The effect of substrate size in the Beckmann rearrangement: MOFs vs. zeolites

Article abstract of DOI:10.1016/j.cattod.2012.09.008

Catalytic activity of CuBTC and FeBTC was investigated in Beckmann rearrangement of a series of aromatic and non-aromatic oximes and compared with that of zeolites Beta and USY. The reactivity of substrates in Beckmann rearrangement increases in the order camphor oxime < cyclohexanone oxime < indanone oxime < acetophenone oxime. While zeolites show higher activity in the transformation of relatively small aromatic (acetophenone oxime, indanone oxime) and non-aromatic oximes (cyclohexanone oxime) providing 100% selectivity to the target lactams in all reactions, CuBTC was the most active in transformation of bulky oximes. It was deduced, that textural preferences of CuBTC may be the reason of its capability to facilitate the transformation of bulky camphor oxime in comparison with zeolites Beta and USY.

Full text of DOI:10.1016/j.cattod.2012.09.008

Catalysis Today 204 (2013) 94–100
Contents lists available at SciVerse ScienceDirect
Catalysis Today
journal homepage: www.elsevier.com/locate/cattod
The effect of substrate size in the Beckmann rearrangement: MOFs vs. zeolites
Maksym Opanasenkoa,b, Mariya Shamzhya,b, Martin Lama cˇ , Ji rˇ í Cejka
a
a,∗
ˇ
a
J. Heyrovsk y´ Institute of Physical Chemistry, Academy of Sciences of Czech Republic, v.v.i., Dolej sˇ kova 3, 182 23 Prague 8, Czech Republic
L.V. Pisarzhevskiy Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 pr. Nauky, Kyiv 03028, Ukraine
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 15 May 2012
Received in revised form
Catalytic activity of CuBTC and FeBTC was investigated in Beckmann rearrangement of a series of aromatic
and non-aromatic oximes and compared with that of zeolites Beta and USY. The reactivity of substrates
in Beckmann rearrangement increases in the order camphor oxime < cyclohexanone oxime < indanone
oxime < acetophenone oxime. While zeolites show higher activity in the transformation of relatively small
aromatic (acetophenone oxime, indanone oxime) and non-aromatic oximes (cyclohexanone oxime) pro-
viding 100% selectivity to the target lactams in all reactions, CuBTC was the most active in transformation
of bulky oximes. It was deduced, that textural preferences of CuBTC may be the reason of its capability
to facilitate the transformation of bulky camphor oxime in comparison with zeolites Beta and USY.
1
0 September 2012
Accepted 18 September 2012
Available online 18 October 2012
Keywords:
Beckmann rearrangement
Oximes
©
2012 Elsevier B.V. All rights reserved.
CuBTC
Metal-organic-frameworks
Zeolites
1
. Introduction
such as high-silica zeolites [13,14], metal oxides [15,16], or clays
◦
[
17] at temperatures as high as 300 C. It was found that high-silica
Beckmann rearrangement of ketoximes (Scheme 1) is known as
ZSM-5 zeolite (silicalite-1) [18–20] and boron-containing zeolite
ZSM-5 [21,22] are highly active catalysts for the transformation
of cyclohexanone oxime to ε-caprolactam. The rearrangement has
been also explored in supercritical water [23,24]. However, the last
2 methods frequently suffer from low selectivity and a rapid decay
of the activity of the catalyst as a result of the high temperatures
used. Recently, Beckmann rearrangement was also reported in ionic
liquids at room temperature [25,26]. Nevertheless, until now the
occurrence of mild conditions was related to the use of rather toxic
solvents and expensive reagents or solvents.
