Biphasic Selective Oxidation of Cyclohexene with Dilute Aqueous Hydrogen Peroxide Using Phase Transfer Catalysts

Sana Salaria; Brianna N. Ruggiero; Adrien Deberghes; Linsey C. Seitz; Justin M. Notestein

doi:10.1021/acs.iecr.4c01988

Biphasic Selective Oxidation of Cyclohexene with Dilute Aqueous Hydrogen Peroxide Using Phase Transfer Catalysts

Sana Salaria, Brianna N. Ruggiero, Adrien Deberghes, Linsey C. Seitz, Justin M. Notestein^*

^*Corresponding author for this work

Chemical and Biological Engineering

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

Abstract

Hydrogen peroxide (H₂O₂) can be produced electrochemically as a replacement for conventional anthraquinone oxidation routes. From a sustainability perspective, it would be best to use it in chemical applications without further purification or added cosolvents. Here, cyclohexene oxidation is carried out with dilute (0.08-0.25 M) aqueous H₂O₂ containing sulfate salts as a probe of the direct use of electrochemically produced oxidants. As catalysts, tungsten and molybdenum salts were combined with ammonium and imidazolium phase transfer agents. A mixture of [CH₃(n-C₈H₁₇)₃N][H₂PO₄] and [Et₃NH][H₂PO₄] with Na₂WO₄ resulted in 95% overall yield of cyclohexene oxidation products─cyclohexene oxide (80%) and cyclohexene-1,2-diol (15%)─using a solution of 0.25 M H₂O₂ and 0.5 M K₂SO₄ in pH 5 water, with no added cosolvent. Results were validated with authentic electrochemically produced H₂O₂, demonstrating the practical applicability of this approach.

Original language	English (US)
Pages (from-to)	14074-14082
Number of pages	9
Journal	Industrial and Engineering Chemistry Research
Volume	63
Issue number	32
DOIs	https://doi.org/10.1021/acs.iecr.4c01988
State	Published - Aug 14 2024

Funding

The authors acknowledge support through the Center for Catalysis and Surface Science, Northwestern University. This work made use of the IMSERC MS and NMR facilities at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), and Northwestern University. Thanks go to Mr. Saman Shafaie (Mass Spectrometry Specialist, IMSERC) for recording MS-ESI samples.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Industrial and Manufacturing Engineering

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title = "Biphasic Selective Oxidation of Cyclohexene with Dilute Aqueous Hydrogen Peroxide Using Phase Transfer Catalysts",

abstract = "Hydrogen peroxide (H2O2) can be produced electrochemically as a replacement for conventional anthraquinone oxidation routes. From a sustainability perspective, it would be best to use it in chemical applications without further purification or added cosolvents. Here, cyclohexene oxidation is carried out with dilute (0.08-0.25 M) aqueous H2O2 containing sulfate salts as a probe of the direct use of electrochemically produced oxidants. As catalysts, tungsten and molybdenum salts were combined with ammonium and imidazolium phase transfer agents. A mixture of [CH3(n-C8H17)3N][H2PO4] and [Et3NH][H2PO4] with Na2WO4 resulted in 95\% overall yield of cyclohexene oxidation products─cyclohexene oxide (80\%) and cyclohexene-1,2-diol (15\%)─using a solution of 0.25 M H2O2 and 0.5 M K2SO4 in pH 5 water, with no added cosolvent. Results were validated with authentic electrochemically produced H2O2, demonstrating the practical applicability of this approach.",

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AU - Seitz, Linsey C.

AU - Notestein, Justin M.

PY - 2024/8/14

Y1 - 2024/8/14

N2 - Hydrogen peroxide (H2O2) can be produced electrochemically as a replacement for conventional anthraquinone oxidation routes. From a sustainability perspective, it would be best to use it in chemical applications without further purification or added cosolvents. Here, cyclohexene oxidation is carried out with dilute (0.08-0.25 M) aqueous H2O2 containing sulfate salts as a probe of the direct use of electrochemically produced oxidants. As catalysts, tungsten and molybdenum salts were combined with ammonium and imidazolium phase transfer agents. A mixture of [CH3(n-C8H17)3N][H2PO4] and [Et3NH][H2PO4] with Na2WO4 resulted in 95% overall yield of cyclohexene oxidation products─cyclohexene oxide (80%) and cyclohexene-1,2-diol (15%)─using a solution of 0.25 M H2O2 and 0.5 M K2SO4 in pH 5 water, with no added cosolvent. Results were validated with authentic electrochemically produced H2O2, demonstrating the practical applicability of this approach.

AB - Hydrogen peroxide (H2O2) can be produced electrochemically as a replacement for conventional anthraquinone oxidation routes. From a sustainability perspective, it would be best to use it in chemical applications without further purification or added cosolvents. Here, cyclohexene oxidation is carried out with dilute (0.08-0.25 M) aqueous H2O2 containing sulfate salts as a probe of the direct use of electrochemically produced oxidants. As catalysts, tungsten and molybdenum salts were combined with ammonium and imidazolium phase transfer agents. A mixture of [CH3(n-C8H17)3N][H2PO4] and [Et3NH][H2PO4] with Na2WO4 resulted in 95% overall yield of cyclohexene oxidation products─cyclohexene oxide (80%) and cyclohexene-1,2-diol (15%)─using a solution of 0.25 M H2O2 and 0.5 M K2SO4 in pH 5 water, with no added cosolvent. Results were validated with authentic electrochemically produced H2O2, demonstrating the practical applicability of this approach.

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Biphasic Selective Oxidation of Cyclohexene with Dilute Aqueous Hydrogen Peroxide Using Phase Transfer Catalysts

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