Transformations of α- And β-ionones in the presence of Al 2O3 in a supercritical solvent in a flow reactor

Article abstract of DOI:10.1134/S0036024413110046

The reactivity of α- and β-ionones under the supercritical conditions in a flow type reactor in the presence of Al₂O₃ at 200-230 C was studied. α-Ionone was reduced to α-ionol, while β-ionol was unstable already at 200 C and underwent dehydration. The secondary reaction products were the corresponding megastigmatrienes.

Full text of DOI:10.1134/S0036024413110046

ISSN 0036ꢀ0244, Russian Journal of Physical Chemistry A, 2013, Vol. 87, No. 11, pp. 1940–1942. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © V.I. Anikeev, V.P. Sivcev, K.P. Volcho, N.F. Salakhutdinov, 2013, published in Zhurnal Fizicheskoi Khimii, 2013, Vol. 87, No. 11, pp. 1975–1977.
SHORT
COMMUNICATIONS
Transformations of
α
ꢀ and ꢀIonones in the Presence of Al2O3
β
in a Supercritical Solvent in a Flow Reactor
V. I. Anikeeva, V. P. Sivcevb, K. P. Volchoc, and N. F. Salakhutdinovc
a Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
b Novosibirsk State University, Novosibirsk, Russia
cVorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
eꢀmail: anik@catalysis.nsk.su
Received February 13, 2013
Abstract—The reactivity of
presence of Al2O3 at 200–230°C was studied.
already at 200 and underwent dehydration. The secondary reaction products were the corresponding
megastigmatrienes.
α
ꢀ and
β
ꢀionones under the supercritical conditions in a flow type reactor in the
α
ꢀIonone was reduced to ꢀionol, while ꢀionol was unstable
α
β
°C
Keywords: ionone, triene, Meerwein–Ponndorf–Verley reaction, supercritical solvent, alumina.
DOI: 10.1134/S0036024413110046
INTRODUCTION
The aim of this work was to study the reactivity of
ꢀ and ꢀionones and in the isopropanol/CO2
supercritical solvent in the presence of Al2O3 in a flow
α
β
1
2
α
ꢀ and
β
ꢀIonones are widespread in nature [1].
They are used in perfumery industry [2–4] and synꢀ
thesis of biologically active compounds, including
carotene [5]. One of the important transformations of
ionones and
reactor.
β
ꢀ
1
2
EXPERIMENTAL
O
O
We used mixtures of
α
ꢀ and βꢀionones 1 and 2, in
which one of these components was dominant, in
ratios of 2.2 : 1 and 1 : 2.2 and Al2O3 (Machereyꢀ
μ
Nagel, pH 7 0.5, 50–200
m, free surface ~130 m2/g
(BET)). The experimental studies of the reactions
under the supercritical solvent conditions were perꢀ
formed on a laboratory unit [11, 12] with a tube reacꢀ
(
1
)
(2)
is the reduction of the carbonyl group to the correꢀ
sponding alcohol [6, 7].
tor (6.0
×
0.8 mm, length 3.0 m), which contained
Recently, we developed an effective system that
allows the reduction of carbonyl groups to be perꢀ
formed in aldehydes and aromatic ketones in a flow
reactor in a complex supercritical solvent isoproꢀ
panol/CO2 in the presence of Al2O3 [8–10]. The
reducing agent in this reaction was isopropanol, which
transformed into acetone (Meerwein–Ponndorf–Verꢀ
ley reaction). We showed that the corresponding alcoꢀ
hols or substituted styrenes could be obtained as the
main products from acetophenone and its derivatives
(depending on the reaction temperature) [10]:
42 cm3 (39.1 g) of granulated Al2O3. The reaction mixꢀ
ture was fed into the reactor in two flows. The first flow,
supercritical СО2 (5 mL/min), was fed, using a syringe
pump, into a mixer located at the inlet of the reactor
through a heat exchanger, where the flow was heated
to the reaction temperature. The second flow, 1%
solution of a mixture of ionones in isopropanol
(3 mL/min), was fed in the same mixer using a piston
pump.
The reaction mixture at the outlet of the reactor
was cooled and forwarded for analysis. The composiꢀ
tion of the reaction products was analyzed by GCꢀMS
on an Agilent 6890N gas chromatograph with an Agiꢀ
lent 5973N quadrupole mass analyzer as a detector. An
HPꢀ5MS quartz column (5% diphenyl–95% dimethꢀ
ylsiloxane copolymer) with a length of 30 m, inner
diameter of 0.25 mm, and film thickness of the staꢀ
O
OH
300°C
210°C
(1)
R
R
R
tionary phase of 0.25
scanning was at from 29 to 500. The components
of the reaction mixture were qualitatively analyzed by
μm was used for analysis. The
R = H, Hal, OMe, NO2; 180 atm,
~5 min, scCO2/ PrOH, Al2O3.
m/z
i
1940

