DOI:
10.1039/B009199P
(Paper)
Green Chem., 2001,
3, 52-56
Potassium exchanged zirconium hydrogen phosphate
Zr(O3POK)2: a heterogeneous basic catalyst for
Knoevenagel reaction without solvent
Received 16th November 2000
First published on 31st January 2001
Abstract
A simple work-up to prepare crystalline potassium exchanged
zirconium hydrogen phosphate Zr(O3POK)2 is proposed.
In addition the synthesis of amorphous potassium exchanged zirconium
hydrogen phosphate Zr(O3POK)2, obtained from an
amorphous sample of Zr(O3POH)2·H2O
is reported. All these exchanged materials Zr(O3POK)2
are powerful catalysts for the Knoevenagel reaction. Furthermore the
absence of solvent increases the rate of the reaction. Products can be
separated from the catalyst by sublimation thus avoiding the use of solvent
in the purification step. The catalyst, which is thus easily recovered,
shows no appreciable loss of activity when recycled three times.
Green ContextHeterogeneous basic catalysts are of importance in the fine chemicals
area, and several have been investigated in reactions such as the
Knoevenagel reaction, an important reaction with pronounced solvent
dependency. This paper deals with a simplified preparation of one such
catalyst, and shows that it is active in the condensation of aromatic
aldehydes with C-acids. Of particular interest is the ability to run the
reactions without solvent, and to isolate the products by sublimation, so
also avoiding the need for solvents in the purification step.DJM |
Introduction
The use of heterogeneous catalysts allows a simplification of the
purification step to a simple filtration, separating the catalyst from the
reaction media. Heterogeneous basic catalysis is an area of growing
interest which has been recently reviewed.1
The structure of inorganic catalysts may be amorphous (silica, alumina) or
organised (Al-MCM, zeolite, clay, etc.).2 Even in the latter class of inorganic basic
catalysts, their structures are frequently unknown on the atomic scale.
This increases the difficulty of characterising the accurate structure of
the catalytic centre. Metal–phosphate materials
M(O3POH)n are a class of compounds that has
been widely studied as proton conductors,3
ionic exchangers,4 catalysts5 or as supports for ionic chromatography.6 The protons of these materials may be exchanged to
yield potentially basic materials. Furthermore the structure of these
exchanged metal–phosphate materials may be determined at the atomic
level. The potassium exchanged zirconium hydrogen phosphate
Zr(O3POK)2 has already been used as a basic catalyst
for Michael addition,7 Henry
reaction,8 cyanosilylation of carbonyl
compounds9 and more recently for the
desilylation of phenol silyl ethers.10
Zr(O3POK)2, is a layered material which possesses
ionic oxygen pointing towards the interlayer space. This compound may be
obtained either from zirconium hydrogen phosphate
Zr(O3POH)2·H2O via an
exchange with potassium hydroxide7 or
directly from a solid-phase synthesis at high temperature.11The Knoevenagel condensation is a useful reaction for the generation of
double bonds from a carbonyl compound and an active methylene compound.
Many homogeneous catalysts have been used to promote this reaction
(triethylamine, pyridine–TiCl4, secondary amines
etc…).12 More recently the
use of heterogeneous basic catalysts have been employed to facilitate the
separation of the catalyst from the reaction media. Furthermore in many
cases the catalyst may be reused. Metal oxides supported on silica gel,
barium hydroxide, zeolites, montmorillonite, magnesium and aluminium
oxides, hydrotalcite,13 Cs-MCM-41,14 modified silicagel,15 and more recently Ga/Al-containing layered
double hydroxides16 are just a few examples
of effective materials which may be used for the Knoevenagel condensation.
In some cases, the reaction can be achieved under dry conditions thus
decreasing both the cost of the synthesis and the amount of waste
flow.17
Here, a simplification of the literature procedure to synthesise
crystalline Zr(O3POK)2 is reported as well as the
synthesis of amorphous samples of Zr(O3POK)2. The
basic properties of these materials are used to catalyse Knoevenagel
condensations.
