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Autoxidation of Ethers to Peroxides and Hydroperoxides

Autoxidation of Ethers to Peroxides and Hydroperoxides

Ethers represent a class of chemical compounds that become more dangerous with prolonged storage because they tend to form explosive peroxides when standing in the air. Autoxidation is the spontaneous oxidation of a compound in air. In the presence of oxygen, ethers slowly oxidize to form hydroperoxides and dialkyl peroxides.

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.

Preparation of Epoxides

Preparation of Epoxides

Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy...

Regioselectivity of Electrophilic Additions-Peroxide Effect

Regioselectivity of Electrophilic Additions-Peroxide Effect

In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.

Oxidative Cleavage of Alkenes: Ozonolysis

Oxidative Cleavage of Alkenes: Ozonolysis

In ozonolysis, ozone is used to cleave a carbon–carbon double bond to form aldehydes and ketones, or carboxylic acids, depending on the work-up.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.

Oxidation of Phenols to Quinones

Oxidation of Phenols to Quinones

In the presence of oxidizing agents, phenols are oxidized to quinones. Quinones can be easily reduced back to phenols using mild reducing agents. The electron-donating hydroxyl group enhances the reactivity of the aromatic ring, enabling oxidation of the ring even in the absence of an α hydrogen.
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...

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Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

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Gas phase structures of peroxides: experiments and computational problems.

Heinz Oberhammer¹

¹Institut für Physikalische und Theoretische Chemie, Universität Tübingen, Auf der Morgenstelle 8, Tübingen (Germany). heinz.oberhammer@uni-tuebingen.de.

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry

|December 6, 2014

Summary

This summary is machine-generated.

Gas-phase structures of organic and inorganic peroxides reveal significant variation in O-O bond lengths and dihedral angles. Computational chemistry methods often struggle to accurately predict these experimental structures, particularly for challenging molecules like dimethoxydioxane and fluorine dioxide.

Keywords:

conformational analysis gas electron diffraction microwave spectroscopy peroxides quantum chemical calculations

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Area of Science:

Physical Chemistry
Computational Chemistry
Spectroscopy

Background:

Peroxides (X-O-O-X and X-O-O-X') are crucial in various chemical processes.
Understanding their gas-phase structures is essential for predicting reactivity and properties.
Experimental techniques like gas electron diffraction and microwave spectroscopy provide accurate structural data.

Purpose of the Study:

To review and discuss experimentally determined gas-phase structures of organic and inorganic peroxides.
To highlight discrepancies between experimental data and computational chemistry predictions.
To identify specific peroxides that pose challenges for theoretical modeling.

Main Methods:

Compilation and analysis of existing experimental data from gas electron diffraction (GED).
Review of experimental data obtained via microwave spectroscopy (MW).
Comparison of experimental structural parameters (O-O bond length, dihedral angle) with computational results.

Main Results:

Significant variation in O-O bond lengths (1.481(8) Å in Me3SiOOSiMe3 to 1.214(2) Å in FOOF) and dihedral angles (0° to near 180°) observed across different peroxides.
Certain peroxides, such as dimethoxydioxane (MeO-OMe) and fluorine dioxide (FO-OF), present substantial challenges for quantum chemistry methods.
For MeO-OMe, only about half of over 100 computational methods correctly predict the double-minimum torsional potential around the O-O bond.
For FO-OF, fewer than 200 computational methods accurately reproduce O-O and O-F bond lengths within ±0.02 Å.

Conclusions:

Experimental gas-phase structures of peroxides exhibit diverse geometries.
Current computational chemistry methods demonstrate limitations in accurately predicting the structures of some organic and inorganic peroxides.
Further development of theoretical models is needed to improve the prediction accuracy for challenging peroxide systems.