Acrolein

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.

Acrolein

Names
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

3D model  Interactive image

(JSmol)  Interactive image

ChEBI  CHEBI:15368

ChEMBL  ChEMBL721

ChemSpider  7559

ECHA InfoCard 100.003.141

IUPHAR/BPS  2418

KEGG  C01471

PubChem CID  7847

 UNII  7864XYD3JJ

InChI
 InChI=1S/C3H4O/c1-2-3-4/h2-3H,1H2
Key: HGINCPLSRVDWNT-UHFFFAOYSA-N
 InChI=1/C3H4O/c1-2-3-4/h2-3H,1H2
Key: HGINCPLSRVDWNT-UHFFFAOYAQ
SMILES
 O=CC=C
 C=CC=O
Properties
Chemical C3H4O
formula
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)
Solubility in Appreciable (> 10%)
water
Vapor pressure 210 mmHg[1]
Hazards
Main hazards Highly poisonous. Causes
severe irritation to exposed
membranes. Extremely
flammable liquid and vapor.
Safety data JT Baker MSDS
sheet
NFPA 704

Flash point −26 °C (−15 °F; 247 K)

Autoignition 278 °C (532 °F; 551 K)
temperature
Explosive limits 2.8-31%[1]
Lethal dose or concentration (LD, LC):
LC50 (median 875 ppm (mouse, 1 min)
concentration) 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]
LCLo (lowest 674 ppm (cat, 2 hr)[2]
published)
 US health exposure limits (NIOSH):
PEL TWA 0.1 ppm (0.25 mg/m3)[1]
(Permissible)
REL TWA 0.1 ppm (0.25 mg/m3)
(Recommended) ST 0.3 ppm (0.8 mg/m3)[1]
IDLH 2 ppm[1]
(Immediate
danger)
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).
verify (what is ?)
Infobox references

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:[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

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
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
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.[4]

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. 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
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

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

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
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 (KHSO4), 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
1. "NIOSH Pocket Guide to Chemical Hazards #0011". National Institute for Occupational
Safety and Health (NIOSH).

2. "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.

4. 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

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.

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.
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. 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. p. 45067. doi:10.1038/srep45067.

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.

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>