Ethenone

From Wikipedia, the free encyclopedia
Jump to navigation Jump to search
Ethenone
Structural formula
Space-filling model
Names
Preferred IUPAC name
Ethenone
Other names
Ketene
Carbomethene
Keto-ethylene
Identifiers
3D model (JSmol)
1098282
ChEBI
ChemSpider
ECHA InfoCard 100.006.671
EC Number 207-336-9
RTECS number OA7700000
Properties
C2H2O
Molar mass 42.037 g/mol
Appearance Colourless gas
Odor penetrating
Density 1.93 g/cm3
Melting point −150.5 °C (−238.9 °F; 122.6 K)
Boiling point −56.1 °C (−69.0 °F; 217.1 K)
decomposes
Solubility soluble in acetone
ethanol
ethyl ether
aromatic solvents
halocarbons
Vapor pressure >1 atm (20°C)[1]
1.4355
Thermochemistry
51.75 J/K mol
-87.24 kJ/mol
Hazards
Safety data sheet External MSDS
NFPA 704
Flammability code 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g., propaneHealth code 4: Very short exposure could cause death or major residual injury. E.g., VX gasReactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g., calciumSpecial hazards (white): no codeNFPA 704 four-colored diamond
4
4
1
Flash point −107 °C (−161 °F; 166 K)
Explosive limits 5.5-18%
Lethal dose or concentration (LD, LC):
1300 mg/kg (oral, rat)
17 ppm (mouse, 10 min)[2]
23 ppm (mouse, 30 min)
53 ppm (rabbit, 2 hr)
53 ppm (guinea pig, 2 hr)
750 ppm (cat, 10 min)
200 ppm (monkey, 10 min)
50 ppm (mouse, 10 min)
1000 ppm (rabbit, 10 min)[2]
US health exposure limits (NIOSH):
PEL (Permissible)
TWA 0.5 ppm (0.9 mg/m3)[1]
REL (Recommended)
TWA 0.5 ppm (0.9 mg/m3) ST 1.5 ppm (3 mg/m3)[1]
IDLH (Immediate danger)
5 ppm[1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is ☑Y☒N ?)
Infobox references

Ethenone is the formal name for ketene, an organic compound with formula C2H2O or H2C=C=O. It is the simplest member of the ketene class. It is a tautomer of the even less stable ethynol.

Properties[edit]

Ethenone is a highly reactive gas (at standard conditions) and has a sharp irritating odour. It is only reasonably stable at low temperatures (−80 °C). It must therefore always be prepared for each use and processed immediately, otherwise a dimerization to diketene occurs or it reacts to polymers that are difficult to handle. The polymer content formed during the preparation is reduced, for example, by adding sulfur dioxide to the ketene gas.[3] Because of its cumulative double bonds, ethenone is highly reactive and reacts in an addition reaction H-acidic compounds to the corresponding acetic acid derivatives. It does for example react with water to acetic acid or with primary or secondary amines to the corresponding acetamides.

Ethenone is highly poisonous; its toxicity is about eight times that of phosgene.[4]

Ethenone tends to spontaneously polymerize. Contact with hydrogen peroxide leads to an explosive reaction. It can form an explosive mixture with air.

It is soluble in acetone, ethanol, ethyl ether, aromatic solvents and halocarbons.

Preparation[edit]

Ethenone was discovered at the same time by Hermann Staudinger (by reaction of bromoacetyl bromide with metallic zinc)[5][6]

Ethenone synthesis from bromoacetyl bromide.png

and by Norman T. M. Wilsmore (by thermal decomposition of acetic anhydride).[7]

Ethenone synthesis from acetic anhydride.png

Ethenone is produced on a large scale industrially for use in the production of acetic anhydride. It can be prepared by pyrolysis of acetone, and this was formerly the main industrial process. When passing acetone vapors through heated pipes or electrically heated metal (like copper) wires at 500-600 °C in the presence of little carbon disulfide (CS2), acetone decomposes into methane and ethenone, with 95% yield.[8][9]

Ethenone synthesis from acetone.png

In industrial chemistry, ketone pyrolysis has largely been replaced by the dehydration of acetic acid (the Schmidlin-Bergman-Wilsmore reaction).[10]

Ethenone synthesis from acetic acid.png

Natural occurrence[edit]

Ethenone has been observed to occur in space, in comets or in gas as part of the interstellar medium.[11]

Use[edit]

Ethenone is used to make acetic anhydride from acetic acid. Generally it is used for the acetylation of chemical compounds.[4]

Darstellung von Acetamid, Ethylacetat, Essigsäure und Essigsäureanhydrid
Mechanism-Ketene Reactions V1.svg

Ethenone reacts with methanal in the presence of catalysts such as Lewis acids (AlCl3, ZnCl2 oder BF3) to give β-propiolactone.[12] The technically most significant use of ethenone is the synthesis of sorbic acid by reaction with 2-butenal (crotonaldehyde) in toluene at about 50 °C in the presence of zinc salts of long-chain carboxylic acids. This produces a polyester of 3-hydroxy-4-hexenoic acid, which is thermally[13] or hydrolytically depolymerized to sorbic acid.

