A green and efficient synthesis of isoxazol-5(4H)-one derivatives in water and a DFT study

Article abstract of DOI:10.1007/s13738-017-1246-2

A series of 4-arylmethylene-3-methylisoxazol-5(4H)-one derivatives are obtained via treating ethyl acetoacetate, hydroxylamine hydrochloride and variety of aromatic aldehyde compounds in the presence of antimony trichloride as an efficient catalyst in aqu

Full text of DOI:10.1007/s13738-017-1246-2

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-017-1246-2
ORIGINAL PAPER
A green and efcient synthesis oꢀ isoxazol‑5(4H)‑one derivatives
in water and a DFT study
Seied Ali Pourmousavi1,2 · Hamid Reza Fattahi · Fatemeh Ghorbani · Ayoub Kanaani · Davood Ajloo
1
1
1
1,2
Received: 22 February 2017 / Accepted: 14 November 2017
©
Iranian Chemical Society 2017
Abstract
A series of 4-arylmethylene-3-methylisoxazol-5(4H)-one derivatives are obtained via treating ethyl acetoacetate, hydroxy-
lamine hydrochloride and variety of aromatic aldehyde compounds in the presence of antimony trichloride as an eꢀcient
catalyst in aqueous media. Mild conditions, safe, short reaction times, commercially available catalyst, environmentally
friendly, no uses of organic solvent and high yields are remarkable advantages to this process. (Z)-4-(3-hydroxybenzylidene)-
1
3
-methylisoxazol-5(4H)-one, (HBIM), is characterized by theoretical (density functional theory) and experimental (IR, H
NMR, CV and UV). The structural parameters, vibrational frequencies, molecular electrostatic potential, frontier molecular
orbital analysis (HOMO–LUMO), thermodynamic properties and nonlinear optical properties are found and discussed.
UV–Vis spectra are recorded in two organic solvents. Thermal stability of HBIM is studied by thermogravimetric analysis.
The molecule orbital contributions are studied using the total and partial density of states (TDOS and PDOS).
Keywords Three-component process · Antimony trichloride · Isoxazol-5(4H)-ones · DFT calculations · Spectroscopy
Introduction
On the other hand, the synthesis of small heterocyclic
systems containing isoxazol ring occupied a signiꢁcant place
in pharmaceutical chemistry and organic synthesis [14, 15].
Among the various clinical applications, isoxazol derivatives
have a considerable active role as: antiviral [16], COX-2
inhibitory [17], anti-tumor [18], analgesic [19], antifungal
[20], antimicrobial [21], antioxidant [22], anti-mycobacte-
rial [23], anti-inꢂammatory [24], treatment of leishmania-
sis [25] and anti-convulsant [26]. During the recent years,
α, β-unsaturated isoxazol-5(4H)-one derivatives were pre-
pared using some of catalysts including: H PW O [27],
Since the ꢁrst multicomponent process (MCP) was described
by Strecker [1], multicomponent processes (MCPs) have
been demonstrated to be highly valuable tools for the expe-
dient creation of natural products and biologically active
compounds [2, 3]. Recently, considerable attention has been
focused on MCPs owing to its high eꢀcacy, mild condi-
tions, simplistic completing, environmentally friendly, and
minimization of time-consuming [4–9]. Carrying out MCPs
in water as the reaction medium will be one of the most
suitable methods, which will be a signiꢁcant component of
green chemistry [10–13].
3
12 40
Na S·9H O [28], pyridine [29], sodium azide [30], DABCO
2
2
[31], sodium silicate [32], sodium ascorbate [33], sodium
benzoate [13], Fe O [27], PPI [34], CH COONa [35] and
2
3
3
sodium tetraborate [34].
Although α, β-unsaturated 4H-isoxazol-5-ones have so
far been synthesized, no results have been reported in the
literature for three-component (3C) cyclocondensation of
aryl aldehydes (1a–r), hydroxylamine hydrochloride (2)
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s13738-017-1246-2) contains
supplementary material, which is available to authorized users.
and β-oxoesters (3) using SbCl as a catalyst. In this report,
*
Seied Ali Pourmousavi
pourmousavi@du.ac.ir
3
SbCl is used as a heterogeneous catalyst for the synthesis
3
of α, β-unsaturated isoxazol-5(4H)-ones in aqueous media
1
2
School of Chemistry, Damghan University,
Damghan 36716-41167, Iran
(
Scheme 1).
The use of the density functional theory (DFT) calcula-
Institute of Biological Science, Damghan University,
Damghan 36716-41167, Iran
tions for predicting the relative stability of diꢃerent isomers
Vol.:(0
1
123456789)
3

Journal of the Iranian Chemical Society
Scheme 1 Synthetic route for
the target compounds 4
and studying the molecular structure as well as spectroscopic
properties of organic compounds is of particular interest
Spectral data
[
36–43]. A (Z)-4-(3-hydroxybenzylidene)-3-methylisoxa-
(Z)‑4‑(3‑hydroxybenzylidene)‑3‑methylisoxazol‑5(4H)‑one
(4j)
zol-5(4H)-one (HBIM) compound was synthesized, and its
spectroscopic properties (IR, 1H NMR, CV and UV spec-
tra) were studied both experimental and theoretical insight.
Furthermore, molecular electrostatic potential (MEP), fron-
tier molecular orbital analysis (HOMO–LUMO), thermo-
dynamic properties and nonlinear optical (NLO) properties
were carried out and evaluated. Thermal stability of HBIM
was analyzed by TGA. The molecule orbital contributions
were presented by using density of states like TDOS and
PDOS.
1
H NMR (400 MHz, DMSO-d6) δ: 2.28 (s, 3H), 7.08 (d,
1H, J = 8.0 Hz), 7.39 (t, 1H, J = 8.0 Hz), 7.79 (d, 1H,
1
3
J = 7.6 Hz), 7.85 (s, 1H), 7.95 (s, 1H), 9.96 (s, 1H).
