Acrolein

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.Jan F. Stevens and Claudia S. Maier, [https://pubmed.ncbi.nlm.nih.gov/18203133/ "Acrolein: Sources, metabolism, and biomolecular interactions relevant to human health and disease"], Mol Nutr Food Res. 2008 Jan; 52(1): 7–25.

Acrolein is prepared industrially by oxidation of propene. The process uses air as the source of oxygen and requires metal oxides as heterogeneous catalysts:{{Ullmann|author1=Dietrich Arntz |author2=Achim Fischer |author3=Mathias Höpp |author4=Sylvia Jacobi |author5=Jörg Sauer |author6=Takashi Ohara |author7=Takahisa Sato |author8=Noboru Shimizu |author9=Helmut Schwind |display-authors=3 |title=Acrolein and Methacrolein||year=2012|doi=10.1002/14356007.a01_149.pub2}}

:{{chem2|CH3CH\dCH2 + O2 → CH2\dCHCHO + 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.{{cite journal | last1 = Martin | first1 = Andreas | last2 = Armbruster | first2 = Udo | last3 = Atia | first3 = Hanan | year = 2012 | title = Recent developments in dehydration of glycerol toward acrolein over heteropolyacids | journal = European Journal of Lipid Science and Technology | volume = 114 | issue = 1| pages = 10–23 | doi = 10.1002/ejlt.201100047 }}{{Cite journal |last1=Abdullah |first1=Anas |last2=Zuhairi Abdullah |first2=Ahmad |last3=Ahmed |first3=Mukhtar |last4=Khan |first4=Junaid |last5=Shahadat |first5=Mohammad |last6=Umar |first6=Khalid |last7=Alim |first7=Md Abdul |date=March 2022 |title=A review on recent developments and progress in sustainable acrolein production through catalytic dehydration of bio-renewable glycerol |url=https://linkinghub.elsevier.com/retrieve/pii/S0959652622005145 |journal=Journal of Cleaner Production |language=en |volume=341 |pages=130876 |doi=10.1016/j.jclepro.2022.130876|bibcode=2022JCPro.34130876A |s2cid=246853148|url-access=subscription }}

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).{{OrgSynth | author1 = Homer Adkins | authorlink1 = Homer Burton Adkins | author2 = W. H. Hartung | title = Acrolein | collvol = 1 | collvolpages = 15 | year = 1926 | volume = 6 | pages = 1 | doi = 10.15227/orgsyn.006.0001 | prep = cv1p0015}}

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. The monomer 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate is also produced from acrolein via the intermediacy of tetrahydrobenzaldehyde.

Acrolein was used in warfare due to its irritant and blistering properties. The French used the chemical in their hand grenades and artillery shells{{cite book |last1=Prentiss |first1=Augustin Mitchell |last2=Fisher |first2=George J. B. |title=Chemicals in War: A Treatise on Chemical Warfare |date=1937 |publisher=McGraw-Hill Book Company, Incorporated |page=139 |url=https://books.google.com/books?id=5zdLAAAAMAAJ |access-date=21 November 2021 |language=en}} during World War I under the name "Papite".{{cite book |last1=Eisler |first1=Ronald |title=Acrolein Hazards to Fish, Wildlife, and Invertebrates: A Synoptic Review |date=1994 |publisher=U.S. Department of the Interior, National Biological Survey |url=https://books.google.com/books?id=sijZELAuYAEC&pg=PA4 |access-date=21 November 2021 |language=en}}

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.

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.{{Ullmann|first1=S. |last1=Shimizu |first2=N. |last2=Watanabe |first3=T. |last3=Kataoka |first4=T. |last4=Shoji |first5=N. |last5=Abe |first6=S. |last6=Morishita |first7=H. |last7=Ichimura |title=Pyridine and Pyridine Derivatives |doi=10.1002/14356007.a22_399}} 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|date=March 2020}}

Acrolein has been used as a fixative in preparation of biological specimens for electron microscopy.{{cite book | author = M J Dykstra, L E Reuss | date = 2003 | title = Biological Electron Microscopy: Theory, Techniques, and Troubleshooting | publisher = Springer | isbn = 0-306-47749-1}}

