Effect of Transition Metal Compounds on the Cyclohexene Oxidation Catalyzed by N-Hydroxyphthalimide Full article
| Journal |
Kinetics and Catalysis
ISSN: 0023-1584 , E-ISSN: 1608-3210 |
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| Output data | Year: 2018, Volume: 59, Number: 6, Pages: 735-743 Pages count : 9 DOI: 10.1134/S0023158418060083 | ||
| Tags | cyclohexene, autoxidation, N-hydroxyphthalimide, transition metal compounds | ||
| Authors |
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| Affiliations |
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Funding (1)
| 1 | Federal Agency for Scientific Organizations | 0303-2016-0006 (V.44.1.6) |
Abstract:
N-Hydroxyphthalimide (NHPI) is an efficient organic catalyst in the oxidation reactions of
organic compounds occurring via a radical mechanism, often used together with redox-active ions or transition metal complexes. In this work the catalytic action of NHPI is studied together with Cu(II), Fe(III), and
Mo(VI) compounds in the reaction of aerobic oxidation of cyclohexene in an acetonitrile solution at 60°C. It
was found that iron(III) benzoate accelerates the reaction by rapidly generating the active form of the
phthalimide-N-oxyl radical (PINO) catalyst, but does not cause decomposition of the hydroperoxide. The
oxidation product is 2-cyclohexenyl hydroperoxide formed with a selectivity of 85% at a cyclohexene conversion of 50%. Copper(II) acetate initiates oxidation and is capable of catalyzing the radical decomposition of
the hydroperoxide and secondary oxidation of allyl oxygenates. When reaching a cyclohexene conversion
close to 80%, the overall selectivity to the main products, 2-cyclohexenyl hydroperoxide and 2-cyclohexen1-on, was 70%. The addition of iron(III) and molybdenum(VI) compounds led to the intensive generation of
hydroperoxide and its activation as an electrophilic reactant capable of cyclohexene epoxidation. As a result
of the use of the multifunctional three-component NHPI–Mo(VI)–Fe(III) catalyst, cyclohexene oxidation
by molecular oxygen occurred with the formation of epoxycyclohexane. The selectivity to the products of
cyclohexene epoxidation was close to 50%, which is a value expected from theory.
Cite:
Kuznetsova L.I.
, Kuznetsova N.I.
, Yakovina O.A.
, Zudin V.N.
, Bal’zhinimaev B.S.
Effect of Transition Metal Compounds on the Cyclohexene Oxidation Catalyzed by N-Hydroxyphthalimide
Kinetics and Catalysis. 2018. V.59. N6. P.735-743. DOI: 10.1134/S0023158418060083 WOS Scopus РИНЦ ANCAN OpenAlex
Effect of Transition Metal Compounds on the Cyclohexene Oxidation Catalyzed by N-Hydroxyphthalimide
Kinetics and Catalysis. 2018. V.59. N6. P.735-743. DOI: 10.1134/S0023158418060083 WOS Scopus РИНЦ ANCAN OpenAlex
Original:
Кузнецова Л.И.
, Кузнецова Н.И.
, Яковина О.А.
, Зудин В.Н.
, Бальжинимаев Б.С.
Влияние соединений переходных металлов на катализируемую N-гидроксифталимидом реакцию окисления циклогексена
Кинетика и катализ. 2018. Т.59. №6. С.694-703. DOI: 10.1134/s0453881118060114 РИНЦ OpenAlex
Влияние соединений переходных металлов на катализируемую N-гидроксифталимидом реакцию окисления циклогексена
Кинетика и катализ. 2018. Т.59. №6. С.694-703. DOI: 10.1134/s0453881118060114 РИНЦ OpenAlex
Dates:
| Submitted: | Mar 23, 2018 |
| Published print: | Nov 1, 2018 |
| Published online: | Mar 4, 2019 |
Identifiers:
| Web of science: | WOS:000460765200006 |
| Scopus: | 2-s2.0-85062634036 |
| Elibrary: | 38705136 |
| Chemical Abstracts: | 2019:795069 |
| Chemical Abstracts (print): | 172:539206 |
| OpenAlex: | W2920622330 |