Novel nano molten salt tetra-2,3-pyridiniumporphyrazinato-oxo-vanadium tricyanomethanide as a vanadium surface-free phthalocyanine catalyst: Application to Strecker synthesis of α-aminonitrile derivatives

Article abstract of DOI:10.1002/aoc.3775

Efficient and recyclable novel nano tetra-2,3-pyridiniumporphyrazinato-oxo-vanadium tricyanomethanide, {[VO(TPPA)][C(CN)₃]₄}, as a vanadium surface-free phthalocyanine-based molten salt catalyst was successfully designed, produced an

Full text of DOI:10.1002/aoc.3775

Received: 22 December 2016
DOI 10.1002/aoc.3775
Revised: 25 January 2017
Accepted: 27 January 2017
F U L L PA P E R
Novel nano molten salt tetra‐2,3‐pyridiniumporphyrazinato‐oxo‐
vanadium tricyanomethanide as a vanadium surface‐free
phthalocyanine catalyst: Application to Strecker synthesis of
α‐aminonitrile derivatives
Saeed Baghery1
| Mohammad Ali Zolfigol1
| Maliheh Safaiee2 | Diego A. Alonso3 |
Abbas Khoshnood3
1 Department of Organic Chemistry, Faculty
of Chemistry, Bu‐Ali Sina University,
Hamedan 6517838683, Iran
2 Department of Medicinal Plants
Production, Nahavand University, Nahavand
6593139565, Iran
3 Instituto de Síntesis Orgánica and
Departamento de Química Orgánica,
Universidad de Alicante, Apdo. 9903080
Alicante, Spain
Efficient and recyclable novel nano tetra‐2,3‐pyridiniumporphyrazinato‐oxo‐
vanadium tricyanomethanide, {[VO(TPPA)][C(CN)3]4}, as a vanadium surface‐free
phthalocyanine‐based molten salt catalyst was successfully designed, produced and
used for the Strecker synthesis of α‐aminonitrile derivatives through a one‐pot
three‐component reaction between aromatic aldehydes, trimethylsilyl cyanide and
aniline derivatives under neat conditions at 50 °C. This catalyst was well character-
ized using Fourier transform infrared, UV–visible, X‐ray photoelectron and energy‐
dispersive X‐ray spectroscopies, X‐ray diffraction, scanning and high‐resolution
transmission electron microscopies, inductively coupled plasma mass spectrometry
and thermogravimetric analysis. The catalyst can be simply recovered and reused
several times without significant loss of catalytic activity.
Correspondence
Saeed Baghery and Mohammad Ali Zolfigo,
Department of Organic Chemistry, Faculty of
Chemistry, Bu‐Ali Sina University, Hamedan
6517838683, Iran.
Email: saadybaghery@yahoo.com;
zolfi@basu.ac.ir; mzolfigol@yahoo.com
KEYWORDS
molten salt, nano tetra‐2,3‐pyridiniumporphyrazinato‐oxo‐vanadium tricyanomethanide, phthalocyanine,
Strecker synthesis, α‐aminonitrile
Maliheh Safaiee, Department of Medicinal
Plants Production, Nahavand University,
Nahavand 6593139565, Iran
Email: azalia_s@yahoo.com;
msafaiee@nahgu.ac.ir
Diego A. Alonso and Abbas Khoshnood,
Instituto de Síntesis Orgánica and
Departamento de Química Orgánica,
Universidad de Alicante, Apdo. 9903080
Alicante, Spain
Email: diego.alonso@ua.es; abbas.
khoshnood@ua.es
1 | INTRODUCTION
synthesis.[1–7] Phthalocyanine derivatives are usually pro-
duced via high‐temperature cyclotetramerization of phthalic
Metal phthalocyanines are stable and simply attainable mac-
rocyclic complexes employed as cost‐effective biomimetic
oxidation catalysts and with numerous applications in organic
acid or dicyano derivatives.[8–16] Metal ion templates can sig-
nificantly increase the yields of these reactions.[8,10,12,14] Het-
erocyclic phthalocyanine derivatives containing pyridine,
Appl Organometal Chem. 2017;e3775.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.3775