Beckmann rearrangement reaction is believed to be a typi-
cal acid-catalyzed reaction. Although the catalytic performance
over solid acid catalysts under vapor phase conditions has been
tested, the nature and position of the active sites in the solid
catalysts remain controversial. Costa et al. reported on the
Beckmann rearrangement of cyclohexanone oxime on alumina
orthophosphate/␥-alumina catalysts [27]. They found that the
reaction was catalyzed by Lewis and Brønsted acid centers and
that the formation of caprolactam and 5-cyanopent-1-ene were
competitive reactions. Yashima et al. [28] examined a range
of different catalysts including H-ZSM-5, silicalite-1, silicagel,
H-mordenite, H-ferrierite, Ca-A, Na-A, and clinoptinolite for Beck-
mann rearrangement. They concluded that weaker acid sites
showed a higher selectivity to caprolactam. In the presence of
stronger acid sites, multiple side reactions, namely ring opening,
decomposition and polymerization were observed. In contrast to
the above results, Corma and Kob with coworkers inferred that the
a fundamental tool in organic synthesis providing the connection
among ketones possessing a remarkable synthetic flexibility and
amides/lactams [1], which are widely used in drugs and pharma-
ceuticals, and also as detergents, lubricants, and raw materials for
polyamides such as nylon-6 and nylon-12 [2].
Conventional methods for the activation of oximes are based on
the use of strong Brønsted or Lewis acids. In a classical method, ε-
caprolactam is industrially produced in the presence of sulfuric acid
or oleum as catalysts [3]. A perceived disadvantage of this route is
a large amount of ammonia sulfate formed as a side product. To
overcome the by-product formation and reactor corrosion prob-
lems, more economic and environmentally friendly processes have
been developed.
Liquid-phase Beckmann rearrangements have been attempted
using chlorosulfonic acid [4], ethyl chloroformate and boron tri-
fluoride diethyl etherate [5], anhydrous oxalic acid [6], chloral
hydrate [7], or organocatalysts such as sulfamic acid [8], cyanuric
chloride [9], diethyl chlorophosphate [10], triphosphazene [11]
and poly(ethylene glycol)-sulfonic acid [12]. However, these cata-
lysts could not be recovered or reused. Vapor-phase methods, with
a particular focus on the sulfate-free industrial production of ε-
caprolactam, have been performed using heterogeneous catalysts,
∗
Corresponding author.
E-mail address: jiri.cejka@jh-inst.cas.cz (J. Cˇ ejka).
0
920-5861/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cattod.2012.09.008

M. Opanasenko et al. / Catalysis Today 204 (2013) 94–100
95
2. Experimental
2.1. Materials
H-Beta (Si/Al = 12.5) and H-USY (Si/Al = 15) zeolites were pur-
chased from Zeolyst. CuBTC (Basolite C300) and FeBTC (Basolite
F300) were purchased from Sigma Aldrich. Cyclohexanone oxime
Scheme 1. Beckmann rearrangement of ketoximes.
(
97%), acetophenone oxime (95%), indanone oxime (≥99%) and
camphor oxime (≥97%) were used as substrates, mesitylene (≥99%)
as internal standard and 1,4-dioxane (≥99%) as solvent in catalytic
experiments. All reactants and solvents were obtained from Sigma
Aldrich and used as received without any further treatment.
strong acid sites on crystalline silica-alumina are favorable for gas
phase Beckmann rearrangement [29–31]. However, the research
group of Hölderich investigated the rearrangement of cyclohex-
anone oxime to caprolactam over high silica zeolites with MFI
structure in fixed bed and fluidized bed reactors to determine the
nature of the active centers on the catalysts [18,32–35]. Accord-
ing to Hölderich, extremely weak acidic silanol nests and vicinal
silanol groups on the external surface of highly siliceous ZSM-
2
.2. Characterization
The crystallinity of samples under study was determined by X-
ray powder diffraction on a Bruker AXS D8 Advance diffractometer
with a Vantec-1 detector in the Bragg-Brentano geometry using
CuK␣ radiation. To limit the effect of preferential orientation of
individual crystals a gentle grinding of the samples was performed
before measurements.
5
zeolites were found to be the most suitable for the Beckmann
rearrangement [18].
Thus, it can be concluded that there is no general agreement on
the influence of the acidic properties of heterogeneous catalyst on
the efficiency of Beckmann rearrangement. The understanding of
this issue can be helpful in the development of efficient and mild
catalytic method for the transformation of ketoximes into respec-
tive amides/lactams.
◦
Adsorption isotherms of nitrogen at −196 C were determined
using an ASAP 2020 (Micromeritics) static volumetric apparatus.
