Allyl chloride

Allyl chloride was first produced in 1857 by Auguste Cahours and August Hofmann by reacting allyl alcohol with phosphorus trichloride.Hofmann. Augustus William and Cahours. Augustus (1857) [http://rstl.royalsocietypublishing.org/content/147/555.full.pdf+html "Researches on a new class of alcohols,"] Philosophical Transactions of the Royal Society of London, 147: 555–574 ; see pp. 558–559.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. Modern preparation protocols economize this approach, replacing relatively expensive phosphorus trichloride with hydrochloric acid and a catalyst such as copper(I) chloride.{{cite book|author1=Furniss, Brian |author2=Hannaford, Antony |author3=Smith, Peter |author4=Tatchell, Austin |title=Vogel's Textbook of Practical Organic Chemistry |edition=5th|year=1996|publisher=Longman Science & Technical|location=London|isbn=9780582462366|pages=[https://archive.org/details/TextbookOfPracticalOrganicChemistry5thEd/page/n582 558]|url=https://archive.org/details/TextbookOfPracticalOrganicChemistry5thEd}}

Allyl 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.

The great majority of allyl chloride is converted to epichlorohydrin. Other commercially significant derivatives include allyl alcohol, allylamine, allyl isothiocyanate (synthetic mustard oil),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}} and 1-bromo-3-chloropropane.

As an alkylating agent, it is useful in the manufacture of pharmaceuticals and pesticides, such as mustard oil.

Illustrative of its reactivity is its cyanation to allyl cyanide (CH₂=CHCH₂CN).{{OrgSynth | author = J. V. Supniewski | author2 = P. L. Salzberg | name-list-style=amp | title = Allyl Cyanide | collvol = 1 | collvolpages = 46 | year = 1941 | prep = CV1P0046}} Being a reactive alkyl halide, it undergoes reductive coupling to give diallyl:{{cite journal|title=Biallyl|author=Amos Turk|author2=Henry Chanan|journal=Org. Synth.|year=1947|volume=27|page=7|doi=10.15227/orgsyn.027.0007}}

: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.

Allyl chloride is highly toxic and flammable. Eye effects may be delayed and may lead to possible impairment of vision.{{cite web|author=International Programme on Chemical Safety & the Commission of the European Communities|title=Allyl Chloride|url=http://siri.org/msds/mf/cards/file/0010.html|work=International Chemical Safety Cards|publisher=© IPCS CEC 1993|accessdate=13 February 2012|archive-url=https://web.archive.org/web/20160304000900/http://siri.org/msds/mf/cards/file/0010.html|archive-date=2016-03-04|url-status=dead}}

• Allyl
• Allyl bromide
• Allyl iodide

• {{ICSC|0010|00}}
• {{PGCH|0018}}
• IARC Monograph *[https://web.archive.org/web/20051012221341/http://www-cie.iarc.fr/htdocs/monographs/vol71/055-allylchl.html Allyl chloride.]

{{reflist|30em}}

{{Authority control}}

Category:Chloroalkenes

Category:IARC Group 3 carcinogens

Category:Allyl compounds

Category:Substances discovered in the 19th century