Synthesis and characterization of two novel organic-inorganic compounds based on tetrahexyl and Tetraheptyl ammonium ions and the preyssler anion and their catalytic activities in the synthesis of 4-aminopyrazolo[3,4-d]- pyrimidines

Article abstract of DOI:10.3390/molecules15042509

Two novel organic-inorganic compounds based on tetrahexylammonium (THA) and tetraheptylammonium (THPA) ions and the Preyssler anion, [NaP5W30O110]14-, were synthesized and formulated as (THA)7.7H6.3 [NaP5W30O110] (A) and (THPA)7.5 H6.5[N aP5W30O110] (B).

Full text of DOI:10.3390/molecules15042509

Molecules 2010, 15, 2509-2519; doi:10.3390/molecules15042509
OPEN ACCESS
molecules
ISSN 1420-3049
www.mdpi.com/journal/molecules
Article
Synthesis and Characterization of Two Novel Organic-Inorganic
Compounds Based on Tetrahexyl and Tetraheptyl Ammonium
Ions and the Preyssler Anion and Their Catalytic Activities in
the Synthesis of 4-Aminopyrazolo[3,4-d]- Pyrimidines
Fatemeh Farrash Bamoharram
Department of Chemistry, Islamic Azad University, Mashhad -Branch, Mashhad, Iran;
E-Mails: abamoharram@yahoo.com or fbamoharram@mshdiau.ac.ir.
Received: 5 February 2010; in revised form: 17 March 2010 / Accepted: 8 April 2010 /
Published: 8 April 2010
Abstract: Two novel organic–inorganic compounds based on tetrahexylammonium (THA)
1
4-
and tetraheptylammonium (THPA) ions and the Preyssler anion, [NaP
synthesized and formulated as (THA)7.7
aP 110] (B). The synthesized compounds were characterized by IR, UV, and TGA and
5
W
30
O110] , were
H
6.3 [NaP
5
W
30
O110] (A) and (THPA)7.5 H6.5[N
5
30
W O
used for the catalytic synthesis of 4-aminopyrazolo[3,4,-d]pyrimidine derivatives 2a-2d.
Our findings showed efficient catalytic activities for A and B.
Keywords: Preyssler anion; catalyst; heteropolyacid; organic–inorganic compound;
tetrahexyl ammonium; tetraheptylammonium
1
. Introduction
Interest in the synthesis of large polytungstates has attracted much attention. In this area, some
examples for species containing more than 18 tungsten atoms have been reported [1]. One of the
1
4-
largest polytungstates is [NaP W O ] , the so-called Preyssler anion. This heteropolyanion consists
5
30 110
3
-
of a cyclic assembly of five [PW
6
O22] units, each derived from the Keggin anion, [PW12O40] . This
anion can be obtained by the removal of two sets of three corner shared WO octahedra. We have
6
shown that the pure acid form of this polyanion, H14[NaP
applications in catalytic reactions [2–6]. Usually, acid-catalyzed reactions are carried out by use of
diverse conventional mineral acids such as H SO , HF, HCl, H PO , etc. The replacement of these
5 30
W O110], has excellent potential
2
4
3
4