Before adsorption experiments the samples were degassed under
turbomolecular pump vacuum at the temperature of 150 C for
MOFs and 250 C for zeolites. This temperature was maintained for
8
◦
Metal-organic-framework (MOFs) represent crystalline hybrid
organic–inorganic nanoporous materials with a reasonable sta-
bility [36,37], adjustable chemical functionality [38], extra-high
porosity [39] and mild Lewis acidity [40–42]. In contrast, alu-
minosilicate zeolites are well-known solid acids, containing both
Lewis and Brønsted acid sites [43–47]. A number of different
reactions have been recently reported showing the interest-
ing catalytic properties of MOFs. These include Friedländer
condensation [40], Knoevenagel condensation [48], one-pot three-
component coupling reaction between amines, aldehydes and
alkynes [49], Huisgen cycloaddition [50], cyclopropanation of
alkenes with diazoacetates [51], selective oxidation of cycloalka-
nes [52], or Friedel–Crafts benzylation [53]. Recently, we reported
on the catalytic benefits of CuBTC and FeBTC (BTC = 1,3,5-
benzenetricarboxylate) over large-pore aluminosilicate zeolites
Beta and USY in Pechmann condensation of naphthol originating
from the mild acidity, the regularity in the arrangement of active
sites within the framework, and preferences in the pore size of
corresponding MOFs [54].
◦
h.
The concentrations of Brønsted and Lewis acid sites in zeolites
◦
were determined by pyridine adsorption at 150 C followed by FTIR
spectroscopy (Nicolet 6700) using self-supporting wafer technique,
according to the methodology reported in Ref. [55]. Generally, a
thin sample wafer of zeolite was activated prior to the experiment
in a high vacuum (10 Torr) of 450 C overnight. Adsorption of
pyridine proceeded at room temperature for 30 min at a partial
pressure of 5 Torr and was followed by 20 min evacuation at the
−4
◦
◦
temperature 150 C. Determination of Lewis acid sites in CuBTC is
discussed in detail elsewhere [42].
2.3. Beckmann rearrangement of oximes
The Beckmann rearrangement of oximes (cyclohexanone oxime,
acetophenone oxime and indanone oxime) was performed in
a liquid phase under atmospheric pressure and temperature of
6
Discovery Technologies UK). Prior to use, 200 mg of the catalyst was
activated at 150 (for MOFs) or 450 (for zeolites) C for 90 min with
a temperature rate 10 C/min in a stream of air. Typically, 2.0 mmol
of oxime, 0.4 g of mesitylene (internal standard) and 200 mg of cat-
alyst were added to the 3-necked vessel, equipped with condenser
and thermometer, stirred and heated. The amount of catalyst was
varied between 0.025 and 0.1 g per 1 mmol of substrate.
To evaluate a potential influence of leaching of active species
from the heterogeneous catalysts, a part of the reaction mixture
was separated at the reaction temperature and the obtained liquid
phase was further investigated in the Beckmann rearrangement
under the same reaction conditions.
◦
0-100 C in a multi-experiment work station StarFish (Radley’s
Our contribution is aimed at the comparison of conventional
large-pore zeolites Al-Beta (Si/Al = 12.5) and USY (Si/Al = 15) with
MOFs (CuBTC, FeBTC) in the liquid-phase Beckmann rearrangement
of cyclohexanone oxime, acetophenone oxime, 1-indanone oxime
◦
◦
(
subsequently – indanone oxime) and camphor oxime (Scheme 2)
to establish the influence of the nature of substrate as well as
the textural and acidic properties (e.g. nature and strength of
active sites) of the catalyst on the efficiency of the Beckmann
rearrangement.
2.4. Reaction product analysis
Aliquots of the reaction mixture were sampled after 60, 120,
80, 240, 360, and 1260 min.
1
The reaction products were analyzed by gas chromatography
(
GC) using an Agilent 6850 with FID detector equipped with a non-
polar HP1 column (diameter 0.25 mm, thickness 0.2 ␮m and length
0 m). Reaction products were identified using GC–MS analysis
ThermoFinnigan, FOCUS DSQ II Single Quadrupole GC/MS). The
3
(
Scheme 2. Substrates for Beckmann rearrangement.

