Окиснення циклічних кетонів H2O2, каталізоване координаційними полімерами Cu(II) та Fe(III)
It has been shown that the oxidation of ketones – analogs of cyclohexanone – by hydrogen peroxide in the presence of Cu3(btc)2 (btc3- = 1,3,5-benzenetricarboxylate) occurred mainly by the radical mechanism, rather than by the Baeyer-Villiger reaction mechanism, and led to a mixture of products forme...
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| Опубліковано в: | Журнал органічної та фармацевтичної хімії |
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| Дата: | 2025 |
| Том: | 22 |
| Випуск: | 4 |
| Сторінки: | 25-35 |
| ISSN: | 2518-1548 |
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| Автори: | , , , , , , , |
| Формат: | Стаття |
| Мова: | Англійська |
| Опубліковано: |
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Репозитарії
Journal of Organic and Pharmaceutical Chemistry| _version_ | 1874364492619448320 |
|---|---|
| author | Abdullayev, Emir N. Mishura, Andrii M. Iermolenko, Ievgenii A. Lytvynenko, Anton S. Kolosov, Maksim O. Shvets, Olena G. Gavrilenko, Kostyantyn S. Kolotilov, Sergiy V. |
| author_facet | Abdullayev, Emir N. Mishura, Andrii M. Iermolenko, Ievgenii A. Lytvynenko, Anton S. Kolosov, Maksim O. Shvets, Olena G. Gavrilenko, Kostyantyn S. Kolotilov, Sergiy V. |
| author_institution_txt_mv | [
{
"author": "Emir N. Abdullayev",
"institution": "L.V. Pisarzhevsky Institute of Physical Chemistry of the National Academy of Sciences of Ukraine",
"orcid": ""
},
{
"author": "Andrii M. Mishura",
"institution": "L.V. Pisarzhevsky Institute of Physical Chemistry of the National Academy of Sciences of Ukraine",
"orcid": ""
},
{
"author": "Ievgenii A. Iermolenko",
"institution": "Enamine Ltd.; Institute of Organic Chemistry of the National Academy of Sciences of Ukraine",
"orcid": ""
},
{
"author": "Anton S. Lytvynenko",
"institution": " L. V. Pisarzhevsky Institute of Physical Chemistry of the National Academy of Sciences of Ukraine",
"orcid": ""
},
{
"author": "Maksim O. Kolosov",
"institution": "V. N. Karazin Kharkiv National University",
"orcid": "0009-0009-3509-5752"
},
{
"author": "Olena G. Shvets",
"institution": "V. N. Karazin Kharkiv National University",
"orcid": ""
},
{
"author": "Kostyantyn S. Gavrilenko",
"institution": "Enamine Ltd.; Taras Shevchenko National University of Kyiv",
"orcid": ""
},
{
"author": "Sergiy V. Kolotilov",
"institution": "L. V. Pisarzhevsky Institute of Physical Chemistry of the National Academy of Sciences of Ukraine",
"orcid": ""
}
] |
| author_orcid_str_mv | 0009-0009-3509-5752 |
| author_sort | Abdullayev, Emir N. |
| baseUrl_str | https://ophcj.nuph.edu.ua/oai |
| collection | OJS |
| container_end_page | 35 |
| container_issue | 4 |
| container_start_page | 25 |
| container_title | Журнал органічної та фармацевтичної хімії |
| container_volume | 22 |
| datestamp_date | 2026-08-23T15:46:26Z |
| description | It has been shown that the oxidation of ketones – analogs of cyclohexanone – by hydrogen peroxide in the presence of Cu3(btc)2 (btc3- = 1,3,5-benzenetricarboxylate) occurred mainly by the radical mechanism, rather than by the Baeyer-Villiger reaction mechanism, and led to a mixture of products formed due to the ring cleavage and reduction of the hydrocarbon chain length. Unlike aliphatic ketones, α-tetralone hardly underwent conversion in the reaction with H2O2 in the presence of HKUST-1, and the oxidation of the same ketone in the presence of Fe2(OH)3(btc) led to the formation of a number of products; among them, 1,4-naphthoquinone was dominant. |
| doi_str_mv | 10.24959/ophcj.24.315358 |
| first_indexed | 2025-07-23T04:43:34Z |
| format | Article |
| fulltext |
ISSN 2308-8303 (Print) / 2518-1548 (Online) 25
Original Research
http://ophcj.nuph.edu.ua
UDC 544.47:547-31/-39:54-39
E. N. Abdullayev1, A. M. Mishura1, I. A. Iermolenko2,3, A. S. Lytvynenko1,
M. A. Kolosov4, E. G. Shvets4, K. S. Gavrilenko2,5, S. V. Kolotilov1
1 L. V. Pisarzhevsky Institute of Physical Chemistry of the National Academy of Sciences of Ukraine,
31 Nauky ave., 03028 Kyiv, Ukraine
2 Enamine Ltd., 78 Winston Churchill str., 02094 Kyiv, Ukraine
3 Institute of Organic Chemistry of the National Academy of Sciences of Ukraine,
5, Academician Kukhar str., 02098 Kyiv, Ukraine
4 V. N. Karazin Kharkiv National University, School of Chemistry, 4 Svobody sq., 61022 Kharkiv, Ukraine
5 Taras Shevchenko National University of Kyiv, 12 Pavlo Skoropadskyi str., 01033 Kyiv, Ukraine
The Oxidation of Cyclic Ketones by H2O2 Catalyzed
by Cu(II) and Fe(III) Coordination Polymers
Abstract
It has been shown that the oxidation of ketones – analogs of cyclohexanone – by hydrogen peroxide in the presence of
Cu3(btc)2 (btc3– = 1,3,5-benzenetricarboxylate) occurred mainly by the radical mechanism, rather than by the Baeyer-Villiger
reaction mechanism, and led to a mixture of products formed due to the ring cleavage and reduction of the hydrocarbon
chain length. Unlike aliphatic ketones, α-tetralone hardly underwent conversion in the reaction with H2O2 in the presence of
HKUST-1, and the oxidation of the same ketone in the presence of Fe2(OH)3(btc) led to the formation of a number of prod-
ucts; among them, 1,4-naphthoquinone was dominant.
Keywords: catalytic oxidation; cyclic ketones; hydrogen peroxide; porous coordination polymers; copper(II); iron(III)
Е. Н. Абдуллаєв1, А. М. Мішура1, Є. А. Єрмоленко2,3, А. С. Литвиненко1, М. О. Колосов4, О. Г. Швець4,
К. С. Гавриленко2,5, С. В. Колотілов1
1 Інститут фізичної хімії ім. Л. В. Писаржевського Національної академії наук України,
просп. Науки, 31, м. Київ, 03028, Україна
2 ТОВ НВП «Єнамін», вул. Вінстона Черчилля, 78, м. Київ, 02094, Україна
3 Інститут органічної хімії Національної академії наук України,
вул. Академіка Кухаря, 5, м. Київ, 02660, Україна
4 Харківський національний університет імені В. Н. Каразіна,
майдан Свободи, 4, м. Харків, 61022, Україна
5 Київський національний університет імені Тараса Шевченка,
вул. Володимирська, 60, м. Київ, 01033, Україна
Окиснення циклічних кетонів H2O2, каталізоване координаційними полімерами Cu(II) та Fe(III)
Анотація
З’ясовано, що окиснення кетонів – аналогів циклогексанону – перекисом водню в присутності Cu3(btc)2 (btc3– =
1,3,5-бензолтрикарбоксилат) проходило переважно за радикальним механізмом, а не за механізмом реакції Баєра-
Віллігера, і призводило до суміші продуктів, що утворювалися внаслідок розщеплення кільця та зменшення довжини
вуглеводневого ланцюга. На відміну від аліфатичних кетонів, α-тетралон майже не вступав у реакцію з H2O2 в присут-
ності HKUST-1, а окиснення цього кетону в присутності Fe2(OH)3(btc) призводило до утворення низки продуктів, серед
яких домінував 1,4-нафтохінон.
