Acrolein

Not to be confused with Propanol, Acyloin, or Propanal.

Acrolein (systematic name: propenal) is the simplest unsaturated aldehyde. It is a colorless liquid with a foul and acrid aroma. The smell of burnt fat (as when cooking oil is heated to its smoke point) is caused by glycerol in the burning fat breaking down into acrolein. It is produced industrially from propene and mainly used as a biocide and a building block to other chemical compounds, such as the amino acid methionine.

Acrolein

Names
Preferred IUPAC name Prop-2-enal
Other names Acraldehyde[1] Acrylic aldehyde[1] Allyl aldehyde[1] Ethylene aldehyde Acrylaldehyde[1]
Identifiers
CAS Number	107-02-8 Y
3D model (JSmol)	Interactive image Interactive image
ChEBI	CHEBI:15368 Y
ChEMBL	ChEMBL721 Y
ChemSpider	7559 Y
ECHA InfoCard	100.003.141
EC Number	203-453-4
IUPHAR/BPS	2418
KEGG	C01471 Y
PubChem CID	7847
RTECS number	AS1050000
UNII	7864XYD3JJ Y
UN number	1092
CompTox Dashboard (EPA)	DTXSID5020023
InChI InChI=1S/C3H4O/c1-2-3-4/h2-3H,1H2 Y Key: HGINCPLSRVDWNT-UHFFFAOYSA-N Y InChI=1/C3H4O/c1-2-3-4/h2-3H,1H2 Key: HGINCPLSRVDWNT-UHFFFAOYAQ
SMILES O=CC=C C=CC=O
Properties
Chemical formula	C3H4O
Molar mass	56.064 g·mol−1
Appearance	Colorless to yellow liquid. Colorless gas in smoke.
Odor	Acrid, Foul, Irritating
Density	0.839 g/mL
Melting point	−88 °C (−126 °F; 185 K)
Boiling point	53 °C (127 °F; 326 K)
Solubility in water	Appreciable (> 10%)
Vapor pressure	210 mmHg[1]
Hazards[2]
Occupational safety and health (OHS/OSH):
Main hazards	Highly poisonous. Causes severe irritation to exposed membranes. Extremely flammable liquid and vapor.
GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H225, H300, H311, H314, H330, H410
Precautionary statements	P210, P233, P240, P241, P242, P243, P260, P264, P270, P271, P273, P280, P284, P301+P310, P301+P330+P331, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P310, P312, P320, P321, P322, P330, P361, P363, P370+P378, P391, P403+P233, P403+P235, P405, P501
NFPA 704 (fire diamond)	4 3 3
Flash point	−26 °C (−15 °F; 247 K)
Autoignition temperature	278 °C (532 °F; 551 K)
Explosive limits	2.8-31%[1]
Lethal dose or concentration (LD, LC):
LC50 (median concentration)	875 ppm (mouse, 1 min) 175 ppm (mouse, 10 min) 150 ppm (dog, 30 min) 8 ppm (rat, 4 hr) 375 ppm (rat, 10 min) 25.4 ppm (hamster, 4 hr) 131 ppm (rat, 30 min)[3]
LCLo (lowest published)	674 ppm (cat, 2 hr)[3]
NIOSH (US health exposure limits):
PEL (Permissible)	TWA 0.1 ppm (0.25 mg/m3)[1]
REL (Recommended)	TWA 0.1 ppm (0.25 mg/m3) ST 0.3 ppm (0.8 mg/m3)[1]
IDLH (Immediate danger)	2 ppm[1]
Safety data sheet (SDS)	Sigma-Aldrich SDS
Related compounds
Related alkenals	Crotonaldehyde cis-3-Hexenal (E,E)-2,4-Decadienal
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 ?) Infobox references

History

Acrolein was first named and characterized as an aldehyde by the Swedish chemist Jöns Jacob Berzelius in 1839. He had been working with it as a thermal degradation product of glycerol, a material used in the manufacture of soap. The name is a contraction of 'acrid' (referring to its pungent smell) and 'oleum' (referring to its oil-like consistency). In the 20th century, acrolein became an important intermediate for the industrial production of acrylic acid and acrylic plastics.^[4]

Production

Acrolein is prepared industrially by oxidation of propene. The process uses air as the source of oxygen and requires metal oxides as heterogeneous catalysts:^[5]

CH₃CH=CH₂ + O₂ → CH₂=CHCHO + H₂O

About 500,000 tons of acrolein are produced in this way annually in North America, Europe, and Japan. Additionally, all acrylic acid is produced via the transient formation of acrolein.

Propane represents a promising but challenging feedstock for the synthesis of acrolein (and acrylic acid).The main challenge is in fact the overoxidation to this acid.