Molecules 2010, 15
2510
conventional hazardous and polluting corrosive liquid acid catalysts by solid acid catalysts is one of
the key current demands in the field of catalysis. Cleaner technologies could be possible by making
use of environmentally friendly catalysts involving the use of solid acids. It was shown that
heteropolyacids in the solid state are pure Bronsted acids and stronger acids that conventional solid
acids such as SiO –Al O , H PO , HNO , H SO , and HX and HY zeolites [7,8]. These compounds
2
2
3
3
4
3
2
4
have several advantages as catalysts which make them economically and environmentally attractive
9–13]. If one applies the proposed principles of Green Chemistry we see that the Preyssler catalyst
[
can be considered a promising green catalyst candidate. This solid acid catalyst is “green” with respect
to corrosiveness, safety, quantity of waste, and separability. Moreover, while some of the acidic
catalysts such as HCl, HNO , H SO , etc, can produce chlorated, nitrated, sulfated, etc, by products,
3
2
4
Preyssler acid does not produce any of these by products. Thus, it can reduce quantity of waste formed.
In our studies it has been found that Preyssler’s anion catalyzes oxidations of organic substances
without any structural degradation. This leads to the recovery and recyclibility of this catalyst, which
is very important in catalytic processes, especially in industry.
We are interested in development of applications of the Preyssler anion in other forms such as
organic-inorganic forms. Recently, we have developed a series of reactions catalyzed by Preyssler and
nano Preyssler acidic or inorganic salt forms [14–17].
Research based on new type organic-inorganic molecular multifunctional materials is continuously
attracting the considerable interest in organic synthesis [18]. Along this line, heteropolyacids are
excellent molecular acceptors and can form novel organic-inorganic complexes with a number of
organic substrates containing N, S and O atoms. Such organic substrates often include several types of
cationic organic species [19].
Tetrahexyammonium (THA) and tetraheptylammonium (THPA) cations are examples of excellent
electron donors that possess high charge and suitable size which makes them very good inorganic
blocks for the construction of organic-inorganic hybrid compounds with the Preyssler anion. In some
cases heteropolyacids can be partly reduced, which offers the opportunity to prepare organic donor-
inorganic acceptor materials with a mixed valance state in the organic and inorganic counterparts. The
presence of strong electron delocalization in the organic chains suggests electron transfer between
organic donors and inorganic acceptors [20].
To the best of our knowledge, there are no reports of the reaction products of the Preyssler
heteropolyacid with THA or THPA as organic cations. Herein, we wish to report two novel organic-
inorganic compounds based on THA and THPA and the Preyssler anion that display good catalytic
activity in organic media.
2
. Results and Discussion
Synthesis of two novel compounds were carried out based on the reactions of the Preyssler anion
with THA and THPA, by neutralization of the Preyssler acid. In this case, diluted solutions were
generally required to avoid the precipitation of mixed salts. The products were studied and
characterized by potentiometeric and conductometeric titrations, IR, and UV spectroscopy and
thermogravimetric method (TGA).

Molecules 2010, 15
2511
2
.1. IR Spectrocopy
The Preyssler anion is made up of five PW
6
units arranged in a crown, so that the whole anion has
an internal fivefold symmetry axis. Perpendicular to this axis is a mirror plane that contains the five
planes containing the five phosphorus atoms. The tungsten atoms are distributed in four parallel planes
perpendicular to the axis. A PW unit consists of two groups of three corner-shared WO octahedra.
6
6
Two pairs of octahedral of each group are joined together by sharing on edge located in the mirror
plane. Each WO octahedron shares a vertex with the central PO tetrahedron [21]. All tungsten atoms
6
4
are octahedrally surrounded by oxygen atoms.
The anion contains W=O double bonds which are directed toward the exterior of the polyanion,
W-O -W bonds (inter bridges between corner-sharing octahedral), W-Oc-W bonds (intra bridges
b
between edge- sharing octahedral) and one XO tetrahedron. The XO tetrahedron is surrounded by
4
4
MO
6
octahedron sets linked together through oxygen atoms.
The IR spectra for A and B exhibited prominent bands for the polyoxoanion and THA and THPA at
-1
-1
6
00-1200 cm and 1,300-3,000 cm , respectively (Figures 1 and 2). The symmetric and asymmetric
stretching for M-O bonds are observed in the following spectral regions for Preyssler anion: W=O
d
-1
-1
-1
bonds (960 cm ), W-O
b
-W bridges (920 cm ), and W-O
c
-W bridges (795 cm ). The P-O stretchings
-1
-1
are observed in 1,000-1,165 cm . The sharp peak in 1,165 cm is a characteristic signal of the
Preyssler anion that cannot be observed in other heteropolyanions. With respect to the fingerprint
-1
region of the Preyssler anion (600-1,200 cm ), the IR spectra showed that the polyanion retains the
Preyssler structure in both A and B, and has electronic interactions with the organic moieties in the
solid state.
Figure 1. IR spectrum of compound A.

Molecules 2010, 15
2512
Figure 2. IR spectrum of compound B.
2.2. UV spectrum
The UV spectra of A and B exhibit two peaks at 217 and 280 nm, ascribed to O
t
→W and Ob,c→W
charge transfer bands, respectively (Figure 3). The maximum wavelength in 280 nm confirms that the
polyanion retains the Preyssler structure in both A and B.
Figure 3. UV spectra of Preyssler (a), A (b) and B (c).