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BAGHERY ET AL.
thionaphthalene, thiophene and pyrazine rings[17] have also
been synthesized and studied in depth. Metal complexes of
tetrapyridinoporphyrazines (pyridine derivatives)[18] are pre-
pared using a template process similar to that of phthalocya-
reactions,[48] herein we introduce nano tetra‐2,3‐
pyridiniumporphyrazinato‐oxo‐vanadium
tricyanomethanide, {[VO(TPPA)][C(CN)3]4}, as a vanadium
surface‐free phthalocyanine‐based molten salt catalyst for the
Strecker synthesis of α‐aminonitrile derivatives by a one‐pot
three‐component reaction of aromatic aldehydes,
trimethylsilyl cyanide (TMSCN) and aniline derivatives
under neat conditions at 50 °C (Scheme 1).
nine.[19–22]
Moreover,
various
syntheses
of
metallotetrapyridinoporphyrazines by 2,3‐ and 3,4‐
pyridinedicarboxylic acid have also been reported.[23–29]
The Strecker synthesis, firstly reported in 1850,[30] is the
oldest known multicomponent reaction[30] and the most facile
method for the synthesis of α‐amino acids on both laboratory
and technical scales. The Strecker reaction includes a con-
densation of an aldehyde with ammonia, in the presence of
a cyanide source to form an α‐aminonitrile, which is
subsequently hydrolysed to the corresponding amino acid.[30]
α‐Aminonitriles are popular bifunctional synthons that have
found numerous synthetic uses, the most important one being
the synthesis of amino acids.[31] Both these substructures (α‐
aminonitriles and α‐amino acids) are generally synthesized
from azomethines via nucleophilic addition reactions, for
instance Grignard–Barbier allylations[32–35] and Strecker‐
type reactions.[36–41] The experimental process of the
Strecker reaction is tedious, and therefore several modified
procedures have been developed using various cyanide
reagents (diethylaluminium cyanide, tri‐n‐butyltin cyanide,
2 | EXPERIMENTAL
2.1 | General
All chemicals and solvents used were of reagent grade and
purchased from Sigma‐Aldrich, Fluka, Merck and Acros
Organics. All reagents were used without any further purifica-
tion. TLC analysis was performed on UV‐active aluminium‐
backed F254 silica gel plates. Melting points were measured
with a Thermo Scientific apparatus and they were not
corrected. Centrifugation procedures were performed with
an Anke TDL80‐2B. Fourier transform infrared (FT‐IR) spec-
tra were recorded with a PerkinElmer FT‐IR 17259 spectrom-
eter using KBr discs. UV–visible spectra were recorded with a
PerkinElmer 35 UV–visible spectrophotometer. The samples
(10 mg) for UV–visible spectral studies were prepared in
aqueous ethanol solutions (EtOH–H2O, 10:1) using a dispers-
diethyl phosphorocyanidate and trimethylsilyl cyanide[42]
)
and catalysts such as lithium perchlorate,[43] vanadyl
triflate,[44] zinc halides,[45] H14[NaP5W30O110],[46] montmo-
rillonite KSF[37] and indium trichloride.[47]
1
ing procedure. H NMR (400 or 300 MHz) spectra were
obtained with Bruker Avance 400 and 300 NMR spectrome-
ters, respectively, in proton coupled mode using deuterated
dimethylsulfoxide (DMSO) as a solvent, unless otherwise
stated. 13C NMR (101 MHz) spectra were acquired with a
In continuation of our previous studies of the synthesis of
novel ionic liquids, molten salts and phthalocyanine‐based
catalysts and their application in multicomponent
SCHEME 1 Synthesis of nano tetra‐2,3‐
pyridiniumporphyrazinato‐oxo‐vanadium
tricyanomethanide, {[VO(TPPA)][C(CN)3]
4}, as a vanadium surface‐free
phthalocyanine‐based molten salt catalyst
and its application for the Strecker synthesis
of α‐aminonitriles

BAGHERY ET AL.
3 of 14
Bruker Avance 400 NMR spectrometer in proton decoupled
mode at 20 °C in deuterated DMSO as solvent, unless other-
wise stated. Chemical shifts are given in parts per million
and the coupling constants (J) in hertz. Data for 1HNMR are
reported as follows: chemical shift (ppm), multiplicity (s, sin-
glet; d, doublet; t, triplet; q, quartet; m, multiplet; and br,
broad), coupling constant (Hz) and integration. Thermogravi-
metric analysis (TGA) was carried out with a Mettler Toledo
apparatus (models TGA/SDTA851 and /SF/1100 TG/DTA).
TGA was performed under a nitrogen atmosphere at 25 °C
and using a heating rate of 20 °C min−1 up to 700 °C. High‐
resolution transmission electron microscopy (HRTEM)
images were obtained using a JEOL JEM‐2010 microscope
operating at an accelerating voltage of 200 kV. Samples were
prepared by drop‐casting dispersed particles onto a 200‐mesh
copper grid coated with a holey carbon film. Scanning elec-
tron microscopy (SEM) studies were performed using a
Hitachi S3000 N, equipped with an X‐ray detector (Bruker
XFlash 3001) for microanalysis (energy‐dispersive X‐ray,
EDX) and mapping (wavelength‐dispersive X‐ray, WDX).
X‐ray diffraction (XRD) analyses were performed using a
Bruker D8‐Advance apparatus using a monochromatized Cu
Kα (λ = 0.154 nm) X‐ray source in the range 5° < 2θ < 60°.
Low‐resolution mass spectra (EI) were obtained at 70 eV
using an Agilent 5973 Network spectrometer, with fragment
ion m/z reported with relative intensities (%) in parentheses.
Inductively coupled plasma mass spectrometry (ICP‐MS)
was performed with an Agilent 7700x apparatus equipped
with HMI (high matrix introduction). X‐ray photoelectron
spectroscopy (XPS; K‐ALPHA, Thermo Scientific) was used
to analyse sample surfaces. All spectra were collected using
Al‐K radiation (1486.6 eV), monochromatized by a twin‐
crystal monochromator, yielding a focused X‐ray spot (ellipti-
cal in shape with a major axis length of 400 μm) at
3 mA × 12 kV. XPS data were analysed using Thermo
Scientific Avantage software. A smart background function
was used to approximate the experimental backgrounds and
surface elemental composition was calculated from back-
ground‐subtracted peak areas. Charge compensation was
achieved with the system flood gun that provides low‐energy
electrons and low‐energy argon ions from a single source.
2.2 | General procedure for synthesis of {[VO
(TPPA)][C(CN)3]4}
{[VO(TPPA)][C(CN)3]4} was synthesized via the method
described by Yokote et al.[25] Urea (13 g), ammonium
molybdate
((NH4)6Mo7O24⋅4H2O;
92
mg),
2,3‐
pyridinedicarboxylic acid (2 g) and vanadium(V) oxide
(V2O5; 200 mg) were ground under neat conditions until a
homogeneous mixture was obtained. The mixture was placed
in a heating mantle, sealed and heated at 200–210 °C for 5 h.
Then, the mixture was allowed to cool to room temperature over
a 5 h period. The crude blue solid obtained (8.56 g) was crushed
and washed consecutively with warm water, a warm aqueous
NaOH solution (5% w/v), warm water, warm diluted aqueous
hydrochloric acid (2.5% v/v) and finally with warm water.
The obtained crude product was dried at 100 °C under vacuum
and finally purified through dissolving in concentrated sulfu-
ric acid and pouring the solution into ice–water. The precip-
itated product was collected via centrifugation (ca 200 rpm/
10 min) and transferred to a fine glass sinter funnel where
FIGURE 1 FT‐IR spectra: (a) V2O5; (b)
urea; (c) 2,3‐pyridinedicarboxylic acid; (d)
tricyanomethane; (e) [VO(TPPA)]; (f) {[VO
(TPPA)][C(CN)3]4}

