Meta-Chloroperoxybenzoic acid

Last updated
meta-Chloroperoxybenzoic acid
Meta-Chloroperoxybenzoic acid.svg
Meta-chloroperbenzoic-acid-Spartan-HF-6-31Gstar-3D-balls.png
Names
Preferred IUPAC name
3-Chlorobenzene-1-carboperoxoic acid
Other names
    • 3-Chloroperoxybenzoic acid
    • 3-Chloroperbenzoic acid
    • 3-Chlorobenzoperoxoic acid
    • meta-Chloroperoxybenzoic acid
    • m-Chloroperoxybenzoic acid
    • meta-Chloroperbenzoic acid
    • mCPBA
    • m-CPBA
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.012.111 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 213-322-3
PubChem CID
RTECS number
  • SD9470000
UNII
UN number 3106
  • InChI=1S/C7H5ClO3/c8-6-3-1-2-5(4-6)7(9)11-10/h1-4,10H X mark.svgN
    Key: NHQDETIJWKXCTC-UHFFFAOYSA-N X mark.svgN
  • InChI=1S/C7H5ClO3/c8-6-3-1-2-5(4-6)7(9)11-10/h1-4,10H
    Key: FQAWBGAIOYWONH-UHFFFAOYAN
  • ClC1=CC(C(OO)=O)=CC=C1
Properties
C7H5ClO3
Molar mass 172.56 g·mol−1
AppearanceWhite powder
Melting point 92 to 94 °C (198 to 201 °F; 365 to 367 K) decomposes
Acidity (pKa)7.57
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Oxidizing, corrosive, explosive
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-acid.svg GHS-pictogram-exclam.svg
Danger
H226, H314, H335
P210, P220, P233, P234, P240, P241, P242, P243, P260, P261, P264, P271, P272, P280, P301+P330+P331, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P310, P312, P321, P332+P313, P333+P313, P337+P313, P362, P363, P370+P378, P403+P233, P403+P235, P405, P411, P420, P501
Related compounds
Related compounds
peroxyacetic acid; peroxybenzoic acid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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meta-Chloroperoxybenzoic acid (mCPBA or mCPBA) is a peroxycarboxylic acid. It is a white solid often used widely as an oxidant in organic synthesis. mCPBA is often preferred to other peroxy acids because of its relative ease of handling. [1] mCPBA is a strong oxidizing agent that may cause fire upon contact with flammable material. [2]

Contents

Preparation and purification

mCPBA can be prepared by reacting m-chlorobenzoyl chloride with a basic solution of hydrogen peroxide, followed by acidification. [3]

It is sold commercially as a shelf-stable mixture that is less than 72% mCPBA, with the balance made up of m-chlorobenzoic acid (10%) and water. [1] The peroxyacid can be purified by washing the commercial material with a sodium hydroxide and potassium phosphate solution buffered at pH = 7.5. [2] [4] Peroxyacids are generally slightly less acidic than their carboxylic acid counterparts, so the acid impurity can be extracted if the pH is carefully controlled. The purified material is reasonably stable against decomposition if stored at low temperatures in a plastic container.

In reactions where the exact amount of mCPBA must be controlled, a sample can be titrated to determine the exact amount of active oxidant.

Reactions

The main areas of use are the conversion of ketones to esters (Baeyer-Villiger oxidation), epoxidation of alkenes (Prilezhaev reaction), conversion of silyl enol ethers to silyl α-hydroxy ketones (Rubottom oxidation), oxidation of sulfides to sulfoxides and sulfones, and oxidation of amines to produce amine oxides. The following scheme shows the epoxidation of cyclohexene with mCPBA.

Reaction of cyclohexene with mCPBA.png

The epoxidation mechanism is concerted: the cis or trans geometry of the alkene starting material is retained in the epoxide ring of the product. The transition state of the Prilezhaev reaction is given below: [5]

Mcpbaepoxidation-updated.png

The geometry of the transition state, with the peracid bisecting the C-C double bond, allows the two primary frontier orbital interactions to occur: πC=C (HOMO) to σ*O-O (LUMO) and nO (HOMO, regarded as a filled p orbital on a sp2 hybridized oxygen) to π*C=C (LUMO), corresponding, in arrow-pushing terms, to formation of one C-O bond and cleavage of the O-O bond and formation of the other C-O bond and cleavage of the C=C π bond.

Related Research Articles

Hydroboration–oxidation reaction is a two-step hydration reaction that converts an alkene into an alcohol. The process results in the syn addition of a hydrogen and a hydroxyl group where the double bond had been. Hydroboration–oxidation is an anti-Markovnikov reaction, with the hydroxyl group attaching to the less-substituted carbon. The reaction thus provides a more stereospecific and complementary regiochemical alternative to other hydration reactions such as acid-catalyzed addition and the oxymercuration–reduction process. The reaction was first reported by Herbert C. Brown in the late 1950s and it was recognized in his receiving the Nobel Prize in Chemistry in 1979.

