Green and efficient synthesis of 1H-indazolo[1,2-b] phthalazine-1,6,11(13H)-triones using ZrO(NO3)2.2H2O as a novel catalyst and theoretical study of synthesized compounds

Article abstract of DOI:10.1002/jhet.3959

The one-pot three-component synthesis for the preparation of 1H-indazolo[1,2-b] phthalazine-1,6,11(13H)-triones through condensation of phthalimide, hydrazine monohydrate, dimedone, and aromatic aldehydes in the presence of a novel catalytic amount of ZrO(NO₃)₂.2H₂O at reflux conditions in water has been reported. Quantum theoretical calculations for the three structures of compounds (5a, 5b, and 5c) were performed using the G3MP2, LC-ωPBE, MP2, and B3LYP methods with the 6-311 + G** basis set. After optimizing the structures, geometric parameters were obtained and experimental measurements were compared with the calculated data. The structures of the products were confirmed by IR, ¹H NMR, ¹³C NMR, and elemental analysis. IR spectra data and ¹H NMR and ¹³C NMR chemical shifts computations of the 1H-indazolo[1,2-b]phthalazine-1,6,11(13H)-trione derivatives in the ground state were calculated. Frontier molecular orbitals, total density of states, thermodynamic parameters, and molecular electrostatic potentials of the title compounds were investigated by theoretical calculations. Molecular properties such as the ionization potential (I), electron affinity (A), chemical hardness (η), electronic chemical potential (μ), and electrophilicity (ω) were investigated for the structures. Consequently, there was an excellent agreement between experimental and theoretical results.

Full text of DOI:10.1002/jhet.3959

Received: 27 December 2019
DOI: 10.1002/jhet.3959
Revised: 26 February 2020
Accepted: 29 February 2020
A R T I C L E
Green and efficient synthesis of 1H-indazolo[1,2-b]
phthalazine-1,6,11(13H)-triones using ZrO(NO3)2.2H2O as a
novel catalyst and theoretical study of synthesized
compounds
Shabnam Saberi Biroon | Nahid Shajari
| Hooriye Yahyaei
Department of Chemistry, Zanjan Branch,
Abstract
Islamic Azad University, Zanjan, Iran
The one-pot three-component synthesis for the preparation of 1H-indazolo
[1,2-b] phthalazine-1,6,11(13H)-triones through condensation of phthalimide,
hydrazine monohydrate, dimedone, and aromatic aldehydes in the presence of
a novel catalytic amount of ZrO(NO3)2.2H2O at reflux conditions in water has
been reported. Quantum theoretical calculations for the three structures of
compounds (5a, 5b, and 5c) were performed using the G3MP2, LC-ωPBE,
MP2, and B3LYP methods with the 6-311 + G** basis set. After optimizing the
structures, geometric parameters were obtained and experimental measure-
ments were compared with the calculated data. The structures of the products
Correspondence
Nahid Shajari, Department of Chemistry,
Zanjan Branch, Islamic Azad University,
P.O. Box 49195-467, Zanjan, Iran.
Email: shajari_nahid@yahoo.com
Funding information
Islamic Azad University
were confirmed by IR, H NMR, 13C NMR, and elemental analysis. IR spectra
1
1
data and H NMR and 13C NMR chemical shifts computations of the 1H-
indazolo[1,2-b]phthalazine-1,6,11(13H)-trione derivatives in the ground state
were calculated. Frontier molecular orbitals, total density of states, thermody-
namic parameters, and molecular electrostatic potentials of the title com-
pounds were investigated by theoretical calculations. Molecular properties
such as the ionization potential (I), electron affinity (A), chemical hardness (η),
electronic chemical potential (μ), and electrophilicity (ω) were investigated for
the structures. Consequently, there was an excellent agreement between exper-
imental and theoretical results.
