An Improved Catalytic Performance of Fe(III)-promoted NHPI in the Oxidation of Hydrocarbons…
7. Dhakshinamoorthy A, Alvaro M, Garcia H (2012) Aerobic oxida-
Production of CHHP and EBHP generally increased with
an increase in concentration of the NHPI catalyst, but kinetics
as shown in Fig. 5. In particular, the rate of formation of EBHP
was below frst order with respect to NHPI at a large fraction of
ethylbenzene in the reaction solution. This indicates that more
the NHPI catalyzed oxidation (lower part in Scheme 1). The
auto-oxidation route must be especially important for oxida-
tion of ethylbenzene without solvent as far as concentration
of NHPI was very small at the beginning of the oxidation.
Accumulated with time EBHP raised the solubility of NHPI,
so that the NHPI catalyzed route became predominant over
auto-oxidation in the formation of the hydroperoxide. As a
result, the selectivity to EBHP determined after 5 h oxidation
was rather high (Fig. 2). This indicates that EBHP remains
stable in the presence of Fe(III) salt even if the NHPI catalyzed
reaction was accompanied by chain auto-oxidation.
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4 Conclusion
Fe(III) salts manifest themselves as an efective promoter
in the NHPI-catalyzed peroxidation of hydrocarbons, and
NHPI in combination with Fe(acac)3 or Fe(benz)3 allows the
oxidation of cyclohexene and ethylbenzene to corresponding
hydroperoxides to be successfully performed at a lower tem-
perature. Moreover, unlike most of existing auto-oxidation
initiators, Fe(III) salts do not worsen the selectivity to perox-
ide. Such an efcacy is probably connected with the ability
of Fe(III) to generate PINO from NHPI but to be inert to the
hydroperoxide products.
14. Gao B, Bi C (2018) Some catalytic characteristics of composi-
tional catalysts of immobilized N-hydroxyphthalimide and metal
salts in aerobic oxidation of 1-phenylethanol. Catal Commun
115:6–11
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Acknowledgements We are thankful to Dr. T.V. Larina for UV–Vis
spectroscopy. This work was supported by budget project No 0303-
2016-0006 for Boreskov Institute of Catalysis.
18. Faraji AR, Ashouri F, Hekmatian Z, Heydari S, Mosazadeh S
(2019) Organosuperbase dendron manganese complex grafted
on magnetic nanoparticles; heterogeneous catalyst for green and
selective oxidation of ethylbenzene, cyclohexene and oximes by
molecular oxygen. Polyhedron 157:90–106
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