Ethenone

Ethenone is the formal name for ketene, an organic compound with formula C

2O or H
2C=C=O. It is the simplest member of the ketene class. It is an important reagent for acetylations.[1][2]

## Contents

* 1 Properties
* 2 Preparation
* 2.1 History
* 3 Natural occurrence
* 4 Use
* 5 Hazards
* 6 References
* 7 Literature
* 8 External links

## Properties

Ethenone is a highly reactive gas (at standard conditions) and has a sharp, irritating odour. It is reasonably stable only at low temperatures (−80 °C). It must therefore always be prepared for each use and processed immediately, otherwise a dimerization to diketene occurs, or polymers are formed that are difficult to handle. Its polymerization can be reduced by adding sulfur dioxide.[3] Because of its cumulative double bonds, it adds readily to H-acidic compounds, reacting with water, for example, to form acetic acid, and with primary or secondary amines to yield the corresponding acetamides.

## Preparation

Ethenone is produced by thermal dehydration of acetic acid at 700–750 °C in the presence of triethyl phosphate as a catalyst:[4][5]

3CO
2H → CH
2=C=O + H

It has also been produced on a laboratory scale by the thermolysis of acetone at 600–700 °C.[6][7]

3COCH
3 →CH
2=C=O + CH

This reaction is called the Schmidlin ketene synthesis.[8]

On a laboratory scale it can be produced by the thermal decomposition of Meldrum's acid at temperatures greater than 200 °C.[citation needed]

### History

Ethenone was first produced in 1907 by N. T. M. Wilsmore through pyrolysis of acetone or acetic anhydride vapours over a hot platinum wire in an apparatus that was later developed by Charles D. Hurd into the "Hurd lamp" or "ketene lamp". This apparatus consists of a heated flask of acetone producing vapours which are pyrolyzed by a metal filament electrically heated to red heat, with a condenser to return unreacted acetone to the boiling flask. Other heating methods have been used and similar methods were used on a larger scale for the industrial production of ketene for acetic anhydride synthesis.[9][10][11]

Ethenone was discovered at the same time by Hermann Staudinger (by reaction of bromoacetyl bromide with metallic zinc)[12][13] The dehydration of acetic acid was reported in 1910.[14]

The thermal decomposition of acetic anhydride was also described.[15]

## Natural occurrence

Ethenone has been observed to occur in space, in comets or in gas as part of the interstellar medium.[16]

## Use

Ethenone is used to make acetic anhydride from acetic acid. Generally it is used for the acetylation of chemical compounds.[17]

Reactions with ammonia, water, ethanol, and acetic acid

Mechanism of the above reactions

Ethenone reacts with formaldehyde in the presence of catalysts such as Lewis acids (AlCl3, ZnCl2 or BF3) to give β-propiolactone.[18] The technically most significant use of ethenone is the synthesis of sorbic acid by reaction with 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[19] 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;[20] with acetic acid to form acetic anhydride; with ammonia and amines to form ethanamides;[21] and with dry hydrogen halides to form acetyl halides.[22]

The formation of acetic acid likely occurs by an initial formation of 1,1-dihydroxyethene, which then tautomerizes to give the final product.[23]

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.[24]

Ketene cycloadditions can be difficult to control; dichloroketene is typically used instead, followed by dehalogenation with zinc-copper couple.[25]

center

## Hazards

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 show ethenone is toxicologically identical to phosgene.[26][17]

The formation of ketene in the pyrolysis of vitamin E acetate, an additive of some e-liquid products, is one possible mechanism of the reported pulmonary damage[27] caused by electronic cigarette use.[28] A number of patents describe the catalytic formation of ketene from carboxylic acids and acetates, using a variety of metals or ceramics, some of which are known to occur in e-cigarette devices from patients with e-cigarette or vaping product-use associated lung injury (EVALI).[29][30]