C
NMR (100 MHz, DMSO-d6) δ: 11.7, 118.9, 119.9, 121.8,
125.8, 130.2, 134.1, 152.3, 157.8, 162.6, 168.2 (Figs. S3,
S4).
(Z)‑4‑(4‑(dimethylamino)
benzylidene)‑3‑methylisoxazol‑5(4H)‑one (4i)
1
Experimental
H NMR (400 MHz, DMSO-d6): δ 2.24 (s, 3H), 3.16 (s, 6H),
6
.72 (dd, J = 8.4 Hz, 2H), 7.22 (s, 1H), 8.41 (d, J = 11.8 Hz,
General
2H) (Fig. S5).
The IR spectrum is recorded on a PerkinElmer RXI Fourier
Computational details
−
1
transform spectrophotometer in the 4000–400 cm region
−
1
by averaging 20 scans with a resolution of 2 cm at room
temperature. The spectrum is measured as KBr pellet. The
ultraviolet absorption spectra are examined over the range of
All calculations for the HBIM have been done using Gauss-
ian 03 W program package [44] with a hybrid functional
B3LYP at 6-311++G(d,p) and 6-311++G(2d,p) basis sets
with the default convergence criteria without any constraint
on the geometry [45]. The molecular structure of the HBIM
in the ground state is optimized. The vibrational frequencies
are calculated and scaled down by the suitable scaling factor
[45]. The vibrational wavenumber assignments are carried
out by combine the results from the GaussView program
[46] and VEDA4 program [47]. For the deconvolution of
IR spectrum, we used Lorentzian functions. Electronic exci-
tations of HBIM are calculated using TD-DFT [48]. The
polarizable continuum model (PCM) is used for solution
phase calculations [49].
2
00–600 nm using PerkinElmer lambda 25 recording spec-
1
trophotometer equipped with a 10 mm quartz cell. The H
1
3
NMR and CNMR spectra of compounds are obtained on
FT-NMR, Bruker AVANCE DRX 400 in the CDCl solu-
3
tion at room temperature with internal TMS standard. The
development of reactions is monitored by thin layer chro-
matography (TLC) on Merck pre-coated silica gel 60 F
2
54
aluminum sheets, visualized by UV light.
General procedure for synthesis
of isoxazol‑5(4H)‑one derivatives (4a–p)
To a mixture of hydroxylamine hydrochloride (0.07 g,
1
mmol) and ethyl acetoacetate (0.130 g, 1 mmol) in 5 mL
Results and discussion
of water, aromatic aldehyde (1 mmol) and SbCl (0.05 g) is
3
added and the reaction mixture is stirred at room tempera-
Preparation of arylmethylene isoxazol‑5(4H)‑ones
ture. After completion of the reaction, as indicated by TLC
(
ethyl acetate/n-hexane 1:6), the precipitate is ꢁltered oꢃ
In the present work, using a three-component, one-pot
method, arylmethylene isoxazol-5(4H)-ones (4a–p) are
obtained via condensation reaction of ethyl acetoacetate,
hydroxylamine hydrochloride and available aryl aldehydes
and washed with water. Finally, the crude product is puriꢁed
by recrystallization from EtOH to aꢃord the corresponding
isoxazol-5(4H)-ones.
1
3

Journal of the Iranian Chemical Society
in the presence of water and SbCl , with the high yield and
Geometrical parameters
3
purity. In order to optimize the reaction conditions, the reac-
tion using benzaldehyde (1), hydroxylamine hydrochloride
The selected torsion angles, bond angles and bond lengths
for optimized of HBIM are listed in Table 4 in accordance
with atom numbering schemes given in Fig. 1. The results
are compared with other similar systems which the crystal
structures were solved [51, 52].
(
2) and ethyl acetoacetate (3) as a model, in the presence
of diꢃerent amounts of catalyst, water and various solvent
is performed at room temperature, and the results are sum-
marized in Table 1.
When the reaction is carried out in the absence of cata-
lyst, small amounts of the product are observed. 0.05 g cata-
lyst and water as solvent, the best results have been achieved
As shown in Table 4, clearly there is a good compro-
mise between theoretical and experimental values. The
O –N , N = C and O –C bond lengths have been calcu-
1
6
6
4
1
2
(
Table 1, entry 2). Thus, 0.05 g SbCl , water as solvent and
lated as 1.429, 1.289 and 1.371 Å, respectively. These bond
lengths have experimentally been found as 1.435, 1.283 and
1.366 Å, respectively [51]. For (Z)-4-[4-(dimethylamino)
benzylidene]-3-methylisoxazol-5(4H)-one, these bond
lengths have been identiꢁed as 1.451, 1.294 and 1.388 Å,
respectively by Chenget al. [52]. Also, for 3-methyl-
4-(thiophen-2-ylmethylene)isoxazol-5(4H)-one these bond
lengths have been identified as 1.43, 1.29 and 1.37 Å,
respectively, by Kiyani et al. [41].
3
room temperature are selected as the optimal conditions
and the other reactions are performed in these conditions.
Selection of water as a solvent has been several beneꢁcial,
including safety, non-toxicity, low cost, availability, being
green and environmentally friendly. These optimized condi-
tions are applied to the conversion of various kinds of aryl
aldehydes into the isoxazol-5(4H)-ones (Table 2).
When aromatic aldehydes containing electron-with-
drawing groups such as nitro and chlorine can be used,
only trace amounts of the corresponding products to be
formed. It is evident that electron-rich aromatic aldehydes
and π-excessive heterocyclic systems such as 4-(dimethyl-
amino) benzaldehyde (1i), 3, 4, 5-trimethoxy benzaldehyde
According to data from Table 4, it is found that the car-
bon–carbon bond lengths in the molecular structure are
between C–C single (1.54 Å) and C=C double (1.34 Å)
bonds. The π electrons in the whole molecule are delocal-
ized, and methyl group on the isoxazolon ring is involved
in the molecular conjugate systems. From Table 4, the C–C
bond length of C –C (1.442 Å) is shorter than that of
(
1l) and 3,5-dihydroxy benzaldehyde (1p) reacted with ethyl
acetoacetate and hydroxylamine hydrochloride to aꢃord high
yields of products (Table 2, entries 10–17).