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BAGHERY ET AL.
the mass was carefully washed with hot water, a warm aque-
ous sodium carbonate solution and finally with warm water.
[VO(TPPA)] product was dried at 100 °C under vacuum
149 mg, 188 μl) and the corresponding aniline derivative
(1 mmol). The resulting mixture was stirred at 50 °C under neat
conditions and the progress of the reaction was studied using
TLC (n‐hexane–ethyl acetate, 5:2). Once the reaction was fin-
ished, the catalyst was filtered and carefully washed with etha-
nol and then dried under vacuum (the products were soluble in
ethanol but {[VO(TPPA)][C(CN)3]4} was insoluble). The
recycled catalyst was used in the next run of the model reaction.
The organic solvent was evaporated and the crude product was
purified by a short column of silica gel using (n‐hexane–ethyl
acetate, 20:1) to yield the corresponding pure products.
(isolated yield 56%; m.p.
> 400 °C) (Scheme 1).
The vanadium content of [VO(TPPA)] was measured via
ICP‐MS, which gave value of about 0.1659% (w/w).
In the next step, to a round‐bottomed flask (50 ml)
containing a tricyanomethane (4 mmol, 360 mg) aqueous
solution (20 ml water), [VO(TPPA)] (1 mmol, 31 mg) was
added and stirred over a period of 5 h under reflux conditions.
The obtained pale greenish blue solid product {[VO(TPPA)]
[C(CN)3]4} was washed three times with diethyl ether, and
then dried under vacuum (isolated yield 93%) (Scheme 1).
{[VO(TPPA)][C(CN)3]4} (m.p. > 370°Cdec) was fully charac-
terized using FT‐IR and UV–visible spectroscopies, XRD,
XPS, SEM, HRTEM, EDX, ICP‐MS and TGA.
2.4 | Selected spectral data for compounds
2.4.1 | 2‐((4‐Bromophenyl)amino)‐2‐(3,4‐
dimethoxyphenyl)acetonitrile (4c)
Isolated as yellow solid (305 mg, 88%); m.p. 178–180 °C.
2.3 | General procedure for strecker synthesis
of α‐aminonitrile derivatives using {[VO
(TPPA)][C(CN)3]4} as phthalocyanine‐based
molten salt catalyst
FT‐IR (KBr, ν, cm−1): 3354, 3011, 2968, 2231, 1593,
1
1515, 1466, 1265. H NMR (300 MHz, DMSO, δ, ppm):
7.37–7.31 (m, 2H), 7.16–7.09 (m, 2H), 7.04 (d, J = 9.0 Hz,
1H), 6.84–6.76 (m, 3H), 5.87 (d, J = 9.2 Hz, 1H), 3.78
(2 s, 6H). 13C NMR (101 MHz, DMSO, δ, ppm): 149.7,
149.4, 145.8, 132.0, 127.3, 120.1, 119.9, 116.3, 112.2,
{[VO(TPPA)][C(CN)3]4} (10 mg) was added to a mixture of
the corresponding aldehyde (1 mmol), TMSCN (1.5 mmol,
FIGURE 2 UV–visible spectra of {[VO
(TPPA)][C(CN)3]4} (solid curve) and [VO
(TPPA)] (dashed curve)
FIGURE 3 EDX spectrum of {[VO
(TPPA)][C(CN)3]4} as a catalyst

BAGHERY ET AL.
5 of 14
1
111.3, 109.8, 56.0, 48.3. MS (EI) m/z (%): 346 (M+, 100),
320 (21), 218 (24), 207 (14), 179 (12), 176 (54), 165 (17),
157 (10), 155 (10), 78 (22), 76 (10), 63 (26).
1220. H NMR (400 MHz, DMSO, δ, ppm): 7.34–7.28 (m,
2H), 7.11 (d, J = 3.0 Hz, 1H), 7.05 (d, J = 9.0 Hz, 1H),
6.97 (dd, J = 9.0, 3.0 Hz, 1H), 6.80–6.75 (m, 2H), 6.72 (d,
J = 9.2 Hz, 1H), 5.83 (d, J = 9.2 Hz, 1H), 3.79 (s, 3H), 3.71
(s, 3H). 13C NMR (75 MHz, DMSO, δ, ppm): 153.6, 150.9,
145.5, 132.1, 123.4, 119.4, 116.1, 115.2, 114.9, 113.3,
109.9, 56.7, 56.0, 43.8. MS (EI) m/z (%): 346 (M+, 8), 335
(12), 174 (40), 165 (100), 78 (13), 63 (18), 44 (14).
2.4.2 | 2‐((4‐Bromophenyl)amino)‐2‐(2,5‐
dimethoxyphenyl)acetonitrile (4e)
Isolated as yellow solid (298 mg, 86%); m.p. 253–255 °C. FT‐
IR (KBr, ν, cm−1): 3374, 2956, 2234, 1677, 1594, 1499,
FIGURE 4 (a) TGA/DTG and inlet TGA/DTA of {[VO(TPPA)][C
(CN)3]4}; (b) TGA/DTG and inlet TGA/DTA of [VO(TPPA)]; (c)
comparing superimposed DTG of both {[VO(TPPA)][C(CN)3]4} and
[VO(TPPA)]
FIGURE 5 XRD patterns: (a) [VO(TPPA)]; (b) {[VO(TPPA)][C
(CN)3]4}; (c) superimposition of [VO(TPPA)] (dashed curve) and
{[VO(TPPA)][C(CN)3]4} (solid curve)