Occupational exposure limits are set at 0.5 ppm (0.9 mg/m3) over an eight-hour time-weighted average.[31] An IDLH limit is set at 5 ppm, as this is the lowest concentration productive of a clinically relevant physiologic response in humans.[32]

## References

1. ↑ Miller, Raimund; Abaecherli, Claudio; Said, Adel; Jackson, Barry (2001). "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a15_063.
2. ↑ Mitzel, Thomas M.; Pigza, Julie A. (2009). "Ketene". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rk000.pub2. ISBN 978-0-471-93623-7.
3. ↑ EP patent 0377438, issued 1990-06-11, assigned to Lonza AG
4. ↑ Miller, Raimund; Abaecherli, Claudio; Said, Adel; Jackson, Barry (2001). "Ketenes". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a15_063. ISBN 978-3-527-30385-4.
5. ↑ Arpe, Hans-Jürgen (2007) (in de), Industrielle organische Chemie: Bedeutende vor- und Zwischenprodukte (6th ed.), Weinheim: Wiley-VCH, pp. 200–201, ISBN 978-3-527-31540-6, https://books.google.com/books?id=36kHHvzx6M8C&q=wacker+verfahren+essigsäureanhydrid&pg=PA200
6. ↑ Weygand/Hilgetag Preparative Organic Chemistry (4th ed.). New York: John Wiley & Sons, Inc.. 1972. pp. 1031–1032. ISBN 978-0471937494.
7. ↑ "Ketene in Organic Syntheses". Organic Syntheses. Collective Vol. 1. 1941. pp. 330. http://www.orgsyn.org/demo.aspx?prep=cv1p0330.
8. ↑ Schmidlin, Julius; Bergman, Maximilian (1910). "Darstellung des Ketens aus Aceton" (in de). Berichte der Deutschen Chemischen Gesellschaft 43 (3): 2821–2823. doi:10.1002/cber.19100430340. http://babel.hathitrust.org/cgi/pt?id=uc1.b3481275;view=1up;seq=565.
9. ↑ Tidwell, Thomas T. (2005-09-12). "The First Century of Ketenes (1905–2005): The Birth of a Versatile Family of Reactive Intermediates" (in en). Angewandte Chemie International Edition 44 (36): 5778–5785. doi:10.1002/anie.200500098. ISSN 1433-7851. PMID 16149113. https://onlinelibrary.wiley.com/doi/10.1002/anie.200500098.
10. ↑ K.-H. Lautenschläger, W. Schröter, A. Wanninger, "Taschenbuch der Chemie", 20. Aufl. 2006, ISBN 978-3-8171-1761-1.
11. ↑ "Ketene". Organic Syntheses. doi:10.15227/orgsyn.004.0039.
12. ↑ 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
13. ↑ 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
14. ↑ J. Schmidlin, M. Bergman (1910): Berichte der deutschen chemischen Gesellschaft, volume 43, pages 2821- doi:10.1002/cber.19100430340
15. ↑ Norman Thomas Mortimer Wilsmore (1907): "Keten". Journal of the Chemical Society, Transactions, volume 91, article CLXXXVIII (188), pages 1938-1941. doi:10.1039/ct9079101938
16. ↑ Hudson, Reggie L.; Loeffler, Mark J. (31 July 2013). "Ketene Formation in Interstellar Ices: A Laboratory Study". The Astrophysical Journal 773 (2): 109. doi:10.1088/0004-637x/773/2/109. Bibcode: 2013ApJ...773..109H.
17. ↑ 17.0 17.1 Entry on Diketen. at: Römpp Online. Georg Thieme Verlag, retrieved 16. Juni 2014.
18. ↑ Hans-Jürgen Arpe, "Industrielle Organische Chemie", 6. Aufl., 2007, WILEY-VCH Verlag, Weinheim, ISBN 978-3-527-31540-6.
19. ↑ EP patent 1295860, issued 26. März 2003-03-26, assigned to Nutrinova GmbH
20. ↑ Tidwell, p. 11.
21. ↑ Tidwell, p. 560.
22. ↑ ChemSpider http://www.chemspider.com/Chemical-Structure.9643.html
23. ↑ Nguyen, Minh Tho; Raspoet, Greet (1999). "The hydration mechanism of ketene: 15 years later". Can. J. Chem. 77 (5–6): 817–829. doi:10.1139/v99-090. Bibcode: 1999CaJCh..77..817N.
24. ↑ Christoph Taeschler :Ketenes, Ketene Dimers, and Related Substances, Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, New York, 2010
25. ↑ McMurry, J. E.; Miller, D. D. Tetrahedron Lett. 1983, 24, 1885.
26. ↑ 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. Bibcode: 1946JAChS..68.2743W.
27. ↑ "The Vaping-Related Lung Disease Outbreak May be Coming to an End". 20 December 2019. https://time.com/5753947/vaping-lung-disease-outbreak-peak/.
28. ↑ Wu, Dan; O’Shea, Donal F. (24 March 2020). "Potential for release of pulmonary toxic ketene from vaping pyrolysis of vitamin E acetate". Proceedings of the National Academy of Sciences 117 (12): 6349–6355. doi:10.1073/pnas.1920925117. PMID 32156732. Bibcode: 2020PNAS..117.6349W.
29. ↑ Attfield, Kathleen R.; Chen, Wenhao; Cummings, Kristin J.; Jacob, Peyton; O’Shea, Donal F.; Wagner, Jeff; Wang, Ping; Fowles, Jefferson (15 October 2020). "Potential of Ethenone (Ketene) to Contribute to Electronic Cigarette, or Vaping, Product Use–associated Lung Injury". American Journal of Respiratory and Critical Care Medicine 202 (8): 1187–1189. doi:10.1164/rccm.202003-0654LE. PMID 32551843. https://figshare.com/articles/journal_contribution/16997875.
30. ↑ U.S. patent No. 5475144. Catalyst and process for synthesis of ketenes from carboxylic acids. Dec 12, 1995. https://patents.google.com/patent/US5475144A/en
31. ↑ Centers for Disease Control and Prevention (4 April 2013). "Ketene". NIOSH Pocket Guide to Chemical Hazards. https://www.cdc.gov/niosh/npg/npgd0367.html. Retrieved 13 November 2013.
32. ↑ Centers for Disease Control and Prevention (May 1994). "Ketene". Documentation for Immediately Dangerous To Life or Health Concentrations (IDLHs). https://www.cdc.gov/niosh/idlh/463514.html. Retrieved 13 November 2013.