1
1
13
C –C (1.478 Å) and C –C (1.452 Å), because of the delo-
2
3
3
4
To further evaluate the overall utility of the current meth-
odology, we compared our results with those obtained using
other techniques previously reported for the synthesis of α,
β-unsaturated 4H-isoxazol-5-ones. As shown in Table 3,
clearly our method both reduced the required reaction times
and generated higher yields of the products.
calization of electron density of C=C phenol. The diꢃer-
ences between the bond lengths in C –C and C –C arise
2
3
3
4
from diꢃerent polarity of groups, which attaching to them.
The bond angles in isoxazole and in benzene ring are
close to 108° and 120°, respectively. The bond angle of
2
O –C –O is 120.9°, which is consistent with the sp hybrid
1
2
5
character of the C atom. For HBIM, all of the torsion
2
angles are close 180° or 0°, which demonstrates that the
molecular frame of HBIM is planar. The torsion angles of
C –C –C –C and C –C –C –C (180.0°) show that
Table 1 Optimization of reaction conditions
4
3
11
13
11
13
15
18
Entry
SbCl (g)
Solvent
Time (min)
Yield (%)
3
phenol group and isoxazol group are absolutely coplanar.
1
2
3
4
5
6
7
8
9
0.03
0.05
0.07
0.1
H O
200
120
120
120
1440
360
90
110
180
360
100
150
50
90
90
75
Trace
50
100
90
40
35
2
H O
Vibrational analysis
2
H O
2
H O
The molecule HBIM contains 24 atoms, which has 66
normal modes of fundamental vibrations. The experimen-
tal and calculated FT-IR spectrum of HBIM in the region
2
–
H O
2
0.05
0.05
0.05
0.05
0.05
0.05
0.05
–
−
1
MeOH
4000–400 cm is shown in Fig. 2a and b, respectively. In
order to clarify the observation of these bands, the band
deconvolution technique is used for the IR spectrum. A
deconvoluted IR spectrum of HBIM is demonstrated in Fig.
S1. The value of a correlation coeꢀcient provides good lin-
earity between the calculated and experimental wavenum-
H O/EtOH (1:1)
2
DCM
n-Hexane
EtOH
10
11
12
95
80
DMF
2
bers (R = 0.9978) and shown in Supplementary Fig. S2.
Reaction conditions: aromatic benzaldehyde (1 mmol), ethyl ace-
toacetate (1 mmol), hydroxylamine hydrochloride (1 mmol), solvent
According to our deconvolution results, the IR spec-
trum of HBIM indicates the presence of a medium FT-IR
(
5 mL)
1
3

Journal of the Iranian Chemical Society
Table 2 Evaluation synthesis of 4-arylmethylene-3-methylisoxazol-5(4H)-ones (4a–p) by reaction of aromatic aldehydes (1), hydroxylamine
a
hydrochloride (2) and ethyl acetoacetate (3) using SbCl as a catalyst
3
Time
min)
Yield
Mp (°C)
Found Lit. (Ref.)
b
Entry Aldehyde
1
Product
c
d
(
(%)
120
90
140–142 142–143
1
a
4
a
e
2
3
4
900
ND
_
_
_
_
1
b
4
b
e
900
140
ND
1
c
4
c
90
135–137 135–136
1
d
4
d
5
6
7
165
145
120
85
94
90
213–215 214–216
175–177 175–177
213–215 211–214
1
e
4
e
1
f
4
f
1
h
4
h
8
9
130
170
90
80
226–229 227–228
201–203 202–203
1
i
4i
1
j
4
j
10
11
12
13
250
120
115
125
60
91
88
90
198–200 198–200
267–270 267–268
238–240 238–241
144–145 146–147
1
k
4
k
1
l
4
l
1
m
4
m
1
n
4
n
1
3

Journal of the Iranian Chemical Society
Table 2 (continued)
1
4
5
110
160
90
85
146–147 146–147
240–241 241–242
1
o
4o
1
1
p
4
p
a
All of the reactions were carried out using aromatic aldehydes (1 mmol), ethyl acetoacetate (1 mmol), hydroxylamine hydrochloride (1 mmol),
water (5 mL), SbCl (0.05 g), room temperature
3
b
All compounds are known, and their structures were established from their spectral data and melting points as compared with literature values
Yields refer to those of pure isolated products
Melting points are listed in the references [13, 27–35, 50]
Not detected
c
d
e
Table 3 Comparison results of SbCl with recently reported catalyst
symmetric methyl stretching. According to our decon-
volution results, the IR spectrum of HBIM indicated the
3
in the synthesis α, β-unsaturated 4H-isoxazol-5-ones
−
1
presence of one band at 1364 cm (see Fig. S1) and at
O
CH3
−1
O
1372 cm (B3LYP) which is assigned for the δ CH . For
s
3
N
O
the title compound, the scissoring modes of the CH group
Ar
H
3
−1
O
O
Ar
are calculated to be 1477, 1476, 1470 cm (B3LYP) and
O
−1
in 1544, 1500, 1458 cm (IR). The bands at 1070 and
NH OH· HCl
2
−1
−1
9
96 cm in the IR spectrum and at 1062 and 1004 cm
(
B3LYP) are assigned as ρCH mode for the HBIM.
3
Entry
Catalyst
Conditions
Time (min)
Yield (%)a
The calculated values of ν(C–CH ) are 901 and
3
−
1
1
2
3
4
9
DABCO
Sodium Azide
Pyridine
EtOH reꢂux
12
200
180
90
70 [29]
92 [28]
71 [27]
88 [26]
90
762 cm . The experimental observed values in the FT-IR
−
1
H O r.t.
spectrum at 894 and 776 cm conꢁrm the assignment on
a comparison with the calculated values.
