Organic Oxidations Using Geomimicry

Ziming Yang; Hilairy Hartnett; Everett Shock; Ian Gould

doi:10.1021/acs.joc.5b02109

Organic Oxidations Using Geomimicry

Research output: Contribution to journal › Article › peer-review

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 language	English (US)
Pages (from-to)	12159-12165
Number of pages	7
Journal	Journal of Organic Chemistry
Volume	80
Issue number	24
DOIs	https://doi.org/10.1021/acs.joc.5b02109
State	Published - Nov 12 2015

ASJC Scopus subject areas

Organic Chemistry

Access to Document

10.1021/acs.joc.5b02109

Cite this

@article{eb60434999904e3d849dcb221cb90521,

title = "Organic Oxidations Using Geomimicry",

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.",

author = "Ziming Yang and Hilairy Hartnett and Everett Shock and Ian Gould",

note = "Funding Information: The authors acknowledge helpful discussions with the members of the Hydrothermal Organic Geochemistry (H.O.G.) group at Arizona State University. We are thankful for National Science Foundation Grant OCE-1357243 for the financial support.",

year = "2015",

month = nov,

day = "12",

doi = "10.1021/acs.joc.5b02109",

language = "English (US)",

volume = "80",

pages = "12159--12165",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "24",

}

TY - JOUR

T1 - Organic Oxidations Using Geomimicry

AU - Yang, Ziming

AU - Hartnett, Hilairy

AU - Shock, Everett

AU - Gould, Ian

N1 - Funding Information: The authors acknowledge helpful discussions with the members of the Hydrothermal Organic Geochemistry (H.O.G.) group at Arizona State University. We are thankful for National Science Foundation Grant OCE-1357243 for the financial support.

PY - 2015/11/12

Y1 - 2015/11/12

N2 - 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.

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.

UR - https://www.scopus.com/pages/publications/84952803327

UR - https://www.scopus.com/pages/publications/84952803327#tab=citedBy

U2 - 10.1021/acs.joc.5b02109

DO - 10.1021/acs.joc.5b02109

M3 - Article

AN - SCOPUS:84952803327

SN - 0022-3263

VL - 80

SP - 12159

EP - 12165

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 24

ER -

Organic Oxidations Using Geomimicry

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this