1 | INTRODUCTION
significance of MCRs for drug discovery has been identified
and significant attempts by both academic and industrial
A multicomponent reaction (MCR) is a procedure in which
three or more easily available units are composed together
in a single reaction container to generate a final product
displaying features of all inputs with a minimum of syn-
thetic time and effort. MCRs constitute an especially attrac-
tive synthetic strategy since they provide easy and rapid
access to large libraries of organic compounds.[1–3] As
MCRs are one-pot reactions, they are easier to carry out
than multistep syntheses. In the last decade, the
researchers have been made, particularly toward the plan-
ning and extension of multicomponent proceedings for the
production of libraries of heterocyclic compounds.[4–7] The
synthesis of nitrogen-containing heterocyclic compounds
has drawn a considerable amount of attention.[8] A large
group of these compounds includes phthalazine moiety that
shows many biological and pharmacological activities such
as anticonvulsant,[9] cardiotonic,[10] and vasorelaxant.[11]
Sevaral methods have been reported in the literature for
J Heterocyclic Chem. 2020;1–13.
wileyonlinelibrary.com/journal/jhet
© 2020 Wiley Periodicals, Inc.
1

2
SABERI BIROON ET AL.
1
the synthesis of 1H-indazolo[1,2-b]phthalazine-1,6,11(13H)-
trione derivatives using Mg(HSO4)2,[12] [Bmim]Br,[13] p-
TSA,[14] silica sulfuric acid,[15] silica-supported poly-
data, H NMR and 13C NMR chemical shifts computa-
tions, molecular electrostatic potentials (MEPs), the ther-
modynamic and electronic properties, and NBO analysis
have been calculated and carried out.
phosphoric
acid,[16]
Ce(SO4)2-4H2O,[17]
TMSCl,[18]
H3PW12O40/IL,[19] H4SiW12O40,[20] N-halosulfonamides,[21]
(OTf)3,
Y
cyanuric chloride,[23] ionic liquids,[24] and
[22]
Phthalhydrazide 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP),[25]
as catalysts. Of course, many of these methods have limita-
tions, such as hard reaction conditions, low yields, relatively
long reaction times, and expensive reagents. Recently, the
combination of two important principles of green chemistry
namely “microwaves” and “water,” has attracted the atten-
tion of chemists.[26] Organic synthesis in aqueous media is
very important because toxic and volatile organic solvents
are not used. In line with our interest in the synthesis of
heterocycles,[27–29] we report a three-component reaction of
phthalhydrazide, dimedone, aromatic aldehydes, and
ZrO(NO3)2.2H2O as a novel catalyst at reflux conditions in
water, leading to the synthesis of 1H-indazolo [1, 2-b]
phthalazinetrione derivatives. The catalyst ZrO(NO3)2.2H2O
that we used to produce 1H-indazolo[1,2-b]phthalazine-1,6,11
(13H)-trione derivatives is important in many respects. Syn-
thesis of these compounds was performed using the catalyst
ZrO(NO3)2.2H2O, which was different from other methods
and catalysts[12–20] with small scale, high speed, and effi-
ciency. Moreover, this catalyst is recyclable and reusable for
synthesizing compounds, with only slightly reduced yields.
Computational chemistry is the application of com-
puter simulation for predicting or expounding the chemi-
cal reactivity and confirmation of the synthesized
product. Computational organic chemistry is an impor-
tant area in determining the mechanisms of chemical
reactions,[30] especially catalysis,[31] structural determina-
tion of organic compounds,[32] prediction of spectroscopic
2 | MATERIALS AND METHODS
The starting materials and solvents were obtained from
Merck (Germany) and Fluka (Switzerland) and were
used without further purification. The melting points
were measured with an Electrothermal 9100 apparatus
and were uncorrected. The IR spectra were recorded on a
Jasco Fourier-transform infrared spectroscopy (FT-IR)
1
6300 spectrometer. The H-NMR and 13C-NMR spectra
were measured (DMSO solution) with a Bruker DRX-250
Avance spectrometer at 250.0 and 62.9 MHz, respectively.
The elemental analyses were realized using a Heraeus
CHN─O-rapid analyzer.
