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Acrolein

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Not to be confused with Propanol, Acyloin, or Propanal.
Acrolein
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 Edit this at Wikidata
KEGG
UNII
  • InChI=1S/C3H4O/c1-2-3-4/h2-3H,1H2 checkY
    Key: HGINCPLSRVDWNT-UHFFFAOYSA-N checkY
  • InChI=1/C3H4O/c1-2-3-4/h2-3H,1H2
    Key: HGINCPLSRVDWNT-UHFFFAOYAQ
  • O=CC=C
  • C=CC=O
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
Occupational safety and health (OHS/OSH):
Main hazards
 Highly poisonous. Causes severe irritation to exposed membranes. Extremely flammable liquid and vapor.
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 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. gasolineInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
3
3
2
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]
Safety data sheet (SDS) JT Baker MSDS
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).
checkY verify (what is checkY☒N ?)

Acrolein (systematic name: propenal) is the simplest unsaturated aldehyde. It is a colourless liquid with a piercing, disagreeable, 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

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. The main challenge is in fact the competing over oxidation 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.[5]

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).[6]

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]

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.[7]

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/day per kilogram of body weight. Although acrolein occurs in French fries, the levels are only a few micrograms per kilogram.[8] 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.[9]

Cigarette smoke

Connections exist between acrolein gas in the smoke from tobacco cigarettes and the risk of lung cancer.[10] In terms of the "noncarcinogenic health quotient" for components in cigarette smoke, acrolein dominates, contributing 40 times more than the next component, hydrogen cyanide.[11] The acrolein content in cigarette smoke depends on the type of cigarette and added glycerin making up up to 220 µg acrolein per cigarette (,[12][13]). 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.[14][15] E-cigarettes, used normally, only generate "negligible" levels of acrolein (less than 10 mcg "per puff").[16][17]

Chemotherapy metabolite

Cyclophosphamide and Ifosfamide treatment results in the production of acrolein.[18] 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 (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.[8]

In the US, EPA method 603 is designed to measure acrolein in industrial and municipal wastewater streams.[19]

References

  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 or 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. {{cite web}}: Unknown parameter |deadurl= ignored (|url-status= suggested) (help)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 "Acrolein and Methacrolein" in Ullmann's Encyclopedia of Industrial Chemistry, 2012, Wiley-VCH, Weinheim. doi:10.1002/14356007.a01_149.pub2
  5. ^ Andreas Martin, Udo Armbruster, Hanan Atia "Recent developments in dehydration of glycerol toward acrolein over heteropolyacids" European Journal of Lipid Science and Technology 2012, Volume 114, pages 10–23. doi:10.1002/ejlt.201100047
  6. ^ Homer Adkins and W. H. Hartung (1941). "Acrolein". Organic Syntheses; Collected Volumes, vol. 1, p. 15.
  7. ^ M J Dykstra, L E Reuss (2003) Biological Electron Microscopy: Theory, Techniques, and Troubleshooting. Springer, ISBN 0-306-47749-1, ISBN 978-0-306-47749-2.
  8. ^ 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
  9. ^ CDC - NIOSH Pocket Guide to Chemical Hazards
  10. ^ 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.
  11. ^ 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
  12. ^ PMID 20161525
  13. ^ PMID 26422308
  14. ^ PMID 26726281
  15. ^ PMID 12033743
  16. ^ 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.{{cite web}}: CS1 maint: multiple names: authors list (link)
  17. ^ Sleiman, M (2016). "Emissions from electronic cigarettes: Key parameters affecting the release of harmful chemicals". pubs.acs.org. US: American Chemistry Society. p. 5. Retrieved 28 July 2016.
  18. ^ 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.
  19. ^ Appendix A To Part 136 Methods For Organic Chemical Analysis of Municipal and Industrial Wastewater, Method 603—Acrolein And Acrylonitrile> [permanent dead link]
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