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Braz. J. Chem. Eng. vol. 15 no.

2 So Paulo June 1998

http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0104-66321998000200004

Aldol Condensation of Citral with Acetone oN Basic Solid Catalysts

C. NODA1, G. P. ALT1, R. M. WERNECK1, C. A. HENRIQUES2


and J. L. F. MONTEIRO1
1
NUCAT - Ncleo de Catlise, COPPE/UFRJ, CP 68502, CEP: 21945-970,
Rio de Janeiro, RJ, Brazil Fax: (021) 290-6626
2
Instituto de Qumica, UERJ, Rio de Janeiro, RJ, Brazil

(Received: November 5, 1997; Accepted: February 3, 1998)

Abstract - The catalytic performance of solids with basic properties,


such as CaO, MgO and hydrotalcites, was evaluated in the aldol
condensation of citral and acetone, the first step in the synthesis of
ionones from citral. The best results were obtained with CaO and
hydrotalcite with high conversions (98%) and selectivities (close to 70%
for the main product) observed for both of the catalyst. Such
pseudoionone yields were greater than those reported in the literature for
the homogeneous reaction.
Keywords: Citral, pseudoionones, basic catalysts, hydrotalcite, calcium
oxide, magnesium oxide.

INTRODUCTION

Aldol condensation of citral with acetone on basic catalysts and the subsequent
cyclization of the intermediates over acid catalysts forming a and b -ionones are
examples of processes involving products obtained from essentials oils used extensively
in the perfumery and soap industries. b -ionone is also important as a precursor in the
synthesis of vitamin A.

Ionones are commercially obtained through a conventional homogeneous catalytic


process involving many operations. The first step consists in the obtention of
pseudoionones using aldol condensation of citral with acetone catalyzed by KOH
solution. Citral conversion is close to 60% and pseudoionone selectivity comes close to
80%. The second step is the obtention of a and b -ionones through the cyclization of
pseudoionones in acid media. In this process conversion is almost 60%. a and b -Ionone
selectivities depend on the strength of the acid used as catalyst. a -Ionone is obtained in
the presence of weak acids, such as phosphoric acid. When a strong acid is used, for
example, sulfuric acid, b -ionones are obtained. Operations such as neutralizations,
washings, phase separations and vacuum distillations are associated with both steps.

The substitution of this conventional process by heterogeneous catalysis can reduce the
consumption of reactants and the number of steps involved. For example, the
neutralization and washing stages can be eliminated and substituted by a filtration stage.
In addition, the possibility of selecting the morst active and/or the morst selective
catalyst can increase the total yield of desired products and can also reduce by-product
formation, thereby simplifying the distillation step.

This work studied the first step of the ionone synthesis process, the obtention of
pseudoionones from citral and acetone by aldol condensation using basic solid catalysts,
aiming at achieving a feasible substitution of classic homogeneous processes by
heterogeneous ones. Pontentially, the latter are more selective and have simpler
separation stages, thus reducing the costs of the process.

EXPERIMENTAL

Citral was obtained by vacuum fractional distillation of Cuban lemongrass essential oil
with 91.3% of the citral isomer mixture (geranial and neral). Acetone (99.5% purity)
containing less than 0.007% water was purchased from VETEC.

The active forms of calcium and magnesium oxide were prepared according to Tsuji et
al. (1994). Calcium and magnesium oxide precursors were dissolved in deionized water
by stirring at room temperature for 24 hours and dried at 383 K for 24 hours. Finally,
the active oxides (CaO and MgO) were obtained from their respective hydroxides by
thermal treatment under vacuum up to 773 K.