<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">Enamine</span> Class of chemical compounds

An enamine is an unsaturated compound derived by the condensation of an aldehyde or ketone with a secondary amine. Enamines are versatile intermediates.

The 1,3-dipolar cycloaddition is a chemical reaction between a 1,3-dipole and a dipolarophile to form a five-membered ring. The earliest 1,3-dipolar cycloadditions were described in the late 19th century to the early 20th century, following the discovery of 1,3-dipoles. Mechanistic investigation and synthetic application were established in the 1960s, primarily through the work of Rolf Huisgen. Hence, the reaction is sometimes referred to as the Huisgen cycloaddition. 1,3-dipolar cycloaddition is an important route to the regio- and stereoselective synthesis of five-membered heterocycles and their ring-opened acyclic derivatives. The dipolarophile is typically an alkene or alkyne, but can be other pi systems. When the dipolarophile is an alkyne, aromatic rings are generally produced.

<span class="mw-page-title-main">Peroxy acid</span> Organic acid having a peroxide bond

A peroxy acid is an acid which contains an acidic –OOH group. The two main classes are those derived from conventional mineral acids, especially sulfuric acid, and the peroxy derivatives of organic carboxylic acids. They are generally strong oxidizers.

The Baeyer–Villiger oxidation is an organic reaction that forms an ester from a ketone or a lactone from a cyclic ketone, using peroxyacids or peroxides as the oxidant. The reaction is named after Adolf von Baeyer and Victor Villiger who first reported the reaction in 1899.

<span class="mw-page-title-main">Danishefsky Taxol total synthesis</span>

The Danishefsky Taxol total synthesis in organic chemistry is an important third Taxol synthesis published by the group of Samuel Danishefsky in 1996 two years after the first two efforts described in the Holton Taxol total synthesis and the Nicolaou Taxol total synthesis. Combined they provide a good insight in the application of organic chemistry in total synthesis.

<span class="mw-page-title-main">Shi epoxidation</span>

The Shi epoxidation is a chemical reaction described as the asymmetric epoxidation of alkenes with oxone and a fructose-derived catalyst (1). This reaction is thought to proceed via a dioxirane intermediate, generated from the catalyst ketone by oxone. The addition of the sulfate group by the oxone facilitates the formation of the dioxirane by acting as a good leaving group during ring closure. It is notable for its use of a non-metal catalyst and represents an early example of organocatalysis.

The Rubottom oxidation is a useful, high-yielding chemical reaction between silyl enol ethers and peroxyacids to give the corresponding α-hydroxy carbonyl product. The mechanism of the reaction was proposed in its original disclosure by A.G. Brook with further evidence later supplied by George M. Rubottom. After a Prilezhaev-type oxidation of the silyl enol ether with the peroxyacid to form the siloxy oxirane intermediate, acid-catalyzed ring-opening yields an oxocarbenium ion. This intermediate then participates in a 1,4-silyl migration to give an α-siloxy carbonyl derivative that can be readily converted to the α-hydroxy carbonyl compound in the presence of acid, base, or a fluoride source.

<span class="mw-page-title-main">Bürgi–Dunitz angle</span>

The Bürgi–Dunitz angle is one of two angles that fully define the geometry of "attack" of a nucleophile on a trigonal unsaturated center in a molecule, originally the carbonyl center in an organic ketone, but now extending to aldehyde, ester, and amide carbonyls, and to alkenes (olefins) as well. The angle was named after crystallographers Hans-Beat Bürgi and Jack D. Dunitz, its first senior investigators.

In organic chemistry, the Ei mechanism, also known as a thermal syn elimination or a pericyclic syn elimination, is a special type of elimination reaction in which two vicinal (adjacent) substituents on an alkane framework leave simultaneously via a cyclic transition state to form an alkene in a syn elimination. This type of elimination is unique because it is thermally activated and does not require additional reagents, unlike regular eliminations, which require an acid or base, or would in many cases involve charged intermediates. This reaction mechanism is often found in pyrolysis.

<span class="mw-page-title-main">Prilezhaev reaction</span> Chemical reaction

The Prilezhaev reaction, also known as the Prileschajew reaction or Prilezhaev epoxidation, is the chemical reaction of an alkene with a peroxy acid to form epoxides. It is named after Nikolai Prilezhaev, who first reported this reaction in 1909. A widely used peroxy acid for this reaction is meta-chloroperoxybenzoic acid (m-CPBA), due to its stability and good solubility in most organic solvents. The reaction is performed in inert solvents (C6H14, C6H6, CH2Cl2, CHCl3, CCl4) between -10 and 60 °C with the yield of 60-80%.