2.1 | General procedure for the synthesis
of 1H-indazolo[1,2-b]phthalazine-1,6,11
(13H)-triones
Phthalimide (1, 1 mmol) and hydrazine monohydrate (2,
1 mmol) were refluxed in water (10 mL) for 15 minutes
to form phthalhydrazide as intermediate. Then, to this
reaction mixture was added dimedone (3, 1 mmol) and
aromatic aldehydes (4, 1 mmol) one after another in the
presence of ZrO(NO3)2.2H2O (2 mol%) as the catalyst,
and then, the mixture was refluxed again for 2 hours.
The completion of the reaction was checked by Thin
Layer Chromatography (TLC) afterward, ice-cold water
(30 mL) was added to the reaction mixture and neutral-
ized with 5% sodium bicarbonate solution. The solid that
separated out was filtered, washed with water (5 mL),
and dried, and the products 5a-c were obtained.
1
data such as H NMR and 13C NMR chemical shifts,[33]
properties calculation of organic molecules,[34] and the
interaction of a substrate with an enzyme.[35] This study
has revealed some potential leads for possible pharma-
ceutical applications and further investigations may help
in the development of new antioxidative agents for
important metabolic functions. Furthermore, three new
crystal structures of the compounds 5a, 5b, and 5c have
been reported. In the present work, we have investigated
the energetic and structural properties of three com-
pounds of 1H-indazolo[1,2-b] phthalazine-1,6,11(13H)-
trione derivatives (5a, 5b, and 5c), which have been
analyzed by means of the G3MP2,[36] the long-range-
corrected version of the Perdew- Burke-Ernzerhof (PBE)
exchange functional (LC-ωPBE),[37] second-order Møller-
Plesset perturbation theory (MP2)[38,39] and hybrid
2.2 | computational studies
In the present study, we carried out quantum theoretical
calculations for the compounds 5a, 5b, and 5c using the
G3MP2, LC-ωPBE, MP2, and B3LYP methods with the
6-311 + G** basis set by the Gaussian 03 W program
package[45] and calculation of its properties. During the
beginning stage, we had an optimized structure (see
1
Figure 1). Then, we calculated the H NMR chemical
shifts using the G3MP2, LC-ωPBE, MP2, and B3LYP
methods with the 6-311 + G** basis set for the title com-
pounds (5a, 5b, and 5c) and 13C NMR.[46] The electronic
properties included energy of the highest occupied
density functional (B3LYP)[40] based methods with the
[41–44]
6-311 + G** basis set
on all atoms. The optimized
geometries, quantum molecular descriptors, IR spectra

SABERI BIROON ET AL.
3
FIGURE 1 A, Calculated frontier
molecular orbitals of compounds 5a, 5b,
and 5c (ΔE: energy gap between LUMO
and HOMO). B, Calculated DOS plots of
the title compounds (using
theB3LYP/6-311 + G**)

4
SABERI BIROON ET AL.
molecular orbital (EHOMO), energy of the lowest unoccu-
pied molecular orbital (ELUMO), HOMO-LUMO energy
gap (ΔE), ELUMO, natural charges, and molecular proper-
ties.[47] The optimized molecular structure and HOMO
and LUMO surfaces were visualized using GaussView
03 program.[48]
m.p. > 250ꢀC; Yield: 75%; Anal. Calcd for C23H20N2O3
(372.4): C, 74.18; H, 5.41; N, 7.52%. Found: C, 74.24; H,
5.44; N, 7.49.; IR (KBr) (υmax, cm−1): 3436, 2951, 1661
1
(C═O), 1625 (C═O), 1576 (C═O), 1492, 1361; H NMR
(DMSO. d6, 250.0 MHz): δH 0.86 (3H, s, CH3), 1.00 (3H, s,
CH3), 2.07-2.34 (4H, m, 2CH2), 4.49 (1H, s, CH), 7.15-8.68
(9H, m, arom CH); 13C NMR (DMSO. d6, 62.9 MHz): δC
26.88 and 29.08 (2CH3), 32.26 (C), 42.40 (CH2), 50.49
(CH2), 65.43 (CH), 115.79, 125.58, 126.59, 127.78, 128.27,
128.47, 128.79, 129.34, 131.78, 133.73, 134.26, and 138.74
(aromatic and olefinic carbons), 161.78, 163.32, and
196.43 (3C═O).