TRANSFORMATIONS OF
α
ꢀ AND
βꢀIONONES IN THE PRESENCE OF Al2O3
1941
Transformations of
Reagents
α
ꢀ and
β
ꢀionones
1 and 2 (UPs are unidentified products)
Conversion, %
Content, %
T, °C
1
2
3
4
5
6
UPs
1
1
:
:
2
2
= 2.2 : 1
= 1 : 2.2
200
230
230
59
96
94
61
94
97
32
29
10
2
3
9
4
19
29
17
20
12
8
36
22
comparing the retention times of the components and carbonyl group in
their complete mass spectra with the data of the NIST ondary transformations, megastigmatrienes
and Wiley7 databases. The structure of megastigmaꢀ identified. Interestingly, ꢀionol was not found in the
4,7,9ꢀtriene ( ), megastigmaꢀ5,7,9ꢀtriene ( ), and reaction mixture probably because of its low stability
megastigmaꢀ4,6,8ꢀtriene ( ) was determined by comꢀ under the reaction conditions. Based on the arrangeꢀ
paring their mass spectra with the corresponding literꢀ ment of double bonds in compounds , we can
ature data. assume that megastigmaꢀ4,7,9ꢀtriene and
megastigmaꢀ5,7,9ꢀtriene ( ) formed as a result of the
1
. In addition, the products of secꢀ
4–6, were
β
7
4
5
6
4–6
(4)
5
β
Megastigmaꢀ4,7,9ꢀtriene (
dehydration of ꢀ ( or
while megastigmaꢀ4,6,8ꢀtriene (
4). Mass spectrum, m/z
α
3)
ꢀ (7)
ionol, respectively,
(relative intensity): 176 (13), 161 (5), 120 (98), 119
(15), 107 (15), 105 (100), 91 (42), 79 (26), 77 (26), 65
(22), and 55 (13). The spectrum coincided with the
one given in [13].
6
) might be the prodꢀ
uct of the transformations of both alcohols
3 and 7.
OH
Megastigmaꢀ5,7,9ꢀtriene (5). Mass spectrum, m/z
(relative intensity): 176 (27), 161 (36), 147 (34), 133
(42), 119 (46), 105 (100), 91 (90), 79 (31), 77 (32), 67
(23), and 55 (12). The spectrum coincided with the
one given in [14].
1
(
3
)
(
(
(
4
6
5
)
)
)
Megastigmaꢀ4,6,8ꢀtriene (6). Mass spectrum, m/z
(relative intensity): 176 (37), 161 (45), 133 (28), 119
(100), 105 (72), 91 (46), 77 (32), 65 (12), and 55 (12).
The spectrum coincided with the one given in [15].
(2)
The percentage composition of the mixtures was
calculated from the peak areas in the chromatograms
without using adjusting factors. The contact time of
OH
the reaction mixture ( ) was calculated as the ratio of
τ
2
the volume of the catalyst in the reactor VС (cm3) to
the total flow rate of the mixture at the inlet of the
(
7)
reactor
8 mL/min). The transformations were performed at
temperatures of 200–230 and at a pressure p =
Q
(cm3/s) (~5.3 min at a flow rate of
Compounds
their mass spectra with the literature data.
4
–6 were identified by comparing
°
C
When the reaction temperature was raised to
°C, the conversion of both ketones increased to
180 atm. The temperature and pressure in the reactor
that provide the supercritical conditions of the reacꢀ
tion mixture were chosen on the basis of thermodyꢀ
namic calculations and phase diagrams.
230
nearly quantitative. In addition, the fraction of
ionol decreased, while the contents of trienes
and unidentified products increased.
For the mixture of ꢀ and ꢀionones
taining mainly ꢀionone , the contents of
decreased, while the fractions of and, to a lesser
extent, increased. The obtained data confirm our
assumption that megastigmatriene can form from
. Previously, compound was
ꢀionol by dehydration in the presꢀ
for 30 min [13].
The use of the suggested system leads to the formation
of triene directly from ꢀionone without using
expensive reagents during the contact time (6 min).
The formation of compound was observed earlier
formed as a result of the reduction of the after ꢀionol acetate was treated in the presence of the
α
ꢀ
3
4–6
α
β
1
and
2
conꢀ
and 4
RESULTS AND DISCUSSION
β
2
3
5
Two mixtures of
α
ꢀ and ꢀionones 1 and 2, in
β
6
which one of these components was dominant, in
ratios of 2.2 : 1 and 1 : 2.2 were used as the starting
6
both ionones
obtained from
ence of (Me2N)3PO at 215–230°C
1
and
2
4
compounds. Mixtures of
α
ꢀ and ꢀionones 1 and 2 in
β
α
3
various ratios are commercially available [16]. At the
start of the experimental studies we used the mixture of
α
ꢀ and
(2.2 : 1).
The conversion of
200 was ~60% (table). The major reaction product
was ꢀionol
β
ꢀionones
1
and
2
containing mainly ꢀionone
α
4
α
1
1
α
ꢀ and ꢀionones 1 and 2 at
β
°
C
α
5
3
β
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 87
No. 11 2013