Ключові слова: каталітичне окиснення; циклічні кетони; пероксид водню; пористі координаційні полімери; мідь(II);
залізо(III)
ISSN 2308-8303 (Print) / 2518-1548 (Online) 26
Журнал органічної та фармацевтичної хімії 2024, 22 (4)
Citation: Abdullayev, E. N.; Mishura, A. M.; Iermolenko, I. A.; Lytvynenko, A. S.; Kolosov, M. A.; Shvets, E. G.; Gavrilenko, K. S.;
Kolotilov, S. V. The oxidation of cyclic ketones by H2O2 catalyzed by Cu(II) and Fe(III) coordination polymers Journal of Organic and
Pharmaceutical Chemistry 2024, 22 (4), 25 – 35.
https://doi.org/10.24959/ophcj.24.315358
Received: 29 September 2024; Revised: 27 November 2024; Accepted: 10 December 2024
Copyright© 2024, E. N. Abdullayev, A. M. Mishura, I. A. Iermolenko, A. S. Lytvynenko, M. A. Kolosov, E. G. Shvets, K. S. Gavrilenko,
S. V. Kolotilov. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0).
Funding: The authors received no specific funding for this work.
Conflict of interests: The authors have no conflict of interests to declare.
■ Introduction
Oxidation reactions have been widely used
in both high-volume organic industry (for exam-
ple, manufacturing of dicarboxylic acids to pro-
duce plastics) and in fine organic synthesis for
the preparation of substances for pharmaceuti-
cals (active pharmaceutical ingredients, APIs)
and agrochemistry [1 – 3]. Many currently used
methods of organic compounds oxidation involve
the application of toxic catalysts based on plati-
num group metals [4, 5] or oxidizing agents,
which contain toxic metals (chromium, manga-
nese, osmium) and, hence, produce toxic wastes
[6 – 8]. Residual impurities formed from reagents
or catalysts can also cause contamination of the
products, which is critical for the production of
APIs. For example, the content of platinum me-
tals in the substance in some cases should not
exceed 10–6 % by weight [9]. The development of
new environmentally friendly methods for the
oxidation of organic compounds and studies of
the pathways of such processes are the tasks of
modern organic and physical chemistry.
The problem of generating large amounts of
waste during oxidation can be solved using en-
vironmentally friendly oxidants, such as hydro-
gen peroxide, which produces water and oxygen
(in the side reaction of decomposition of H2O2)
[10, 11]. At the same time, the widespread use
of hydrogen peroxide as an oxidant in organic
chemistry is limited because of the formation of
an unpredictable mixture of products due to mul-
tiple parallel processes and/or different mecha-
nisms, which can occur simultaneously [11, 12].
Nevertheless, there are many examples of the
successful use of H2O2 for the selective oxidation
of organic compounds in literature. High selec-
tivity is achieved when the reaction proceeds by
a single mechanism, unlike radical oxidation.
For example, the oxidation of ketones by the Baeyer-
Villiger mechanism in the presence of metal-con-
taining catalysts usually leads to lactones with
high yields [13 – 18]. In contrast, it has been found
that hydrogen peroxide can decompose in the pre-
sence of Cu3(btc)2 (btc3– is 3,5-benzenetricarboxylate),
forming OH radicals, which cause deep oxidation
of organic molecules and the formation of a mix-
ture of products [19]. It has been noted that ·OH ra-
dical is one of the most potent oxidants. Thus, the
study of the conditions under which the oxidation
reaction involving H2O2 proceeds by the Baeyer-
Villiger or radical mechanism is a problem of
high importance for selecting catalysts and de-
termining the scope of their application.
The use of porous coordination polymers (PCP)
of the 3d metals as catalysts is of particular in-
terest since these compounds may have high ca-
talytic performance in oxidation processes [12, 20],
and their selectivity can be associated with dif-
ferences in the sorption capacity of PCP with
respect to reagents [21 – 23]. In addition, the use
of PCP allows one to carry out reactions in a he-
terogeneous catalytic mode; this feature signifi-
cantly simplifies the purification of products from
the catalyst (transition metal ions) and makes
possible a simple reuse of the catalyst or trans-
fer of the reaction to the flow mode.
The aim of the study was to determine the
catalytic properties of two well-known PCPs –
1,3,5-benzenetricarboxylates (btc3–, also known
as an anion of trimesic acid) of copper(II)
(known as HKUST-1 [24]) and iron(III) [25] – in
the process of cyclic ketone oxidation with hyd-
rogen peroxide, and to determine their place among
the catalysts used for the oxidation of organic
compounds with hydrogen peroxide. The PCPs
Cu3(btc)2 and Fe(btc) are widely used and are ma-
nufactured and distributed under trademarks
Basolite® C300 and Basolite® F300, respectively.
Though the synthesis of the first compound is
simple and straightforward, the second one usu-
ally forms species with a high hydroxide content
and corresponds to formula Fe2(OH)3(btc). The use
of these PCP made it possible to compare the ca-
talytic activity of compounds containing metal
ions with different Lewis acidity [26] and oxida-
tive capacity [27].
The study used 1,2,3,4-tetrahydro-1-naphtha-
lenone (I, α-tetralone) as a carbocyclic ketone.
This compound is similar to industrially im-
portant cyclohexanone, but less volatile. It has
ISSN 2308-8303 (Print) / 2518-1548 (Online) 27
Journal of Organic and Pharmaceutical Chemistry 2024, 22 (4)
a simpler NMR spectrum and can be easily ana-
lyzed by chromatography without modification.
To reveal the peculiarities of oxidation of orga-
nic compounds containing several sensitive to oxi-
dation fragments, other ketones, including ethyl
4-oxocyclohexane-1-carboxylate (II), tert-butyl 4-oxo-
piperidine-1-carboxylate (III), tetrahydro-4H-
pyran-4-one (IV), were also studied (Figure 1).
■ Materials and methods
Cu3(btc)2 and Fe2(OH)3(btc) were obtained by
anodic dissolution of the corresponding metals
in a solution of 1,3,5-benzenetricarboxylic acid.
The method of obtaining Cu3(btc)2 was described
earlier [28]. Fe2(OH)3(btc) was obtained by mod-
ification of the known method [29]. Two prelimi-
narily cleaned iron rods with a diameter of 2 mm
were immersed in a beaker with the electrolyte
(0.5 g Bu4NBF4 and 0.2 g H3btc in 20 mL of etha-
nol) and 3 F of electricity per 1 mol of trimesic acid
was passed through the solution at a tempera-
ture of 32 ºC and a current density of 3.8 A dm–2.
The contact area of iron with the electrolyte was
107 mm2, current – 40 mA, electrolysis time –
2.2 h. During the reaction, the air was blown
through the electrolyte with a peristaltic pump
throughout the electrolysis and for an additional
2.5 h after its completion. The reaction mixture
was then stirred for 12 h. A beige precipitate fell
out during the process, which gradually turned
light red. After the process, the precipitate was
filtered off, washed with water, and dried at
70 – 80 ºC. The CHN analysis: calculated for
Fe2(OH)3(btc)(H2O)1,3: C9H8.6O10.3Fe2, %: C 27.50;
H 2.20; found C 27.60; H 2.52.
Powder diffraction patterns of the coordina-
tion polymers were measured using a DRON-3M
X-ray diffractometer, Cu-Kα radiation in the ran-
ge of angles 2θ = 5 – 80° with a step of 2θ = 0.05°.