3 | RESULTS AND DISCUSSION
The phthalhydrazide (6), dimedone (3), and aromatic
aldehydes (4) reacted under reflux conditions in water and
in the presence of a catalytic amount of ZrO(NO3)2.2H2O
via a three-component reaction to give 1H-indazolo[1,2-b]
phthalazine-1,6,11(13H)-trione derivatives (5a-c) in high
yields (Scheme 1 and Table 1). The reaction proceeded
smoothly and cleanly, and no undesirable side reactions
were observed. A mechanistic rationalization for this reac-
tion is provided in Scheme 2. The structures of the prod-
13-(4-Chlorophenyl)-3,3-Dimethyl-2,3,4,13-tetrahydro-
1H-indazolo[1,2-b] phthalazine-1,6,11(13H)-trione (5b):
Yellow solid; m.p. > 250ꢀC; Yield: 79%; Anal. Calcd for
C23H19ClN2O3 (406.9): C, 67.90; H, 4.71; N, 6.89%.
Found: C, 67.95; H, 4.68; N, 6.92; IR (KBr) (υmax, cm−1):
3436, 2951, 1663 (C═O), 1627 (C═O), 1575 (C═O), 1492,
1
1361; H NMR (DMSO. d6, 250.0 MHz): δH 0.87 (3H, s,
1
ucts were deduced from their IR, H-NMR, 13C-NMR, and
2CH3), 1.01 (3H, s, 2CH3), 2.02-2.35 (4H, m, 2CH2), 4.47
(1H, s, CH), 7.13-7.47 (3H, m, arom CH), 7.56 (2H, d,
1
elemental analyses. For example, the H-NMR spectrum of
3
5a exhibited distinct signals arising from two CH3 groups
(0.86 and 1.00 ppm, 2s), two CH2 groups (2.07-2.34 ppm,
m), aliphatic CH (4.49 ppm, s), and nine aromatic CHs
(7.15-8.68 ppm, m). The 13C NMR spectrum of 5a shows
21 distinct resonances arising from two CH3 groups (26.88
and 29.08 ppm), C (32.26 ppm), two CH2 groups (42.40 and
50.49 ppm), aliphatic CH (65.43 ppm), aromatic and ole-
finic carbons (115.79, 125.58, 126.59, 127.78, 128.27, 128.47,
128.79, 129.34, 131.78, 133.73, 134.26, and 138.74 ppm), and
C═O carbons (161.78, 163.32, and 196.43 ppm).
3JHH = 8.25 Hz, arom CH), 7.88 (2H, d, JHH = 8.25 Hz,
arom CH), 8.69 (1H, s, arom CH); 13C NMR (DMSO. d6,
62.9 MHz): δC 26.93 and 29.04 (2CH3), 31.38 (C), 32.30
and 50.40 (2CH2), 63.34 (CH), 114.40, 114.65, 128.27,
128.96, 129.34, 129.54, 130.36, 130.47, 131.23, 133.05,
136.48, and 143.69 (aromatic and olefinic carbons),
161.04, 163.52, and 196.54 (3C═O).
13-(2,
4-Dichlorophenyl)-3,3-dimethyl-2,3,4,13-tetra-
hydro-1H-indazolo[1,2-b]- phthalazine-1,6,11(13H)-trione
TABLE 1 Synthesis of 1H-indazolo[1,2-b]phthalazine-1,6,11
(13H)-trione derivatives (5a-c)
3.1 | Characterization data for the
synthesis of 1H-indazolo[1,2-b]phthalazine-
1,6,11(13H)-triones
(4)
a
R1
H
R2
H
(5) Yield%
75
79
83
b
H
Cl
Cl
3,3-Dimethyl-13-phenyl-2,3,4,13-tetrahydro-1H-indazolo
[1,2-b] phthalazine-1,6,11(13H)-trione (5a): Yellow solid;
c
Cl
SCHEME 1 Three-component reaction of phthalimide, hydrazine monohydrate, dimedone, and aromatic aldehydes (see Table 1)

SABERI BIROON ET AL.