6 of 14
BAGHERY ET AL.
1
1553, 1495, 1384, 1228. H NMR (300 MHz, CDCl3, δ,
ppm): 7.54–7.45 (m, 2H), 7.40–7.32 (m, 2H), 7.02–6.92
(m, 2H), 6.70–6.61 (m, 2H), 5.32 (d, J = 8.1 Hz, 1H), 4.02
(d, J = 8.1 Hz, 1H), 3.84 (s, 3H). 13C NMR (75 MHz,
DMSO, δ, ppm): 160.1, 145.8, 132.0, 129.1, 127.0, 119.9,
116.3, 114.8, 109.7, 55.7, 48.1. MS (EI) m/z (%): 316 (M+,
30), 290 (29), 146 (100), 63 (10).
2.4.3 | 2‐((4‐Bromophenyl)amino)‐2‐
(naphthalen‐1‐yl)acetonitrile (4f)
Isolated as yellow solid (303 mg, 90%); m.p. 156–158 °C. FT‐
IR (KBr, ν, cm−1): 3433, 3293, 3065, 2226, 1653, 1623, 1551,
1497, 1386, 1285. 1H NMR (300 MHz, DMSO, δ, ppm): 8.11–
7.96 (m, 3H), 7.89 (d, J = 7.0 Hz, 1H), 7.69–7.56 (m, 3H), 7.39
(d, J = 9.0 Hz, 2H), 6.95 (t, J = 8.5 Hz, 3H), 6.66 (d,
J = 9.0 Hz, 1H). 13C NMR (101 MHz, DMSO, δ, ppm):
145.9, 134.0, 132.2, 130.4, 130.3, 130.2, 129.2, 127.4, 126.9,
126.2, 125.8, 123.8, 119.6, 116.0, 109.8, 47.1. MS (EI) m/z
(%): 336 (M+, 26), 310 (16), 166 (100), 127 (10), 127 (10).
2.4.6 | 2‐((4‐Bromophenyl)amino)‐2‐
(naphthalen‐2‐yl)acetonitrile (4j)
Isolated as yellow solid (303 mg, 90%); m.p. 263–265 °C. FT‐
IR (KBr, ν, cm−1): 3547, 3475, 3413, 3233, 3058, 2242,
1638, 1618, 1488, 1384, 1105. 1H NMR (300 MHz, DMSO,
δ, ppm): 8.13 (s, 1H), 8.06–7.95 (m, 3H), 7.66 (dd, J = 9.0,
1.8 Hz, 1H), 7.62–7.55 (m, 2H), 7.38–7.32 (m, 2H), 7.03
(d, J = 9.2 Hz, 1H), 6.90–6.77 (m, 2H), 6.21 (d, J = 9.2 Hz,
1H). 13C NMR (101 MHz, DMSO, δ, ppm): 145.8, 133.3,
133.1, 132.6, 132.1, 129.3, 128.5, 128.1, 127.3 (2c), 126.6,
125.3, 119.6, 116.3, 109.9, 48.8. MS (EI) m/z (%): 336 (M+
+ 2, 11), 334 (M+, 11), 327 (14), 155 (100), 127 (51).
2.4.4 | 2‐([1,1′‐biphenyl]‐4‐yl)‐2‐((4‐
bromophenyl)amino)acetonitrile (4 g)
Isolated as yellow solid (330 mg, 91%); m.p. 151–153 °C.
FT‐IR (KBr, ν, cm−1): 3306, 3064, 2216, 1634, 1605,
1578, 1547, 1384, 1302, 1184. 1H NMR (300 MHz, DMSO,
δ, ppm): 7.80–7.75 (m, 2H), 7.71–7.61 (m, 4H), 7.56–7.43
(m, 3H), 7.36–7.31 (m, 2H), 6.96 (d, J = 9.2 Hz, 1H),
6.88–6.74 (m, 2H), 6.06 (d, J = 9.2 Hz, 1H). 13C NMR
(75 MHz, DMSO, δ, ppm): 145.7, 141.2, 134.2, 132.1,
131.9, 129.5, 128.3, 127.7, 127.2, 127.1, 122.7, 116.3,
109.9, 48.4. MS (EI) m/z (%): 362 (M+, 72), 351 (12), 334
(16), 281 (23), 181 (100), 152 (51).
2.4.7 | 2,2′‐(1,4‐phenylene)bis(2‐((4‐
bromophenyl)amino)acetonitrile) (4q)
Isolated as yellow solid (446 mg, 90%); m.p. 194–196 °C.
FT‐IR (KBr, ν, cm−1): 3377, 3347, 2182, 1593, 1492,
1
1397, 1297, 1071. H NMR (400 MHz, DMSO, δ, ppm):
2.4.5 | 2‐((4‐Bromophenyl)amino)‐2‐(4‐
methoxyphenyl)acetonitrile (4i)
7.67 (s, 4H), 7.37–7.32 (m, 4H), 6.96 (dd, J = 9.3, 2.1 Hz,
2H), 6.81–6.77 (m, 4H), 6.08 (d, J = 8.8 Hz, 2H). 13C
NMR (101 MHz, DMSO, δ, ppm): 145.6, 135.9, 132.1,
128.4, 119.5, 116.3, 110.0, 48.3. MS (EI) m/z (%): 495 (M
Isolated as yellow solid (282 mg, 89%); m.p. 146–148 °C.
FT‐IR (KBr, ν, cm−1): 3435, 3092, 2191, 1633, 1588,
FIGURE 6 SEM images and WDX
elemental maps of [VO(TPPA)] (1–8) and
{[VO(TPPA)][C(CN)3]4} (9–16)