9
6
M. Opanasenko et al. / Catalysis Today 204 (2013) 94–100
Fig. 1. XRD patterns of the catalysts: Beta and USY (a); CuBTC and FeBTC (b).
identity of reaction products was also confirmed using 1H NMR
spectroscopy (Varian Unity 300 spectrometer). The observed spec-
tra corresponded to the previously published data [56].
a 3.0
2
2
.5
.0
after Py
adsorption
3
. Results and discussion
USY
Beta
3
.1. Structural and acid properties
1.5
1.0
The X-ray diffraction patterns of CuBTC and zeolites under inves-
after
tigation match well with those reported in the literature thus all
catalysts are found to be highly crystalline and without the pres-
ence of any other phases (Fig. 1). At the same time it was confirmed
that FeBTC is low-ordered material.
Nitrogen adsorption isotherms of individual catalysts are
depicted in Fig. 2. While CuBTC, FeBTC, and Beta showed a type
I isotherm, which is typical for microporous solids, adsorption
isotherm for USY is a combination of types I and IV with hysteresis
loop evidencing the presence of ink-bottle-type mesopores within
USY pore system [57].
activation
0
0
.5
USY
Beta
.0
3
800 3750 3700 3650 3600 3550 3500 3450 3400
-1
Wavenumber, cm
b 2,5
2,0
after Py
adsorption
Beta
USY
Acidic properties of zeolites, namely the type and concen-
trations of Brønsted and Lewis acid sites were analyzed using
adsorption of pyridine followed by FTIR (Fig. 3). FTIR spectra of
both Beta and USY exhibit characteristic absorption band at about
1,5
1,0
−
1
3
739–3747 cm , attributed to the silanol OH groups. The absorp-
−
1
after
activation
tion bands of acidic bridging OH groups appear at 3609 cm for
0,5
USY
Beta
0
,0
7
6
5
4
3
2
1
00
00
00
00
00
00
00
0
1
600 1575 1550 1525 1500 1475 1450 1425 1400
-
1
Wavenumber, cm
◦
−4
Fig. 3. FTIR spectra of USY, Beta after activation at 450 C and 10 Torr and after
◦
−1
pyridine adsorption after 20 min desorption at 150 C: region 3400–3800 cm (a);
−
1
region 1400–1600 cm (b).
zeolite Beta and at 3564 and 3630 cm 1 for USY zeolites (Fig. 3a).
−
Adsorption of pyridine removed these bands while new absorp-
−
1
tion bands appeared in the region 1400–1600 cm . The absorption
−
1
0
.0
0.2
0.4
0.6
0.8
1.0
band around 1545 cm is due to the interaction of pyridine with
−
1
p/p0
Brønsted acid sites while a new band around 1455 cm is char-
acteristic of the pyridine adsorbed on Lewis acid sites (Fig. 3b).
Using the extinction coefficients [58], concentrations of Brønsted
and Lewis acid sites were determined, see Table 1.
Fig. 2. N2 adsorption isotherms of the catalysts: CuBTC (ꢀ); FeBTC (ꢁ); Beta (ꢀ);
USY (ꢁ), open points represent adsorption, full points – desorption.

M. Opanasenko et al. / Catalysis Today 204 (2013) 94–100
97
Table 1
Textural and acid properties of used catalysts.
2
Catalyst
Dpore, nm
SBET, m /g
IR
◦
+
T des.,
C
PyH , mmol/g
PyL, mmol/g
CuBTC
FeBTC
0.90, 0.50, 0.35
0.86
1500
1060
200
200
–
–
2.30
2.56
0.23
0.18
0.17
0.13
0.32
0.24
0.22
0.19
150
250
350
450
150
0.30
0.22
0.17
0.08
0.21
0.18
0.12
0.05
USY
Beta
0.74
770
670
0
0
.66,
.56
250
350
450
The distribution of Brønsted acid sites with regard to their
strength was estimated by a stepwise desorption at increasing tem-
peratures on zeolites having pre-adsorbed pyridine while recording
the residual intensity of the remaining characteristic IR bands. With
increasing of desorption temperature, the band of pyridinium ions
oxime over zeolite Beta and CuBTC are very close (13% and 11%,
respectively) while accessibility of active centers within CuBTC is
obviously higher due to the presence of large micropores (Table 1).