Acrolein is toxic and is a strong irritant for the skin, eyes, and nasal passages. 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. 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.[https://www.cdc.gov/niosh/npg/npgd0011.html CDC - NIOSH Pocket Guide to Chemical Hazards] Acrolein acts in an immunosuppressive manner and may promote regulatory cells,{{cite journal |last1=Roth-Walter |first1=Franziska |last2=Bergmayr |first2=Cornelia |last3=Meitz |first3=Sarah |last4=Buchleitner |first4=Stefan |last5=Stremnitzer |first5=Caroline |last6=Fazekas |first6=Judit |last7=Moskovskich |first7=Anna |last8=Müller |first8=Mario A. |last9=Roth |first9=Georg A. |last10=Manzano-Szalai |first10=Krisztina |last11=Dvorak |first11=Zdenek |last12=Neunkirchner |first12=Alina |last13=Jensen-Jarolim |first13=Erika |author-link13=Erika Jensen-Jarolim |date=2017 |title=Janus-faced Acrolein prevents allergy, but accelerates tumor growth by promoting immunoregulatory Foxp3+ cells: Mouse model for passive respiratory exposure |journal=Scientific Reports |volume=7 |pages=45067 |bibcode=2017NatSR...745067R |doi=10.1038/srep45067 |pmc=5362909 |pmid=28332605}} 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.{{cite web |last1=Tara Thiagarajan |title=8 Chemicals Have Been Identified in Pasir Gudang's Kim Kim River, Here's What They Are |url=https://worldofbuzz.com/8-chemicals-have-been-identified-in-pasir-gudangs-kim-kim-river-heres-what-they-are/ |website=World of Buzz |date=Mar 15, 2019}}

Connections exist between acrolein gas in the smoke from tobacco cigarettes and the risk of lung cancer.{{cite journal | last =Feng | first =Z |author2=Hu W|author3=Hu Y|author4=Tang M | title =Acrolein is a major cigarette-related lung cancer agent: Preferential binding at p53 mutational hotspots and inhibition of DNA repair | journal = Proceedings of the National Academy of Sciences| volume =103 | issue =42 | pages =15404–15409 |date=October 2006 | pmid =17030796 | doi=10.1073/pnas.0607031103 | pmc =1592536 | bibcode=2006PNAS..10315404F| doi-access =free }} Acrolein is one of seven toxicants in cigarette smoke that are most associated with respiratory tract carcinogenesis.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}} The mechanism of action of acrolein appears to involve induction of increased reactive oxygen species and DNA damage related to oxidative stress.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}}

In terms of the "noncarcinogenic health quotient"{{Technical inline|date=January 2023}} for components in cigarette smoke, acrolein dominates, contributing 40 times more than the next component, hydrogen cyanide.{{cite journal | last1 = Haussmann | first1 = Hans-Juergen | year = 2012 | title = Use of Hazard Indices for a Theoretical Evaluation of Cigarette Smoke Composition | journal = Chem. Res. Toxicol. | volume = 25 | issue = 4 | pages = 794–810 | doi = 10.1021/tx200536w | pmid = 22352345 }} The acrolein content in cigarette smoke depends on the type of cigarette and added glycerin, making up to 220 μg acrolein per cigarette.{{cite journal | pmid = 20161525 | doi=10.1016/j.atmosenv.2009.10.004 | volume=44 | issue=1 | title=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. | date=Jan 2010 | journal=Atmos Environ | pages=8–14 | pmc=2801144 | last1 = Daher | first1 = N | last2 = Saleh | first2 = R | last3 = Jaroudi | first3 = E | last4 = Sheheitli | first4 = H | last5 = Badr | first5 = T | last6 = Sepetdjian | first6 = E | last7 = Al Rashidi | first7 = M | last8 = Saliba | first8 = N | last9 = Shihadeh | first9 = A| bibcode=2010AtmEn..44....8D }}{{cite journal | pmid = 26422308 | doi=10.1016/j.chroma.2015.09.034 | volume=1418 | title=Electronic cigarette solutions and resultant aerosol profiles | year=2015 | journal=J Chromatogr A | pages=192–9 | last1 = Herrington | first1 = JS | last2 = Myers | first2 = C| doi-access=free}} 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.{{cite journal | pmid = 26726281 | doi=10.1080/02786826.2015.1076156 | volume=49 | issue=9 | title=A Real-Time Fast-Flow Tube Study of VOC and Particulate Emissions from Electronic, Potentially Reduced-Harm, Conventional, and Reference Cigarettes | pmc=4696598 | year=2015 | journal=Aerosol Sci Technol | pages=816–827 | last1 = Blair | first1 = SL | last2 = Epstein | first2 = SA | last3 = Nizkorodov | first3 = SA | last4 = Staimer | first4 = N| bibcode=2015AerST..49..816B }}{{cite journal | pmid = 12033743 | doi=10.1038/nri803 | volume=2 | issue=5 | title=Effects of cigarette smoke on the immune system | date=May 2002 | journal=Nat. Rev. Immunol. | pages=372–7 | last1 = Sopori | first1 = M| s2cid=26116099 }} E-cigarettes, used normally, only generate "negligible" levels of acrolein (less than 10 μg "per puff").{{cite web|last1=McNeill|first1=A, SC|title=E - cigarettes: an evidence update A report commissioned by Public Health England|url=https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/454516/Ecigarettes_an_evidence_update_A_report_commissioned_by_Public_Health_England.pdf|website=www.gov.uk|publisher=Public Health England|access-date=20 August 2015|pages=76–78|location=UK|date=2015}}{{Cite journal|last1=Sleiman|first1=M|title=Emissions from electronic cigarettes: Key parameters affecting the release of harmful chemicals|journal=Environmental Science and Technology|volume=50|issue=17|pages=9644–9651|date=2016|doi=10.1021/acs.est.6b01741|pmid=27461870|bibcode=2016EnST...50.9644S|s2cid=31872198|url=http://www.escholarship.org/uc/item/9s90850c|hdl=11336/105702|hdl-access=free}}