When glycerol (also called glycerin) is heated to 280 °C, it decomposes into acrolein:

(CH₂OH)₂CHOH → CH₂=CHCHO + 2 H₂O

This route is attractive when glycerol is co-generated in the production of biodiesel from vegetable oils or animal fats. The dehydration of glycerol has been demonstrated but has not proven competitive with the route from petrochemicals.^[6][7]

Niche or laboratory methods

The original industrial route to acrolein, developed by Degussa, involves aldol condensation of formaldehyde and acetaldehyde:

HCHO + CH₃CHO → CH₂=CHCHO + H₂O

Acrolein may also be produced on lab scale by the action of potassium bisulfate on glycerol (glycerine).^[8]

Reactions

Acrolein is a relatively electrophilic compound and a reactive one, hence its high toxicity. It is a good Michael acceptor, hence its useful reaction with thiols. It forms acetals readily, a prominent one being the spirocycle derived from pentaerythritol, diallylidene pentaerythritol. Acrolein participates in many Diels-Alder reactions, even with itself. Via Diels-Alder reactions, it is a precursor to some commercial fragrances, including myrac aldehyde ("lyral") and norbornene-2-carboxaldehyde.^[5] The monomer 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate is also produced from acrolein via the intermediacy of tetrahydrobenzaldehyde.

Uses

Military uses

Acrolein was used in warfare due to its irritant and blistering properties. The French used the chemical in their hand grenades and artillery shells^[9] during World War I under the name "Papite".^[10]

Biocide

Acrolein is mainly used as a contact herbicide to control submersed and floating weeds, as well as algae, in irrigation canals. It is used at a level of 10 ppm in irrigation and recirculating waters. In the oil and gas industry, it is used as a biocide in drilling waters, as well as a scavenger for hydrogen sulfide and mercaptans.^[5]

Chemical precursor

A number of useful compounds are made from acrolein, exploiting its bifunctionality. The amino acid methionine is produced by addition of methanethiol followed by the Strecker synthesis. Acrolein condenses with acetaldehyde and amines to give methylpyridines.^[11] It is also an intermediate in the Skraup synthesis of quinolines.

Acrolein will polymerize in the presence of oxygen and in water at concentrations above 22%. The color and texture of the polymer depends on the conditions. The polymer is a clear, yellow solid. In water, it will form a hard, porous plastic.^{[citation needed]}

Acrolein has been used as a fixative in preparation of biological specimens for electron microscopy.^[12]

Health risks

Acrolein is toxic and is a strong irritant for the skin, eyes, and nasal passages.^[5] The main metabolic pathway for acrolein is the alkylation of glutathione. The WHO suggests a "tolerable oral acrolein intake" of 7.5 μg per day per kg of body weight. Although acrolein occurs in French fries (and other fried foods), the levels are only a few μg per kg.^[13] In response to occupational exposures to acrolein, the US Occupational Safety and Health Administration has set a permissible exposure limit at 0.1 ppm (0.25 mg/m³) at an eight-hour time-weighted average.^[14] Acrolein acts in an immunosuppressive manner and may promote regulatory cells,^[15] thereby preventing the generation of allergies on the one hand, but also increasing the risk of cancer.

Acrolein was identified as one of the chemicals involved in the 2019 Kim Kim River toxic pollution incident.^[16]

Cigarette smoke

Connections exist between acrolein gas in the smoke from tobacco cigarettes and the risk of lung cancer.^[17] Acrolein is one of seven toxicants in cigarette smoke that are most associated with respiratory tract carcinogenesis.^[18] The mechanism of action of acrolein appears to involve induction of increased reactive oxygen species and DNA damage related to oxidative stress.^[19]

In terms of the "noncarcinogenic health quotient"^[jargon] for components in cigarette smoke, acrolein dominates, contributing 40 times more than the next component, hydrogen cyanide.^[20] The acrolein content in cigarette smoke depends on the type of cigarette and added glycerin, making up to 220 μg acrolein per cigarette.^[21][22] Importantly, while the concentration of the constituents in mainstream smoke can be reduced by filters, this has no significant effect on the composition of the side-stream smoke where acrolein usually resides, and which is inhaled by passive smoking.^[23][24] E-cigarettes, used normally, only generate "negligible" levels of acrolein (less than 10 μg "per puff").^[25][26]

Chemotherapy metabolite

Cyclophosphamide and ifosfamide treatment results in the production of acrolein.^[27] Acrolein produced during cyclophosphamide treatment collects in the urinary bladder and if untreated can cause hemorrhagic cystitis.