2
EtOH reꢂux
EtOH r.t.
Na S.9H O
In HBIM, the FT-IR bands in 1590, 1566, 1458, 1230
2
2
−
1
SbCl3
H O r.t.
120
and 1174 cm are assigned to ring stretching vibrations.
The CCC in-plane bending modes of HBIM occurred
2
Reaction conditions: benzaldehyde (1 mmol), hydroxylamine hydro-
chloride (1 mmol) and ethyl acetoacetate (1 mmol) and catalyst under
diꢃerent conditions
−1
at 826 and 650 cm . The band is assigned to CCC out-
−
1
of-plane bending vibrations is observed at 560 cm in
HBIM. The main ring stretching vibration is the ring
breathing vibration. In the experimental infrared spectrum
a
Isolated yields
−
1
of HBIM, this mode appears at 858 cm .
−
1
band observed the C–O stretching vibrations at 1130 cm
All the above-mentioned vibrations are in good agree-
ment with we reported in our previous work [41].
The free hydroxyl group absorbs strongly in the
−
1
(
Table 5) and at 1144 cm (B3LYP). In HBIM, the C=O
−
1
stretching vibration is calculated at 1779 cm and is
−
1
−1
observed a strong band in IR spectrum at 1728 cm . The
dominant in-plane C=O bending vibrations in the case of
3700–3584 cm region [53]. The computed wavenumber
−
1
for the O–H stretching is at 3801 cm (mode No. 1) by
B3LYP/6-311++G(2d,p) method with PED contribution
of 100%, while the recorded FT-IR spectrum shows a weak
−
1
HBIM are calculated at 566 and 525 cm .
Deconvoluted IR spectrum of HBIM displays the attend-
−
1
−1
ance of two bands in 1620 and 1598 cm in IR spectrum
peak at 3735 cm which is assigned to O–H stretching
−
1
and 1626 and 1610 cm given by calculation are assigned
vibration. The O–H in-plane bending vibration in phenol,
−
1
−1
as υC = N. A band observed at 894 cm in the FT-IR spec-
in general, lies in the region 1150–1250 cm [54]. In
trum is assigned to N–O stretching vibration mixed with
HBIM, the in-plane bending mode of O–H group is iden-
−
1
the C–CH stretching.
tiꢁed at 1174 cm in infrared, which shows good agree-
ment with the theoretically computed value by B3LYP/6-
311++G(2d,p) method with PED contribution of 49%.
3
In this case, the asymmetric methyl stretching bands
−
1
are observed at 3035 and 2953 cm in IR spectrum. One
IR band identiꢁed at 2929 cm− which is assigned for
1
1
3

Journal of the Iranian Chemical Society
Table 4 Optimized geometrical
parameters of HBIM obtained
by B3LYP/6-311++G(2d,p)
level of theory
Parametersa
Exp.b
Exp.c
Exp.b
Exp.c
Cal.
Cal.
Bond lengths (Å)
O –C
Bond lengths (Å)
C –C
1.371
1.429
1.478
1.207
1.452
1.361
1.289
1.492
1.088
1.366
1.435
1.467
1.201
1.434
1.359
1.283
1.479
0.930
1.388
1.451
1.446
1.220
1.451
1.365
1.294
1.481
0.930
1.442
1.412
1.410
1.379
1.396
1.397
1.382
1.357
0.965
1.434
1.413
1.392
1.382
1.363
1.389
1.364
1.426
1.409
1.405
1.371
1.407
1.412
1.375
1
2
11
13
14
15
16
20
20
18
O –N
C –C
1
6
13
C –C
C –C
2
3
13
C –O
C –C
2
5
14
C –C
C –C
3
4
16
C –C
C –C
3
11
18
C –N
C –C
4
6
15
C –C
C –O
4
7
18 23
C –H
O –H
23 24
1
1
12
Bond angles (°)
O –C –C
Bond angles (°)
C –C –C
106.2
120.9
103.3
132.4
112.4
127.8
113.5
134.2
106.7
119.1
103.3
132.6
113.2
127.5
113.4
133.2
107.3
118.0
103.6
132.2
113.3
127.1
112.5
135.0
117.1
125.3
121.9
119.3
120.7
120.5
117.3
122.6
110.1
117.5
125.0
120.4
120.1
122.0
119.2
117.8
125.4
122.7
120.4
120.9
122.0
1
2
3
11
13
14
15
16
20
18
20
O –C –O
C –C –C
1
2
5
11 13
C –C –C
C –C –C
13 14
2
3
4
C –C –C
C –C –C
2
3
11
14 16
C –C –N
C –C –C
13 15
3
4
6
C –C –C
C –C –C
3
4
6
15 18
C –C –H
C –C –O
C –C –O
20 18
3
11
12
13
15 18
23
23
C –C –C
3
11
C –O –H
1
8
23
24
Dihedral angles (°)
O –C –C –C
Dihedral angles (°)
C –C –C –C
C –C –C –C
3 11 13
0.0
− 1.0
−0.9
176.5
0.3
180.0
0.0
180.0
–180.0
0.0
0.0
− 180.0
180.0
− 176.4 − 179.7
4.8 − 0.4
− 179.0 − 179.8
1
2
3
4
3
11
13
14
15
O –C –C –C
− 180.0 179.1
0.0
180.0
0.0
180.0
0.0
1
2
3
11
C –C –C –N
0.0
C –C –C –C
2
3
4
6
11
13
14
16
18
20
20
23
23
C –C –C –C
− 179.7 − 178.2
0.9 0.4
− 179.3 178.9
2.1 0.8
C –C –C –C
178.7
0.3
− 179.5
− 0.4
− 0.9
2
3
4
7
11
13
15
O –N –C –C
C –C –C –C
13 14 16
1
6
4
3
O –N –C –C
C –C –C –C
− 0.1
1
6
4
7
13
15
18
C –C –C –C
C –C –C –C
2
3
11
13
13
15
18
C –C –C –C
− 180.0 − 177.8 177.6
C –C –C –C
16 20 18
4
3
11
13
a
b
c
For atom numbering from Fig. 1
Ref. [51]
Ref. [52]
The C–H stretching vibrations are calculated at
−
1
3
197–3113 cm . These vibrations are in good agree-
ment with the experimental values. For example, the
−
1
experimental value is assigned at 3157 cm , and the
−
1
calculated one is obtained at 3156 cm . These modes
are pure stretching modes as seen from PED column
shown in Table 5. The in-plane and out-of-plane C–H
bending vibrations emerged in the range 1000–1300 and
−
1
7
50–1000 cm , respectively. In this work, the C–H in-
plane and out-of-plane bending vibrations also lie within
the characteristic region. As an example, the C–H out-
of-plane bending vibration (or wagging) modes started
−
1
appearing from 968 cm and had contributed up to
−
1
5
9
60 cm , whereas these are predicted in the region of
Fig. 1 Theoretically optimized geometric structure with atoms num-
−
1
72–527 cm .
