Allyl alcohol
Skeletal formula
Ball-and-stick model
Names
Preferred IUPAC name
Prop-2-en-1-ol
Other names
Allyl alcohol
2-Propen-1-ol
1-Propen-3-ol[1]
Vinyl carbinol[1]
Allylic alcohol
Weed drench[citation needed]
Identifiers
3D model (JSmol)
3DMet
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.156 Edit this at Wikidata
EC Number
  • 203-470-7
KEGG
RTECS number
  • BA5075000
UNII
UN number 1098
  • InChI=1S/C3H6O/c1-2-3-4/h2,4H,1,3H2 checkY
    Key: XXROGKLTLUQVRX-UHFFFAOYSA-N checkY
  • InChI=1/C3H6O/c1-2-3-4/h2,4H,1,3H2
    Key: XXROGKLTLUQVRX-UHFFFAOYAC
  • C=CCO
Properties
C3H6O
Molar mass 58.080 g·mol−1
Appearance colorless liquid[1]
Odor mustard-like[1]
Density 0.854 g/ml
Melting point −129 °C
Boiling point 97 °C (207 °F; 370 K)
Miscible
Vapor pressure 17 mmHg[1]
Acidity (pKa) 15.5 (H2O)[2]
-36.70·10−6 cm3/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Highly toxic, lachrymator
GHS labelling:
GHS02: FlammableGHS06: ToxicGHS07: Exclamation markGHS09: Environmental hazard
Danger
H225, H301, H302, H311, H315, H319, H331, H335, H400
P210, P233, P240, P241, P242, P243, P261, P264, P270, P271, P273, P280, P301+P310, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P311, P312, P321, P322, P330, P332+P313, P337+P313, P361, P362, P363, P370+P378, P391, P403+P233, P403+P235, P405, P501
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 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
3
3
1
Flash point 21 °C (70 °F; 294 K)
378 °C (712 °F; 651 K)
Explosive limits 2.5–18.0%
Lethal dose or concentration (LD, LC):
80 mg/kg (rat, orally)[3]
1000 ppm (mammal, 1 hr)
76 ppm (rat, 8 hr)
207 ppm (mouse, 2 hr)
1000 ppm (rabbit, 3.5 hr)
1000 ppm (monkey, 4 hr)
1060 ppm (rat, 1 hr)
165 ppm (rat, 4 hr)
76 ppm (rat, 8 hr)[4]
NIOSH (US health exposure limits):
PEL (Permissible)
2 ppm[1]
REL (Recommended)
TWA 2 ppm (5 mg/m3) ST 4 ppm (10 mg/m3) [skin] [1]
IDLH (Immediate danger)
20 ppm[1]
Safety data sheet (SDS) External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Allyl alcohol (IUPAC name: prop-2-en-1-ol) is an organic compound with the structural formula CH2=CHCH2OH. Like many alcohols, it is a water-soluble, colourless liquid. It is more toxic than typical small alcohols. Allyl alcohol is used as a precursor to many specialized compounds such as flame-resistant materials, drying oils, and plasticizers.[5] Allyl alcohol is the smallest representative of the allylic alcohols.

Production

Allyl alcohol is produced commercially by the Olin and Shell corporations through the hydrolysis of allyl chloride:

Allyl alcohol can also be made by the rearrangement of propylene oxide, a reaction that is catalyzed by potassium alum at high temperature. The advantage of this method relative to the allyl chloride route is that it does not generate salt. Also avoiding chloride-containing intermediates is the "acetoxylation" of propylene to allyl acetate:

Hydrolysis of this acetate gives allyl alcohol. In alternative fashion, propylene can be oxidized to acrolein, which upon hydrogenation gives the alcohol.

In principle, allyl alcohol can be obtained by dehydrogenation of propanol.

Laboratory methods

In the laboratory, glycerol reacts with oxalic or formic acids to give (respectively) dioxalin or glyceric formate, either of which decarboxylate and dehydrate to allylol.[6][7]

Allyl alcohols in general are prepared by allylic oxidation of allyl compounds, using selenium dioxide or organic peroxides. Other methods include carbon-carbon bond-forming reactions such as the Prins reaction, the Morita-Baylis-Hillman reaction, or a variant of the Ramberg-Bäcklund reaction. Hydrogenation of enones is another route. Some of these methods are achieved by the Luche reduction, Wharton reaction, and the Mislow-Evans rearrangement.

Allyl alcohol was first prepared in 1856 by Auguste Cahours and August Hofmann by hydrolysis of allyl iodide.[5] Today a Allyl alcohol can be formed after trituration of garlic (Allium sativum) cloves (producing from garlic in two ways: firstly by a self-condensation reaction of allicin and its decomposition products such as diallyl trisulphide and diallyl disulphide and secondly by the reaction between alliin, the precursor of allicin, and water).[8]

Applications

Allyl alcohol is converted mainly to glycidol, which is a chemical intermediate in the synthesis of glycerol, glycidyl ethers, esters, and amines. Also, a variety of polymerizable esters are prepared from allyl alcohol, e.g. diallyl phthalate.[5]

Allyl alcohol can both enhance and inhibit the growth of living organisms, which depends on the species and strain.