BAGHERY ET AL.
7 of 14
+, 3), 492 (20), 467 (100), 442 (97), 299 (11), 286 (13), 259
(12), 182 (17), 155 (59), 116 (14), 76 (29).
3 | RESULTS AND DISCUSSION
3.1 | Characterization of {[VO(TPPA)][C(CN)
3]4} as Phthalocyanine‐Based Molten Salt
Catalyst
Catalyst {[VO(TPPA)][C(CN)3]4} was synthesized via the
method described by Yokote et al. using urea, tetrahydrated
ammonium molybdate ((NH4)6Mo7O24⋅4H2O), 2,3‐
pyridinedicarboxylic acid and vanadium(V) oxide.[25] The
structure of {[VO(TPPA)][C(CN)3]4} was investigated and
fully characterized via FT‐IR and UV–visible spectroscopies,
XRD, XPS, SEM, HRTEM, EDX, ICP‐MS and TGA.
In the FT‐IR spectrum of {[VO(TPPA)][C(CN)3]4}, the
absorption bands at 991 and 622 cm−1 are related to the
stretching vibrational modes of V═O. Additionally, the
absorption bands at 1611 cm−1 (linked to C═N stretching)
and at 1458 cm−1 (related to C═C stretching) are also
observed in the FT‐IR spectrum of the catalyst. The known
peaks at 2242, 2182 and 2082 cm−1 are linked to C☰N
stretching on tricyanomethanide counter ion. Also, the iden-
tified peaks at 3446, 3356 and 3204 cm−1 are assigned to
the N─H stretching absorptions of the pyridinium ring. A
comparison of the FT‐IR spectrum of catalyst {[VO(TPPA)]
[C(CN)3]4} with those of other substrates and [VO(TPPA)]
is presented in Figure 1.
The structure of {[VO(TPPA)][C(CN)3]4} was also studied
and compared with that of [VO(TPPA)] using UV–visible
spectroscopy. Thus, aqueous ethanol solutions (EtOH–H2O,
10:1) of {[VO(TPPA)][C(CN)3]4} and [VO(TPPA)] were pre-
pared and analysed. As depicted in Figure 2, these compounds
show strong absorption bands at 821 and 767 nm (visible
region), respectively. Furthermore, the optical bandgap ener-
gies (Ebg = 1240/λmax) for {[VO(TPPA)][C(CN)3]4} and [VO
(TPPA)] were calculated, resulting 1.510 and 1.616 eV, respec-
tively. It is important to underline that while synthesizing {[VO
(TPPA)][C(CN)3]4}, the colour of the aqueous reaction solu-
tion changed from green to pale green while adding
tricyanomethanide counter ion (see Section 1). This acid–base
behaviour mechanism is found to be similar in UV–visible
analysis. Thus, the red‐shift differences in the absorption max-
imum between the catalyst and [VO(TPPA)] can be considered
as proof of the formation of the catalyst.
The metallic composition of {[VO(TPPA)][C(CN)3]4}
and [VO(TPPA)] was determined using EDX, ICP‐MS and
TGA.
The EDX data obtained for {[VO(TPPA)][C(CN)3]4}
confirm the presence of the anticipated elements in the struc-
ture of the catalyst: carbon, nitrogen, oxygen and vanadium
(Figure 3). No extra peaks connected with any impurity are
FIGURE 7 HRTEM images of (a, b) [VO(TPPA)] and (c, d) {[VO
(TPPA)][C(CN)3]4}

8 of 14
BAGHERY ET AL.
detected in SEM‐coupled EDX analysis, confirming the cata-
lyst composition: C (22.84%), N (21.50%), O (34.07%) and V
(0.27%). Moreover, a catalyst vanadium content of 0.08112%
(w/w) was determined using ICP‐MS. In addition, the vana-
dium content of [VO(TPPA)] was measured via ICP‐MS,
which gives a value of 0.1659% (w/w).
Figure 4 shows the thermal behaviour of {[VO(TPPA)][C
(CN)3]4} and [VO(TPPA)] under nitrogen atmosphere. TGA,
derivative thermogravimetric analysis (DTG) and differential
thermal analysis (DTA) of the catalyst were generally
investigated.
The DTA diagram shows a general negative downward
slope between 25 and 700 °C in which decomposition of cat-
alyst and its precursor in nitrogen atmosphere is exothermic.
Moreover, the TGA, DTG and DTA thermal decomposition
processes, as shown in Figure 4(a–c), include three steps.
The first one, related to the removal of surface‐adsorbed
water and organic solvents, takes place between 25 and
TABLE 1 XRD data for {[VO(TPPA)][C(CN)3]4}
Peak width,
FWHM (°)
Size
(nm)
Inter‐planar
distance (nm)
Entry 2θ (°)
1
18.05
21.85
24.40
28.85
30.50
31.60
36.90
38.70
41.30
44.45
49.90
55.55
56.20
0.34
0.25
0.27
0.45
0.22
0.20
0.27
0.36
0.59
0.26
0.44
0.41
0.39
23.66
32.37
30.11
18.23
37.43
41.28
31.02
23.39
14.39
33.01
19.91
21.90
23.10
0.490868
0.406172
0.364368
0.309098
0.292741
0.282797
0.243304
0.232391
0.218342
0.203572
0.182539
0.165236
0.163478
2
3
4
5
6
7
8
9
10
11
12
13
TABLE 2 XRD data for [VO(TPPA)]
Peak width,
FWHM (°)
Size
(nm)
Inter‐planar
distance (nm)
Entry 2θ (°)
1
19.05
22.25
23.15
28.05
29.00
32.15
33.90
38.65
48.80
49.45
50.80
54.60
55.20
59.50
59.55
0.15
0.23
0.23
0.17
0.20
0.10
0.21
0.18
0.24
0.24
0.25
0.14
0.29
0.14
0.31
53.70
35.21
35.26
48.25
41.03
82.81
39.56
46.78
36.35
36.44
35.17
63.87
30.91
65.37
29.53
0.465319
0.399067
0.383753
0.317729
0.307533
0.278084
0.264117
0.232680
0.186394
0.184095
0.179845
0.167884
0.166200
0.155174
0.155056
2
3
4
5
6
7
8
9
10
11
12
13
14
15
FIGURE 8 High‐resolution XPS spectra: (a) V 2p in [VO(TPPA)]
(red lines with blue residuals lines) and in {[VO(TPPA)][C(CN)3]4}
(orange residuals lines); (b) C 1 s in [VO(TPPA)] (dashed curves) and in
{[VO(TPPA)][C(CN)3]4} (solid curves); (c) N 1 s in [VO(TPPA)]
(dashed curves) and in {[VO(TPPA)][C(CN)3]4} (solid curves)