bering of HBIM
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Journal of the Iranian Chemical Society
UV–Vis spectra and electronic properties
(
a)
Gauss-Sum 2.2 Program [55] is used to calculate group con-
tributions to the molecular orbitals (HOMO and LUMO) and
provide the density of the state (DOS) as shown in Fig. 5.
DOS plot shows population analysis per orbital and indicates
an easy outlook of the makeup of the molecular orbitals in
a certain energy range.
The energy gap between the HOMO and LUMO charac-
terizes the molecular chemical stability, softness, hardness
and chemical reactivity of the molecule [56]. The energy
diꢃerence between the HOMO and LUMO is 3.663 eV (see
Fig. 6), for the HBIM. For the HBIM, wavelength (λ), oscil-
lator strength (f) and major contributions of calculated tran-
sitions are given in Table 7. The UV–Vis electronic spectra
of (Z)-4-(3-hydroxybenzylidene)-3-methylisoxazol-5(4H)-
one in two organic solvents are recorded and calculated.
Representative spectra are shown in Fig. 7. It is also
found that the absorption maxima showed a clear red shift
when passing from the low-polar solvents to the high-polar
solvents. It is suggested that HBIM with π–π* transitions are
less polar in their ground state than in their excited states.
The transitions at 249, 302, 342 and 394 nm in ethanol sol-
vent are assigned to n → σ*, n → π*, n → π* and π → π*
transitions, respectively.
(
b)
400
800
1200
1600
2000
3000 3500 4000
-
1
Wavenumber (cm )
Fig. 2 Comparison of observed and calculated IR spectra of HBIM a
observed, b calculated with B3LYP/6-31++G(2d,p)
Molecular electrostatic potential (MEP) surface
Electrochemical properties
To foretaste reactive sites for electrophilic ad nucleophilic
attack for HBIM, the MEP at the B3LYP/6-311++G(2d,p)
method is calculated. The sliced 2D MEP contour map is
plotted in Fig. 3, which this map drawn in the molecular
plane manifested maximum values of positive potential
and negative potential corresponding to the electrophilic
and nucleophilic region.
Ionization potential (IP) and electron aꢀnity (EA) are com-
monly calculated by diꢃerences of total energies of the neu-
tral (E
) and ionic systems (E
, E
) obtained from
anion
neutral
cation
optimized molecular conꢁgurations. The EA and IP obtained
from total energies via B3LYP/6-311++G(2d,p) basis set
are listed in Table 8.
The 3D plot of the MEP surface for the HBIM is shown
in Fig. 4. The negative (red and yellow) and the positive
The electrochemical properties of HBIM are investigated
by cyclic voltammetry with DMSO as a solvent in the pres-
ence of Bu NBF as the supporting electrolyte using Pt as
(
blue) regions of MEP are linked to electrophilic and
4
4
nucleophilic reactivity. As shown in Fig. 4, the negative
region of the compound is observed around the O and
N atoms. The values of the electric potential (a.u) and
charges (e) of the HBIM are reported in Table 6. The max-
imum negative electrostatic potential is prominent over
working and counter electrodes and Ag/AgCl as the refer-
ence electrodes the ambient electrode at the ambient tem-
perature (Fig. 8). Upon scanning the potential from − 1.5
to + 1.5 V, an oxidation wave is observed with an anodic
peak potential of 1.289 V and a cathodic peak potential of
− 1.060 V.
O atom. The maximum negative electrostatic potential
5
value for these electrophilic sites calculated at B3LYP/6-
Using cyclic voltammetry the IP is estimated from the
onset of the first oxidation peak whereas EA from the
onset of the ꢁrst reduction peak. The oxidation and reduc-
tion peaks are associated with the HOMO and LUMO
3
11++G(2d,p) is about − 22.376 (a.u) with point charge
−
0.570 e. Also the hydrogen atoms illustrate suitable sites
for nucleophilic attack. These sites give information about
the region where the compound can have intramolecular
interaction. For the MEP surface of the studied molecule,
levels, respectively. The HOMO energy level, E , is esti-
H
ox
mated by equation [57]: E
= E + 4.4 V. The LUMO
HOMO
the strong negative regions associated with the O atom
energy level, E , is obtained by adding the energy of the
5
L
and also the weak positive region by the nearby H atom
HOMO–LUMO gap, ΔE , to E value, while the energy
1
9
HL
H
are indicative of intramolecular (O …H –C ) hydrogen
gap ΔE is determined from the diꢃerence between oxida-
5
19
15
HL
bonding.
tion and reduction potentials.