Results and discussion
The synthesis of potassium exchanged zirconium phosphate
Zr(O3POK)2 according to the literature [from
Zr(O3- POH)2·H2O] is quite
laborious as it needs several steps. Nevertheless this method is more
convenient for organic chemists, compared to the solid-phase
synthesis,11 since it does not need special
equipment (high temperature oven). The first step, as reported in the
literature, is to increase the specific surface area of the parent material
Zr(O3POH)2·H2O. Exfoliation with
n-butylamine followed by a reprecipitation leads to an increase in
the specific surface of the parent material from 0.5 to 17 m2
g−1. In order to reduce the number of steps to produce
Zr(O3POK)2 we have utilized crystalline
α-zirconium hydrogen phosphate directly in the exchange process.
α-Zirconium hydrogen phosphate
Zr(O3POH)2·H2O 1a was
obtained according to a modification of the literature procedure18 (the BET specific surface area of
Zr(O3POH)·H2O thus obtained was 7.8
m2 g−1). In order to produce a large amount of
Zr(O3POK)22a the concentration of the KOH
and KCl solutions in ultra-pure water was dramatically increased (1 M
instead of 0.1 M). Thus 8 g of Zr(O3POK)22a
were produced with a reasonable volume of solution. The X-ray powder
diffraction pattern of Zr(O3- POK)2 thus synthesised
is compared (Fig. 1) to the structure
obtained by Dörffel and Liebertz11
from a single-crystal X-ray diffraction study. The only notable differences
concern the cell parameters which are slightly larger in our study (average
0.18%; see Experimental section). As expected from the crystal structure, a
singlet is observed for the 31P MAS NMR spectrum of
Zr(O3POK)2 (Fig. 2)
indicating the equivalence of all the phosphorus atoms in the structure and
thus demonstrating the efficiency of the exchange. The chemical shift of
Zr(O3POK)22a is displaced towards low field
(δiso = −11.4 ppm) compared to the parent
material Zr(O3POH)2·H2O
(δiso = −18.7 ppm). Previous work
describing the high-resolution 31P MAS NMR in some antimony
phosphates reported that the 31P chemical shift
(δiso) was closely dependent on the P–O
bond length.19 In compounds which possess a
non-coordinated oxygen, the shorter the P–O bond is the larger the
shielding effect is on the phosphorus. It is of note that in the present
example, that the opposite behavior is observed. Indeed, the P–O bond
length (the bond pointing to the interlayer space) in compounds 1a
and 2a are 1.542 Å25 and
1.508 Å,11 respectively. This
behaviour could arise from the three P–O bonds connected to zirconium
that are longer in compound 2a (1.548 Å) than in compound
1a (average: 1.515 Å). The excellent thermal stability of
Zr(O3- POK)22a, which is stable up to 1200
°C as reported earlier,7 was confirmed
by TDA analysis which revealed no transition upto 1000 °C except a
transition at 150 °C due to the loss of residual water [Fig. 5(c)]. FTIR analysis [Fig. 6(a)] clearly indicates two P–O
stretching vibrations: one at 1174 cm−1 arising from the
shortest P–O bond (1.508 Å) and one at 976
cm−1 which may be attributed to the three P–O bonds
with a length of 1.548 Å. It is worth noting that compound
2a absorbs water from the atmosphere leading to an increase in the
broad band at 3450 cm−1 thus decreasing the resolution of
the two bands at 974 and 1174 cm−1. The two bands at 552
and 614 cm−1 disappear in the amorphous sample 2c
supporting the assumption that these two bands correspond to the vibrations
of the network that can be observed only in a well organised structure. |
| Fig. 1 Calculated (×), observed (—) and difference X-ray profiles
for Zr(O3POK)2. Reflection marks are shown for the
P space group. | |
 |
| Fig. 2 31P MAS NMR spectra (12 kHz, NS = 4; d1 = 60 s): (a)
Zr(O3POH)2·H2O 1a: (b)
Zr(O3POK)22a. | |
The amorphous samples of Zr(O3POK)2, 2b
and 2c, were obtained by an exchange process of
Zr(O3POH)2·H2O 1b and
1c in the presence of KCl and KOH aqueous solutions. Compounds
1b and 1c were synthesised by the reaction of
ZrOCl2·8H2O with H3PO4
in water without HF and were obtained, owing to the different conditions of
reaction (1b: 14 h at reflux; 1c, 4 h at room
temperature), with different specific surface areas (BET), 9 and 226
m2 g−1, respectively. The specific surface area
(BET) of the potassium exchanged material 2b is 7 m2
g−1 while that of compound 2c is dramatically
reduced (55.9 m2 g−1) compared to the specific
surface area of the parent material 1c (226 m2
g−1). The FTIR spectra of these exchanged amorphous
samples [Fig. 6(c)] clearly indicates the
bands corresponding to the P–O stretching (950–1180
cm−1). Figs. 3 and 4 show the 31P MAS NMR of the parent
materials Zr(O3POH)2·H2O
1b and 1c and materials 2b and 2c
resulting from the exchange of the hydrogen atoms by potassium. In
agreement with previous work,20 the
amorphous samples of Zr(O3POH)2·H2O
1b and 1c show several signals while the crystalline
sample simply shows a singlet (Fig. 2). Both
the relative intensities of the signals and the specific surface area
depend on the advancement of the crystallisation. The chemical shifts of
the exchanged compounds 2b and 2c are displaced towards
lower field as found for the crystalline sample 2a (Fig. 2) indicating the efficiency of the
exchange.
