Abstract

Oxidations of phenylacetic acid to benzaldehyde, benzyl alcohol to benzaldehyde, and benzaldehyde to benzoic acid have been observed, in water as the solvent and using only copper(II) chloride as the oxidant. The reactions are performed at 250°C and 40 bar, conditions that mimic hydrothermal reactions that are geochemically relevant. Speciation calculations show that the oxidizing agent is not freely solvated copper(II) ions, but complexes of copper(II) with chloride and carboxylate anions. Measurements of the reaction stoichiometries and also of substituent effects on reactivity allow plausible mechanisms to be proposed. These oxidation reactions are relevant to green chemistry in that they proceed in high chemical yield in water as the solvent and avoid the use of toxic heavy metal oxidizing reagents.

Original languageEnglish (US)
Pages (from-to)12159-12165
Number of pages7
JournalJournal of Organic Chemistry
Volume80
Issue number24
DOIs
StatePublished - Nov 12 2015

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Oxidants
Oxidation
Copper
Benzyl Alcohol
Benzoic Acid
Water
Poisons
Heavy Metals
Stoichiometry
Anions
Chlorides
Ions
benzaldehyde
cupric chloride
phenylacetic acid

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Organic Oxidations Using Geomimicry. / Yang, Ziming; Hartnett, Hilairy; Shock, Everett; Gould, Ian.

In: Journal of Organic Chemistry, Vol. 80, No. 24, 12.11.2015, p. 12159-12165.

Research output: Contribution to journalArticle

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AB - Oxidations of phenylacetic acid to benzaldehyde, benzyl alcohol to benzaldehyde, and benzaldehyde to benzoic acid have been observed, in water as the solvent and using only copper(II) chloride as the oxidant. The reactions are performed at 250°C and 40 bar, conditions that mimic hydrothermal reactions that are geochemically relevant. Speciation calculations show that the oxidizing agent is not freely solvated copper(II) ions, but complexes of copper(II) with chloride and carboxylate anions. Measurements of the reaction stoichiometries and also of substituent effects on reactivity allow plausible mechanisms to be proposed. These oxidation reactions are relevant to green chemistry in that they proceed in high chemical yield in water as the solvent and avoid the use of toxic heavy metal oxidizing reagents.

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