It may be explained by a higher concentration of strong acid sites
within Beta in contrast to CuBTC, but at the moment there is not
enough information about the strength of the Lewis acid sites of
CuBTC for confirmation of this assumption. Despite the compa-
rable activity of Beta and CuBTC in Beckmann rearrangement of
cyclohexanone oxime the selectivity to caprolactam was much
higher over Beta. Based on the earlier investigations of Beckmann
rearrangement of cyclohexanone oxime [59], we can infer that the
selective formation of caprolactam mostly occurred at the active
sites on the external surface of zeolite Beta. In the case of cyclo-
hexanone oxime rearrangement over CuBTC we can assume that
the reaction proceeds inside the pore system of the catalyst. This
may result in suffering of the target product from diffusion resis-
tance in the pores, increasing the possibility of side reactions like
decomposition or polymerization. The highest conversion of USY
in comparison with zeolite Beta and both MOFs may be connected
with the presence of transport mesopores within USY. It results in
an accessibility of a higher amount of active sites for the substrate
in comparison with zeolite Beta. High selectivity to ε-caprolactam
over both Beta and USY, which are characterized by the strong
acidity, should also be pointed out. This is in agreement with the
results, obtained earlier by Corma’s group [30,31,60], which proved
that strong Brønsted acid sites are very active and selective for the
formation of the amide in Beckmann rearrangement.
−
1
(
1545 cm ) gradually decreases. It can be concluded that both USY
and Beta contain significant amount of strong acid sites, which are
◦
able to retain adsorbed base even after desorption at 450 C.
Lewis acidity of CuBTC, arising from the presence of unsatu-
rated Cu(II) centers [42], by analogy to zeolites, may be determined
quantitatively by the adsorption of basic probe molecules. To esti-
−
1
mate the acidity of the CuBTC band at 1069 cm assigned to C
C
out-of-plane vibrations was chosen. Characteristic bands in region
−1
1
400–1600 cm
were not used for computation of the amount
of acid sites within MOFs because of an undesirable overlap with
the bands corresponding to MOF’s framework. At the same time
−1
band at 1069 cm cannot be used for evaluation of the concen-
tration of acid centers in zeolites as it overlaps with the bands
which corresponds to the vibration of Si O bond. The concentra-
tion of coordinatively bonded pyridine was determined to be equal
◦
to 2.30 mmol/g for CuBTC activated at 200 C [42].
Textural and acidic properties of the catalysts under investiga-
tion are summarized in Table 1.
3.2. Beckmann rearrangement
To compare catalytic properties of conventional zeolites and
MOFs in Beckmann rearrangement, cyclohexanone oxime was
chosen as a model substrate. Fig. 4 provides conversion of cyclo-
hexanone oxime after 360 min of TOS (Time-On-Stream) at 80 C
over zeolites and MOFs, as well as selectivity to caprolactam (at
maximal conversion).
As it can be seen, the activity of the catalysts increases in the
order FeBTC < CuBTC ≈ Beta < USY. Conversions of cyclohexanone
In contrast, when using acetophenone oxime having almost
the same kinetic diameter as cyclohexanone oxime but containing
aryl substituent near oxime group, we achieved much higher con-
versions of the initial substance over all used catalyst, except
FeBTC (Fig. 5). The conversions of acetophenone oxime increased
in the same order, as in the case of cyclohexanone oxime:
FeBTC ꢂ Beta ≈ CuBTC < USY. For comparison, after 360 min of TOS
◦
a
b
1
100
00
80
60
40
20
0
8
6
4
2
0
0
0
0
0
Beta
USY
FeBTC
CuBTC
USY
FeBTC
Beta
CuBTC
◦
Fig. 4. Conversion (a) of cyclohexanone oxime (at TOS = 360 min) and selectivity (at maximum conversion) of caprolactam (b) at 80 C over Beta (Si/Al = 12.5), USY (Si/Al = 15),
CuBTC, FeBTC.

