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g., canola oil Health code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g., chloroform Reactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g., liquid nitrogen Special hazards (white): no codeNFPA 704 four-colored diamond
1
2
0
Flash point 154 °C (309 °F; 427 K) (closed cup)
US health exposure limits (NIOSH):
none[1]
TWA 10 ppm (15 mg/m3) [skin][1]
N.D.[1]
Related compounds
Related compounds
 Carbamic acid
Dimethylformamide
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Formamide, also known as methanamide, is an amide derived from formic acid. It is a clear liquid which is miscible with water and has an ammonia-like odor. It is chemical feedstock for the manufacture of sulfa drugs, other pharmaceuticals, herbicides, pesticides and the manufacture of hydrocyanic acid. It has been used as a softener for paper and fiber. It is a solvent for many ionic compounds. It has also been used as a solvent for resins and plasticizers.[3]

Formamide will begin to partially decompose into carbon monoxide and ammonia at 180 °C. When heated strongly, formamide decomposes to hydrogen cyanide (HCN) and water vapor.

Production

Historical production

In the past, formic acid was reacted with ammonia to produce ammonium formate, which yielded formamide by heating:[4]

HCOOH + NH3 → HCOONH4
HCOONH4 → HCONH2 + H2O

Later a higher yielding process, aminolysis of ethyl formate, replaced this method:[5]

HCOOCH2CH3 + NH3 → HCONH2 + CH3CH2OH

Modern production

The current industrial process for the manufacture of formamide involves either the reaction of carbon monoxide and ammonia:[3]

CO + NH3 → HCONH2

or the more important two-stage process involving the aminolysis of methyl formate (formed from carbon monoxide and methanol):

HCOOCH3 + NH3 → HCONH2 + CH3OH

with the possibility of the resulting methanol being recycled into more methyl formate, by reaction with carbon monoxide:

CO + CH3OH → HCOOCH3

Applications

Formamide is also a constituent of cryoprotectant vitrification mixtures used for cryopreservation of tissues and organs.

Formamide is also used as an RNA stabiliser in gel electrophoresis by deionizing RNA. In capillary electrophoresis, it is used for stabilizing (single) strands of denatured DNA.

Another use is to add it in sol-gel solutions in order to avoid cracking during sintering.

Formamide, in its pure state, has been used as an alternative solvent for the electrostatic self-assembly of polymer nanofilms.[6]

Formamide is used to prepare primary amines directly from ketones via their N-formyl derivatives, using the Leuckart reaction.

Hypothetical biochemistry

Formamide has also been proposed as an alternative solvent to water, perhaps with the ability to support life with alternative biochemistries to that currently found on Earth. It can be formed by the reaction of hydrogen cyanide and water, has a large dipole moment, and dissolves almost everything that will dissolve in water.[7]

RNA base creation

Formamide has been shown to create guanine at 130 °C in the presence of ultra violet light.[8]

Safety

Formamide is highly corrosive on contact with skin or eyes and may be deadly if ingested. Inhalation of large amounts of formamide vapor may require medical attention.[9][10] It is also a teratogen.[11] Formamide should never be handled without proper safety attire including gloves and goggles. There is a small risk of decomposition into hydrogen cyanide and water.

References

  1. ↑ 1.0 1.1 1.2 1.3 "NIOSH Pocket Guide to Chemical Hazards #0295". National Institute for Occupational Safety and Health (NIOSH).
  2. ↑ F. G. Bordwell, J. E. Bartmess and J. A. Hautala (1978). "Alkyl effects on equilibrium acidities of carbon acids in protic and dipolar aprotic media and the gas phase". J. Org. Chem. 43 (16): 3095–3101. doi:10.1021/jo00410a001.
  3. ↑ 3.0 3.1 Hohn, A. (1999). "Formamide". In Kroschwitz, Jacqueline I. Kirk-Othmer Concise Encylclopedia of Chemical Technology (4th ed.). New York: John Wiley & Sons, Inc. pp. 943–944. ISBN 978-0471419617.
  4. ↑ Lorin, M. (1864). "Preparation of Formamide by means of Formiates and Oxalates". The Chemical News and Journal of Physical Science IX: 291. Retrieved 14 June 2014.
  5. ↑ Phelps, I.K.; Deming, C.D. (1908). "The Preparation of Formamide from Ethyl Formate and Ammonium Hydroxide". The Chemical News and Journal of Physical Science. XCVII: 86–87. Retrieved 14 June 2014.
  6. ↑ Vimal K. Kamineni, Yuri M. Lvov, and Tabbetha A. Dobbins (2007). "Layer-by-Layer Nanoassembly of Polyelectrolytes Using Formamide as the Working Medium". Langmuir 23 (14): 7423–7427. doi:10.1021/la700465n. PMID 17536845.
  7. ↑ Committee On The Limits Of Organic Life In Planetary Systems (2007). The Limits of Organic Life in Planetary Systems. Washington, DC: The National Academies Press. p. 74. ISBN 0-309-66906-5. Retrieved 2012-08-29.
  8. ↑ "Origin of Life: Adding UV Light Helps Form 'Missing G' of RNA Building Blocks". Science Daily. June 14, 2010.
  9. ↑ Warheit DB1, Kinney LA, Carakostas MC, Ross PE (1989). "Inhalation toxicity study of formamide in rats". FUNDAMENTAL AND APPLIED TOXICOLOGY 13 (4): 702–713. PMID 2620791.
  10. ↑ MSDS for formamide, hazard.com
  11. ↑ Lab use of formamide, University of Bath