The active form of hydrotalcite (HTC450) was obtained from the original material
synthesized by Andrade (1997) by thermal decomposition in a flow of air up to 723 K.
The chemical composition of the catalysts used was determined by atomic absorption
(Perkin-Elmer AAS 1100B spectrophotometer) and the textural characteristics were
determined by physical adsorption of N2 at 77 K (Micromeritics ASAP 2000). The water
and carbon dioxide contents in these samples were determined by TGA/DTA (Rigaku
TAS 1000). Samples of calcium oxide (CaO), magnesium oxide (MgO) and hydrotalcite
(in the original form and after thermal treatment) were studied by DRX (type F Siemens
Difractometer), with CuKa radiation, 35 KV and 30 mA. The LSUCRI (Least Square
Unit Cell Refinement) program was employed for structural refinement.

The reaction was carried out in liquid phase in a stainless steel batch reactor with a 50
ml capacity. The reactor was magnetically stirred and heated with an oil bath. Each
catalyst was preactivated ex-situ in a glass calcination cell. After activation, it was
rapidly transferred to the reactor and a mixture of citral and acetone (1:1 molar) was
immediatly added. The catalyst concentration was always 2% w/w.

The tests with hydrotalcite and magnesium oxide as catalyst were done at 330 and 398
K under autogenous pressure for 4 hours. When calcium oxide was used as catalyst the
reaction was studied for 1, 2 and 4 hours at 330, 363, 383 and 398 K. At the end of each
run, the system was cooled to room temperature and the two phases separated by
decantation. The liquid phase was stored in a dark flask and kept in a freezer. For the
chromatographic analysis (VARIAN 3700 Chromatograph, 35 m Carbowax 20 M
capillary column and FID) it was dissolved in n-hexane (purity of 90% v/v). Gas
chromatography mass spectrometry (Shimatzu QP 2000 A GC/MS) was also used for
the identification of the reaction products.

RESULTS AND DISCUSSION

The Mg/Al ratio of the original hydrotalcite sample was 2.7. This value and the results
of the TGA/DTA analysis allowed the following composition to be established for this
sample:

Mg5.84Al2.16(OH)16(CO3)1.08.4.98 H2O

For a calcium oxide sample prepared as described above and stored in a closed flask
with no special precautions, atomic absorption analyses gave a calcium content lower
than that anticipated for pure CaO. DRX analyses showed that this sample was a
mixture of calcium carbonate and calcium hydroxide. The absence of a calcium oxide
phase was attributed to the fast rehydratation and carbonation of the sample upon being
exposed to ambient air.

Progressive carbonation of the original calcium hydroxide was also observed, since the
amount of calcium carbonate in this sample increased with time up to a limiting value of
about 40 wt% CaCO3. The so-called calcium oxide obtained by the decomposition of
this sample was indeed a mixture of about 53 wt% CaO and 47 wt% CaCO3. This was
the sample used in the catalytic runs.

For the magnesium hydroxide no carbonation was observed when the sample was
treated and stored under conditions similar to those described above for Ca(OH)2. So,
upon in-situ calcination of this sample, pure magnesium oxide was generated and used
as catalyst. DRX analyses indicated that this sample suffered a slow rehydratation
process upon being exposed to ambient air.

Table 1 shows the results of the textural characterization of the samples. It was observed
that the BET area of magnesium oxide is four times larger than that of calcium oxide.
This result could be attributed to a pore obstruction caused by the growth of a
superficial phase of calcium carbonate. The inspection of the magnesium oxide isotherm
suggests that the high mesoporosity of this material is due to intercrystalline voids. No
microporosity was observed for either material.

When the results of the textural analysis of the calcined hydrotalcite were compared to
those of the magnesium oxide, a lower BET area and a lower mesoporosity were
observed. The mesoporosity of this material can also be attributed to intercrystalline
spaces.

When the aldol condensation of citral with acetone was studied at 330 K, the conversion
of citral was not significant. The highest values for citral conversion were obtained at
398 K, particularly for the calcium oxide (CaO) and the calcined hydrotalcite (HTC450)
catalysts. When magnesium oxide (MgO) was employed as the catalyst, citral
conversion was about 20%. These results, associated with those from Noda et al. (1997)
for the self-condensation of acetone, indicate that the aldol condensation of citral with
acetone requires stronger basic sites and higher temperatures than the self-condensation
of acetone. This derives from the fact that when the acetone carbanion attacks the citral
molecule forming a new carbon-carbon bond with the carbonylic carbon of citral, as
seen in Scheme 2, the resonance stability of the citral molecule is lost.