BAGHERY ET AL.
9 of 14
110 °C and involves a weight loss of 0.9 and 5.6% for [VO
(TPPA)] and {[VO(TPPA)][C(CN)3]4}, respectively. The
higher percentage of absorbed water for catalyst when com-
pared with its precursor can be reasoned for the ionic molten
salt nature of {[VO(TPPA)][C(CN)3]4}. The second weight
loss region shown between 110 and 405 °C is attributed to
the continuing decomposition of the phthalocyanine ring.
Weight losses of 10.2 and 4.7 wt% are observed for [VO
(TPPA)] for {[VO(TPPA)][C(CN)3]4}, respectively. Finally,
the third weight loss region for {[VO(TPPA)][C(CN)3]4}
(between 405 and 510 °C) can be ascribed to the continuing
decomposition of the ionic (pyridinium/tricyanomethanide)
moieties of the catalyst. On the contrary, no distinct weight
loss is detected in this temperature range for [VO(TPPA)],
suggesting a non‐ionic nature of this material. The weight
loss for this third step is calculated to be lower than 0.1%
for [VO(TPPA)] and 8.5% for {[VO(TPPA)][C(CN)3]4}. In
addition, above 700 °C, no significant weight loss is
observed. As clearly indicated in Figure 4(c) for the results
of the DTG analysis, the thermal stability of the catalyst is
improved from 110–405 to 405–510 °C when compared with
its precursor, which can be attributed to the ionic character of
the pyridinium functional groups.
The particle size and shape as well as the morphology of
{[VO(TPPA)][C(CN)3]4} and [VO(TPPA)] were studied
using XRD, SEM and HRTEM (Figures 5–7). Characteriza-
tion by XRD was performed to investigate the crystalline
structure of {[VO(TPPA)][C(CN)3]4} and [VO(TPPA)] in
the range 2θ = 2.5–60° (Figure 5). The XRD analysis reveals
13 characteristic peaks for the catalyst between 18.05° and
56.20°. The peak width (FWHM), size and inter‐planar dis-
tance from the XRD pattern of the catalyst were studied
and the results are summarized in Table 1. A similar analysis
for [VO(TPPA)] is summarized in Table 2. These
TABLE 3 Reaction conditions optimization of Strecker synthesis under neat conditionsa
Entry
Catalyst
Catalyst loading (Mol%)
Reaction temperature (°C)
Time (min)
Yield (%)b
1
{[Vo(TPPA)][C(CN)3]4}
[Msim]Cl
0.016
2
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
r.t.
75
100
50
50
20
30
45
30
30
45
30
45
30
30
30
20
20
20
60
30
20
20
30
60
91
85
—
87
78
53
85
—
85
61
75
91
88
85
—
57
91
91
88
—
2
3
NH2SO3H
10
4
[MIMPS]3PW12O40
H3PW12O40
2
5
5
6
Acetic acid
20
7
[Dsim]Cl
2
8
Ce(HSO4)3⋅7H2O
[TEAPS]3PW12O40
HBF4
20
9
2
10
11
12
13
14
15
16
17
18
19
20
10
{[Vo(TPPA)][C(CN)3]4}
{[Vo(TPPA)][C(CN)3]4}
{[Vo(TPPA)][C(CN)3]4}
{[Vo(TPPA)][C(CN)3]4}
Catalyst‐free
0.008
0.032
0.08
0.16
—
{[Vo(TPPA)][C(CN)3]4}
{[Vo(TPPA)][C(CN)3]4}
{[Vo(TPPA)][C(CN)3]4}
[Vo(TPPA)]
0.016
0.016
0.016
0.032
0.5
NaCl
aReaction conditions: 4‐chlorobenzaldehyde (1 mmol, 140 mg), TMSCN (1.5 mmol, 149 mg, 188 μl), 4‐bromoaniline (1 mmol, 172 mg).
bIsolated yield.