 |
| Fig. 3 31P MAS NMR spectra (12 kHz): (a)
Zr(O3POH)2·H2O 1b; (b)
Zr(O3POK)22b (peaks marked with * are
rotation bands). | |
 |
| Fig. 4 31P MAS NMR spectra (12 kHz): (a)
Zr(O3POH)2·H2O 1c; (b)
Zr(O3POK)22c (peaks marked with * are
rotation bands). | |
 |
| Fig. 5 DTA analyses under argon (heating rate: 10 °C
min−1): (a) compound 2c; (b) compound
2b; (c) compound 2a. | |
 |
| Fig. 6 FTIR spectra of Zr(O3POK)2 in KBr: (a) anhydrous
crystalline sample 2a; (b) wet crystalline sample 2a
(sample left in an open flask for 1 month); (c) anhydrous amorphous sample
2c (peak marked as * is an artefact due to the presence of
CO2). | |
Thermal analysis of these two amorphous exchanged materials 2b
and 2c (DTA) reveals an endothermic transition from 80 to 250
°C which is due to the loss of residual water [Fig. 5(a) and 5(b)]. Two (740 and 795 °C) and
three (545, 701 and 722 °C) exothermic transitions, respectively are
observed for compounds 2c [Fig.
5(a)] and 2b [Fig. 5(b)].
Partial hydrogen exchange in compound 2b could explain its thermal
behaviour. Indeed, the first transition (545 °C) could be attributed to
the condensation of phosphate groups into pyrophosphates as was previously
reported for the non-exchanged materials Zr(O3POH)2
(transition observed at 550 °C20). The
two transitions observed for compounds 2b (701 and 722 °C) and
2c (740 and 795 °C), that have almost the same relative
intensity, could arise from the same transformation. These transitions were
previously reported for a copper salt intercalated in α-zirconium
phosphate.21 The different position of
these transitions could arise from a partial exchange in compound
2b. Furthermore the absence of a transition around 550 °C for
compound 2c indicates a fully exchanged material.
Zr(O3POK)2 was first tested as a basic catalyst
for the Knoevenagel condensation of piperonal and Meldrum’s acid.
According to the kinetic data obtained using the amorphous catalyst
2b (Table 1, entries 1 and 3),
THF was the best solvent while the use of ethanol (Table 1, entry 5) inhibited the reaction. The
superiority of THF over CH2Cl2 may be explained by
the fact that Knovenagel condensation produces one mol of water per mol of
product. Owing to the non-miscibility of water and dichlorormethane and
taking into account the polar character of the catalyst, water produced by
this condensation could be readily localised on the catalyst when
dichloromethane is used as a solvent. Thus the efficiency of the catalyst
could be affected. Nevertheless, when the reaction is carried out without
solvent the reaction time is even shorter (Table
1, entries 7 and 9). Noteworthy is that the reaction times and
yields are identical whatever the structure (amorphous or crystalline) of
the catalyst used for the reaction (Table
1, entries 2 and 4). This is the first example of the use of
amorphous potassium exchanged zirconium phosphate as a basic catalyst. In
absence of solvent a total conversion is reached after only 14 minutes.