Molecules 2010, 15
.3. Thermogravimetric analysis
Thermogravimetric analysis (TGA), coupled with spectroscopic measurements could
2513
2
unambiguously elucidate the structure of the compounds. The TGA of the two compounds was
performed in the range of 50–600 °C. The TG curves generally show two steps. The first one occurs at
temperatures lower than 120 °C, and corresponds to the loss of crystallization water. This leads to the
corresponding anhydrous heteropolycompound. The second step occurs at temperatures higher than
2
00 °C, dependoing on the metal, heteroatom and the counterion. It corresponds to the decomposition
of the heteropolycompound.
For the acids, the protons come off with oxygen, as n/2H O. In the case of a mixed salt with acidic
2
hydrogen and tetraalkylammonium cations, the weight loss is expressed as
x
(
tetraalkylammonium) O+n/2 H O to take into account the departure of the organic material and
2 2
the protons.
From room temperature to 130 °C, A remains stable and there is no weight loss (Figure 4). This
means that this compound is anhydrous and contains no crystallization water. In the range of
1
80–400 °C, the total weight loss of A is 28.15% (calculated value: 28.21%), corresponding to 7.7/2
(
THA) O+ 6.3/2 H O. Thus the synthesized compound A can be formulated as (THA)
7.7
H
2
2
6
5 30
.3[NaP W O110].
From room temperature to 130 °C, there was no weight loss for compound B (Figure 5). Thus, this
compound is anhydrous. In the range of 200–440 °C, the weight loss was 30.30% (calculated value:
0.35%), corresponding to 7.5/2 (THPA) O+ 6.5/2 H O. Therefore the compound B is formulated as
3
2
2
5 30
(THPA)7.5 H6.5[NaP W O110].
Figure 4. Thermogravimetric data for compound A.

Molecules 2010, 15
2514
Figure 5. Thermogravimetric data for compound B.
2
.4. Potentiometeric titrations
-14
w
The pH scale in an aqueous solution is governed by k (10 ) and the equilibrium in water predicts
a potential change of 0.059 V for each unit change in pH for the linear region of equation
E = k + 0.059 pH [22]. In a similar way, the pH scale in non-aqueous solvents is governed by the
autoprotolysis constants of the solvent. The solvents with small autoprotolysis constants were thought
to be advantageous for titrations. They provide a better opportunity for precise titrations, because of
their longer milivolt scales. In our study, we used solvents such as acetone, N,N-dimethylformamide
and acetonitrile with longer milivolt ranges for the potentiometric titrations [22].
However in every case, the potentiometeric titration curves of A and B showed two or three protons
were dissociated. This is attributed to the behavior of the glass electrode. A glass electrode is widely
used as the indicator electrode in non-aqueous as well as in aqueous titrations. Its response to pH has
been shown to be Nernstian in various non-aqueous solvents [23] and many acid dissociation constants
in aprotic solvents have been obtained by using a glass electrode as pH sensor [24].
In non-aqueous solutions media, these electrodes show certain undesirable features. For example
the potential response of a glass electrode in non-aqueous solutions is often very slow, so in some
cases, it takes many hours before the equilibrium potential is reached. Some efforts have been made to
improve the response speed, but without sufficient success [25]. In addition, the solvents dehydrate the
glass membrane, thereby reducing its affinity for, or response to, hydrogen ions.
Thus, it is difficult to obtain reliable information concerning the number of acidic protons with a
glass electrode. It is suggested that solvent as well as glass electrode can affect the number of
titrated protons.

Molecules 2010, 15
.5. Conductometric titration
For A and B, determination of acidic hydrogens was carried out via conductometric titration in
2515
2
acetone, N,N-dimethylformamide and acetonitrile. In all cases the conductometric curves showed two
or three protons were dissociated. It is well known that the proton conductivity of heteropolyacids is
strictly related to the number of coordinated water molecules to the heteropolyanions. According to
Kreuer, the heteropolyacid acts as a Bronsted acid toward the hydration water, which is loosely bound
in the structure, resulting in proton conductivity [26].
Consequently, the conductivity of heteropolyacid is strictly related to the number of water
molecules coordinated to the anion and a large uptake of water is essential for fast proton conduction.
As indicated by the obtained thermogravimetric results, there are no water molecules in A and B. This
leads to the absence of proton conduction.
Another reason can be explained based on hydrogen bonding. We have recently developed a
systematic vibrational study of Keggin heteropolyacids with aminoacids [27]. Our study showed that
intermolecular interactions such as hydrogen bonds between external oxygens and water molecules
and aminoacids led to a change and split in the frequencies of the metal-oxygen stretching for
polyanion. In Figures 1 and 2 we can see the characteristic bands of Preyssler anion are unchanged.
This is attributed to absence of water molecules, resulted in absence of hydrogen bonding, so can lead
to absence of proton conductivity.
2
.6. Catalytic activity
In connection with our earlier work using Keggin heteropolyacids in the synthesis of 4-amino[3,4-
d] pyrimidines [28], we wish to report the results of our study on the use of A and B in this reaction.
When a mixture of 5-amino-4-cyano-1 substituted-1H-pyrazoles and formamide in acetic acid was
refluxed in the presence of A and B as catalyst, 4-amino[3,4-d]pyrimidines were obtained (Scheme 1).
The results are summarized in Table 1. The results show that the catalysts can catalyze this reaction in
1
mild conditions. All compounds were characterized by mass, IR, and H-NMR spectra (Table 2).
Scheme 1. Catalytic synthesis of 4-amino[3,4-d]pyrimidines (2a-d) in the presence of A and B.