10 of 14
BAGHERY ET AL.
characteristic peaks indicate crystallographic planes of the
indicates the presence of C, N, O and V, which proves the
regular uniformity of the synthesized catalyst.
catalyst. The broad peak (2θ
= 24.40°) represents
nanometre‐sized crystallites. In addition the average crystal-
line size D (nm) of the catalyst can be estimated according
to the Scherrer equation: D = Kλ/(βcos θ). The calculated
average particle sizes for {[VO(TPPA)][C(CN)3]4} and [VO
(TPPA)] are summarized in Tables 1 and 2, respectively. On
the other hand, the average inter‐planar distance (nm) of
{[VO(TPPA)][C(CN)3]4} and [VO(TPPA)] were calculated
according to the Bragg equation: dhkl = λ/(2sin θ). Moreover,
the crystalline diffraction lines of {[VO(TPPA)][C(CN)3]4}
show different angle from those of [VO(TPPA)], as depicted
in Figure 5(c), where the superimposed XRD patterns of both
materials are shown. Also, the XRD pattern changes of {[VO
(TPPA)][C(CN)3]4} catalyst in comparison with [VO(TPPA)]
indicate the production of the catalyst (Figure 5).
The surface texture and morphological properties of the
catalyst were also studied using SEM (Figure 6).and HRTEM
(Figure 7). Both analyses show that the catalyst morphology
is fibrillar and with suitable monodispersity. The catalyst
synthesis employed in this investigation produces a uniform
dispersion of small particles with average size of 14.39–
41.28 nm, which is in accordance with the XRD results. More-
over, in combination with SEM, WDX provides qualitative
information about the distribution of various chemical ele-
ments in the catalyst matrix. Figure 6 collects representative
SEM images and WDX elemental maps for the produced cat-
alyst. It can be seen that vanadium metal particles are finely
dispersed in the material. The selected‐area elemental analysis
XPS studies were next performed of {[VO(TPPA)][C
(CN)3]4} and [VO(TPPA)] in order to obtain an insight into
the surface composition of these materials. As depicted in
Figure 8(a) for [VO(TPPA)] (red and blue lines), the V 2p
peaks can be fitted into the two different peaks located at
516.39 and 523.89 eV (in red) corresponding to 2p3/2 and
2p1/2 levels with a relative area of 1 to 0.52, respectively, with
a blue residuals lines located at 523.48 eV. On the other hand,
for {[VO(TPPA)][C(CN)3]4} (Figure 8a, orange lines), the
peaks for vanadium 2p3/2 and 2p1/2 are not detected, and only
orange residuals lines located at 522.68 eV is observed. Since
the ICP‐MS, EDX and elemental mapping analyses had pre-
viously indicated the presence of vanadium in both {[VO
(TPPA)][C(CN)3]4} and [VO(TPPA)], this result suggests
the absence of vanadium oxide on the surface of the cata-
lyst.[49] Moreover, the C 1 s XPS spectrum of [VO(TPPA)]
(Figure 8b, red lines) can be deconvoluted into three peaks
at 286.64, 285.74 and 288.54 eV, revealing the existence of
C═C, C═N and N─C═N moieties, respectively (ratio of
1:0.55:0.63). However, compared with [VO(TPPA)], the
binding energy of C═N and N─C═N of {[VO(TPPA)][C
(CN)3]4} shifts to 285.84 and 288.71 eV. This positive shift
of the binding energy suggests the presence of pyridinium
NH+ moieties. In addition, Figure 8(a,b) also shows the
reduction of the C═N (0.55 to 0.23) and N─C═N (0.63 to
0.30) functional groups in the catalyst when compared with
the precursor.
TABLE 4 {[VO(TPPA)][C(CN)3]4}‐catalysed Strecker reaction: solvent optimizationa
Entry
Solvent
H2O
Time (min)
Yield (%)b
1
2
3
4
5c
6
7
8
30
30
30
45
45
60
60
20
84
87
81
75
68
51
45
91
C2H5OH
CH3CN
CH3CO2Et
CH2Cl2
Toluene
n‐hexane
Neat
aReaction conditions: 4‐chlorobenzaldehyde (1 mmol, 140 mg), TMSCN (1.5 mmol, 149 mg, 188 μl), 4‐bromoaniline (1 mmol, 172 mg).
bIsolated yield.
cReaction in CH2Cl2 as a solvent was investigated under reflux condition.

BAGHERY ET AL.
11 of 14
conditions provides an 88% yield (Table 3, entry 13) of the
desired product. Optimization of the reaction conditions
was undertaken to increase the yield employing various
amounts of catalyst. The yield is increased to 91% using 10
or 20 mg of catalyst (Table 3, entries 1 and 12). However,
the addition of 100 mg of the catalyst is found to have an
inhibitory effect on the production of α‐aminonitriles
(Table 3, entry 14), while a reduction in yield is observed
by decreasing the catalyst loading to 5 mg (Table 3, entry
11). The influence of other catalysts was also examined. With
NH2SO3H, Ce(HSO4)3⋅7H2O and NaCl the reaction does not
proceed (Table 3, entries 3, 8 and 20) and with other catalysts
the isolated yield of desired product is appropriately
obtained. The results achieved with other catalysts are sum-
marized in Table 3. Also, for the model reaction in the
3.2 | Application of {[VO(TPPA)][C(CN)3]4}
as phthalocyanine‐based molten salt catalyst for
strecker synthesis of α‐aminonitriles
In continuation of our studies[48] related to the applications of
{[VO(TPPA)][C(CN)3]4} in organic synthesis, we next stud-
ied the use of this catalyst in the Strecker synthesis of α‐
aminonitriles (Scheme 1). To find simple and appropriate
conditions for the Strecker synthesis of α‐aminonitriles, we
performed the corresponding optimization for a model reac-
tion between 4‐chlorobenzaldehyde (1 eq.) and 4‐
bromoaniline (1 eq.) in the presence of TMSCN (1.5 eq.).
To optimize the reaction conditions, the reaction was
studied using various catalysts under neat conditions. The
use of 50 mg of {[VO(TPPA)][C(CN)3]4} under these
TABLE 5 Strecker synthesis of α‐aminonitrile derivatives in the presence of 10 mg of {[VO(TPPA)][C(CN)3]4} as phthalocyanine‐based molten
salt catalyst under solvent‐free conditions at 50 °Ca
Entry
Aldehyde
Aniline
M.p. (°C)
Time (min)
Yield (%)b
TOF
4a
4b
4c
4‐Chlorobenzaldehyde
4‐Nitrobenzaldehyde
3,4‐Dimethoxybenzaldehyde
4‐Nitrobenzaldehyde
2,5‐Dimethoxybenzaldehyde
Naphthalene‐1‐carbaldehyde
Biphenyl‐4‐carbaldehyde
4‐Nitrobenzaldehyde
4‐Methoxybenzaldehyde
Naphthalene‐2‐carbaldehyde
4‐Chlorobenzaldehyde
4‐Chlorobenzaldehyde
4‐Methylbenzaldehyde
4‐Methylbenzaldehyde
Terephthaldehyde
4‐Bromoaniline
Aniline
337–339 (yellow solid)[50]
33–35 (red solid)[51]
20
25
30
15
30
25
25
20
30
25
30
25
40
35
30
35
25
30
45
40
91
90
88
93
86
90
91
91
89
90
87
89
85
87
88
86
90
89
85
87
284.38
225.00
183.33
387.50
179.17
225.00
227.50
284.38
185.42
225.00
181.25
222.50
132.81
155.36
183.33
153.57
225.00
185.42
118.06
135.94
4‐Bromoaniline
4‐Bromoaniline
4‐Bromoaniline
4‐Bromoaniline
4‐Bromoaniline
4‐methylaniline
4‐Bromoaniline
4‐Bromoaniline
Aniline
178–180 (yellow solid)
303–305 (orange solid)[50]
253–255 (yellow solid)
156–158 (yellow solid)
151–153 (yellow solid)
87–89 (red solid)[51]
4d
4e
4f
4 g
4 h
4i
146–148 (yellow solid)
263–265 (yellow solid)
110–112 (brown solid)[51]
87–89 (brown solid)[52]
73–75 (green solid)[51]
105–107 (green solid)[51]
161–163 (yellow solid)[53]
105–107 (red solid)[54]
194–196 (yellow solid)
218–220 (yellow solid)[54]
83–85 (green solid)[51]
106–108 (green solid)[51]
4j
4 k
4 l
4 m
4n
4o
4p
4q
4r
4‐methylaniline
Aniline
4‐methylaniline
Aniline
4‐Dimethylaminobenzaldehyde
Terephthaldehyde
Aniline
4‐Bromoaniline
4‐Bromoaniline
Aniline
4‐Methylbenzaldehyde
Benzaldehyde
4 s
4 t
Benzaldehyde
4‐methylaniline
aReaction conditions: aldehyde (1 mmol), TMSCN (1.5 mmol, 149 mg, 188 μl), aniline derivatives (1 mmol).
bIsolated yield.