The transmission electron microscopy studies
were performed using a PEM-125K SELMI mi-
croscope with an accelerating voltage of 100 kV.
Test samples in the form of alcohol suspensions
were applied to copper mesh covered with a film
of amorphous carbon and then dried. The CHN
analysis was performed using a CarloErba 1106
instrument. Nitrogen adsorption isotherms were
measured by the volumetric method using a
Sorptomatic 1990 instrument. Optical micro-
graphs were obtained using an XY-B2 trinocu-
lar microscope (Ningbo Sunny Instruments Co.,
Ltd., PRC) equipped with the attached PowerShot
G6 Canon camera in the mode of illumination
of the sample, the light source was a lamp built
into the microscope. The composition of the reac-
tion mixtures in the ketone oxidation processes
was determined by 1H NMR (a Bruker Advan-
ce 400 spectrometer), gas chromatography with
mass spectrometric detection (an Agilent 7890 A
chromatograph) and in individual experiments
with mass spectrometry (a Shimadzu GCMS QP-
2020 instrument using a column type HP-5 and
a direct sample inlet (DI) into the ion source).
Mass spectra of mixtures were obtained by
the direct introduction of samples into an ion
source (DI) on a Shimadzu GCMS QP-2020 in-
strument (ionization energy 70 eV). In addition
to DI, an attempt was made to chromatographi-
cally separate mixtures of reaction products fol-
lowed by the mass spectrometric detection of in-
dividual substances (GCMS) using a Shimadzu
GCMS QP‑2020 instrument, the carrier gas was
helium (99.999 % vol.), the sample solvent – ethyl
acetate, the sample volume – 1 μL, the injector
temperature – 150 ºC. Column: the stationary
phase was 5 % diphenylpolysiloxane, 95 % dime-
thylpolysiloxane; the length – 30 m; the inner dia-
meter – 0.25 mm; the thickness of the stationa-
ry phase film – 0.25 μm. Column temperature
control: the initial temperature was 35 ºC; the
initial isotherm time – 1 min; the temperature
gradient – 15 ºC min–1; the final temperature –
200 ºC; the time of the final isotherm – 5 min
(the detector temperature – 200 ºС; the ioniza-
tion energy – 70 eV). The NIST 17.0 database
was used to assign mass spectra.
Ketone oxidation experiments were perfor-
med according to the method similar to that de-
scribed in the literature [11]. A portion of the
appropriate PCP and a portion of a ketone (con-
centrations of reaction mixtures are indicated in
the Results and discussion section) were added
to the solution obtained by mixing acetonitrile
with aqueous hydrogen peroxide. In most cases
the solutions were prepared by mixing 40 mL of
acetonitrile with 7 mL of 35 % aqueous solution
of H2O2 (d = 1.1 g cm–1); the solution obtained con-
tained 1.7 M H2O2 and 5.9 M water. The resulting
O O
N
Boc
O
O
O
COOEt
I II III IV
Figure 1. Ketones studied in this work
ISSN 2308-8303 (Print) / 2518-1548 (Online) 28
Журнал органічної та фармацевтичної хімії 2024, 22 (4)
suspension was stirred at 25 °C for 24 h on a mag-
netic stirrer. After standing for a certain time,
50 mL of 1.1 M aqueous Na2SO3 solution was
added to the reaction mixture, the organic com-
pounds were extracted with ethyl acetate (2 por-
tions of 75 mL), the extracts were dried over sodium
sulfate, and the solvents were removed on a rota-
ry evaporator under reduced pressure. The reac-
tion products were analyzed as described above.
■ Results and discussion
The powder diffraction pattern of the
HKUST-1 sample obtained in this work was si-
milar to the diffraction pattern of the hydrated
form of copper(II) benzenetricarboxylate
Cu3(btc)2(H2O)3 · xH2O [30]. In contrast, there
were no distinct reflections on the diffraction pat-
tern of the coordination polymer Fe2(OH)3(btc),
which was a sign of a disordered structure.
The results obtained are in good agreement
with the literature – copper(II) 1,3,5-benzen-
etricarboxylate is almost always characterized
by a well-defined crystalline structure, while
iron(III) 1,3,5-benzenetricarboxylate, according
to X-ray diffraction, is usually referred to as a
material with low crystallinity or even amor-
phous one [31].
The TEM studies showed that the HKUST-1
sample mainly consisted of particles of ca.
0.5 μm size (Figure 2, a). The particle size of
Fe2(OH)3(btc), determined by optical microsco-
py, was 0.7 – 0.8 μm (Figure 2, c). Particles of
Fe2(OH)3(btc) were unstable in the electron beam
of TEM.
According to nitrogen adsorption data,
HKUST-1 was characterized by the value of
SBET = 1435 m2 g–1, the volume of micropores ac-
cording to the Dubinin-Radushkevich equation
VDR was equal to 0.533 cm3 g–1 [28]. In the case
of Fe2(OH)3(btc) the value of SBET was 520 m2 g–1,
the volume of micropores according to the Dubinin-
Radushkevich equation was VDR = 0.196 cm3 g–1.
The distribution of pores by size was calculat-
ed using the Saito-Foley method, the sample
Fe2(OH)3(btc) had dominating pores size with a
diameter of 1.0 nm, and there were pores with a
diameter of 1.2 – 1.4 nm. The values of SBET and
Figure 2. Images of HKUST-1 obtained by TEM (a) and optical microscopy (b), the image of Fe2(OH)3(btc),
obtained by optical microscopy (c) and nitrogen adsorption isotherm of PCP Fe2(OH)3(btc) (d)
ISSN 2308-8303 (Print) / 2518-1548 (Online) 29
Journal of Organic and Pharmaceutical Chemistry 2024, 22 (4)
VDR for HKUST-1 were close to the upper limit of
the range of sorption characteristics typical for
these PCPs [24], and in the case of Fe2(OH)3(btc)
SBET and VDR were significantly lower than the
values published for similar compounds [31].
At room temperature, α-tetralone (I) was not
oxidized by hydrogen peroxide in the presence
of HKUST-1 (0.1 M of a ketone, 1.7 M of H2O2,
1.5·10–2 M of HKUST-1) as the organic mixture
after the experiment contained almost pure star-
ting ketone (hereinafter the “effective concentra-
tion” of PCP in the reaction mixture is given as
the ratio of the amount of PCP expressed in mo-
les per 1 mol of a metal ion to the volume of the
solution. The PCP is suspended as a fine solid).
The interaction of I with hydrogen peroxide in
the presence of HKUST-1 for 3 h at 55 ºC also
did not lead to the formation of a significant
amount of oxidation products: according to the
gas chromatography and NMR methods, the re-
action mixture contained more than 97 % of the
initial ketone I, and among the minor oxidation
products a lactone resulting from the Baeyer-
Villiger oxidation could be identified.
Upon the oxidation of I (0.14 M) with hydro-
gen peroxide (1.7 M) in the presence of
Fe2(OH)3(btc) (1×10–3 M) at 25 °C in 5 h, ca.
5 – 8 % of quinone was found in the results of two
experiments, while about 90 % of the initial ke-
tone I remained unchanged. At the same time,
the formation of several products was detected
by gas chromatography. These products could be
attributed to the lactone or the products of the
compound I hydroxylation in the aromatic core,
the yield of each of these products did not exceed
2 %. Increasing the reaction time to 24 h had lit-
tle effect on the formation of oxidation products.
