Acrolein

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Not to be confused with Propanol, Acyloin, or Propanal.
Acrolein
Acrolein-2D.png
Acrolein-3D-balls.png
Acrolein-3D-vdW.png
Names
IUPAC name
Prop-2-enal
Other names
Acraldehyde[1]
Acrylic aldehyde[1]
Allyl Aldehyde[1]
Ethylene Aldehyde
Acrylaldehyde[1]
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.141
KEGG
UNII
Properties
C3H4O
Molar mass 56.064 g·mol−1
Appearance Colorless to yellow liquid. Colorless gas in smoke.
Odor Irritating
Density 0.839 g/mL
Melting point −88 °C (−126 °F; 185 K)
Boiling point 53 °C (127 °F; 326 K)
Appreciable (> 10%)
Vapor pressure 210 mmHg[1]
Hazards
Main hazards Highly poisonous. Causes severe irritation to exposed membranes. Extremely flammable liquid and vapor.
Safety data sheet JT Baker MSDS
NFPA 704 (fire diamond)
Flammability code 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineHealth code 4: Very short exposure could cause death or major residual injury. E.g. VX gasReactivity code 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazards (white): no codeNFPA 704 four-colored diamond
3
4
3
Flash point −26 °C (−15 °F; 247 K)
278 °C (532 °F; 551 K)
Explosive limits 2.8-31%[1]
Lethal dose or concentration (LD, LC):
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)[2]
674 ppm (cat, 2 hr)[2]
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]
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).
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Infobox references

Acrolein (systematic name: propenal) is the simplest unsaturated aldehyde. It is a colourless liquid with a piercing, acrid smell. 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 propylene and mainly used as a biocide and a building block to other chemical compounds, such as the amino acid methionine.

Production[edit]

Acrolein is prepared industrially by oxidation of propene. The process uses air as the source of oxygen and requires metal oxides as heterogeneous catalysts:[4]

CH2CHCH3 + O2 → CH2CHCHO + 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.[5][6] The main challenge is in fact the competing overoxidation to this acid. Propane represents a promising but challenging feedstock for the synthesis of acrolein (and acrylic 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.[7]

Niche or laboratory methods[edit]

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

HCHO + CH3CHO → CH2=CHCHO + H2O

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

Reactions[edit]

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 lyral, norbornene-2-carboxaldehyde, and myrac aldehyde.[4] The monomer 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexane carboxylate is also produced from acrolein via the intermediacy of tetrahydrobenzaldehyde.

Uses[edit]

Biocide[edit]

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.[4]

Chemical precursor[edit]

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. It is also thought to be an intermediate in the Skraup synthesis of quinolines, but is rarely used as such due to its instability.

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. Over time, it will polymerize with itself to form a clear, yellow solid. In water, it will form a hard, porous plastic.

Acrolein is sometimes used as a fixative in preparation of biological specimens for electron microscopy.[9]

Health risks[edit]

Acrolein is toxic and is a strong irritant for the skin, eyes, and nasal passages.[4] 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, the levels are only a few μg per kg.[10] 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.[11] Acrolein acts in an immunosuppressive manner and may promote regulatory cells,[12] thereby preventing the generation of allergy on the one hand, but also increasing the risk of cancer.

Cigarette smoke[edit]

Connections exist between acrolein gas in the smoke from tobacco cigarettes and the risk of lung cancer.[13] In terms of the "noncarcinogenic health quotient" for components in cigarette smoke, acrolein dominates, contributing 40 times more than the next component, hydrogen cyanide.[14] The acrolein content in cigarette smoke depends on the type of cigarette and added glycerin, making up to 220 µg acrolein per cigarette.[15][16] 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.[17][18] E-cigarettes, used normally, only generate "negligible" levels of acrolein (less than 10 µg "per puff").[19][20]

Chemotherapy metabolite[edit]

Cyclophosphamide and ifosfamide treatment results in the production of acrolein.[21] Acrolein produced during cyclophosphamide treatment collects in the urinary bladder and if untreated can cause hemorrhagic cystitis.