Interestingly, no difference (yield, reaction times) was observed by the
use of microwave heating or classical heating (isomantle). Nevertheless for
the expediancy of the procedure, microwave heating (commercial microwave
oven Whirlpool) was chosen. The powder X-ray diffraction of the catalyst
after the condensation of piperonal with Meldrum’s acid, and before
the elimination of the product, did not reveal any modifications of the
d001 peak (9.02 Å), indicating that neither the
substrate nor the product are present in the interlayer space. This
observation indicates that the catalytic process is only located on the
surface of the catalyst. Nevertheless the kinetics of the Knoevenagel
condensation of piperonal with Meldrum’s acid (experiments carried
out in THF, Table 1 entries 2–4)
did not show any significant difference between catalysts 2a,
2b and 2c despite their different specific surface
areas.
Table 1 Knoevenagel condensation of piperonal to Meldrum’s acid

Taking into account the fact that reactions carried out without solvent
contribute to a reduction in costs and waste flow it is of note that all
the following reactions were achieved without solvent. The mixing step of
the catalyst with substrates can affect the reproducibility of the results.
The first method, which is completely solvent-free, is to mechanically mix
for the catalyst with the substrates for several minutes. The second method
is less laborious and consists of dissolving the substrates in a minimum of
solvent followed by the addition of this solution to the catalyst. Finally
the solvent is removed in vacuo leading to the substrates being
absorbed on the catalyst. Although the results of these two methods were
identical, we chose the second method due to the rapidity of the work up.
Selected data corresponding to the condensation of piperonal with different
active methylene compounds are reported in Table
2. The mechanism of the Knoevenagel condensation (under basic
conditions) is that one proton from the acidic methylene compound is
removed by the base to generate a nucleophile that will react with the
aldehyde. In view of the results of Table
2, it appears that the catalyst 2a is efficient for
methylene compounds which possess a pKa (determined in
water) in the range 4–12. Surprisingly, the use of tetronic acid as
the methylenic acid compound (Table 2,
entry 6 ; pKa = 3.76) does not yield the condensation
product. Despite the coloration of the catalyst almost all the piperonal is
recovered; this coloration might be due to the auto-condensation of
tetronic acid. Despite the lack of reactivity of tetronic acid it is worth
mentioning that other methods are able to catalyse the aldol type
condensation of tetronic acid with aldehyde in a 1∶122 or 2∶123
ratio. On the other hand, catalysts 2a are not sufficiently basic
to be efficient when methylenic compounds possessing a
pKa > 13 are used. To illustrate the reusability of
the catalyst, catalyst 2a was engaged three times in the
condensation of piperonal with Meldrum’s acid (Table 3). After each reaction the product was
separated from the catalyst by sublimation. After three cycles the catalyst
was still efficient as reported in Table
3.
Table 2 Condensation of piperonal to methylene acid compounds using microwave
heating (450 W, 7 × 2 min)

Table 3 Illustration of the reusability of catalyst 2a

Conclusion
The present article deals with the simplification of the synthesis of
crystalline potassium exchanged zirconium hydrogen phosphate 2a.
Furthermore the synthesis of the amorphous equivalent of compound
2a is described. The basic properties of these materials, which
are readily available in large amounts, were used to catalyse the
Knoevenagel condensation. Interestingly, both amorphous and crystalline
potassium exchanged zirconium hydrogen phosphate are able to catalyse the
Knoevenagel reaction. These catalysts are efficient for methylenic
compounds possessing pKa values in the range of
4–12. It is noteworthy the efficiency of these catalysts is increased
by the absence of solvent. The yields reported and the reaction times are
identical to or better than those previously reported. Furthermore the