9
8
M. Opanasenko et al. / Catalysis Today 204 (2013) 94–100
1
00
USY
0.2
6
5
0
0
CuBTC
Beta
0
.1
8
6
4
2
0
0
0
0
0
0
.05
40
3
2
1
0
0
0
0
FeBTC
0
100
200
t [min]
300
400
0
100
200
t [min]
300
400
Fig. 7. Effect of catalyst loading (0.2, 0.1, 0.05 g) with respect to acetophenone
Fig. 5. Conversion of acetophenone oxime over Beta (Si/Al = 12.5), USY (Si/Al = 15),
CuBTC, FeBTC at 80 C.
oxime on yield of the corresponding amide in Beckmann rearrangement over CuBTC
◦
◦
(
100 C).
the conversion of cyclohexanone and acetophenone oxime over
CuBTC was equal to 11% and 80% (approximately), respectively.
Similarly to cyclohexanone oxime rearrangement, the less-ordered
FeBTC appeared to be practically inactive in the transformation of
acetophenone oxime.
The results imply that electron-rich aryl groups have better
migrating aptitude than the alkyl group toward the oximino nitro-
gen. In this case, the reaction can proceed easily because aryl group
stabilizes the reaction intermediate (Scheme 3) [61].
Indanone oxime also contains aryl group, that can facilitate the
Beckmann rearrangement due to the stabilization of the reaction
intermediate. But it is bulkier in comparison with acetophenone
oxime. For indanone oxime we observed lower conversions in
comparison with acetophenone oxime over USY (77% vs. 36% at
In contrast to cyclohexanone oxime, the selectivities to respec-
tive amides or lactams in acetophenone oxime and indanone oxime
transformations, respectively, were 100% over all catalysts under
investigation. The last result, obviously, is caused by the presence
of aromatic ring in the two latter substrates hindering the side
transformation of both substrates and products.
Conversion
of
acetophenone
oxime
in
Beckmann
rearrangement decreases with decreasing amount of MOF
used (Fig. 7). 62% yield of the lactam after 400 min of the reaction
was achieved in acetophenone oxime rearrangement over CuBTC
using 0.2 g of the catalyst per 2 mmol of oxime. When 0.1 g of the
catalyst was used, the yield of respective amide totaled only 52%.
As expected, the selectivity was not dependent on the amount of
the MOF used, it was found to be constantly 100%.
2
40 min TOS) and CuBTC (54 vs. 29% at 240 min TOS). In contrast, the
conversions over zeolite Beta in the rearrangements of either ace-
tophenone oxime or indanone oxime were nearly identical (Fig. 6).
This result strongly confirms that the reactions of respective oximes
proceed on the external surface of zeolite Beta.
Unexpectedly, the increase in the reaction temperature resulted
in decreasing conversion of acetophenone oxime over CuBTC. For
comparison, when increasing the reaction temperature from 60 to
80 C and even to 100 C, the yield of the respective amide was
reduced after 400 min of the reaction time over CuBTC from 100 to
◦
◦
9
5 and 62%, respectively (Fig. 8).
XRD patterns confirmed that the framework of MOFs remains
unchanged during the liquid-phase Beckmann rearrangement of
all substrates under investigation (Fig. 9). Thus, the unexpected
influence of the reaction temperature on the conversion of ace-
tophenone oxime over CuBTC may be explained in terms of the
formation of a small amount of undesired products at higher tem-
peratures leading to the fast deactivation of the catalyst.
Scheme 3. Rearrangement of aryl-containing substrate.
1
00
Beta
o
6
0 C
1
00
USY
o
8
0 C
9
8
7
6
5
40
3
20
1
0
0
0
0
0
8
6
4
2
0
0
0
0
0
CuBTC
o
1
00 C
0
FeBTC
0
0
0
100
200
300
400
0
200
400
600
t [min]
800
1000
1200
t [min]
◦
Fig. 8. Effect of the temperature (60, 80, 100 C) on the conversion of acetophenone
Fig. 6. Conversion of indanone oxime over Beta (Si/Al = 12.5), USY (Si/Al = 15),
CuBTC, FeBTC at 80 C.