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Journal of the Iranian Chemical Society
Table 5 Experimental (FT-IR
B3LYP/6-
11++G(d,p)
B3LYP/6-311++G(2d,p)
−
1
wavenumbers (in cm )) and
3
theoretical (scaled wavenumbers
−
1
(
in cm )) of HBIM at
Freq I.IR AR
3652 127 265 3801 125 260 3735 (2) νOH(100)
3068 30 28 3197 32 28 3329 (14) ν CH (98)
Freq I.IR AR
IR (neat) Vibrational assignments (PED)
B3LYP/6-311++G(d,p) and
B3LYP/6-311++G(2d,p) level
of theory
s
ph
3
3
3
2
2
2
2
058
028
3
5
179 3186
70 3156
3
5
177 3255 (28) ν CH (93)
s ph
67
3157 (16) ν CH (93)
a ph
018 15 119 3145 15 118 3137 (22) ν CH (98)
991
987
a
ph
5
8
117 3116
4
8
9
110 3035 (6) ν CH (83), νC H (15)
a 3 11 12
38
3113
3071
41
52
νC H (97)
11 12
948 10 52
2953 (2) ν CH (100)
a 3
898 11 182 3021 10 181 2929 (4) ν CH (100)
s
3
2
1
1
1
1
1
1
024
999
967
934
923
878
867
996 + 1030
825 + 1174
668 + 1300
2*968
815 + 1108
650 + 1230
756 + 1108
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
9
9
9
9
9
9
8
8
8
7
7
7
716 283 36
591 35 112 1655 29 75
562 132 154 1626 134 164 1620 (24) νC=N(52), δ CH (15)
1779 274 37
1728 (55) νC=O(83)
1708 (15) ν CC (31), ν C =C –C(17)
a
ph
a
3
11
a
3
546 584 1668 1610 432 1200 1598 (34) νC=N(15), ν C =C –C (12), ν CC (17)
a
3
11
13
a
ph
535 146 642 1599 263 1034 1590 (38) ν CC (17), ν C =C –C (12), νC=N(13)
a
ph
a
3
11
13
475 69 78
415 12 10
1541 57 93
1477 10
1476 22 31
1470 117 83
1429 15 17
1409 37 28
1379 34 11
1556 (70) ν CC (10), δCH (56)
1544 (43) δ CH (80), δCH (15)
a 3 ph
a ph ph
9
414
4
16
1500 (40) δ CH (51), δCH (11)
a 3 ph
407 123 79
370 17 26
350 43 32
319 69 55
1458 (17) δ CH (13), ν CC (25), δCH (10)
a 3 a ph ph
1430 (7) νC–CH (10), δC H (20)
3
11 12
1412 (15) δ CH (10), δC H (28), δCH (10)
s
3
11 12
ph
1380 (34) ν CC (11), δCH (26), δOH(19)
a
ph
ph
315
287 14 103 1339 12 97
246 221 68 1298 215 67
198 13 237 1249 10 240 1230 (68) ν CC (12), δCH (12), δC H (32)
7
71
1372 47 121 1364 (29) δ CH (30), ν C –C –C (24)
s 3 a 3 4 7
1300 (56) ν CC (17), δCH (14), ν C –C –C (16)
a
ph
ph
a
2
3
4
1258 (13) νC –O (51), ν CC (10)
2
0
23
s
ph
a
ph
ph
11 12
156 61 155 1206 50 153 1182 (36) δCH (26), δOH(28)
ph
137 284 92
ph a ph
095 28
1
3
0
076 222
011
1
93 18 15
1037 18 18
1030 (17) ν O –C –C –C (20)
a 1 2 3 4
80
64
0
2
0
0
1025
1005
0
2
0
0
δCCC (71), δCH (11)
ph ph
γCH (69), γC H (20)
ph
11 12
62 68 39
1004 68 40
996 (30) ρCH (57), ν C –C –C =N (13)
968 (16) γCH (47), γC H (39)
ph 11 12
3 a 2 3 4 6
32
4
1
2
972
947
4
9
1
1
04 11
942 (8)
γCH (70), γC H (10)
ph 11 12
63 87 21
40 17 35
901 82 20
876 17 35
894 (26) νC –O –N (28), νC–CH (51)
858 (25) Ring breathing (31), νC –C (10)
2
1
6
3
1
1
13
09 48
0
847 44
0
γCH (47), γCC (21)
ph ph
92
90
36 18
4
0
43
0
1
827
820
801 16
3
0
45
0
1
826 (5)
814 (8)
δCCC (30), νC –O (19)
ph 20 23
γCH (55), γCC (35)
ph
ph
γIsox(64), γC H (12)
11 12
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Journal of the Iranian Chemical Society
Table 5 (continued)
B3LYP/6-
11++G(d,p)
B3LYP/6-311++G(2d,p)
3
Freq I.IR AR
Freq I.IR AR
762 17 13
IR (neat) Vibrational assignments (PED)
776 (25) νC–CH (12), δC –O –N (52)
7
7
6
6
5
5
5
5
5
31 18 12
3
2
1
6
20
93
24
70 13
70
5
0
1
11
1
10
8
752
736
652
614
5
0
1
3
10
1
10
1
756 (6)
668 (5)
ν C –C –O –N (17), δC =C –C (12)
s 3 2 1 6 3 11 13
γCH (73)
ph
650 (10) δCCC (69)
ph
634 (6)
γIsox(53)
3
1
595 13
7
596 (11) δC –C –C (12), δC–CH (35), δCCC (12)
2
3
4
3
ph
42 31 11
566 32 11
590 (11) δC–CH (13), δC =O (24), δIsox(14)
3 2 5
04 16
03 25
0
8
527 18
525 27
0
8
560 (15) γCH (11), γCC (48)
ph ph
518 (20) δC =O (22), δIsox(19), δC =C –C (12), δCCC (14)
2
5
3
11
13
ph
Freq, vibrational wavenumber; I.IR, IR intensities in kM/mol; AR., Raman scattering activities in A**4/
AM; experimental relative intensities are given in parentheses; s, symmetric; as, asymmetric; υ, stretching;
δ, in-plane bending; γ, out-of-plane bending; ρ, in-plane rocking
Fig. 3 2D contour map of HBIM
Thermal analysis
10 min. The thermogravimetric (TG) and diꢃerential ther-
mal gravimetry (DTG) curves are shown in Fig. 9. TGA
Thermal analysis of HBIM is carried out using a Perki-
nElmer model, simultaneous thermogravimetric/differ-
ential thermal (TG/DT) analyzer. The sample is scanned
in the temperature range 20–800 °C at a rate of 20 °C for
measurements of HBIM showed that weight of complex is
constant up to 180 °C; thus, title compound did not con-
tain crystallization water. Two major weight losses have
been observed above 180 °C. The ꢁrst one 24% loss occurs
1
3

Journal of the Iranian Chemical Society
between 218 and 300 °C, and the major weight loss (56%)
takes place over a large temperature range (440–765 °C),
where almost all the compounds decomposed as gaseous
products. The remaining 12% charred material left behind.