For the three catalysts the main products of the aldol condensation of citral with acetone
at 398 K were the pseudoionone isomers. The formation of superior condensation
products. as a result of the reaction between pseudoionone and a molecule of acetone,
was also observed. Selectivities for the main products (pseudoionones and the superior
condensation products) at 98% conversion of citral are compared in Figure 2.

Table 1: Textural characterization of the samples

Mesopore
BETspecific area Micropore volume
Sample volume
(m2/g) (cm3/g)a
(cm3/g)b
CaO 48 0.00 0.17
MgO 212 0.00 0.82
HTC450 174 0.01 0.61

(a) t-plot method; (b) BJH method


Scheme 1: Obtention of ionones from citral.

Scheme 2: Acetone carbanion formation and reaction with the citral molecule.

Figure 1: Aldol condensation of citral with acetone at 398 K, 4 hours and 3 atm on the
different catalysts.
Figure 2: Product selectivities for the aldol condensation of citral with acetone at 398
K, 4 hours and 3 atm on calcium oxide and hydrotalcite. PSI= Pseudoionones; PCS=
Superior condensation products.

For the HTC450 catalyst pseudoionone (PSI) selectivity was higher than 70% and that
of the superior condensation products (PCS) was lower than 10%. The use of calcium
oxide as catalyst increased PCS selectivity to 15%.

The effect of temperature and reaction time on the reaction was evaluated for the
calcium oxide catalyst. Figure 3 shows the variation in the conversion of citral with
temperature and reaction time, while the results obtained for selectivity and yield of PSI
are presented in Figures 4 and 5, respectively. As expected, reaction time presented a
more significant influence at lower temperatures since total conversion was attained
after two hours at 398 K. For a reaction time of 1 hour, increasing temperature caused a
slight increase in PSI selectivity but a strong increase in citral conversion. For larger
reaction times, temperature hardly affected PSI selectivity, which reached values
between 60 and 70%.

PSI yields as a function of temperature at different reaction times are presented in


Figure 5. It can be observed that at the highest temperature (398 K) the PSI yields
achieved in this work were greater than those reported in the literature (Noda et all.,
1987) for the reaction in homogeneous medium (48%).

Figure 3: Influence of temperature and reaction time on citral conversion using calcium
oxide as catalyst.
Figure 4: Influence of temperature and reaction time on the pseudoionone selectivity
using calcium oxide as catalyst.

Figure 5: Influence of temperature and reaction time on pseudoionone yield using


calcium oxide as catalyst.

CONCLUSIONS

The aldol condensation of citral with acetone on basic solid catalysts was studied. The
best results were obtained using calcium oxide and calcined hydrotalcite as catalysts.
Citral conversion at 398 K and 3 atm was about 98% and pseudoionone selectivity was
greater than 68%. Pseudoionone yield was higher than that reported in the literature for
the homogeneous process, confirming the success of the substitution of the
homogeneous catalyst by a heterogeneous one.

The effect of temperature and reaction time was also studied with calcium oxide as
catalyst, and it was observed that both citral conversion and pseudoionone yield were
favored by an increase in these parameters.

The reaction products were confirmed by CG/MS analyses and they were in accordance
with the reaction mechanism proposed in the literature.
REFERENCES

H.Tsuji, F. Yagi, H. Hattori and H. Kita, "Self-condensation of n-butiraldehyde over


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Noda, C., Masters thesis, PEQ/COPPE/UFRJ, Rio de Janeiro, RJ (1997). [ Links ]

C. Noda,; J. Magraner and P.J. Diaz, Rev. Cubana de Qumica (1987). [ Links ]