Endogenous production

Acrolein is a component of reuterin.^[28] Reuterin can be produced by gut microbes when glycerol is present. Microbe-produced reuterin is a potential resource of acrolein.^[29]

Analytical methods

The "acrolein test" is for the presence of glycerin or fats. A sample is heated with potassium bisulfate, and acrolein is released if the test is positive. When a fat is heated strongly in the presence of a dehydrating agent such as potassium bisulfate (KHSO
₄), the glycerol portion of the molecule is dehydrated to form the unsaturated aldehyde, acrolein (CH₂=CH–CHO), which has the odor peculiar to burnt cooking grease. More modern methods exist.^[13]

In the US, EPA methods 603 and 624.1 are designed to measure acrolein in industrial and municipal wastewater streams.^[30][31]

References

1. NIOSH Pocket Guide to Chemical Hazards. "#0011". National Institute for Occupational Safety and Health (NIOSH).
2. "Archived copy". Archived from the original on 2015-04-02. Retrieved 2015-03-26.{{cite web}}: CS1 maint: archived copy as title (link)
3. "Acrolein". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
4. Jan F. Stevens and Claudia S. Maier, "Acrolein: Sources, metabolism, and biomolecular interactions relevant to human health and disease", Mol Nutr Food Res. 2008 Jan; 52(1): 7–25.
5. Dietrich Arntz; Achim Fischer; Mathias Höpp; et al. (2012). "Acrolein and Methacrolein". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a01_149.pub2. ISBN 978-3527306732.
6. Martin, Andreas; Armbruster, Udo; Atia, Hanan (2012). "Recent developments in dehydration of glycerol toward acrolein over heteropolyacids". European Journal of Lipid Science and Technology. 114 (1): 10–23. doi:10.1002/ejlt.201100047.
7. Abdullah, Anas; Zuhairi Abdullah, Ahmad; Ahmed, Mukhtar; Khan, Junaid; Shahadat, Mohammad; Umar, Khalid; Alim, Md Abdul (March 2022). "A review on recent developments and progress in sustainable acrolein production through catalytic dehydration of bio-renewable glycerol". Journal of Cleaner Production. 341: 130876. Bibcode:2022JCPro.34130876A. doi:10.1016/j.jclepro.2022.130876. S2CID 246853148.
8. Homer Adkins; W. H. Hartung (1926). "Acrolein". Organic Syntheses. 6: 1. doi:10.15227/orgsyn.006.0001; Collected Volumes, vol. 1, p. 15.
9. Prentiss, Augustin Mitchell; Fisher, George J. B. (1937). Chemicals in War: A Treatise on Chemical Warfare. McGraw-Hill Book Company, Incorporated. p. 139. Retrieved 21 November 2021.
10. Eisler, Ronald (1994). Acrolein Hazards to Fish, Wildlife, and Invertebrates: A Synoptic Review. U.S. Department of the Interior, National Biological Survey. Retrieved 21 November 2021.
11. Shimizu, S.; Watanabe, N.; Kataoka, T.; Shoji, T.; Abe, N.; Morishita, S.; Ichimura, H. "Pyridine and Pyridine Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a22_399. ISBN 978-3527306732.
12. M J Dykstra, L E Reuss (2003). Biological Electron Microscopy: Theory, Techniques, and Troubleshooting. Springer. ISBN 0-306-47749-1.
13. Abraham, Klaus; Andres, Susanne; Palavinskas, Richard; Berg, Katharina; Appel, Klaus E.; Lampen, Alfonso (2011). "Toxicology and risk assessment of acrolein in food". Mol. Nutr. Food Res. 55 (9): 1277–1290. doi:10.1002/mnfr.201100481. PMID 21898908.
14. CDC - NIOSH Pocket Guide to Chemical Hazards
15. Roth-Walter, Franziska; Bergmayr, Cornelia; Meitz, Sarah; Buchleitner, Stefan; Stremnitzer, Caroline; Fazekas, Judit; Moskovskich, Anna; Müller, Mario A.; Roth, Georg A.; Manzano-Szalai, Krisztina; Dvorak, Zdenek; Neunkirchner, Alina; Jensen-Jarolim, Erika (2017). "Janus-faced Acrolein prevents allergy, but accelerates tumor growth by promoting immunoregulatory Foxp3+ cells: Mouse model for passive respiratory exposure". Scientific Reports. 7: 45067. Bibcode:2017NatSR...745067R. doi:10.1038/srep45067. PMC 5362909. PMID 28332605.
16. Tara Thiagarajan (Mar 15, 2019). "8 Chemicals Have Been Identified in Pasir Gudang's Kim Kim River, Here's What They Are". World of Buzz.
