Diethyl ether peroxide: Difference between revisions

|Watchedfields = changed

|verifiedrevid = 445507000

|Name = Diethyl ether hydroperoxide

|ImageFile = Diethyl ether peroxide.svg

|ImageSize = 136px

|ImageFile1 = Diethyl Ether Peroxide.png

|ImageSize1 = 160

|Section1={{Chembox Identifiers

|InChI = 1/C4H10O3/c1-3-6-4(2)7-5/h4-5H,3H2,1-2H3

|InChIKey = CXWWPQGYBJCHJL-UHFFFAOYAS

|SMILES1 = CC(OCC)OO

|StdInChI_Ref = {{stdinchicite|correct|chemspider}}

|StdInChI = 1S/C4H10O3/c1-3-6-4(2)7-5/h4-5H,3H2,1-2H3

|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

|StdInChIKey = CXWWPQGYBJCHJL-UHFFFAOYSA-N

|CASNo_Ref = {{cascite|correct|??}}

|CASNo = 18321-53-4

|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

|ChemSpiderID =19985446

|PubChem = 126387

|SMILES = CCOC(OO)C

|Section2={{Chembox Properties

|C=4|H=10|O=3

|Appearance = colorless liquid

|Density = 1.005 g/cm³

|BoilingPtC = 62 to 64

|BoilingPt_notes = at 18.7 hPa (reduced pressure)

}}

|Section3={{Chembox Hazards

|MainHazards = Explosive

|NFPA-F = 4 | NFPA-H = 2 | NFPA-R = 4 | NFPA-S =

}}

}}

'''Diethyl ether hydroperoxide''' is the [[organic compound]] with the formula C₂H₅OCH(OOH)CH₃. It is a colorless liquid. Diethyl ether hydroperoxide and its condensation products are responsible for the explosive [[organic peroxide]]s that slowly form upon exposure of [[diethyl ether]] to ambient air and temperature conditions.<ref name=jacs>{{cite journal |doi=10.1021/ja01638a012|title=Organic Peroxides. XIX. α-Hydroperoxyethers and Related Peroxides|year=1954|last1=Milas|first1=Nicholas A.|last2=Peeler|first2=Robert L.|last3=Mageli|first3=Orville L.|journal=Journal of the American Chemical Society|volume=76|issue=9|pages=2322–2325}}</ref><ref>{{cite journal | author = A. Rieche, R. Meister | title = Modellversuche zur Autoxidation der Äther | journal = [[Angewandte Chemie]] | volume = 49 | issue = 5 | pages = 101–103 | year = 1936 | doi = 10.1002/ange.19360490502 | bibcode = 1936AngCh..49..101R | language = de}}</ref>

==Synthesis and reactions==

Diethyl ether hydroperoxide can be formed by the [[photooxygenation]] of diethyl ether. This is a radical process, driven by UV excitation of molecular oxygen into a more reactive form. Its formation is usually undesirable due to the associated risk of explosion. For this reason commercial samples of diethyl ether will usually contain [[antioxidant]]s such as [[Butylated hydroxytoluene|BHT]] and be contained in a material able to block UV rays, such as amber glass.

:[[File:Ether-autoxidation.png|400px]]

It can be intentionally prepared in high yield by the acid-catalyzed addition of [[hydrogen peroxide]] to [[ethyl vinyl ether]]:<ref name=jacs/>

:C₂H₅OCH=CH₂ + H₂O₂ → C₂H₅OCH(OOH)CH₃

Related hydroperoxides can be produced similarly.

Diethyl ether hydroperoxide, upon heating in water, decomposes to [[acetaldehyde]]:

:C₂H₅OCH(OOH)CH₃ → CH₃CHO + C₂H₅OH + H₂O₂

Diethyl ether hydroperoxide forms polymers known as '''diethyl ether peroxide''', or '''ethylidene peroxide''':

The peroxide is a colorless oil that is an extremely [[Brisance|brisant]] and [[friction]] sensitive [[explosive material]], however the polymeric materials are solid making them more dangerous as evaporation of the volatile diethyl ether can leave thin films of pure explosive.

Diethyl ether peroxides can be detected with a [[potassium iodide]] (KI) solution in acetic acid or [[potassium iodide]]/[[starch]] paper. A positive test results in the formation of [[iodine]] (I₂) that causes a yellow or brown color of the ether phase or a dark bluish spot on the paper strip.<ref>{{cite web|url=https://www.sigmaaldrich.com/chemistry/solvents/learning-center/peroxide-formation.html |title=Peroxide Forming Solvents|website=Sigma-Aldrich|accessdate=2014-07-09}}</ref>

{{Reflist}}

[[Category:Ethers]]

[[Category:Liquid explosives]]

[[Category:Organic peroxide explosives]]

[[Category:Ethoxy compounds]]