12 of 14
BAGHERY ET AL.
1
absence of catalyst the desired product is not obtained
(Table 3, entry 15). Other catalysts are not efficient under
similar conditions, and therefore {[VO(TPPA)][C(CN)3]4}
was chosen as the best catalyst. Next, the effect of tempera-
ture on the rate of reaction was investigated. When the reac-
tion is performed at 50 °C, the maximum yield is obtained
in a short reaction time (Table 3, entry 1). Furthermore,
increasing the temperature to more than 50 °C has no change
on the yield or reaction time (Table 3, entries 17 and 18).
Also, it is found that, at room temperature, the reaction is
very slow and does not progress to completion (Table 3, entry
16).
Next, we carried out an optimization of the reaction
media (Table 4). Generally, polar solvents lead to higher
yields than non‐polar ones. However, as evident from entries
1–7, the use of solvent is detrimental for the reaction yield.
Finally, it is evident that neat conditions afford the best result
in terms of reaction time and yield (Table 4, entry 8) probably
due to a more intimate contact between the reactants and the
catalyst surface under these conditions.
To study the versatility and generality of the optimized
process, the reaction was extended to various aromatic alde-
hydes. The results are summarized in Table 5. It is obvious
that the product yield is influenced by both electronic and
steric effects of the substituted groups. Aromatic aldehydes
with electron‐donating groups give lower yields than those
bearing electron‐withdrawing substituents. Additionally, the
effect of steric hindrance on the aromatic aldehydes is impor-
tant. In general, ortho‐substituted aromatic aldehydes provide
lower yields. On the other hand, hetero‐aromatic aldehydes
require longer reaction times than aromatic aldehydes
affording lower yields as well. The structures of
α‐aminonitriles were determined from H NMR, 13C NMR,
GC–MS and FT‐IR spectral data. In order to evaluate the effi-
cacy of {[VO(TPPA)][C(CN)3]4} as a catalyst for the
Strecker synthesis of α‐aminonitrile derivatives, turnover fre-
quency (TOF) values were also calculated (according to the
ICP‐MS results, 10 mg of catalyst is equivalent to
0.016 mol% of catalyst). Furthermore, for this reaction condi-
tion 4‐bromoaniline reacts faster than 4‐methylaniline and
aniline. Moreover, in the presence of terephthalaldehyde as
an aldehyde derivative, α‐bisaminonitrile products are
obtained (Table 5, entries 15 and 17). No by‐products from
the cyanide addition to the aldehydes are detected in the
crude reaction mixtures due to the rapid activation of the in
situ produced imine by the catalyst.[51,55,56]
According to previous studies,[51,55,56] we present a plau-
sible pathway for the Strecker synthesis of α‐aminonitriles in
the presence of {[VO(TPPA)][C(CN)3]4} as a vanadium sur-
face‐free phthalocyanine‐based molten salt catalyst in
Scheme 2. Thus, in the absence of vanadium oxide in the sur-
face of the catalyst, the pyridinium NH+ moieties of {[VO
(TPPA)][C(CN)3]4} activate the carbonyl group of the aro-
matic aldehydes 1 via hydrogen bonding towards nucleo-
philic attack of the aniline derivatives 3. This reaction
would produce the corresponding imines 7, a process pro-
moted by the water physically and/or chemically adsorbed
on the catalyst surface. In the next step, a similar catalyst
hydrogen‐bonding activation on both the generated imine 7
and TMSCN (by generation of pentacoordinated Si) takes
place affording the corresponding α‐aminonitriles 4 and
trimethylsilanol (Scheme 2).
The recyclability of the catalyst was also investigated by
running seven consecutive cycles of the model synthesis of
SCHEME 2 Plausible mechanism for
Strecker synthesis of α‐aminonitriles using
{[VO(TPPA)][C(CN)3]4} as a
phthalocyanine‐based molten salt catalyst

BAGHERY ET AL.
13 of 14
Economíay Competitividad (CTQ2015‐66624‐P) for finan-
cial support to our research groups.
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and
TGA)
nano
tetra‐2,3‐
pyridiniumporphyrazinato‐oxo‐vanadium
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How to cite this article: Baghery S, Zolfigol MA,
Safaiee M, Alonso DA, Khoshnood A. Novel nano
molten salt tetra‐2,3‐pyridiniumporphyrazinato‐oxo‐
vanadium tricyanomethanide as a vanadium surface‐
free phthalocyanine catalyst: Application to Strecker
synthesis of α‐aminonitrile derivatives. Appl
Organometal Chem. 2017;e3775. https://doi.org/
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