The oxidation of organic compounds in the
presence of PCPs occurs on the metal ions loca-
ted in pores and on the outer surface of the cata-
lyst particles. Clearly, not all metal ions are ac-
cessible to a substrate in this case. In order to
compare the outcome of the oxidation process
with the one that occurred in homogeneous con-
ditions, a similar reaction was carried out in the
presence of soluble copper(II) salt. In order to re-
veal if there was any contribution of Lewis aci-
dity of the metal ion (in contrast to possible redox
activity), the oxidation in the presence of AlCl3
was tested. It was found that in a similar reac-
tion of the oxidation of I in the presence of CuCl2
(0.1 M ketone, 1.7 M of H2O2, 1·10–2 M CuCl2,
24 h at 25 ºC), 95 % of the starting ketone and
about 3 % of quinone were found in the reaction
mixture, and when CuCl2 was replaced with an
equimolar amount of AlCl3, 98 % of the starting
material were found unchanged. It can be con-
cluded that the low yield in the oxidation of I in
the presence of HKUST-1 was associated with
the intrinsic low catalytic activity of Cu2+ ions
rather than their low accessibility. Moreover, the
low Lewis acidity does not cause such low cata-
lytic activity.
The oxidation of ketones II-IV in the presence
of HKUST-1 at room temperature led to the for-
mation of mixtures of products at the ketone/
H2O2 ratio of 1:2 (0.05 M of ketone, 0.1 M of H2O2,
5·10–3 M of HKUST-1), as well as at a 17-fold ex-
cess of H2O2 (0.1 M of II, 1.7 M H2O2, 1·10–2 M
of HKUST-1). The mass spectrum (direct injec-
tion of the sample into the ion source) of the
reaction mixture sample obtained by the oxida-
tion of II (0.1 M of II, 1.7 M of H2O2, 1·10–2 M of
HKUST-1 for 24 h at 25 ºC with further process-
ing) is shown in Figure 3 (a). The mass spec-
trum obtained corresponds to cyclic lactone IIa
(the Baeyer-Villiger oxidation product, Figure 4)
and other substances that could form upon its
oxidation by the radical mechanism, which led
to a decrease in the carbon chain length [32].
The 1H NMR spectrum of the reaction mixture
after the oxidation of II could also be interpre-
ted with the assumption that the resulting mix-
ture contained lactone IIa and the products of its
deeper oxidation (the products were determined
by comparing the positions of the signals with
the calculated values; the positions of the signals
in the NMR spectrum were calculated using
ACD Labs 10.08 software pack program), how-
ever the quantitative composition of the reaction
mixture could not be determined. The possible
oxidation products are shown in Figure 3 (b).
The GCMS analysis of the reaction mixture
obtained in the experiment of the compound II
oxidation revealed at least three other compounds
with longer retention times compared to II; mo-
lar fractions of II and these 3 products had the
ratio of 15:23:17:45. The mass spectrum of the
second compound in this series corresponded to
cyclohexanone IIe (Figure 3, b), which could be
formed due to the hydrolysis and the subsequent
decarboxylation of II. Taking into account the re-
sults of several experiments conducted under dif-
ferent conditions, it can be concluded that most
of the oxidation products decompose on the co-
lumn during chromatographic separation (the re-
lease of individual portions of water and CO2 at
certain intervals indicates such decomposition).
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At the same time, not all possible products, es-
pecially di- and polycarboxylic acids, gave peaks
in GCMS due to low volatility, the ability to re-
arrange and decarboxylation, as well as the ten-
dency to form multicharged ions. Thus, it can
be concluded that the oxidation of II resulted in
the formation of a mixture of products, in which
no predominant compounds could be isolated.
In a separate experiment, changes in the
composition of the reaction mixture in the pro-
cess of the oxidation of II (0.1 M) with hydrogen
peroxide (1.7 M) in the presence of 2·10–2 M of
HKUST-1 at 70 ºC were monitored. The amount
of lactone IIa could be estimated by the integral
intensity of peak at δ = 4.35 ppm, which corre-
sponded to the CH2 group near the oxygen atom
in the 7-membered lactone cycle, the amount of
acid IId – by the integral intensity of the signal
at δ = 3.65 ppm, which corresponded to the CH
group in the malonate fragment. Taking into
account that the positions of the signals of the
CH3 and CH2 groups in the -CO2C2H5 fragment
coincided in all oxidation products, the integral
intensity of the CH2 group (δ = 4.10 – 4.14) could
be considered as an indicator of the total con-
tent of unreacted II and all products of its oxi-
dation, except the products formed upon the hy-
drolysis of the ester and subsequent reactions.
The content of other possible reaction products
could not be considered in this calculation since
there were no signals in their spectra that did
not overlap each other. It can be noted that in
the period from 60 to 150 min at 70 ºC, the con-
tent of lactone IIa and acid IId remained almost
unchanged and was equal to 15 and 20-30 %, re-
spectively (Figure 4). When the reaction time
increased to 180 min, the content of lactone IIa
and acid IId increased to 22 and 50 %, respec-
tively (the percentage was calculated relative to
the total amount of all compounds in the mixture
having the ethyl group). The stable level of con-
centrations of IIa and IId in the reaction mix-
ture over a long period of time can be explained
by similar values of the rates of the formation of
these substances and subsequent oxidation and
agreed well with the above conclusion about the
formation of several oxidation products.
The formation of lactone IIa was a conse-
quence of the Baeyer-Villiger oxidation of the
ketone, which took place at the acidic sites of
the catalyst [4, 5]. Further oxidation occurred,
most likely, by the radical mechanism, and led
to a shortening of the hydrocarbon chain [12, 33].
At the same time, it should be noted that the for-
mation of carboxylic acids (such as IIc and IId)
could take place without the formation of lacto-
ne IIa and the product of its hydrolysis IIb as
intermediates.
(a)
O
OEtO EtO O
O
O
EtO O
OH
O
OH
+
EtO O
OH
O
OH
O
+
EtO O
O
HO
O
OH
+ +
OH2O2
II IIa IIb IIc IId IIe
(b)
Figure 3. The mass spectrum of the products of the oxidation of II by H2O2 in the presence of HKUST-1 (a) and the scheme showing
the oxidation of products II (b)
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Journal of Organic and Pharmaceutical Chemistry 2024, 22 (4)
The reaction of III with H2O2 in the presence
of HKUST-1 under the same conditions as in the
case of II (0.1 M of ketone, 1.7 M of H2O2, 1·10–2 M
of HKUST-1, 24 h at 25 ºC) led to the formation
of a mixture of products. The DI-mass spectrum
of this mixture contained several peaks. Some of
them could be assigned to 4-piperidinone and lac-
tone formed upon oxidation of III and elimination
of the tert-butoxycarbonyl group (Figure 5, b).
The NMR spectrum of the reaction mixture con-
tained signals that could be attributed to the
starting material, lactone, and products of the
subsequent oxidation with cleavage of the cycle,
similar to the oxidation of II. It was not possible
to reliably identify all the signals in the NMR
spectrum, but several characteristic features of
the spectrum could be noted. Thus, the spectrum
of the mixture of the reaction products contained
at least four signals of the tert-butyl group in
the range of δ = 1.44 – 1.53 ppm instead of one
signal of such a group in the starting ketone at
δ = 1.45 ppm and the similar group in lactone
at δ = 1.53 ppm (calculated value; signal of tert-
butanol formed upon the hydrolytic cleavage of
the Boc group was observed at δ = 1.28 ppm).
The increase in the number of signals was an indica-
tor of the formation of at least four compounds con-
taining the unchanged fragment -N–C(=O)–OtBu,
upon the oxidation of III. A signal at δ = 4.6 ppm
could be attributed to the CH2 group near the
O atom in a 7-membered lactone cycle. In addi-
tion, there were new signals at δ = 8.01, 7.25 and
5.14 ppm in the spectrum of the reaction mix-
ture, which could be attributed to nitrone IIIc
and its tautomer IIId.
