Diethyl ether peroxide

Last updated
Diethyl ether hydroperoxide
Diethyl ether peroxide.svg
Diethyl Ether Peroxide.png
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/C4H10O3/c1-3-6-4(2)7-5/h4-5H,3H2,1-2H3 Yes check.svgY
    Key: CXWWPQGYBJCHJL-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C4H10O3/c1-3-6-4(2)7-5/h4-5H,3H2,1-2H3
    Key: CXWWPQGYBJCHJL-UHFFFAOYAS
  • CCOC(OO)C
  • CC(OCC)OO
Properties
C4H10O3
Molar mass 106.121 g·mol−1
Appearancecolorless liquid
Density 1.005 g/cm3
Boiling point 62 to 64 °C (144 to 147 °F; 335 to 337 K) at 18.7 hPa (reduced pressure)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Explosive
NFPA 704 (fire diamond)
2
4
4
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

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 peroxides that slowly form upon exposure of diethyl ether to ambient air and temperature conditions. [1] [2]

Contents

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 antioxidants such as BHT and be contained in a material able to block UV rays, such as amber glass.

Ether-autoxidation.png

It can be intentionally prepared in high yield by the acid-catalyzed addition of hydrogen peroxide to ethyl vinyl ether: [1]

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:

Diethylether peroxide.png

The peroxide is a colorless oil that is an extremely 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.

Tests

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. [3]

Related Research Articles

<span class="mw-page-title-main">Ether</span> Organic compounds made of alkyl/aryl groups bound to oxygen (R–O–R)

In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula R−O−R′, where R and R′ represent the alkyl or aryl groups. Ethers can again be classified into two varieties: if the alkyl or aryl groups are the same on both sides of the oxygen atom, then it is a simple or symmetrical ether, whereas if they are different, the ethers are called mixed or unsymmetrical ethers. A typical example of the first group is the solvent and anaesthetic diethyl ether, commonly referred to simply as "ether". Ethers are common in organic chemistry and even more prevalent in biochemistry, as they are common linkages in carbohydrates and lignin.

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Solvent</span> Substance dissolving a solute resulting in a solution

A solvent is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for polar molecules and the most common solvent used by living things; all the ions and proteins in a cell are dissolved in water within the cell.

<span class="mw-page-title-main">Tetrahydrofuran</span> Cyclic chemical compound, (CH₂)₄O

Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water-miscible organic liquid with low viscosity. It is mainly used as a precursor to polymers. Being polar and having a wide liquid range, THF is a versatile solvent.

<span class="mw-page-title-main">Ethylene oxide</span> Cyclic compound (C2H4O)

Ethylene oxide is an organic compound with the formula C2H4O. It is a cyclic ether and the simplest epoxide: a three-membered ring consisting of one oxygen atom and two carbon atoms. Ethylene oxide is a colorless and flammable gas with a faintly sweet odor. Because it is a strained ring, ethylene oxide easily participates in a number of addition reactions that result in ring-opening. Ethylene oxide is isomeric with acetaldehyde and with vinyl alcohol. Ethylene oxide is industrially produced by oxidation of ethylene in the presence of silver catalyst.

<span class="mw-page-title-main">Epoxide</span> Organic compounds with a carbon-carbon-oxygen ring

In organic chemistry, an epoxide is a cyclic ether, where the ether forms a three-atom ring: two atoms of carbon and one atom of oxygen. This triangular structure has substantial ring strain, making epoxides highly reactive, more so than other ethers. They are produced on a large scale for many applications. In general, low molecular weight epoxides are colourless and nonpolar, and often volatile.

<span class="mw-page-title-main">Diethyl ether</span> Organic chemical compound

Diethyl ether, or simply ether, is an organic compound in the ether class with the formula C4H10O or (C2H5)2O, sometimes abbreviated as Et2O. It is a colourless, highly volatile, sweet-smelling, extremely flammable liquid. It is commonly used as a solvent in laboratories and as a starting fluid for some engines. It was formerly used as a general anesthetic, until non-flammable drugs were developed, such as halothane. It has been used as a recreational drug to cause intoxication.

In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. The reverse of disproportionation, such as when a compound in an intermediate oxidation state is formed from precursors of lower and higher oxidation states, is called comproportionation, also known as synproportionation.

<i>tert</i>-Butyl alcohol Chemical compound

tert-Butyl alcohol is the simplest tertiary alcohol, with a formula of (CH3)3COH (sometimes represented as t-BuOH). Its isomers are 1-butanol, isobutanol, and butan-2-ol. tert-Butyl alcohol is a colorless solid, which melts near room temperature and has a camphor-like odor. It is miscible with water, ethanol and diethyl ether.