Allyl alcohol is a herbicide (can be used as a weed eradicant[9]), fungicide (toxic to numerous unrelated fungi; inhibiting the growth of such pathogens as Candida albicans[8], Rhizoctonia solani, Sclerotinia sclerotiorum, Fusarium solani, Rhizopus nigricans[10]), nematocide. It is rapidly detoxified in soil (the treatment with allyl alcohol did not destroy the microbes so completely[9]), and inhibitory effects in studies were absent after 4 days on Rhizoctonia solani, and after 4-8 days on barley seedlings.[10]

Application of allyl alcohol to soils free from mycorrhizal fungi resulted in an increased growth of pine seedlings and improvement of their root health[10] (allyl alcohol retards the fungal infection, has stimulatory effects on microbial antagonists and has little effect on the formation of mycorrhizae, causing abnormalities in the structure of the mycorrhizae[9]). Allyl alcohol was stimulatory to such beneficial fungi as Trichoderma spp.[10] Trichoderma has proved to be able to utilize allyl alcohol as a nutrient.[9] Many species of Trichoderma have been reported as mycoparasites of soilborne pathogens, including the pathogen S. sclerotiorum, hence allyl alcohol may have potential for use as a soil amendment for enhancing biocontrol of diseases caused by S. sclerotiorum or R. solani. Trichoderma viride, which only occurred sporadically in the controls and other treatments in one study, became the overwhelmingly dominant mold after allyl alcohol treatment. The predominance of Trichoderma continued even through the second growing season[9]. Trichoderma sp. PDR1-7 can be utile for pine reforestation and phytoremediation of Pb-contaminated mine soil[11]. Allyl alcohol also increased bacterial populations (especially such beneficial[12] as Pseudomonas fluorescens and P. putida[10][12]).

Safety

Allyl alcohol is more toxic, especially hepatotoxic (in rats, in vivo, allyl alcohol is metabolized by liver alcohol dehydrogenase to acrolein; causes severe damage to the microtubules of rat hepatocyte mitochondria and depletion of glutathione[8]) than related alcohols.[5][13] Its threshold limit value (TLV) is 2 ppm. It is a lachrymator.[5]

A well-researched mechanism of allyl alcohol toxicity is by its inhibition of alcohol dehydrogenase after its conversion to the toxic aldehyde acrolein[8]. Acrolein is also known to deplete intracellular stores of glutathione and cause peroxidation of cellular lipids. This affects the permeability of the membrane and consequently undermines the viability of the cell[8].

Allyl alcohol decreases both cytosolic and mitochondrial NADH of C. albicans, depletion of NAD(P)H, the co-substrate for glutathione reductase, would diminish the recovery of the GSH pools in both compartments. As allyl alcohol depletes glutathione, one might predict an increase in reactive oxygen species.[8]

See also

References

  1. ^ a b c d e f g h NIOSH Pocket Guide to Chemical Hazards. "#0017". National Institute for Occupational Safety and Health (NIOSH).
  2. ^ Haynes, William M., ed. (2016). CRC Handbook of Chemistry and Physics (97th ed.). CRC Press. p. 5–88. ISBN 978-1498754286.
  3. ^ Allyl alcohol toxicity
  4. ^ "Allyl alcohol". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  5. ^ a b c d e Ludger Krähling; Jürgen Krey; Gerald Jakobson; Johann Grolig; Leopold Miksche (2002). "Allyl Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a01_425. ISBN 978-3527306732.
  6. ^ Oliver Kamm & C. S. Marvel (1941). "Allyl alcohol". Organic Syntheses. 1: 15. doi:10.15227/orgsyn.001.0015.
  7. ^ Cohen, Julius (1900). Practical Organic Chemistry (2nd ed.). London: Macmillan and Co., Limited. p. 96. Practical Organic Chemistry Cohen Julius.
  8. ^ a b c d e f Lemar, Katey M.; Passa, Ourania; Aon, Miguel A.; Cortassa, Sonia; Müller, Carsten T.; Plummer, Sue; O'Rourke, Brian; Lloyd, David (2005). "Allyl alcohol and garlic (Allium sativum) extract produce oxidative stress in Candida albicans". Microbiology. 151 (10): 3257–3265. doi:10.1099/mic.0.28095-0. ISSN 1465-2080. PMC 2711876. PMID 16207909.
  9. ^ a b c d e Laiho, Mikola, O., P. "Studies on the effect of some eradicants on mycorrhizal development in forest nurseries" (PDF). helda.helsinki.fi. Retrieved 2024-01-24.((cite web)): CS1 maint: multiple names: authors list (link)
  10. ^ a b c d e Huang, H.C.; Huang, J.; Saindon, G.; Erickson, R.S. (March 1997). "Effect of allyl alcohol and fermented agricultural wastes on carpogenic germination of sclerotia of Sclerotinia sclerotiorum and colonization by Trichoderma spp". Canadian Journal of Plant Pathology. 19 (1): 43–46. Bibcode:1997CaJPP..19...43H. doi:10.1080/07060669709500570. ISSN 0706-0661.
  11. ^ Babu, A. Giridhar; Shea, Patrick J.; Oh, Byung-Taek (2014-04-01). "Trichoderma sp. PDR1-7 promotes Pinus sylvestris reforestation of lead-contaminated mine tailing sites". Science of the Total Environment. 476–477: 561–567. Bibcode:2014ScTEn.476..561B. doi:10.1016/j.scitotenv.2013.12.119. ISSN 0048-9697. PMID 24496029.
  12. ^ a b Hewavitharana, Shashika (2013). "Carbon source dependent efficacy of anaerobic soil disinfestation in controlling apple replant disease". rex.libraries.wsu.edu. Retrieved 2024-01-24.
  13. ^ "National Technical Information Service". US Environmental Protection Agency. 1984.