The reaction of IV with H2O2 in the presence
of HKUST-1 under the same conditions led to
the formation of a mixture. The DI-mass spec-
trum of this mixture corresponded to the lactone
formed upon the Bayer-Villiger oxidation of IV
(Figure 6). However, the formation of the com-
pounds with a lower molecular weight could not
be excluded.
Higher conversions of II – IV in reactions with
H2O2 compared to the conversion of I may be ex-
plained by a higher reactivity of the aliphatic
ketones, which is possibly due to steric effects
(the presence of a bulk benzene ring near the
carbonyl group in aromatic ketones) or differen-
ces in the electronic structure of such ketones.
A similar dependence of the conversion on the
nature of the ketone was observed in the process
of oxidation of ketones by H2O2 in the presence
of tungsten-containing heteropolyacids [34].
The catalytic oxidation of ketones by H2O2 can
occur by the Baeyer-Villiger mechanism or by the
radical mechanism (Figure 7). However, a clear
dependence on the nature of the catalyst can-
not be found. Generally, it can be noted that the
use of mild Lewis acids like Sn-, Ge-containing
silicates, MoO3, or complexes of Pt(II) resulted
in the Baeyer-Villiger oxidation. The same effect
was also found in the case of strong Lewis acids like
AlCl3. All catalysts shown on Figure 7, which fa-
vored radical oxidation, contained redox-active
Figure 4. The change of 1H NMR spectra of the reaction mixture
in the process of oxidation of II (0.1 M) with hydrogen peroxide
(1.7 M) in the presence of 2·10–2 M of HKUST-1 at 70 ºC along
with the spectrum of the starting compound: (1) starting II,
(2) in 60 min, (3) in 90 min, (4) in 120 min, and (5) in 150 min
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sites. However, a potentially redox-active cata-
lyst Co(III) salen was found to catalyze the Baeyer-
Villiger oxidation (probably, as its redox poten-
tial falls out of the suitable range for generation
of radicals from H2O2) [15]. Notably, the Baeyer-
Villiger oxidation can be followed by the radical
oxidation [35] in the presence of the same cata-
lyst. The PCPs, studied herein, seem to be able to
catalyze the Baeyer-Villiger oxidation, but there
are evidences of radical oxidation pathway in the
presence of such catalysts.
Generally, soft Lewis acids are considered as
the most efficient catalysts for the Bayer-Villiger
oxidation [5, 36]. There are examples of the Bae-
yer-Villiger ketone oxidation catalyzed by coor-
dination compounds of Cu(II) [23, 37, 38] and
(a)
N
Boc
O
H2O2
HKUST-1
N
Boc
O
O
N
O
O
+
N
O
+
O
N
OH
O
+
III IIIa IIIb IIIc IIId
H
(b)
Figure 5. The mass spectrum of the products of oxidation of III by H2O2 in the presence of HKUST-1 (a) and the scheme showing products
of oxidation of III (b)
Figure 6. The mass spectrum of the products of oxidation
of IV by H2O2 in the presence of HKUST-1
O
O
O
Baeyer-Villiger
oxidation
AlCl3 [13]
MoO3 [17]
Ge- or Sn-silicates [16]
Al-containing zeolite beta [14]
Co(III)(salen) [15]
Pt(II) complex with diphosphine [18]
OH
O
HO
O
HO
O
OH
O
HO
O
OH
O
Deep oxidation
K6P2W18O62
K6P2Mo6W12O62
K7P2Mo5VW12O62 [44]
H3-2(x+y)MnxCoyPMo12O40 [45]
Cu2(btc)3 [this work]
Baeyer-Villiger oxidation followed by
thermally activated radical reaction
Titanium silicalite-1 [35]
Figure 7. The catalytic oxidation of ketones by H2O2 in the presence of different catalysts
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Journal of Organic and Pharmaceutical Chemistry 2024, 22 (4)
Fe(III) by oxygen [39]. Cu(OTf)2 was found to be
an efficient catalyst for the Baeyer-Villiger oxi-
dation of cyclic ketones by mCPBA [17]. Several
Fe- and Cu-containing systems were found to
be efficient catalysts of the Baeyer-Villiger oxi-
dation in the O2/benzaldehyde system, such as
Fe–Sn–O catalysts for the oxidation of cyclohex-
anone to ε-caprolactone [40], iron(III)-contain-
ing mesoporous silica (MCM-41) [41], a Cu-SiO2
catalyst with highly dispersed copper species
and various metal valences for the oxidation of
cyclohexanone to ε-caprolactone [42], a bifunc-
tional hybrid catalyst originated from copper
tetrasulfophthalocyanine (CuPcTs) and hydro-
talcite [43]
■ Conclusions
The oxidation of cyclohexanone analogs with
hydrogen peroxide in the presence of a porous
coordination polymer HKUST-1 led to the for-
mation of a mixture of products containing the
corresponding lactones (formed by the Baeyer-
Villiger process) and other compounds formed
by a deeper oxidation of the organic compounds
with cleavage of the ring and reduction of the
hydrocarbon chain length. Unlike aliphatic ke-
tones, α-tetralone underwent almost no conver-
sion in the reaction with H2O2 in the presence of
HKUST-1, and the oxidation of the same ketone
in the presence of Fe2(OH)3(btc) led to the for-
mation of a number of products with low yields.
Among them, 1,4-naphthoquinone was domi-
nant (in contrast to cyclic lactone – the expected
Baeyer-Villiger oxidation product). The oxida-
tion of ketones in the presence of the PCPs stud-
ied occurred mainly by the radical mechanism,
which can be explained by insufficient Lewis
acidity of Cu2+ and Fe3+ ions in the environment
of oxygen atoms.
■ References
1. Valange, S.; Vedrine, J. C. General and Prospective Views on Oxidation Reactions in Heterogeneous Catalysis. Catalysts 2018, 8 (10),
483. https://doi.org/10.3390/catal8100483.
2. Trusau, K. I.; Kirillova, M. V.; André, V. A.; Usevich, I.; Kirillov, A. M. Mild Oxidative Functionalization of Cycloalkanes Catalyzed by Novel
Dicopper(II) Cores. Mol. Catal. 2021, 503, 111401. https://doi.org/10.1016/j.mcat.2021.111401.
3. Tereshchenko, O. D.; Perebiynis, M. Y.; Knysh, I. V.; Vasylets, O. V.; Sorochenko, A. A.; Slobodyanyuk, E. Y.; Rusanov, E. B.; Borysov, O. V.;
Kolotilov, S. V.; Ryabukhin, S. V.; Volochnyuk, D. M. Electrochemical Scaled-up Synthesis of Cyclic Enecarbamates as Starting Materials for
Medicinal Chemistry Relevant Building Blocks. Adv. Synth. Catal. 2020, 362 (15), 3229 – 3242. https://doi.org/10.1002/adsc.202000450.
4. Strukul, G.; Scarso, A. Metal-Catalyzed Baeyer-Villiger Oxidations. In Applied Homogeneous Catalysis with Organometallic Compounds:
A Comprehensive Handbook in Four Volumes, Third Edition; B. Cornils, WA Herrmann, M. Beller, R. Paciello Eds., Wiley – VCH Verlag
GmbH & Co. KGaA, 2018, Chapter 29, pp 1485 – 1508. https://doi.org/10.1002/9783527651733.ch29.
5. Michelina, R. A.; Sgarbossa, P.; Scarso, A.; Strukul. G. The Baeyer – Villiger Oxidation of Ketones: A Paradigm for the Role of Soft Lewis
Acidity in Homogeneous Catalysis. Coord. Chem. Rev. 2010, 254 (5 – 6), 646 – 660. https://doi.org/10.1016/j.ccr.2009.09.014.