<i>n</i>-Butyllithium Chemical compound

n-Butyllithium C4H9Li (abbreviated n-BuLi) is an organolithium reagent. It is widely used as a polymerization initiator in the production of elastomers such as polybutadiene or styrene-butadiene-styrene (SBS). Also, it is broadly employed as a strong base (superbase) in the synthesis of organic compounds as in the pharmaceutical industry.

<span class="mw-page-title-main">Organic peroxides</span> Organic compounds of the form R–O–O–R’

In organic chemistry, organic peroxides are organic compounds containing the peroxide functional group. If the R′ is hydrogen, the compounds are called hydroperoxides, which are discussed in that article. The O−O bond of peroxides easily breaks, producing free radicals of the form RO. Thus, organic peroxides are useful as initiators for some types of polymerization, such as the acrylic, unsaturated polyester, and vinyl ester resins used in glass-reinforced plastics. MEKP and benzoyl peroxide are commonly used for this purpose. However, the same property also means that organic peroxides can explosively combust. Organic peroxides, like their inorganic counterparts, are often powerful bleaching agents.

<span class="mw-page-title-main">Ethyl sulfate</span> Chemical compound

Ethyl sulfate, also known as sulfovinic acid, is an organic chemical compound used as an intermediate in the production of ethanol from ethylene. It is the ethyl ester of sulfuric acid.

<span class="mw-page-title-main">Enol ether</span> Class of chemical compounds

In organic chemistry an enol ether is an alkene with an alkoxy substituent. The general structure is R2C=CR-OR where R = H, alkyl or aryl. A common subfamily of enol ethers are vinyl ethers, with the formula ROCH=CH2. Important enol ethers include the reagent 3,4-dihydropyran and the monomers methyl vinyl ether and ethyl vinyl ether.

Dibutyl ether is a chemical compound belonging to the ether family with the molecular formula of C
8
H
18
O
. It is colorless, volatile, and flammable liquid and has peculiar ethereal smell.

<span class="mw-page-title-main">Hydroperoxide</span> Class of chemical compounds

Hydroperoxides or peroxols are compounds of the form ROOH, which contain the hydroperoxy functional group (–OOH). The hydroperoxide anion and the neutral hydroperoxyl radical (HOO·) consist of an unbond hydroperoxy group. When R is organic, the compounds are called organic hydroperoxides. Such compounds are a subset of organic peroxides, which have the formula ROOR. Organic hydroperoxides can either intentionally or unintentionally initiate explosive polymerisation in materials with unsaturated chemical bonds.

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<span class="mw-page-title-main">Sulfonmethane</span> Chemical compound

Sulfonmethane is a chemical compound first synthesized by Eugen Baumann in 1888 and introduced as a hypnotic drug by Alfred Kast later on, but now superseded by newer and safer sedatives. Its appearance is either in colorless crystalline or powdered form. In United States, it is scheduled as a Schedule III drug in the Controlled Substance Act.

<span class="mw-page-title-main">Methyltrichlorosilane</span> Chemical compound

Methyltrichlorosilane, also known as trichloromethylsilane, is a monomer and organosilicon compound with the formula CH3SiCl3. It is a colorless liquid with a sharp odor similar to that of hydrochloric acid. As methyltrichlorosilane is a reactive compound, it is mainly used a precursor for forming various cross-linked siloxane polymers.

<span class="mw-page-title-main">Oxygen compounds</span>

The oxidation state of oxygen is −2 in almost all known compounds of oxygen. The oxidation state −1 is found in a few compounds such as peroxides. Compounds containing oxygen in other oxidation states are very uncommon: −12 (superoxides), −13 (ozonides), 0, +12 (dioxygenyl), +1, and +2.

<span class="mw-page-title-main">Ethyl hydroperoxide</span> Chemical compound

Ethyl hydroperoxide is the organic compound with the formula CH3CH2OOH. It is a colorless liquid that is miscible with water and diethyl ether.

References

  1. 1 2 Milas, Nicholas A.; Peeler, Robert L.; Mageli, Orville L. (1954). "Organic Peroxides. XIX. α-Hydroperoxyethers and Related Peroxides". Journal of the American Chemical Society. 76 (9): 2322–2325. doi:10.1021/ja01638a012.
  2. A. Rieche, R. Meister (1936). "Modellversuche zur Autoxidation der Äther". Angewandte Chemie (in German). 49 (5): 101–103. Bibcode:1936AngCh..49..101R. doi:10.1002/ange.19360490502.
  3. "Peroxide Forming Solvents". Sigma-Aldrich. Retrieved 2014-07-09.