Selenoxide elimination is a method for the chemical synthesis of alkenes from selenoxides. It is most commonly used to synthesize α,β-unsaturated carbonyl compounds from the corresponding saturated analogues. It is mechanistically related to the Cope reaction.

The Fleming–Tamao oxidation, or Tamao–Kumada–Fleming oxidation, converts a carbon–silicon bond to a carbon–oxygen bond with a peroxy acid or hydrogen peroxide. Fleming–Tamao oxidation refers to two slightly different conditions developed concurrently in the early 1980s by the Kohei Tamao and Ian Fleming research groups.

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

An oxaziridine is an organic molecule that features a three-membered heterocycle containing oxygen, nitrogen, and carbon. In their largest application, oxaziridines are intermediates in the industrial production of hydrazine. Oxaziridine derivatives are also used as specialized reagents in organic chemistry for a variety of oxidations, including alpha hydroxylation of enolates, epoxidation and aziridination of olefins, and other heteroatom transfer reactions. Oxaziridines also serve as precursors to nitrones and participate in [3+2] cycloadditions with various heterocumulenes to form substituted five-membered heterocycles. Chiral oxaziridine derivatives effect asymmetric oxygen transfer to prochiral enolates as well as other substrates. Some oxaziridines also have the property of a high barrier to inversion of the nitrogen, allowing for the possibility of chirality at the nitrogen center.

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

Magnesium monoperoxyphthalate (MMPP) is a water-soluble peroxy acid used as an oxidant in organic synthesis. Its main areas of use are the conversion of ketones to esters, epoxidation of alkenes, oxidation of sulfides to sulfoxides and sulfones, oxidation of amines to produce amine oxides, and in the oxidative cleavage of hydrazones.

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

Trifluoroperacetic acid is an organofluorine compound, the peroxy acid analog of trifluoroacetic acid, with the condensed structural formula CF
3
COOOH
. It is a strong oxidizing agent for organic oxidation reactions, such as in Baeyer–Villiger oxidations of ketones. It is the most reactive of the organic peroxy acids, allowing it to successfully oxidise relatively unreactive alkenes to epoxides where other peroxy acids are ineffective. It can also oxidise the chalcogens in some functional groups, such as by transforming selenoethers to selones. It is a potentially explosive material and is not commercially available, but it can be quickly prepared as needed. Its use as a laboratory reagent was pioneered and developed by William D. Emmons.

A phosphetane is a 4-membered organophosphorus heterocycle. The parent phosphetane molecule, which has the formula C3H7P, is one atom larger than phosphiranes, one smaller than phospholes, and is the heavy-atom analogue of azetidines. The first known phosphetane synthesis was reported in 1957 by Kosolapoff and Struck, but the method was both inefficient and hard to reproduce, with yields rarely exceeding 1%. A far more efficient method was reported in 1962 by McBride, whose method allowed for the first studies into the physical and chemical properties of phosphetanes. Phosphetanes are a well understood class of molecules that have found broad applications as chemical building blocks, reagents for organic/inorganic synthesis, and ligands in coordination chemistry.

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

Tellurophenes are the tellurium analogue of thiophenes and selenophenes.

<span class="mw-page-title-main">Epoxidation of allylic alcohols</span>

The epoxidation of allylic alcohols is a class of epoxidation reactions in organic chemistry. One implementation of this reaction is the Sharpless epoxidation. Early work showed that allylic alcohols give facial selectivity when using meta-chloroperoxybenzoic acid (m-CPBA) as an oxidant. This selectivity was reversed when the allylic alcohol was acetylated. This finding leads to the conclusion that hydrogen bonding played a key role in selectivity and the following model was proposed.

References

  1. 1 2 "3-Chloroperoxybenzoic acid". Organic Chemistry Portal.
  2. 1 2 Rao, A. Somasekar; Mohan, H. Rama; Charette, André (2005). "m‐Chloroperbenzoic Acid". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rc140.pub2. ISBN   0471936235.
  3. McDonald, Richard N.; Steppel, Richard N. & Dorsey, James E. (1970). "m-Chloroperbenzoic Acid". Organic Syntheses . 50: 15. doi:10.15227/orgsyn.050.0015 .
  4. Armarego, W. L. F.; Perrin, D. D. (1996). Purification of Laboratory Chemicals (4th ed.). Oxford: Butterworth-Heinemann. p. 145. ISBN   0-7506-3761-7.
  5. Li, Jie Jack (2003). Name Reactions: A Collection of Detailed Reaction Mechanisms (2nd ed.). Berlin, Heidelberg, New York: Springer. p. 323. ISBN   978-3-662-05338-6.