6. González-Núñez, M. E.; Mello, R.; Olmos, A.; Acerete, R.; Asensio, G. Oxidation of Alcohols to Carbonyl Compounds with CrO3·SiO2 in
Supercritical Carbon Dioxide. J. Org. Chem. 2006, 71 (3), 1039 – 1042. https://doi.org/10.1021/jo052137j.
7. Bridges, L.; Mohamed, R. A. M.; Khan, N. A.; Brusseau, M. L.; Carroll, K. C. Comparison of Manganese Dioxide and Permanganate as
Amendments with Persulfate for Aqueous 1,4-Dioxane Oxidation. Water 2020, 12 (11), 3061. https://doi.org/10.3390/w12113061.
8. Fujii, H.; Ogawa, R.; Jinbo, E.; Tsumura, S.; Nemoto, T.; Nagase, H. Novel Oxidation Reaction of Tertiary Amines with Osmium Tetroxide.
Synlett 2009, 14, 2341 – 2345. https://doi.org/10.1055/s-0029-1217811.
9. Guideline for elemental impurities (Doc. Ref. EMA/CHMP/ICH/353369/2013), Committee for Human Medicinal Products, European
Medicines Agency, Amsterdam, 2019.
10. Lee, J.; Lee, J. C. An Efficient Oxidation of Alcohols by Aqueous H2O2 with 1,3-Dibromo-5,5-Dimethylhydantoin. Lett. Org. Chem. 2018,
15 (10), 895 – 898. https://doi.org/10.2174/1570178615666180613080548.
11. Coelho, J. V.; Oliveira, L. C. A.; Moura, F. C. C.; de Souza, P. P.; Silva, C. A.; Batista, K. B.; da Silva, M. J. β-Pinene Oxidation by Hydrogen Peroxide
Catalyzed by Modified Niobium – MCM. Applied Catal. A: General 2012, 419 – 420, 215 – 220. https://doi.org/10.1016/j.apcata.2012.01.032.
12. Shul’pin, G. B.; Shul’pina, L. S. Oxidation of Organic Compounds with Peroxides Catalyzed by Polynuclear Metal Compounds. Catalysts
2021, 11 (2), 186. https://doi.org/10.3390/catal11020186.
13. Lei, Z.; Ma, G.; Wei, L.; Yang, Q.; Su, B. Clean Baeyer–Villiger Oxidation Using Hydrogen Peroxide as Oxidant Catalyzed by Aluminium
Trichloride in Ethanol. Catal. Lett. 2008, 124 (3-4), 330 – 333. https://doi.org/10.1007/s10562-008-9470-0.
14. Ohno, R.; Taniya, K.; Tsuruya, S.; Ichihashi, Y.; Nishiyama, S. Oxidation of Cyclohexane with Hydrogen Peroxide Over Zeolites with Vari-
ous Si/Al Ratios. Catal. Today 2013, 203, 60 – 65. https://doi.org/10.1016/j.cattod.2012.03.007.
15. Uchida, T.; Katsuki, T. Cationic Co(III)(salen)–Catalyzed Enantioselective Baeyer–Villiger Oxidation of 3–Arylcyclobutanones Using Hy-
drogen Peroxide as a Terminal Oxidant. Tetrahedron Lett. 2001, 42 (39), 6911 – 6914. https://doi.org/10.1016/S0040-4039(01)01445-9.
16. Xu, H.; Jiang, J.; Yang, B.; Wu, H.; Wu, P. Effective Baeyer – Villiger Oxidation of Ketones over Germanosilicates. Catal. Commun. 2014,
55, 83 – 86. https://doi.org/10.1016/j.catcom.2014.06.019.
17. Ma, Q.; Xing, W.; Xu, J.; Peng, X. Baeyer–Villiger Oxidation of Cyclic Ketones with Aqueous Hydrogen Peroxide Catalyzed by Transition
Metal Oxides. Catal. Commun. 2014, 53, 5 – 8. https://doi.org/10.1016/j.catcom.2014.04.017.
18. Frisone, M. D. T.; Pinna, F.; Strukul, G. Baeyer-Villiger oxidation of cyclic ketones with hydrogen peroxide catalyzed by cationic complexes of
platinum(II): selectivity properties and mechanistic studies. Organometallics 1993, 12 (1), 148 – 156. https://doi.org/10.1021/om00025a027.
19. Granato, T.; Testa, F.; Olivo. R. Catalytic Activity of HKUST-1 Coated on Ceramic Foam. Micropor. Mesopor. Mater. 2012, 153, 236 – 246.
https://doi.org/10.1016/j.micromeso.2011.12.055.
ISSN 2308-8303 (Print) / 2518-1548 (Online) 34
Журнал органічної та фармацевтичної хімії 2024, 22 (4)
20. Konnerth, H.; Matsagar, B. M. Chen, S. S.; Prechtl, M. H. G.; Shieh, F.-K.; Wu, K. C.-W. Metal – Organic Framework (MOF) – Derived
Catalysts for Fine Chemical Production Coord. Chem. Rev. 2020, 416, 213319. https://doi.org/10.1016/j.ccr.2020.213319.
21. Sotnik, S. A.; Gavrilenko, K. S.; Lytvynenko, A. S.; Kolotilov, S. V. Catalytic Activity of Copper(II) Benzenetricarboxylate (HKUST-1) in Re-
actions of Aromatic Aldehydes Condensation with Nitromethane: Kinetic and Diffusion Study. Inorg. Chim. Acta 2015, 426, 119 – 125.
https://doi.org/10.1016/j.ica.2014.11.018.
22. Lytvynenko, A. S.; Kolotilov, S. V.; Kiskin, M. A.; Cador, O.; Golhen, S.; Aleksandrov, G. G.; Mishura, A. M.; Titov, V. E.; Ouahab, L.; Ere-
menko, I. L.; Novotortsev, V. M. Redox-Active Porous Coordination Polymers Prepared by Trinuclear Heterometallic Pivalate Linking
with the Redox-Active Nickel(II) Complex: Synthesis, Structure, Magnetic and Redox Properties, and Electrocatalytic Activity in Organic
Compound Dehalogenation in Heterogeneous Medium. Inorg. Chem. 2014, 53 (10), 4970 – 4979. https://doi.org/10.1021/ic403167m.
23. Yurchenko, D. V.; Lytvynenko, A. S.; Abdullayev, E. N.; Peregon, N. V.; Gavrilenko, K. S.; Gorlova, A. O.; Ryabukhin, S. V.; Volochnyuk, D. M.;
Kolotilov, S. V. Catalytic oxidation of benzoins by hydrogen peroxide on nanosized HKUST-1: influence of substituents on the reaction
rates and DFT modeling of the reaction path. Molecules 2023, 28 (2), 747. https://doi.org/10.3390/molecules28020747.
24. Chowdhury, P.; Bikkina, C.; Meister, D.; Dreisbach, F.; Gumma, S. Comparison of Adsorption Isotherms on Cu-BTC Metal Organic Frameworks
Synthesized from Different Routes. Micropor. Mesopor. Mater. 2009, 117 (1 – 2), 406 – 413. https://doi.org/10.1016/j.micromeso.2008.07.029.
25. Hu, X.; Lou, X.; Li, C.; Ning, Y.; Liao, Y.; Chen, Q.; Mananga, E. S.; Shen, M.; Hua, B. Facile Synthesis of the Basolite F300 – like Nanoscale
Fe-BTC Framework and Its Lithium Storage Properties. RSC Adv. 2016, 6 (115), 114483 – 114490. https://doi.org/10.1039/C6RA22738D.