## Literature

* Tidwell, Thomas T. Ketenes , 2nd edition. John Wiley & Sons, 2006, ISBN 978-0-471-69282-9.

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Molecules|

| Diatomic|

* Aluminium monochloride
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|
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Triatomic|

* Aluminium hydroxide
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Four
atoms|

* Acetylene
* Ammonia
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* Cyanoethynyl
* Cyclopropynylidyne
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* Tricarbon sulfide
* Thiocyanic acid

Five
atoms|

* Ammonium ion
* Butadiynyl
* Carbodiimide
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* Cyanoformaldehyde
* Cyanomethyl
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Six
atoms|

* Acetonitrile
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* Ketenimine
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Seven
atoms|

* Acetaldehyde
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Eight
atoms|

* Acetic acid
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Nine
atoms|

* Acetamide
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* Dimethyl ether
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atoms
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* Pyrimidine

Deuterated
molecules|

* Ammonia
* Ammonium ion
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* Formyl radical
* Heavy water
* Hydrogen cyanide
* Hydrogen deuteride
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* Methylacetylene
* N2D+
* Trihydrogen cation

Unconfirmed|

* Anthracene
* Dihydroxyacetone
* Ethyl methyl ether
* Glycine
* Graphene
* H2NCO+
* Linear C5
* Naphthalene cation
* Phosphine
* Pyrene
* Silylidine

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