Analytical methods[edit]

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.[10]

In the US, EPA methods 603 and 624.1 are designed to measure acrolein in industrial and municipal wastewater streams.[22][23]

References[edit]

  1. ^ a b c d e f g h i NIOSH Pocket Guide to Chemical Hazards. "#0011". National Institute for Occupational Safety and Health (NIOSH).
  2. ^ a b "Acrolein". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  3. ^ "Archived copy". Archived from the original on 2015-04-02. Retrieved 2015-03-26.CS1 maint: archived copy as title (link)
  4. ^ a b c d Dietrich Arntz, Achim Fischer, Mathias Höpp, Sylvia Jacobi, Jörg Sauer, Takashi Ohara, Takahisa Sato, Noboru Shimizu and Helmut Schwind (2012). "Acrolein and Methacrolein". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a01_149.pub2.CS1 maint: uses authors parameter (link)
  5. ^ Naumann d'Alnoncourt, Raoul; Csepei, Lénárd-István; Hävecker, Michael; Girgsdies, Frank; Schuster, Manfred E.; Schlögl, Robert; Trunschke, Annette (2014). "The reaction network in propane oxidation over phase-pure MoVTeNb M1 oxide catalysts" (PDF). Journal of Catalysis. 311: 369–385. doi:10.1016/j.jcat.2013.12.008. hdl:11858/00-001M-0000-0014-F434-5. Archived from the original (PDF) on 2016-02-15. Retrieved 2017-12-26.
  6. ^ Hävecker, Michael; Wrabetz, Sabine; Kröhnert, Jutta; Csepei, Lenard-Istvan; Naumann d'Alnoncourt, Raoul; Kolen'Ko, Yury V.; Girgsdies, Frank; Schlögl, Robert; Trunschke, Annette (2013). "Surface chemistry of phase-pure M1 MoVTeNb oxide during operation in selective oxidation of propane to acrylic acid" (PDF). Journal of Catalysis. 285: 48–60. doi:10.1016/j.jcat.2011.09.012. hdl:11858/00-001M-0000-0012-1BEB-F. Archived from the original (PDF) on 2016-10-30. Retrieved 2017-12-26.
  7. ^ 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.
  8. ^ Homer Adkins; W. H. Hartung (1926). "Acrolein". Organic Syntheses. 6: 1. doi:10.15227/orgsyn.006.0001.; Collective Volume, 1, p. 15
  9. ^ M J Dykstra, L E Reuss (2003). Biological Electron Microscopy: Theory, Techniques, and Troubleshooting. Springer. ISBN 0-306-47749-1.
  10. ^ a b Klaus Abraham, Susanne Andres, Richard Palavinskas, Katharina Berg, Klaus E. Appel, Alfonso Lampen "Toxicology and risk assessment of acrolein in food" Mol. Nutr. Food Res. 2011, vol. 55, pp. 1277–1290. doi:10.1002/mnfr.201100481
  11. ^ CDC - NIOSH Pocket Guide to Chemical Hazards
  12. ^ 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. doi:10.1038/srep45067. PMC 5362909. PMID 28332605.
  13. ^ 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.
  14. ^ Hans-Juergen Haussmann, "Use of Hazard Indices for a Theoretical Evaluation of Cigarette Smoke Composition" Chem. Res. Toxicol., 2012, vol. 25, pp 794–810. doi:10.1021/tx200536w
  15. ^ 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.
  16. ^ 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.
  17. ^ 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.
  18. ^ 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.
  19. ^ McNeill, A, SC (2015). "E - cigarettes: an evidence update A report commissioned by Public Health England" (PDF). www.gov.uk. UK: Public Health England. p. 76–78. Retrieved 20 August 2015.
  20. ^ 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. PMID 27461870.
  21. ^ 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.
  22. ^ Appendix A To Part 136 Methods For Organic Chemical Analysis of Municipal and Industrial Wastewater, Method 603—Acrolein And Acrylonitrile>
  23. ^ Method 624.1 — Purgables by GC-MS>
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