26. Misono, M.; Ochiai, E.; Saito, Y.; Yoneda, Y. A New Dual Parameter Scale for the Strength of Lewis Acids and Bases with the Evaluation
of their Softness. J. Inorg. Nucl. Chem. 1967, 29 (11), 2685 – 2691. https://doi.org/10.1016/0022-1902(67)80006-X.
27. Razavi, S. A. A.; Chen, W.; Zhou, H.-C.; Morsali, A. Tuning Redox Activity in Metal-Organic Frameworks: From Structure to Application.
Coord. Chem. Rev. 2024, 517, 216004. https://doi.org/10.1016/j.ccr.2024.216004.
28. Lagoshniak, D. A.; Mishura, A. M.; Kurmach, M. M.; Lytvynenko, A. S.; Grabovaya, N. V.; Gavrilenko, K. S.; Manoilenko, O. V.; Kolotilov, S. V.
Influence of the Structures of the Carboxylate Porous Coordination Polymers as Stationary Phases for Liquid Chromatography on the Sepa-
ration Efficiency of the Aniline Derivatives. Russ. J. Coord. Chem. 2020, 46 (7), 458 – 465. https://doi.org/10.1134/s1070328420070040.
29. Achmann, S.; Hagen, G.; Kita, J.; Malkowsky, I. M.; Kiener, C.; Moos, R. Metal-Organic Frameworks for Sensing Applications in the Gas
Phase. Sensors 2009, 9, 1574 – 1589. https://doi.org/10.3390/s90301574.
30. Schlichte, K.; Kratzke, T.; Kaskel, S. Improved Synthesis, Thermal Stability and Catalytic Properties of the Metal – Organic Framework
Compound Cu3(BTC)2 Micropor. Mesopor. Mater. 2004, 73 (1 – 2), 81 – 88. https://doi.org/10.1016/j.micromeso.2003.12.027.
31. Torres, N.; Galicia, J.; Plasencia, Y.; Cano, A.; Echevarría, F.; Desdin-Garcia. L. F. Implications of Structural Differences between Cu-BTC
and Fe-BTC on their Hydrogen Storage Capacity. Colloids Surf., A 2018, 549, 138 – 146. https://doi.org/10.1016/j.colsurfa.2018.04.016.
32. Hamann, H. J.; Bunge, A.; Liebscher, J. Reaction of Epoxyketones with Hydrogen Peroxide – Ethane-1,1-dihydroperoxide as a Surpris-
ingly Stable Product. Chem. Eur. J. 2008, 14 (23), 6849 – 6851. https://doi.org/10.1002/chem.200800932.
33. Ros, D.; Gianferrara, T.; Crotti, C.; Farnetti, E. Iron-Catalyzed Oxidation of 1-Phenylethanol and Glycerol with Hydrogen Per-
oxide in Water Medium: Effect of the Nitrogen Ligand on Catalytic Activity and Selectivity. Front. Chem. 2020, 8 (810), 1 – 13.
https://doi.org/10.3389/fchem.2020.00810.
34. Li, X.; Cao, R.; Lin, Q. Solvent – Free Baeyer–Villiger Oxidation with H2O2 as Oxidant Catalyzed by Multi-SO3H Functionalized Heteropoly-
anion – Based Ionic Hybrids. Catal. Commun. 2015, 63, 79 – 83. https://doi.org/10.1016/j.catcom.2014.12.028.
35. Cavani, F.; Raabova, K.; Bigi, F.; Quarantelli, C. A Rationale of the Baeyer–Villiger Oxidation of Cyclohexanone to ε-Caprolactone with Hy-
drogen Peroxide: Unprecedented Evidence for a Radical Mechanism Controlling Reactivity. Chem. Eur. J. 2010, 16 (43), 12962 – 12969.
https://doi.org/10.1002/chem.201001777.
36. Gorban, O.; Danilenko, I.; Nosolev, I.; Abdullayev, E.; Islamov, A.; Gavrilenko, K.; Doroshkevich, A.; Shvets, O.; Kolotilov, S. Impact of
chemical and physical modification of zirconia on structure, surface state, and catalytic activity in oxidation of α-tetralol. J. Nanopart.
Res., 2022, 24, 197. https://doi.org/10.1007/s11051-022-05566-5.
37. Bolm, C.; Schlingloff, G.; Weickhardt, K. Optically Active Lactones from a Baeyer–Villiger-Type Metal-Catalyzed Oxidation with Molecu-
lar Oxygen. Angew. Chem. Int. Ed. Engl. 1994, 33 (18), 1848 – 1849. https://doi.org/10.1002/anie.199418481.
38. Duc, D. X.; Nguyet, N. T. Microwave – Assisted Claisen – Schmidt Condensation Between Arylmethyl Ketones and Aryl Aldehydes Cata-
lyzed by Cu(OTf)2 under Solvent – Free Conditions: Synthesis of Chalcones. Vietnam J. Sci. Techn. 2020, 58 (6A), 1 – 9.
39. Cao, Q.; Yin, Q.; Chen, Q.; Dong, Z. B.; Han, B. H. Fluorinated Porous Conjugated Polyporphyrins through Direct C−H Arylation Poly-
condensation: Preparation, Porosity, and Use as Heterogeneous Catalysts for Baeyer – Villiger Oxidation. Chem. Eur. J. 2017, 23 (41),
9831 – 9837. https://doi.org/10.1002/chem.201700916.
40. Sun, J.; Zhu, Q.; Guo, X.; Jin, H.; He, G.; Ma, L.; Zhang, R.; Gu, Q.; Yang, S. Baeyer –Villiger Co – oxidation of Cyclohexanone with Fe – Sn
– O Catalysts in an O2 / Benzaldehyde System. Green Process. Synth. 2021, 10 (1), 677 – 686. https://doi.org/10.1515/gps-2021-0045.
41. Kawabata, T.; Ohishi, Y.; Itsuki, S.; Fujisaki, N.; Shishido, T.; Takaki, K.; Zhang, Q.; Wang, Y.; Takehira, K. Iron – containing MCM – 41 catalysts
for Baeyer – Villiger oxidation of ketones using molecular oxygen and benzaldehyde. J. Mol. Catal. A: Chem. 2005, 236 (1 – 2), 99 – 106.
https://doi.org/10.1016/j.molcata.2005.03.027.
42. Chen, L.; Liu, Y.; Chi, J.; Xiong, W.; Liu, P.; Hao, F. A Highly Efficient Bifunctional Copper Catalyst for Baeyer–Villiger Oxidation of Cyclohexanone: Two
Different Active Centers and the Reaction Path Investigation. Appl. Surf. Sci. 2023, 638 (158045). https://doi.org/10.1016/j.apsusc.2023.158045.
43. Zhou, W.; Chen, Y.; Qian, J.; Sun, F.; He, M.; Chen, Q. Copper Tetrasulfophthalocyanine Intercalated Hydrotalcite as an Efficient Bifunc-
tional Catalyst for the Baeyer–Villiger Oxidation. Catal. Lett. 2016, 146 (10), 2157 – 2164. https://doi.org/10.1007/s10562-016-1823-5.
44. Moudjahed, M.; Dermeche, L.; Idrissou, Y.; Mazari, T.; Rabia, C. Dawson – Type Polyoxometalates as Green Catalysts for Adipic Acid
Synthesis. J. Mol. Catal. A: Chem. 2016, 414, 72 – 77. https://doi.org/10.1016/j.molcata.2015.12.014.
45. Mouanni, S.; Mazari, T.; Amitouche, D.; Benadji, S.; Dermeche, L.; Roch-Marchal, C.; Rabia, C. Preparation and Characterization of
H3-2(x+y)MnxCoyPMo12O40 Heteropolysalts. Application to Adipic Acid Green Synthesis from Cyclohexanone Oxidation with Hydrogen
Peroxide. Comptes Rendus Chimie 2019, 22, 327 – 336. https://doi.org/10.1016/j.crci.2019.01.003.