5
SCHEME 2 A proposed mechanism for the formulation of 1H-indazolo[1,2-b]phthalazine-1,6,11(13H)-trione derivatives
TABLE 2 The selected experimental and theoretical frequencies of the title compounds using G3MP2, LC-ωPBE/6-311 + G**,
B3LYP/6-311 + G**, and MP2/6-311 + G** for compounds 5a, 5b, and 5c
Calculated vibrational wavenumbers by HF and DFT methods (cm−1
)
Experimental wavenumbers by FT-IR (cm−1
)
G3MP2
3402
LC-ωPBE/6-311 + G**
B3LYP/6-311 + G**
MP2/6-311 + G**
Assigments
C─H aromatic
C─H aliphatic
C═O
3436
2951
1661
1625
1576
3407
2938
1658
1628
1569
3433
2950
1660
1624
1574
3431
2953
1659
1623
1570
5a
2937
1657
C═O
1620
C═O
1568
Assigments
5b
C─H aromatic
C─H aliphatic
C═O
3436
2951
1663
1627
1575
3430
2946
1673
1619
1597
3436
2946
1680
1612
1562
3436
2949
1681
1620
1570
3435
2950
1688
1611
1563
C═O
C═O
Assigments
5c
C─H aromatic
C─H aliphatic
C═O
3434
2962
1723
1659
1615
3429
2964
1773
1653
1632
3432
2966
1780
1650
1637
3433
2969
1781
1659
1617
3430
2960
1788
1658
1631
C═O
C═O
Abbreviations: DFT, Density Functional Theory; FT-IR, Fourier-Transform Infrared Spectroscopy; HF, Hartree-Fock.
1
(5c):Yellow Solid; m.p. >250ꢀC; Yield: 83%; Anal. Calcd
for C23H18Cl2N2O3 (441.3): C, 62.60; H, 4.11; N, 6.35%.
Found: C, 62.54; H, 4.15; N, 6.28; IR (KBr) (υmax, cm−1):
3434, 2962, 1723 (C═O), 1659 (C═O), 1615 (C═O), 1583,
1468, 1385; H NMR (DMSO. d6, 250.0 MHz): δH 1.02
(3H, s, CH3), 1.03 (3H, s, CH3), 2.26-2.34 (4H, m, 2CH2),
4.51 (1H, s, CH), 6.95-7.81 (7H, m, arom CH); 13C NMR
(DMSO. d6, 62.9 MHz): δC 26.91 and 28.22 (2CH3), 32.61

6
SABERI BIROON ET AL.
(C), 42.46 (CH2), 50.48 (CH2), 63.56 (CH), 113.94, 123.36,
126.37, 127.22, 128.28, 128.63, 129.14, 129.83, 132.17,
132.82, 133.39, and 134.75 (aromatic and olefinic car-
bons), 163.82, 168.09, and 196.35 (3C═O).
difference between the experimental and calculated
vibrational modes was observed. This difference might
have been due to intermolecular hydrogen bonding for-
mation. Also, the experimental results belonged to a solid
phase while the theoretical calculations belonged to the
isolated gaseous phase.
