Organic Process Research & Development 2002, 6, 394−400
Lecture Transcripts
Catalytic Oxidation of Acenaphthene and Its Derivatives in Acetic Acid
Tatiana V. Bukharkina,* Olga S. Grechishkina, Nikolai G. Digurov, and Ivan I. Kon’kov
Department of Process Chemistry of Carbon Materials, Faculty of Organic Compounds Technology, D. I. MendeleeV
UniVersity of Chemical Technology of Russia, 9 Miusskaya Square, Moscow, 125047, Russia
Abstract:
propagation. At first glance this scheme seems sensible and
self-consistent; however, it contradicts some of the experi-
mental findings. Should it be true, then the fractional yield
of different oxidation products would be independent of the
nature of the catalyst metal ion, as the products would rather
be formed in the chain propagation steps without the catalyst
participation. Nevertheless, it is noted in ref 1, p 118, that
in the ethyl benzene oxidation in acetic acid in the presence
of Co bromide catalyst mainly acetophenone is formed, and
in the presence of Mn bromide catalyst the main product is
benzoic acid. We have found also that the oxidation of
acenaphthene and its derivatives in aliphatic acids in the
presence of Co-Br catalyst leads to acenaphthene quinone,
and in the presence of Mn-Br catalyst the main product is
naphthalic anhydride.2,3 These findings can be rationalised
if one assumes that the oxidation chain length is close to
unity and that the product composition is determined in the
interaction of a metal ion with a substrate. In this case the
metal ion is a true catalyst participating in a nearly every
act of the product formation and not just the initiator of a
radical generation. This conclusion is further confirmed by
the fact that in the oxidation of toluene in the presence of
transient metal ions the rates of initiation and product
accumulation are practically equal.4
In our opinion the concept of the nonchain mechanism
of acenaphthene oxidation is more to the point than that of
the radical-chain concept. Its application in developing the
processes of manufacturing acenaphthene quinone, naphthalic
anhydride, their derivatives, and naphthalene tetracarboxylic
acid allowed us to run the reactions under milder conditions
and obtain higher fractional yield.
Oxygen-containing products of the acenaphthene oxida-
tion are used in the manufacture of dyes, luminophores, and
thermostable polymers.5
The chemistry of formation of products of acenaphthene
oxidation in the presence of the catalyst containing both
manganese and cobalt bromides under batch conditions is
discussed. The main reaction products are acenaphthene
quinone, acenaphthenol-9, trans-acenaphthylene glycol, naph-
thalide, and naphthalic anhydride. The sequence of reactions
leading to the final products is established. It is shown that the
main oxidation product in the presence of the manganese-based
catalyst is naphthalic anhydride, and the main product in the
presence of the cobalt-based catalyst is acenaphthene quinone.
The process and engineering techniques providing for the high
overall and fractional yields of the desired products are
discussed.
Introduction
Liquid-phase air or oxygen oxidation of alkyl-substituted
aromatic hydrocarbons in the presence of a catalytic system
containing both cobalt and manganese salts and bromide
anion is a well-established method in organic process
industries for the production of various chemicals. As a
general rule, the kinetics and mechanisms of industrially
important reactions are subjected to a thorough investigation.
Then a generally accepted reaction concept is formed on the
basis of these studies. Such a concept allows predicting the
influence of different factors on a reaction course and product
composition. On our opinion, the above-mentioned oxidation
reactions constitute an exception from this usual practice. A
lot of journal and patent publications including comprehen-
sive Partenheimer review1 are devoted to the topic. According
to the opinion of the immense majority of investigators the
reaction proceeds by the radical-chain mechanism, where the
catalytic species (transient metal ion in its highest or lowest
oxidation state) participate in the initiation step and catalyse
hydroperoxide decomposition to radicals, thus causing
degenerate chain branching. The chain termination occurs
either by the quadratic recombination of peroxide radicals
or linearly on the metal ion. The interaction of peroxyl
(ROO•) or peracyl (R′C(O)OO•) radicals with the starting
hydrocarbon or reaction intermediates provides for the chain
Results and Discussion
The oxidation of acenaphthene by oxygen to naphthalic
anhydride in the presence of cobalt and manganese bromide
catalyst was studied earlier.3,4 The compositions of catalytic
(2) Kamiya, Y.; Kashima, M. J. Catal. 1972, 25, 326-372.
(3) Digurov, N. G.; Kon’kov, I. I.; Bukharkina, T. V. IzV. VuzoV. Khimiya i
Khim. Tekhnologiya 1990, 33, 43-47.
(4) Digurov, N. G.; Kon’kov, I. I.; Bukharkina, T. V. IzV. VuzoV. Khimiya i
Khim. Tekhnologiya 1990, 33, 48-52.
(5) Dashevskii, M. M. Atsenaphten [Acenaphthene]. Khimiya: Moscow, 1966;
459 pp.
* To whom correspondence should be addressed. Fax: +7 (095) 973 3136.
E-mail: htum@muctr.edu.ru.
(1) Parteheimer, W. Catal. Today 1995, 23, 69-158.
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Vol. 6, No. 4, 2002 / Organic Process Research & Development
10.1021/op0100448 CCC: $22.00 © 2002 American Chemical Society
Published on Web 06/19/2002