Cyclophosphamide and ifosfamide treatment results in the production of acrolein.{{cite journal | last1 = Paci | first1 = A |last2=Rieutord |first2=A |last3=Guillaume |first3=D |last4=Traore |first4=F |last5=Ropenga |first5=J |last6=Husson |first6=H-P |last7=Brion |first7=F. |display-authors=3 |title=Quantitative high-performance liquid chromatography chromatographic determination of acrolein in plasma after derivatization with Luminarin 3 |journal=Journal of Chromatography B |volume=739 |issue=2 |pages = 239–246 |date=March 2000 | doi=10.1016/S0378-4347(99)00485-5 | pmid = 10755368 }} Acrolein produced during cyclophosphamide treatment collects in the urinary bladder and if untreated can cause hemorrhagic cystitis.

Acrolein is a component of reuterin.{{Cite journal |last1=Engels |first1=Christina |last2=Schwab |first2=Clarissa |last3=Zhang |first3=Jianbo |last4=Stevens |first4=Marc J. A. |last5=Bieri |first5=Corinne |last6=Ebert |first6=Marc-Olivier |last7=McNeill |first7=Kristopher |last8=Sturla |first8=Shana J. |last9=Lacroix |first9=Christophe |date=2016-11-07 |title=Acrolein contributes strongly to antimicrobial and heterocyclic amine transformation activities of reuterin |journal=Scientific Reports |language=en |volume=6 |issue=1 |pages=36246 |doi=10.1038/srep36246 |issn=2045-2322 |pmc=5098142 |pmid=27819285|bibcode=2016NatSR...636246E }} Reuterin can be produced by gut microbes when glycerol is present. Microbe-produced reuterin is a potential resource of acrolein.{{Cite journal |last1=Zhang |first1=Jianbo |last2=Sturla |first2=Shana |last3=Lacroix |first3=Christophe |last4=Schwab |first4=Clarissa |date=2018-03-07 |editor-last=Johnson |editor-first=Eric A. |title=Gut Microbial Glycerol Metabolism as an Endogenous Acrolein Source |journal=mBio |language=en |volume=9 |issue=1 |pages=e01947–17 |doi=10.1128/mBio.01947-17 |issn=2161-2129 |pmc=5770549 |pmid=29339426}}

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 ({{chem|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.{{cite journal | last1 = Abraham | first1 = Klaus | last2 = Andres | first2 = Susanne | last3 = Palavinskas | first3 = Richard | last4 = Berg | first4 = Katharina | last5 = Appel | first5 = Klaus E. | last6 = Lampen | first6 = Alfonso | year = 2011 | title = Toxicology and risk assessment of acrolein in food | journal = Mol. Nutr. Food Res. | volume = 55 | issue = 9 | pages = 1277–1290 | doi = 10.1002/mnfr.201100481 | pmid = 21898908}}

In the US, EPA methods 603 and 624.1 are designed to measure acrolein in industrial and municipal wastewater streams.[https://web.archive.org/web/20081121222220/http://www.accustandard.com/asi/pdfs/epa_methods/603.pdf Appendix A To Part 136 Methods For Organic Chemical Analysis of Municipal and Industrial Wastewater, Method 603—Acrolein And Acrylonitrile> ][https://www.epa.gov/sites/production/files/2017-08/documents/method_624-1_2016.pdf Method 624.1 — Purgables by GC-MS> ]

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