Decomposition of cyclohexyl hydroperoxide under the action of chromium and molybdenum compounds

Пустарнакова, Г. Ф.; Solyanikov, V. M.; Денисов, Е. Т.

doi:10.1007/bf00927458

Cited by 1 publication

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“…Although the total installed capacity worldwide is around 7 million tons per year of KA oil, very little is known about the selective decomposition of cyclohexyl hydroperoxide to cyclohexanone as the sole product. , In the last several decades, a number of papers were published concerning the decomposition of secondary alkyl hydroperoxides to a mixture of the corresponding alcohols and ketones, mainly focused on the radical mechanism. ,− Very recently, investigations with several vanadium complexes were published . Herein, the cyclohexane was oxidized by tert -butyl hydroperoxide under microwave irradiation to the ketone and alcohol in different ratios.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Mono- and Dinuclear Vanadium Complexes and Their Reactivity toward Dehydroperoxidation of Alkyl Hydroperoxides

Schmidt¹,

Hermsen

Röminger

et al. 2017

Inorg. Chem.

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Several vanadium(V) complexes with either dipic-based or Schiff base ligands were synthesized. The complexes were fully characterized by elemental analysis, IR, H,C, and V NMR spectroscopy, as well as mass spectrometry and X-ray diffraction. Furthermore, they were tested toward their catalytic deperoxidation behavior and a significant difference between 4-heptyl hydroperoxide and cyclohexyl hydroperoxide was observed. In the case of 4-heptyl hydroperoxide, the selectivity toward the corresponding ketone was higher than with cyclohexyl hydroperoxide. DFT calculations performed on the vanadium complex showed that selective decomposition of secondary hydroperoxides with vanadium(V) to yield the corresponding ketone and water is indeed energetically feasible. The computed catalytic path, involving cleavage of the O-O bond, hydrogen transfer, release of ketone/water, and finally addition of hydroperoxide, can proceed without the generation of radical species.

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