◦
oxime in Beckmann rearrangement over CuBTC.

M. Opanasenko et al. / Catalysis Today 204 (2013) 94–100
99
a
b
0
0
after AcPhOx (100 C)
after AcPhOx (100 C)
0
0
after AcPhOx (80 C)
after AcPhOx (80 C)
0
0
after IndOx (80 C)
after IndOx (80 C)
0
0
after ChOx (80 C)
after ChOx (80 C)
before catalysis
before catalysis
5
10
15
20
25
30
35
40
5
10
15
20
25
30
35
40
2
θ, degrees
2θ, degrees
Fig. 9. XRD patterns of CuBTC (a) and FeBTC (b) before and after catalysis.
60
50
40
30
20
10
0
Heterogeneous
Homogeneous
0
200
400
600
800
1000 1200
Scheme 4. Transformations of camphor oxime under Beckmann rearrangement
conditions.
t [min]
Fig. 10. Leaching test of Cu2+ ions from the catalyst (CuBTC) under conditions of
◦
Beckmann rearrangement of acetophenone oxime (reaction temperature – 100 C).
noted the fragmentation of camphor oxime to nitriles [62] and also
the formation of ␦-lactams [63] under Beckmann reaction condi-
tions (Scheme 4) were observed and the mixture was not analyzed
further.
Also results of leaching test (obtained for acetophenone oxime
rearrangement over CuBTC, Fig. 10) indicate that practically no
leaching of the active species takes place.
Most probably, the transformation of camphor oxime proceeds
on the outer surface/in the pore mouths of the catalysts. Zeolite
BEA and FeBTC were practically inactive in this reaction. It can be
assumed that the molecule of camphor oxime cannot enter the pore
entrances to reach the active sites of the catalyst. We assume that
both CuBTC and zeolite USY are active in the transformation of cam-
phor oxime as a result of appropriate size/curvature of their pore
entrances, allowing the interaction of substrate and the active site.
The mesopore entrances in USY zeolite, created by dealumination
and steaming are obviously depleted in the concentration of active
centers in comparison with CuBTC. It may be the reason of slightly
higher conversion of camphor oxime over CuBTC (31% at 360 min
of TOS) in comparison with USY (22.5 at 360 min of TOS).
It seems that the size effect dominates over acidic features of
the catalysts studied in the case of the most bulky substrate –
camphor oxime. While zeolite Beta appeared to be completely
inactive in the process of Beckmann rearrangement of camphor
oxime into 1,8,8-trimethyl-2-azabicyclo[3.2.1]octan-3-one, zeolite
USY and CuBTC demonstrated quite high conversion of the sub-
strate. As it can be seen (Fig. 11) the conversion value of camphor
oxime increased together with increasing the pore size within the
range of investigated catalysts Beta ꢂ USY < CuBTC. It should be
1
00
8
6
4
2
0
0
0
0
0
CuBTC
USY
4
. Conclusions
In comparison with MOFs, zeolites show higher activity in
transformations of relatively small aromatic (acetophenone oxime,
indanone oxime) and non-aromatic oximes (cyclohexanone oxime)
providing 100% selectivity to the target lactams or amides, respec-
tively, in all reactions. While CuBTC is quite active in Beckmann
rearrangement of indanone oxime and acetophenone oxime, it is
the most active in transformation of bulky camphor oxime. It can
be assumed, that due to the diffusional preferences, larger pore
size of CuBTC may be the main reason of its capability to facilitate
the transformation of bulky camphor oxime in comparison with
zeolites Beta and USY.
Beta FeBTC
0
200
400
600
t [min]
800
1000
1200
Fig. 11. Conversion of camphor oxime over Beta (Si/Al = 12.5), USY (Si/Al = 15),
CuBTC, FeBTC at 80 C.
◦

1
00
M. Opanasenko et al. / Catalysis Today 204 (2013) 94–100
Acknowledgements
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1
The research of M.O. leading to these results has received
funding from the European Community’s Seventh Framework Pro-
gramme (FP7/2007–2013) under grant agreement no. 228862. J.C.
thanks the Czech Grant Agency for the financial support (Centre of
Excellence – P106/12/G015).
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