HBIM is chemically stable up to 218 °C, above which tem-
perature the sample gradually decomposes. In the diꢃerential
thermal gravimetry (DTG) curve, two peaks are identiꢁed at
temperatures of 239 and 562 °C, showing that by increasing
heat weight loss occurs in two steps.
Nonlinear optical properties
Based on the finite-field approach, the nonlinear opti-
cal parameters such as dipole moment, polarizability,
anisotropy polarizability and first-order hyperpolariz-
ability of title molecule obtained by B3LYP level with
the 6-311++G(d,p) and the 6-311++G(2d,p) basis sets.
Nonlinear optics deals with the interaction of applied
electromagnetic fields in various materials to generate
new electromagnetic fields, altered in wavenumber, phase
or other physical properties [58]. In the presence of an
applied electric field, the energy of a system is a function
of the electric field. First hyperpolarizability is a third-
rank tensor that can be described by a 3 × 3 × 3 matrix.
The 27 components of the 3D matrix can be reduced to
10 components due to the Kleinman symmetry [58]. The
components of β are defined as the coefficients in the
Taylor series expansion of the energy in the external elec-
tric field. When the electric field is weak and homogene-
ous, this expansion becomes
Fig. 4 Molecular electrostatic potential map (MEP) of HBIM. (For
interpretation of the references to color in this ꢁgure, the reader is
referred to the web version of the article)
Table 6 Values of the electric potential (a.u) and charges (e) for
HBIM at B3LYP/6-311++G(2d,p) level
Atoms
Charges (e)
Electric
potential
(
a.u)
O1
C2
C3
C4
O5
N6
C7
H8
H9
H10
C11
H12
C13
C14
C15
C16
H17
C18
H19
C20
H21
H22
O23
H24
− 0.399
0.787
− 0.214
0.208
− 0.570
− 0.120
− 0.611
0.217
− 22.306
− 14.640
− 14.733
− 14.716
− 22.376
− 18.354
− 14.749
− 1.087
− 1.087
− 1.092
− 14.718
− 1.071
− 14.734
− 14.752
− 14.763
− 14.750
− 1.084
− 14.691
− 1.098
− 14.747
− 1.085
− 1.073
− 22.321
− 0.959
ꢀ
ꢀ
1
i
j
E =E −
0
ꢀiF −
ꢁ F F
ij
0.217
0.236
2
j
ij
ꢀ
ꢀ
1
−
1
i
j
ꢂ F F F −
K
i
j
k
l
ꢃ F F F F +
ijkl
− 0.035
0.198
− 0.102
− 0.169
− 0.204
− 0.195
0.202
0.320
0.262
− 0.242
0.210
0.203
ijk
6
24
ij
ijkl
i
where E is the energy of the unperturbed molecule, F is
0
the ꢁeld at the origin, μ , α , β and γ are the components
i
ij ijk
ijkl
of dipole moment, polarizability, the ꢁrst hyperpolarizabili-
ties and second hyperpolarizabilities, respectively. The total
static dipole moment, mean polarizability (α ), anisotropy
tot
polarizability (Δα) and the average value of the ꢁrst hyper-
polarizability (<β>) can be calculated using the following
equations.
− 0.670
0.472
1
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Journal of the Iranian Chemical Society
�
ꢀ
2
1
2
2
2
ꢀ
= ꢀ + ꢀ + ꢀ
x y z
1ꢁ
3
ꢂ
ꢁtot
=
ꢁ + ꢁ + ꢁ
xx
yy
zz
ꢃ
ꢄ
2
1
2
ꢁ
ꢂ2
ꢁxx − ꢁyy + ꢁ − ꢁ
ꢁ
ꢂ2
ꢁ
ꢂ2
1
2
+ 6ꢁ + 6ꢁ + 6ꢁ
2
Δꢁ = √
+ ꢁ − ꢁ
zz
yy
zz
xx
xz xy yz
2
ꢃ
ꢁ
ꢄ
1
+ ꢂzzzꢂ2
ꢁ
+ ꢂyxxꢂ2 ꢁ + ꢂzyyꢂ2
+ ꢂ + ꢂzxx
zzz
2
⟨
ꢂ⟩ = ꢂxxx + ꢂyyy
+ ꢂ + ꢂyzz
yyy
The numerical values of above-mentioned param-
eters are listed in Table S1 (Supplementary data). The
calculated dipole moment is equal to 6.094 Debye (D)
in HBIM, which is bigger than to the value for urea.
Nonlinear optical materials (NLO) have been marvelous in
last years with respect to their future potential uses in the
communications and photonic industries [59]. Urea is one
of the sample molecules used for the research of the NLO
properties of molecular systems. So, it has been used fre-
quently for comparative purposes. Clearly the higher values
of hyperpolarizability, molecular polarizability and dipole
moments are important for more active NLO properties.
Total polarizability (α ) and anisotropy of polariz-
tot
−
24
ability (Δα) are calculated as − 12.989 × 10
and
−
24
7
.070 × 10
esu. The first hyperpolarizability value β
tot
−
30
of HBIM is equal to 10.678 × 10
esu, which greater
Fig. 5 DOS and PDOS plot of
HBIM
1
3

Journal of the Iranian Chemical Society
Fig. 7 UV–Vis absorption spectra of HBIM
than that of the standard NLO material urea (µ and β of
−
30
urea are 1.372 D and 0.3728 × 10
esu) [60].
