Cyclization of Pseudoionone Using Acid Carbon Obtained
from Biodiesel Waste: Comparison with Classical
Catalyst and Study of Reaction Parameters
Gabriela Nohemi Nuñez Esteves,1 Michelle Mantovani1, Marcos Lopes de Araújo1, Wagner Alves Carvalho1,
Maraisa Gonçalves2, Reynaldo Gisto Gabriel Sandrini1, Dalmo Mandelli1*
1
Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, 09210-070, Brazil.
Instituto de Ciências e Tecnologia, Universidade Federal de São Paulo, São José dos Campos, 12231-280, Brazil.
*Corresponding author: [email protected]
2
Keywords: Cyclization, Pseudoionone, Acid carbon, Amberlyst
1. Introduction
Pseudoionone isomers (α, β and γ) are compounds
widely used as fragrances and starting materials for
the pharmaceutical industry, for example β-ionone is
the preferred reagent for different syntheses leading
to vitamin A formation, while α- and γ-ionones are
widely used in the fragrance industry [1,2].
Currently, the commercial synthesis method of
ionones is carried out in two homogeneously
catalyzed stages, as shown in the Figure 1 [3].
MCM-41 polymer resins and heteropolyacids
supported on silica [1,4-8]. Here we prepared an
acid carbon using glycerol, a waste from biodiesel
industry and tested it in the cyclization of
pseudoionone. To optimize and understand the
system, we also made reactions with a classical
catalyst, the resin Amberlyst 35. Reactions
parameters as temperature, time and speed of stirring
were evaluated.
2. Experimental
Preparation of Acid Carbon from Glycerol
Carbons
were
prepared
by
hydrothermal
carbonization of glycerol in a stainless steel reactor
using a ratio of glycerol: sulfuric acid (1: 3), 180°C
for 15 min, 6 h or 24 h. The obtained carbons were
washed with water and dried at 80°C. The solids
were analyzed by infrared spectroscopy. One sample
of glycerin from an industrial biodiesel Brazilian
company (Oxiteno) was also used.
Figure 1. Process for synthesis of ionones from citral
These methods of synthesis, via homogeneous
catalysis, involve restrictions related to high toxicity,
undesirable residues, corrosion and costs with the
separation of the homogeneous catalyst. Therefore it
is interesting to develop heterogeneous acidic
catalysts that are efficient for the processes of
obtaining ionones, favoring a more environmentally
correct alternative. In the literature, several works
using heterogeneous systems have been published,
using different catalysts for this process as zeolites,
Pseudoionone Cyclization Reactions
The reactions were performed at 60 or 80°C in a
glass reactor under stirring, reflux and inert
atmosphere. After pseudoionone (1.8 mmol),
dehydrated solvent (toluene, 10 mL) was added and
the mixture purged with nitrogen. After few minutes
the system was heated and the catalyst (Amberlyst
35 or Carbon, 0.2 g) was added. The reaction was
analyzed by gas chromatography, using an HP
Shimadzu 2010 chromatograph, equipped with a
polyethylene glycol column (Innowax, 25 m x 0.2
mm x 0.4 μm), combined with flame ionization and
an automatic injector. Quantification of the products
was made by constructing product calibration curves
using known concentration standards and nitrobenzene as the internal standard.
3. Results and discussion
The infrared spectra of acid carbons prepared with
different times of carbonization are shown in the
Figure 2. All spectra were very similar. Carbons
showed characteristic stretching bands from –SO3H
Table 1: Pseudoionone cyclization to ionone isomers
using Amberlyst-35 or Carbon as Catalysts
Catalyst
t
(h)
T
( C)
Conv
(%)
Amberlyst
Amberlyst
Amberlyst
Amberlyst
Amberlyst
Amberlysta
Amberlysta
Amberlysta,b
Amberlysta,b
Carbon
Carbon
Carbon
Carbon
1
3
10
1
3
1
3
1
3
3
5
10
24
60
60
60
80
80
80
80
80
80
60
60
60
60
20
56
91
81
94
61
85
90
97
21
29
44
92
o
Selectivity (%)
ionone ionone
18
10
22
8
20
7
23
9
23
8
12
6
14
7
12
7
16
8
4
6
6
14
7
18
4
15
M.B.
(%)
83
59
36
42
36
50
39
23
12
85
80
70
27
a: weak stirring; b: pseudoionone added slowly, during 40 min. Conv =
pseudoionone conversion; M. B = mass balance.
Figure 2. Infrared spectra of carbons prepared with
different times of hydrothermal carbonization: 15 min,
6 h and 24 h.
(1030 cm-1 and 1175 cm-1), carbonyl (1701cm-1),
–COOH (broad at 3370 cm-1) and aromatics groups
(1590 cm-1). These results indicate the success on
the incorporation of –SO3H in the structure of the
catalyst. One acid carbon prepared using glycerin
from an industrial biodiesel company gave similar
spectra. Their acidities, determined via Boehm
titration using NaOH were all close to 4 mmol H+/g.
The
carbon
prepared
with
hydrothermal
carbonization (t = 15 min) was used in the cyclization of pseudoionone. The results, compared with
those ones obtained with commercial Amberlyst 35
are shown in the Table 1. The effect of different
experimental variables such as reaction time, speed
of stirring and speed of pseudoionone addition was
investigated. Amberlyst is very active, giving
conversions of 94% after 3 h at 80oC. A decrease in
the temperature to 60oC reduced the conversion to
56% (after 3 h) However the resin shows poor
selectivity, probably due to the degradation of both
substrate and ionone isomers to mainly polymers [9].
The principal product obtained with this commercial
resin was -ionone, with a typical selectivity of 20%,
followed by -ionone, with 6-10%. Absence of
-ionone can be justified by high reactivity and low
stability of this isomer, and is easily transformed
to more stable -ionone [8]. The slower addition
of pseudoionone did not affect the selectivity.
However, the use of weaker speed of stirring
decreased the conversion at 80oC/1h from 81% to
61%; the selectivity to -ionone also fell from 23%
to 12%. Acid carbon gave smaller conversions than
Amberlyst, however interesting results were
obtained: the better mass balance and the highest
ratio / ionones (3.7), against typically 0.5 for the
resin. Probably stronger acid sites on carbon
converted -ionone to -ionone, improving the
proportion of this isomer.
4. Conclusions
Acid carbon is a promising catalyst for pseudoinone
cyclization to -ionone. More experiments must be
done to improve the activity of this catalyst that can
be easily obtained from biodiesel industry waste.
Acknowledgments
CNPq 311585/2013-2 and UFABC for grants.
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