3.2 | Computational section
3.2.1 | IR spectroscopy
3.2.2 | NMR parameters
1
Harmonic vibrational frequencies of the title compounds
were calculated using the G3MP2, LC-ωPBE, MP2, and
B3LYP methods with the 6-311 + G** basis set. The
vibrational frequencies assignments were made using the
GaussView program. Some of the characteristic frequen-
cies are provided in Tables 2–4. The harmonic frequen-
cies calculated by B3LYP are usually higher than the
corresponding experimental values due to the approxi-
The calculation of H NMR and 13C NMR chemical shifts
of compounds 5a, 5b, and 5c was done at G3MP2, LC-
wPBE/6-311 + G**, B3LYP/6-311 + G**, and MP2/6-311
+ G**. The experimental and calculated H NMR and 13C
1
NMR chemical shifts of 1H-indazolo[1,2-b] phthalazine-
1,6,11(13H)-trione derivatives (5a, 5b, and 5c) are demon-
strated in Tables 3–8. Based on our calculations and experi-
mental spectra, we made
a
reliable one-to-one
mate
treatment
of
the
electron
correlation,
correspondence between our fundamentals and any of the
chemical shifts that were calculated by the G3MP2, LC-
ωPBE, MP2, and B3LYP methods with the 6-311 + G**
basis set. For the title compound (5a), according to Tables 3
and 4, the aromatic CH protons appear at δH
7.15-8.68 ppm, the calculated amounts at LC-wPBE/6-311
+ G** and B3LYP/6-311 + G** basis set levels are 7.11-8.59
and 7.23-9.66 ppm, respectively. Protons of two methyl
groups appear at δH 0.86 and 1.00 ppm, the calculated
amounts at LC-wPBE/6-311 + G** and B3LYP/6-311 + G**
basis set levels are 0.83 and 1.12 ppm, and 0.86 and
1.09 ppm, respectively. Also, chemical shifts of three car-
bonyl groups appear at δc 161.78, 163.32, and 196.43 ppm,
the calculated amounts at LC-wPBE/6-311 + G**/6-311
+ G** and B3LYP/6-311 + G** levels are 159.51, 161.27,
and 197.32 ppm, and 160.25, 162.11, and 196.44 ppm,
respectively. The same is true about other compounds in
Tables 5–8. For example, according to Tables 5 and 6, for
compound (5b), the 3H, m, and aromatic CH protons
appear at δH 7.13-7.47 ppm, the calculated amounts at LC-
wPBE/6-311 + G** and B3LYP/6-311 + G** basis set levels
anharmonicity effects and basis set deficiencies.[46]
For the compound (5a), the strong band at 3436 cm−1
in the FT-IR spectrum was assigned as v C─H aromatic
mode. The calculated values for this mode were 3402,
3407, 3433, and 3431 cm−1 for G3MP2, LC-ωPBE/6-311
+ G**, B3LYP/6-311 + G**, and MP2/6-311 + G**,
respectively. For the title compound (5a), the strong band
at 1728 cm−1 in the FT-IR spectrum was assigned as
vC═O mode. The calculated values for this mode were
the
same
for
G3MP2,
LC-ωPBE/6-311 + G**,
B3LYP/6-311 + G**, and MP2/6-311 + G**, respectively.
The B3LYP/6-311 + G** computation predicteds this
vibrational mode in vC─H aliphatic at 2951 cm−1 for 5a,
2951 cm−1 for the compound 5b and 2962 cm−1 for the
compound 5c. This observed frequency coincided well
with the expected value.[49] There was an excellent agree-
ment between experimental and theoretical results for all
the methods employed. In order to compare this agree-
ment, the correlation graphic based on the theoretical
and experimental data was investigated.
A small
TABLE 3 Experimentally measured and calculated 1H chemical shifts δ (ppm, vs TMS) using G3MP2, LC-ωPBE/6-311 + G**,
B3LYP/6-311 + G**, and MP2/6-311 + G** for compound 5a
Calculated
1H NMR
EXP
G3MP2
0.80
LC-ωPBE/6-311 + G**
B3LYP/6-311 + G**
MP2/6-311 + G**
0.96
3H, s, CH3
0.86
0.83
0.86
3H, s, CH3
1.00
1.11
1.12
1.02
1.05
4H, m, 2CH2
1H, s, CH
2.07-2.34
4.49
2.03-2.39
5.01
2.04-2.32
4.48
2.06-2.38
4.48
2.11-2.40
4.47
9H, m, aromatic CHs
7.15-8.68
7.10-8.61
7.11-8.59
7.15-8.67
7.23-9.66
Abbreviations: EXP, Experimental; NMR, Nuclear Magnetic Resonance spectroscopy; TMS, Tetramethylsilane.

SABERI BIROON ET AL.