catalyst is easily recovered and can be reused without significant loss of
its efficiency.Experimental
Catalyst preparation
α-Zr(O3POH)2·H2
O 1a. A modification of the method of slow decomposition of a zirconium fluoro
complex was used.24 8.2 ml of 40% aqueous
HF solution (188 mmol) was added to a solution of
ZrOCl2·8H2O (15.01 g, 46.6 mmol) in 217 ml of
ultra-pure water placed in a 1 l round bottomed-flask fitted with an air
condenser. 75% aqueous H3PO4 (163.3 ml; 1.97 mol) was
added to this solution. The homogeneous solution was heated at 90–95
°C for 7 days. The precipitate was recovered by filtration, washed with
ultra-pure water (150 ml), acetone (20 ml) and dried at room temperature
for 48 h. According to powder X-ray diffraction, the structure of the
product is in excellent agreement with literature data.2531P MAS NMR (12 KHz; d1 = 60 s; NS =
4): −18.7 ppm (lit.,26
−18.7
ppm); BET surface area 7.8 m2 g−1 (lit.,27 0.5 m2 g−1). Amorphous zirconium phosphate
Zr(O3POH)2·H2O 1b. The literature procedure28 was modified
as follows: a solution of ZrOCl2·8H2O (10 g,
31 mmol) in water (55 ml) was added to a solution of 85% aqueous
H3PO4 (7.15 g; 62 mmol) in 30 ml of water. The
solution was refluxed for 14 h, the solid filtered off, and washed with
ultra-pure water (50 ml), acetone (20 ml) and dried at 100 °C for 5 h
to yield a white solid (9.3 g; 100%). The specific surface area (BET) of
the resulting compound was 9.0 m2 g−1. Amorphous zirconium phosphate
Zr(O3POH)2·H2O 1c. The literature procedure25 was modified
as follows: a solution of ZrOCl2·8H2O (10 g,
31 mmol) in water (55 ml) was added to a solution of 85% aqueous
H3PO4 (7.15 g; 62 mmol) in water (30 ml). The
solution was stirred at room temperature for 4 h, the solid filtered off,
and washed with ultra-pure water (50 ml) and acetone (20 ml) and then dried
at 100 °C for 10 h to yield a white solid (9.3 g; 100%). The specific
surface area (BET) of the resulting compound was 226.0 m2
g−1. Crystalline potassium exchanged zirconium phosphate
Zr(O3POK)2 2a. A modification of the method described by Costantino et
al.7 was used: 50 ml of KOH (1 M in
ultra pure water) and 50 ml of KCl (1 M in ultra pure water) was added to
6.9 g of crystalline
α-Zr(O3POH)2·H2O 1a
(21.6 mmol). After 24 h of slow stirring KCl (7 ml; 1 M) and KOH (7 ml; 1
M) were added. The heterogeneous solution was stirred for a further 6 days.
The precipitate was filtered off, washed with potassium hydrogenphosphate
(20 ml; 1 M in ultra pure water) and dried at room temperature for 2 days.
The product was dried further at 190 °C for 24 h to yield 7.75 g of
white solid (100%). The specific surface area (BET) of the product was 11.0
m2 g−1. 31P MAS NMR (12 kHz ; d1=
60s ; NS = 4) δiso = −11.3 ppm; powder
X-ray diffraction (see Fig. 1): trigonal,
space group P
a = 5.188(9) [lit.,11a = b = 5.176(1)], c
= 9.022(2) [lit.,11c = 9.012(8)],
number of reflections: 162; GOF = 1.7, Rp = 0.067;
RWp = 0.093; RI = 0.08. Amorphous potassium exchanged zirconium phosphate
Zr(O3POK)2 2b and 2c. The same procedure described for compound 2a was used. The
starting compounds were 1b and 1c, respectively. The
specific surface area of the exchanged materials 2b and
2c were 7.0 and 55.9 m2 g−1,
respectively.
Knoevenagel condensations
In a typical experiment 200 mg of compound 2a were added to a
solution of piperonal (75 mg; 5 mmol) and Meldrum’s acid (72 mg ; 5
mmol) in dichloromethane (2 ml) placed in a 100 ml round bottomed flask.
The solvent was removed under reduced pressure. The round bottomed flask
was placed in a microwave oven (Whirlpool, M430, Jet 900) and irradiated
(450 W) for a total of 14 min and in 2 min intervals. After cooling, the
crude product was purified by sublimation (10 mTorr, isomantle at a
temperature between 180 and 220 °C) to give
5-(3,4-methylenedioxyphenyl)methylene-2,2-dimethyl[1,3]dioxane-4,6-dione
(0.14 g; 100%). mp 179 °C (lit.,29
178.5–179.5 °C). The results of other experiments are summarised
in Table 2. Acknowledgements
We thank Valérie Montouillout and Christian Fernandez
(Laboratoire de Catalyse et Spectroscopie, L.C.S. UMR CNRS 6506) for
assistance in the solid-state NMR experiments.References
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