17. Feng, Z; Hu W; Hu Y; Tang M (October 2006). "Acrolein is a major cigarette-related lung cancer agent: Preferential binding at p53 mutational hotspots and inhibition of DNA repair". Proceedings of the National Academy of Sciences. 103 (42): 15404–15409. Bibcode:2006PNAS..10315404F. doi:10.1073/pnas.0607031103. PMC 1592536. PMID 17030796.
18. Cunningham FH, Fiebelkorn S, Johnson M, Meredith C. A novel application of the Margin of Exposure approach: segregation of tobacco smoke toxicants. Food Chem Toxicol. 2011 Nov;49(11):2921-33. doi: 10.1016/j.fct.2011.07.019. Epub 2011 Jul 23. PMID 21802474
19. Li L, Jiang L, Geng C, Cao J, Zhong L. The role of oxidative stress in acrolein-induced DNA damage in HepG2 cells. Free Radic Res. 2008 Apr;42(4):354-61. doi: 10.1080/10715760802008114 PMID 18404534
20. Haussmann, Hans-Juergen (2012). "Use of Hazard Indices for a Theoretical Evaluation of Cigarette Smoke Composition". Chem. Res. Toxicol. 25 (4): 794–810. doi:10.1021/tx200536w. PMID 22352345.
21. Daher, N; Saleh, R; Jaroudi, E; Sheheitli, H; Badr, T; Sepetdjian, E; Al Rashidi, M; Saliba, N; Shihadeh, A (Jan 2010). "Comparison of carcinogen, carbon monoxide, and ultrafine particle emissions from narghile waterpipe and cigarette smoking: Sidestream smoke measurements and assessment of second-hand smoke emission factors". Atmos Environ. 44 (1): 8–14. Bibcode:2010AtmEn..44....8D. doi:10.1016/j.atmosenv.2009.10.004. PMC 2801144. PMID 20161525.
22. Herrington, JS; Myers, C (2015). "Electronic cigarette solutions and resultant aerosol profiles". J Chromatogr A. 1418: 192–9. doi:10.1016/j.chroma.2015.09.034. PMID 26422308.
23. Blair, SL; Epstein, SA; Nizkorodov, SA; Staimer, N (2015). "A Real-Time Fast-Flow Tube Study of VOC and Particulate Emissions from Electronic, Potentially Reduced-Harm, Conventional, and Reference Cigarettes". Aerosol Sci Technol. 49 (9): 816–827. Bibcode:2015AerST..49..816B. doi:10.1080/02786826.2015.1076156. PMC 4696598. PMID 26726281.
24. Sopori, M (May 2002). "Effects of cigarette smoke on the immune system". Nat. Rev. Immunol. 2 (5): 372–7. doi:10.1038/nri803. PMID 12033743. S2CID 26116099.
25. McNeill, A, SC (2015). "E - cigarettes: an evidence update A report commissioned by Public Health England" (PDF). www.gov.uk. UK: Public Health England. pp. 76–78. Retrieved 20 August 2015.{{cite web}}: CS1 maint: multiple names: authors list (link)
26. Sleiman, M (2016). "Emissions from electronic cigarettes: Key parameters affecting the release of harmful chemicals". Environmental Science and Technology. 50 (17): 9644–9651. Bibcode:2016EnST...50.9644S. doi:10.1021/acs.est.6b01741. hdl:11336/105702. PMID 27461870. S2CID 31872198.
27. Paci, A; Rieutord, A; Guillaume, D; et al. (March 2000). "Quantitative high-performance liquid chromatography chromatographic determination of acrolein in plasma after derivatization with Luminarin 3". Journal of Chromatography B. 739 (2): 239–246. doi:10.1016/S0378-4347(99)00485-5. PMID 10755368.
28. Engels, Christina; Schwab, Clarissa; Zhang, Jianbo; Stevens, Marc J. A.; Bieri, Corinne; Ebert, Marc-Olivier; McNeill, Kristopher; Sturla, Shana J.; Lacroix, Christophe (2016-11-07). "Acrolein contributes strongly to antimicrobial and heterocyclic amine transformation activities of reuterin". Scientific Reports. 6 (1): 36246. Bibcode:2016NatSR...636246E. doi:10.1038/srep36246. ISSN 2045-2322. PMC 5098142. PMID 27819285.
29. Zhang, Jianbo; Sturla, Shana; Lacroix, Christophe; Schwab, Clarissa (2018-03-07). Johnson, Eric A. (ed.). "Gut Microbial Glycerol Metabolism as an Endogenous Acrolein Source". mBio. 9 (1): e01947–17. doi:10.1128/mBio.01947-17. ISSN 2161-2129. PMC 5770549. PMID 29339426.
30. Appendix A To Part 136 Methods For Organic Chemical Analysis of Municipal and Industrial Wastewater, Method 603—Acrolein And Acrylonitrile>
31. Method 624.1 — Purgables by GC-MS>