Molecules 2010, 15
2516
Table 1. Catalytic synthesis of 4-amino[3,4-d ]pyrimidines 2a-d.
%
with 1
yield % yield M. p/ °C
M. p/ °C
(Reported)
266-268 [29]
210 [29]
Entry Compound
R1
R2
with 2
57
(Found)
266
1
2
3
4
2a
2b
2c
2d
H
H
CH
Ph
CH
Ph
3
52
57
40
69
56
208
CH
CH
3
3
50
288
286 [30]
3
62
220-221
Table 2. Spectral data for 2a-d.
max
-1
1
Entry m/z mass IR υ cm (KBr)
H-NMR data (DMSO-d
,s) 7.68 (2H, NH
CH pyrazole ring, s )
6
)
+
2
2
2
2
a
b
c
148 (M ) 3,000-3,200 (NH
2
)
3.92 (3H,CH
3
2
, br ), 8.10 (1H,
,br), 8.2 (2H,
3 3
3.36 (3H, CH , s), 2.42 (3H, CH , s), 7.4 (2H,
+
211 (M ) 3,320 (NH
2
), 1,592 (Ar-H)
8.4 (3H,Ar-H,m), 7.51(2H, NH
Ar-H, m), 8.31(1H, ==CH, s)
2
+
163 (M ) 3,100 ( NH
2
)
NH , br)
2.43 (3H, CH
2
+
d
225 (M ) 3,350 (NH
2
), 1,580 (Ar-H)
3
, s), 7.23 (5H, Ar-H, m), 7.30
(
2H, NH , br), 9.10 (1H, C==H, s)
2
3
. Experimental
3
.1. Chemicals and apparatus
Preyssler anion was synthesized according to our earlier work [6]. Pyrazole derivatives were
prepared according to literature procedures [29,30]. All of the reagents used were obtained from
commercial sources. All yields were calculated from crystallized products. IR spectra were obtained
1
with a Bruker 500 scientific spectrometer. H-NMR spectra were recorded on a Bruker 100 MHz
Aspect 3000 FT NMR spectrometer. Mass spectra were obtained with a Varian CH-7 instrument. The
UV spectra were obtained with a double beam UV-Vis spectrophotometer (Philips 8800). The TG
curves were recorded using a TGA-1500 instrument. Melting points were obtained
on an Electrothermal type 9100 apparatus. All of the titrations were performed with
tetrabutylammonium hydroxide.
3
.2. General procedure for synthesis of compounds A and B
To a stirred aqueous solution of H [NaP W O ]·25.5 H O was added dropwise a solution of
1
4
5
30 110
2
THABr or THPABr (molar ratio: 1:14). The mixture was stirred for about 6 hours and induced the
formation of a viscous solid and an oil for THA and THPA, respectively. The separated compounds
were purified in a mixture of water and acetonitrile. Recrystalization was performed in water
and acetonitrile.
3
.3. Catalytic test
An appropriate pyrazole (0.1 mmole) mixed with formamide (0.2 mmol) and catalyst (0.05 mmol)
in acetic acid (10 mL) and refluxed for 6 hours. After the reaction was completed, the catalyst was

Molecules 2010, 15
2517
separated. The residue was evaporated and water was added. The product was filtered and purified
from a mixture of water and ethanol (Table 1). All compounds were characterized by mass, IR, and
1
H-NMR spectra (Table 2).
4
. Conclusions
Two novel organic- norganic heteropolyanions were prepared for the first time and showed
catalytic activity in the synthesis of pyrazolopyrimidines. Thermogravimetric analysis showed that A
and B consist of 7.7 and 7.5 tetraalkylammonium cations, respectively. This work demonstrates the
applicability of the Preyssler anion for some reactions that require bifunctional catalysts with hydrogen
ions and organic section along with catalytic activity and functionality over a wide range of pH.
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©
2010 by the authors; licensee Molecular Diversity Preservation International, Basel, Switzerland.
This article is an open-access article distributed under the terms and conditions of the Creative
Commons Attribution license (http://creativecommons.org/licenses/by/3.0/).