Allyl chloride is the organic compound with the formula CH2=CHCH2Cl. This colorless liquid is insoluble in water but soluble in common organic solvents. It is mainly converted to epichlorohydrin, used in the production of plastics. It is a chlorinated derivative of propylene. It is an alkylating agent, which makes it both useful and hazardous to handle.[4]
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| Preferred IUPAC name
3-Chloroprop-1-ene | |||
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| Identifiers | |||
3D model (JSmol)
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| ChEBI | |||
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| ChemSpider | |||
| ECHA InfoCard | 100.003.144 | ||
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PubChem CID
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| UNII | |||
| UN number | 1100 | ||
CompTox Dashboard (EPA)
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| Properties | |||
| C3H5Cl | |||
| Molar mass | 76.52 g·mol−1 | ||
| Appearance | Colorless, brown, yellow, or purple liquid[1] | ||
| Odor | pungent, unpleasant[1] | ||
| Density | 0.94 g/mL | ||
| Melting point | −135 °C (−211 °F; 138 K) | ||
| Boiling point | 45 °C (113 °F; 318 K) | ||
| 0.36 g/100 ml (20 °C) | |||
| Solubility | soluble in ether, acetone, benzene, chloroform | ||
| Vapor pressure | 295 mmHg[1] | ||
Refractive index (nD)
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1.4055 | ||
| Viscosity | 0.3130 mPa·s[2] | ||
| Hazards | |||
| GHS labelling: | |||
   
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| Danger | |||
| H225, H302, H312, H315, H319, H332, H335, H341, H351, H373, H400 | |||
| P201, P202, P210, P233, P240, P241, P242, P243, P260, P261, P264, P270, P271, P273, P280, P281, P301+P312, P302+P352, P303+P361+P353, P304+P312, P304+P340, P305+P351+P338, P308+P313, P312, P314, P321, P322, P330, P332+P313, P337+P313, P362, P363, P370+P378, P391, P403+P233, P403+P235, P405, P501 | |||
| NFPA 704 (fire diamond) | |||
| Flash point | −32 °C (−26 °F; 241 K) | ||
| 390 °C (734 °F; 663 K) | |||
| Explosive limits | 2.9–11.2% | ||
| Lethal dose or concentration (LD, LC): | |||
LC50 (median concentration)
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11000 mg/m3 (rat, 2 hr) 11500 mg/m3 (mouse, 2 hr) 5800 mg/m3 (guinea pig, 2 hr) 22500 mg/m3 (rabbit, 2 hr) 10500 mg/m3 (cat, 2 hr)[3] | ||
| NIOSH (US health exposure limits): | |||
PEL (Permissible)
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TWA 1 ppm (3 mg/m3)[1] | ||
REL (Recommended)
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TWA 1 ppm (3 mg/m3) ST 2 ppm (6 mg/m3)[1] | ||
IDLH (Immediate danger)
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250 ppm[1] | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Production
editLaboratory scale
editAllyl chloride was first produced in 1857 by Auguste Cahours and August Hofmann by reacting allyl alcohol with phosphorus trichloride.[5][4] Modern preparation protocols economize this approach, replacing relatively expensive phosphorus trichloride with hydrochloric acid and a catalyst such as copper(I) chloride.[6]
Industrial scale
editAllyl chloride is produced by the chlorination of propylene. At lower temperatures, the main product is 1,2-dichloropropane, but at 500 °C, allyl chloride predominates, being formed via a free radical reaction:
- CH3CH=CH2 + Cl2 → ClCH2CH=CH2 + HCl
An estimated 800,000 tonnes were produced this way in 1997.[4]
Reactions and uses
editThe great majority of allyl chloride is converted to epichlorohydrin.[4] Other commercially significant derivatives include allyl alcohol, allylamine, allyl isothiocyanate (synthetic mustard oil),[7] and 1-bromo-3-chloropropane.
As an alkylating agent, it is useful in the manufacture of pharmaceuticals and pesticides, such as mustard oil.
Illustrative reactions
editIllustrative of its reactivity is its cyanation to allyl cyanide (CH2=CHCH2CN).[8] Being a reactive alkyl halide, it undergoes reductive coupling to give diallyl:[9]
- 2 ClCH2CH=CH2 + Mg → (CH2)2(CH=CH2)2 + MgCl2
It undergoes oxidative addition to palladium(0) to give allylpalladium chloride dimer, (C3H5)2Pd2Cl2. Dehydrohalogenation gives cyclopropene.
Safety
editAllyl chloride is highly toxic and flammable. Eye effects may be delayed and may lead to possible impairment of vision.[10]
See also
editExternal links
edit- International Chemical Safety Card 0010
- NIOSH Pocket Guide to Chemical Hazards. "#0018". National Institute for Occupational Safety and Health (NIOSH).
- IARC Monograph *Allyl chloride.
References
edit- ^ a b c d e f g h NIOSH Pocket Guide to Chemical Hazards. "#0018". National Institute for Occupational Safety and Health (NIOSH).
- ^ Viswanath, D.S.; Natarajan, G. (1989). Data Book on the Viscosity of Liquids. Hemisphere Publishing Corporation. ISBN 0-89116-778-1.
- ^ "Allyl chloride". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
- ^ a b c d Ludger Krähling, Jürgen Krey, Gerald Jakobson, Johann Grolig, Leopold Miksche “Allyl Compounds” in Ullmann's Encyclopedia of Industrial Chemistry Wiley-VCH, Weinheim, 2005. Published online: 15 June 2000.
- ^ Hofmann. Augustus William and Cahours. Augustus (1857) "Researches on a new class of alcohols," Philosophical Transactions of the Royal Society of London, 147: 555–574 ; see pp. 558–559.
- ^ Furniss, Brian; Hannaford, Antony; Smith, Peter; Tatchell, Austin (1996). Vogel's Textbook of Practical Organic Chemistry (5th ed.). London: Longman Science & Technical. pp. 558. ISBN 9780582462366.
- ^ F. Romanowski, H. Klenk "Thiocyanates and Isothiocyanates, Organic" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH: Weinheim. doi:10.1002/14356007.a26_749
- ^ J. V. Supniewski & P. L. Salzberg (1941). "Allyl Cyanide". Organic Syntheses; Collected Volumes, vol. 1, p. 46.
- ^ Amos Turk; Henry Chanan (1947). "Biallyl". Org. Synth. 27: 7. doi:10.15227/orgsyn.027.0007.
- ^ International Programme on Chemical Safety & the Commission of the European Communities. "Allyl Chloride". International Chemical Safety Cards. © IPCS CEC 1993. Archived from the original on 2016-03-04. Retrieved 13 February 2012.