Ethenone is very reactive, tending to react with nucleophiles to form an acetyl group. For example, it reacts with water to form acetic acid;[14] with acetic acid to form acetic anhydride; with ammonia and amines to form ethanamides;[15] and with dry hydrogen halides to form acetyl halides.[16]

The formation of acetic acid likely occurs by an initial formation of 1,1-dihydroxyethene, which then tautomerizes to give the final product.[17]

Ethenone will also react with itself via [2 + 2] photocycloadditions to form cyclic dimers known as diketenes. For this reason, it should not be stored for long periods.[18]

Hazards[edit]

Exposure to concentrated levels causes humans to experience irritation of body parts such as the eye, nose, throat and lungs. Extended toxicity testing on mice, rats, guinea pigs and rabbits showed that ten-minute exposures to concentrations of freshly generated ethenone as low as 0.2 mg/liter (116 ppm) may produce a high percentage of deaths in small animals. These findings put ethenone in the same order of toxicity as phosgene (0.2–20 mg/liter) and hydrogen cyanide (0.2-0.5 mg/liter). Death is from pulmonary edema and is entirely similar to, but much more rapid than is the case with phosgene poisoning.[19]

Occupational exposure limits are set at 0.5 ppm (0.9 mg/m3) over an eight-hour time-weighted average.[20] An IDLH limit is set at 5 ppm, as this is the lowest concentration productive of a clinically relevant physiologic response in humans.[21]

References[edit]

  1. ^ a b c d NIOSH Pocket Guide to Chemical Hazards. "#0367". National Institute for Occupational Safety and Health (NIOSH).
  2. ^ a b "Ketene". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  3. ^ EP 0377438, R. Bergamin et al., issued 1990-06-11, assigned to Lonza AG 
  4. ^ a b Entry on Diketen. at: Römpp Online. Georg Thieme Verlag, retrieved 16. Juni 2014.
  5. ^ H. Staudinger H. W. Klever (1908): "Keten. Bemerkung zur Abhandlung zur Abhandlung der HHrn. V.T. Wilsmore und A. W. Stewart". Berichte der deutschen chemischen Gesellschaft, volume 41, issue 1, pages 1516-1517. doi:10.1002/cber.190804101275
  6. ^ Tidwell, T. T. (2005), "Ein Jahrhundert Ketene (1905–2005): die Entdeckung einer vielseitigen Klasse reaktiver Intermediate". Angewandte Chemie, volume 117, pages 5926–5933. doi:10.1002/ange.200500098
  7. ^ Norman Thomas Mortimer Wilsmore (1907): "Keten". Journal of the Chemical Society, Transactions, volume 91, article CLXXXVIII (188), pages 1938-1941. doi:10.1039/ct9079101938
  8. ^ K.-H. Lautenschläger, W. Schröter, A. Wanninger, "Taschenbuch der Chemie", 20. Aufl. 2006, ISBN 978-3-8171-1761-1.
  9. ^ "Ketene". Organic Syntheses. doi:10.15227/orgsyn.004.0039.
  10. ^ J. Schmidlin, M. Bergman (1910): Berichte der deutschen chemischen Gesellschaft, volume 43, pages 2821-. doi:10.1002/cber.19100430340.
  11. ^ Hudson, Reggie L.; Loeffler, Mark J. (2013). "Ketene Formation in Interstellar Ices: A Laboratory Study". The Astrophysical Journal. 773 (2): 109. doi:10.1088/0004-637x/773/2/109. hdl:2060/20140010162. ISSN 0004-637X.
  12. ^ Hans-Jürgen Arpe, "Industrielle Organische Chemie", 6. Aufl., 2007, WILEY-VCH Verlag, Weinheim, ISBN 978-3-527-31540-6.
  13. ^ EP 1295860, D. Decker et al., issued 26. März 2003-03-26, assigned to Nutrinova GmbH 
  14. ^ Tidwell, p. 11.
  15. ^ Tidwell, p. 560.
  16. ^ ChemSpider http://www.chemspider.com/Chemical-Structure.9643.html
  17. ^ Nguyen, Minh Tho; Raspoet, Greet (1999). "The hydration mechanism of ketene: 15 years later". Can. J. Chem. 77: 817–829. doi:10.1139/v99-090.
  18. ^ Christoph Taeschler :Ketenes, Ketene Dimers, and Related Substances, Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, New York, 2010
  19. ^ H. A. Wooster; C. C. Lushbaugh; C. E. Redeman (1946). "The Inhalation Toxicity of Ketene and of Ketene Dimer". J. Am. Chem. Soc. 68 (12): 2743. doi:10.1021/ja01216a526.
  20. ^ Centers for Disease Control and Prevention (4 April 2013). "Ketene". NIOSH Pocket Guide to Chemical Hazards. Retrieved 13 November 2013.
  21. ^ Centers for Disease Control and Prevention (May 1994). "Ketene". Documentation for Immediately Dangerous To Life or Health Concentrations (IDLHs). Retrieved 13 November 2013.

Literature[edit]

External links[edit]

  • Media related to Ethenone at Wikimedia Commons