1942
ANIKEEV et al.
4. J. Lalko, A. Lapczynski, D. McGinty, et al., Food
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5. B. D. Ribeiro, D. W. Barreto, and M. A. Z. Coelho,
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Pd[(PPh3)]4/PPh3 complex in DMSO at 100°C for
14 h [17]. Synthesis of triene
6 by the reduction of
β
ꢀionone
ꢀionol
230
respectively. Note that compound
2
using Na(Me2N)BH3 or by dehydration of
β
7 in the presence of (Me2N)3PO at 215–
°C
for 30 min was described in [18] and [15],
is an important
Chem., Int. Ed. Engl. 42, 5333 (2003).
6
component of passion fruit juice that is responsible for
its odor [15].
7. B. N. Joshi, R. Seshadri, K. K. Chakravarti, and
S. C. BhaꢀJtacharyya, Tetrahedron 20, 2911 (1964).
To summarize, we have studied the reactivity of
and ꢀionones and under the conditions of a superꢀ
critical solvent in a flow reactor in the presence of
Al2O3. Under these conditions, ꢀionone was
reduced with the solvent component, giving ꢀionol
At the same time, ꢀionol was unstable already at
200 and underwent dehydration. The secondary
reaction products were megastigmatrienes ; the
α
ꢀ
8. I. V. Il’ina, V. P. Sivcev, K. P. Volcho, et al., J. Supercrit.
Fluids 61, 115 (2012).
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1
2
α
1
α
3.
β
7
°C
4–6
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ACKNOWLEDGMENTS
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This study was financially supported by the Russian
Foundation for Basic Research (project no. 11ꢀ08ꢀ
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RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 87
No. 11 2013