Thermodynamic functions
0
The statically thermodynamic functions: enthalpy (H ),
m
0
0
entropy (S ), molecular energy (E) and heat capacity (C ) for
m
p,m
HBIM are computed at B3LYP/6-311++G(2d,p) and listed
in Table S2. It can be concluded that these thermodynamic
functions are growing with temperature from 100 to 800 K.
The correlation equations between heat capacity, entropy,
enthalpy changes, molecular energy and temperatures are ꢁt-
Fig. 6 Atomic orbital compositions of the frontier molecular orbital
for HBIM
Table 7 Theoretical and experimental absorption wavelength
λ
3
(nm) and oscillator strengths (f) of HBIM using TD-DFT/6-
max
ted by quadratic formulas. The corresponding ꢁtting factors
11G++(2d,p)
2
(
R ) for these thermodynamic properties are 0.9996, 1.0000,
Experiment Calculated
0.9999 and 0.9997, respectively. The corresponding quadratic
equations obtained by B3LYP/6-311++G(2d,p) are as follows,
and the related ꢁgure is shown in Fig. 10.
a
λ
λ
f
Major contribution (≥ 10%)
Gas
–
–
–
–
379 0.0678 H → L(65%), H-1 → L (33%)
340 0.3297 H-1 → L(64%), H → L (31%)
288 0.2031 H-3 → L (92%)
ꢀ
R = 0.9996ꢁ
0
−5
= 1.8738 + 0.1914T − 9 × 10 T
2
2
C
p,m
ꢀ
R = 1.0000ꢁ
0 −5
S = 56.243 + 0.2007T − 5 × 10 T
2
2
235 0.0621 H → L + 1 (66%), H-4 → L
m
ꢀ
R = 0.9999ꢁ
0 −4
H = −2.5513 + 0.0814T + 1 × 10 T
2
2
(
13%), H-1 → L + 4 (11%)
m
ꢀ
R = 0.9997ꢁ
Ethanol 394
395 0.1145 H → L (84%), H-1 → L (14%)
343 0.4806 H-1 → L (85%), H → L (14%)
289 0.1251 H-3 → L (95%)
−
E = 111.85 + 0.0146T − 6 × 10 T
5
2
2
3
3
2
42
02
49
236 0.0980 H → L + 1 (63%), H-4 → L
(
22%)
All the computed thermodynamic data are helpful for
the further study on the HBIM molecule. They can be used
to compute the other thermodynamic energies according
to relationships of thermodynamic functions and estimate
directions of chemical reactions according to the second law
of thermodynamics in thermochemical ꢁeld [61]. Notice: all
thermodynamic calculations are done in gas phase, and they
could not be used in solution.
DMSO 395
396 0.1214 H → L (86%), H-1 → L (13%)
343 0.4893 H-1 → L (86%), H → L (13%)
289 0.1233 H-3 → L (95%)
3
3
2
45
04
52
236 0.1004 H → L + 1 (63%), H-4 → L
(
22%)
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Journal of the Iranian Chemical Society
Table 8 Electrochemical
Band gapa
EHOMO/Ea
ox
b
c
(eV)
IP
EA
IP/EA
E onset (V) EHOMO/E
(eV)
LUMO
LUMO
properties of the title compound
3
.663
− 6.561/− 2.898
8.427 1.493 8.427/1.493
− 1.289
− 5.689/− 2.026
a
DFT/B3LYP calculated values
b
Oxidation potential in DMSO (2 × 10 mol L− 1) containing 0.1 mol L− 1 Bu NBF with a scan rate of
− 3
4
4
00 mV s−
1
1
c
EHOMO was calculated by Eox + 4.4 V, and ELUMO = EHOMO − ΔEHL [57]
a one-pot MCR of hydroxylamine hydrochloride, ethyl ace-
toacetate, aryl aldehydes and catalytic amount of SbCl in
3
water at room temperature has been developed. The catalyst
is simple, readily available and possesses advantageous such
as environmentally friendly, easy workup, green, simplicity,
relatively better yields and shorter reaction times. In this
study, we have synthesized a (Z)-4-(3-hydroxybenzylidene)-
3
-methylisoxazol-5(4H)-one and characterized by spectro-
1
scopic (IR, H NMR, CV and UV spectra) and structural
techniques as well as the theoretical methods. The vibra-
tional wavenumbers were examined theoretically using
the Gaussian 03 set of quantum chemistry codes and were
assigned by potential energy distribution calculation. The
UV–Vis electronic spectra of HBIM in two organic solvents
are recorded and calculated. It is also found that the absorp-
tion maxima showed a clear red shift when passing from the
low-polar solvents to the high-polar solvents. It is suggested
that HBIM with π–π* transitions are less polar in their
ground state than in their excited states. The geometrical
parameters of the title compound are in agreement with the
XRD results of similar systems. A computation of the ꢁrst
hyperpolarizability indicates that the compound may be a
good candidate as a NLO material. The diꢃerence in HOMO
and LUMO energy supports the charge transfer interaction
within the molecule. To predict the reactive sites for elec-
trophilic and nucleophilic attack for the title compound, the
Fig. 8 Cyclic voltammogram of HBIM (2 × 10 mol L− 1), scan rate
−
3
−
1
1
00 mV s , electrolyte 0.1 M Bu NBF in DMSO
4 4
Conclusion
In summary, antimony trichloride shows good catalytic
activity in the preparation of 4-arylmethylene-3-methyl-
isoxazol-5(4H)-ones and gives high yields under above-
mentioned conditions. Also, an eꢀcient, safe, green and
facial protocol for the synthesis of isoxazol-5(4H)-ones by
Fig. 9 TG and DTG curves of
HBIM
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Journal of the Iranian Chemical Society
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1
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