ISSN 2308-8303 (Print) / 2518-1548 (Online) 35
Journal of Organic and Pharmaceutical Chemistry 2024, 22 (4)
Information about the authors:
Emir N. Abdullayev, Engineer of the Department of Porous Compounds and Materials, L. V. Pisarzhevsky Institute of Physical Chemistry
of the National Academy of Sciences of Ukraine.
Andrii M. Mishura, Leading Engineer of the Department of Free Radicals, L. V. Pisarzhevsky Institute of Physical Chemistry
of the National Academy of Sciences of Ukraine.
Ievgenii A. Iermolenko, Ph.D. Student of Institute of Organic Chemistry of the National Academy of Sciences of Ukraine; Chemist,
Enamine Ltd.
Anton S. Lytvynenko, Ph.D. in Chemistry, Research Fellow of the Department of Porous Compounds and Materials, L. V. Pisarzhevsky
Institute of Physical Chemistry of the National Academy of Sciences of Ukraine; https://orcid.org/0000-0001-5528-9989.
Maksim O. Kolosov, Ph.D. in Chemistry, Deputy Dean for Research, School of Chemistry, V. N. Karazin Kharkiv National University;
https://orcid.org/0000-0002-6714-0513.
Olena G. Shvets, Ph.D. in Chemistry, Junior Researcher, School of Chemistry, V. N. Karazin Kharkiv National University;
https://orcid.org/0000-0003-4791-2114.
Kostyantyn S. Gavrilenko, Ph.D. in Chemistry, Senior Researcher, Faculty of Chemistry, Taras Shevchenko National University of Kyiv;
Manager, Enamine Ltd.; https://orcid.org/0000-0001-7487-6660.
Sergiy V. Kolotilov (corresponding author), Corresponding Member of the National Academy of Sciences of Ukraine, Dr.Sci. in Chemistry,
Deputy Director for Research, L. V. Pisarzhevsky Institute of Physical Chemistry of the National Academy of Sciences of Ukraine;
https://orcid.org/0000-0002-4780-4378; e-mail for correspondence: s.v.kolotilov@gmail.com.
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| id | oai:ojs.journals.uran.ua:article-315358 |
| institution | Journal of Organic and Pharmaceutical Chemistry |
| issn | 2518-1548 |
| keywords_txt_mv | |
| language | English |
| last_indexed | 2026-08-24T01:01:16Z |
| publishDate | 2025 |
| publisher | National University of Pharmacy |
| record_format | ojs |
| resource_txt_mv | ophcjnupheduua/28/edee1f5b04d8d80ef92ea67e031bb428.pdf |
| spelling | oai:ojs.journals.uran.ua:article-3153582026-08-23T15:46:26Z The Oxidation of Cyclic Ketones by H2O2 Catalyzed by Cu(II) and Fe(III) Coordination Polymers Окиснення циклічних кетонів H2O2, каталізоване координаційними полімерами Cu(II) та Fe(III) Abdullayev, Emir N. Mishura, Andrii M. Iermolenko, Ievgenii A. Lytvynenko, Anton S. Kolosov, Maksim O. Shvets, Olena G. Gavrilenko, Kostyantyn S. Kolotilov, Sergiy V. каталітичне окиснення циклічні кетони пероксид водню пористі координаційні полімери мідь(II) залізо(III) catalytic oxidation cyclic ketones hydrogen peroxide porous coordination polymers copper(II) iron(III) It has been shown that the oxidation of ketones – analogs of cyclohexanone – by hydrogen peroxide in the presence of Cu3(btc)2 (btc3- = 1,3,5-benzenetricarboxylate) occurred mainly by the radical mechanism, rather than by the Baeyer-Villiger reaction mechanism, and led to a mixture of products formed due to the ring cleavage and reduction of the hydrocarbon chain length. Unlike aliphatic ketones, α-tetralone hardly underwent conversion in the reaction with H2O2 in the presence of HKUST-1, and the oxidation of the same ketone in the presence of Fe2(OH)3(btc) led to the formation of a number of products; among them, 1,4-naphthoquinone was dominant. З’ясовано, що окиснення кетонів – аналогів циклогексанону – перекисом водню в присутності Cu3(btc)2 (btc3- = 1,3,5-бензолтрикарбоксилат) проходило переважно за радикальним механізмом, а не за механізмом реакції Байєра-Віллігера, і призводило до суміші продуктів, що утворювалися внаслідок розщеплення кільця та зменшення довжини вуглеводневого ланцюга. На відміну від аліфатичних кетонів, α-тетралон майже не вступав в реакцію з H2O2 у присутності HKUST-1, а окиснення цього кетону в присутності Fe2(OH)3(btc) призводило до утворення низки продуктів, серед яких домінував 1,4-нафтохінон. National University of Pharmacy 2025-02-19 Article Article application/pdf https://ophcj.nuph.edu.ua/article/view/315358 10.24959/ophcj.24.315358 Journal of Organic and Pharmaceutical Chemistry; Vol. 22 No. 4 (2024); 25-35 Журнал органической и фармацевтической химии; Том 22 № 4 (2024); 25-35 Журнал органічної та фармацевтичної хімії; Том 22 № 4 (2024); 25-35 2518-1548 2308-8303 en https://ophcj.nuph.edu.ua/article/view/315358/313484 Copyright (c) 2025 Emir N. Abdullayev, Andrii M. Mishura, Ievgenii A. Iermolenko, Anton S. Lytvynenko, Maksim O. Kolosov, Olena G. Shvets, Kostyantyn S. Gavrilenko, Sergiy V. Kolotilov http://creativecommons.org/licenses/by/4.0 |
| spellingShingle | каталітичне окиснення циклічні кетони пероксид водню пористі координаційні полімери мідь(II) залізо(III) Abdullayev, Emir N. Mishura, Andrii M. Iermolenko, Ievgenii A. Lytvynenko, Anton S. Kolosov, Maksim O. Shvets, Olena G. Gavrilenko, Kostyantyn S. Kolotilov, Sergiy V. Окиснення циклічних кетонів H2O2, каталізоване координаційними полімерами Cu(II) та Fe(III) |
| title | Окиснення циклічних кетонів H2O2, каталізоване координаційними полімерами Cu(II) та Fe(III) |
| title_alt | The Oxidation of Cyclic Ketones by H2O2 Catalyzed by Cu(II) and Fe(III) Coordination Polymers |
| title_full | Окиснення циклічних кетонів H2O2, каталізоване координаційними полімерами Cu(II) та Fe(III) |
| title_fullStr | Окиснення циклічних кетонів H2O2, каталізоване координаційними полімерами Cu(II) та Fe(III) |
| title_full_unstemmed | Окиснення циклічних кетонів H2O2, каталізоване координаційними полімерами Cu(II) та Fe(III) |
| title_short | Окиснення циклічних кетонів H2O2, каталізоване координаційними полімерами Cu(II) та Fe(III) |
| title_sort | окиснення циклічних кетонів h2o2, каталізоване координаційними полімерами cu(ii) та fe(iii) |
| topic | каталітичне окиснення циклічні кетони пероксид водню пористі координаційні полімери мідь(II) залізо(III) |
| topic_facet | каталітичне окиснення циклічні кетони пероксид водню пористі координаційні полімери мідь(II) залізо(III) catalytic oxidation cyclic ketones hydrogen peroxide porous coordination polymers copper(II) iron(III) |
| url | https://ophcj.nuph.edu.ua/article/view/315358 |
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