7
TABLE 4 Experimentally measured and calculated 13C chemical shifts δ (ppm, vs TMS) using G3MP2, LC-ωPBE/6-311 + G**,
B3LYP/6-311 + G**, and MP2/6-311 + G** for compound 5a
Calculated
LC-ωPBE/
13C NMR
2CH3
C
EXP
G3MP2
26.26-29.18
32.10
6-311 + G**
26.91-29.19
32.99
B3LYP/6-311 + G**
26.82-29.10
32.27
MP2/6-311 + G**
26.80-28.01
30.37
26.88-29.08
32.26
CH2
42.40
42.83
42.73
42.45
44.99
CH2
50.49
50.01
50.31
50.44
50.39
CH
65.43
65.98
65.49
65.42
65.47
aromatic and
olefinic carbons
115.79
125.58
126.59
127.78
128.27
128.47
128.79
129.34
131.78
133.73
134.26
138.74
161.78
163.32
196.43
115.78
121.99
124.08
125.39
127.14
127.87
127.93
129.65
129.11
132.79
137.76
139.30
160.11
162.12
170.11
115.52
125.99
126.31
127.07
128.05
128.66
128.98
129.75
130.41
133.28
135.00
139.11
159.51
161.27
197.32
115.69
114.69
125.59
126.43
127.11
128.24
128.26
128.99
129.30
134.90
134.01
134.44
138.46
159.88
163.99
197.11
125.59
126.39
127.70
128.17
128.37
128.80
129.24
131.68
133.63
134.67
138.56
C═O (1)
C═O (2)
C═O (3)
160.25
162.11
196.44
Abbreviations: EXP, Experimental; NMR, Nuclear Magnetic Resonance spectroscopy; TMS, Tetramethylsilane.
TABLE 5 Experimentally measured and calculated 1H chemical shifts δ (ppm, vs TMS) using G3MP2, LC-ωPBE/6-311 + G**,
B3LYP/6-311 + G**, and MP2/6-311 + G** for compound 5b
Calculated
1H NMR
EXP
0.87
G3MP2
0.91
LC-ωPBE/-311 + G**
B3LYP/6-311 + G**
MP2/6-311 + G**
3H, s, CH3
0.88
0.86
0.82
3H, s, CH3
1.01
1.12
1.05
1.05
1.06
4H, m, 2CH2
2.0-2.35
4.47
2.22-2.64
4.51
2.12-2.54
4.38
2.01-2.44
4.48
2.11-2.47
4.49
1H, s, CH
3H, m, aromatic CHs
2H, aromatic CHs
2H, aromatic CHs
1H, s, aromatic CHs
7.13-7.47
7.56
7.17-7.49
7.53
7.37-7.48
7.59
7.30-7.48
7.55
7.23-7.31
7.59
7.88
7.99
7.93
7.89
7.90
8.69
8.85
8.80
8.73
8.73
Abbreviations: EXP, Experimental; NMR, Nuclear Magnetic Resonance spectroscopy; TMS, Tetramethylsilane.
are 7.37 to 7.48 and 7.30 to 7.48 ppm, respectively. Protons
of two methyl groups appear at δH 0.87 and 1.01 ppm, the
calculated amounts at LC-wPBE/6-311 + G** and
B3LYP/6-311 + G** basis set levels are 0.88 and 1.05 ppm
and 0.86 and 1.05 ppm, respectively. Also, chemical shifts
of three carbonyl groups appear at δc 161.04, 163.52, and
199.54 ppm, the calculated amounts at LC-wPBE/6-311
+ G** and B3LYP/6-311 + G** levels are 160.51, 162.27,

8
SABERI BIROON ET AL.
TABLE 6 Experimentally measured and calculated 13C chemical shifts δ (ppm, vs TMS) using G3MP2, LC-ωPBE/6-311 + G**,
B3LYP/6-311 + G**, and MP2/6-311 + G** for compound 5b
Calculated
13C NMR
EXP
G3MP2
26.46-29.12
31.11
LC-ωPBE/6-311 + G**
26.99-29.18
32.99
B3LYP/6-311 + G**
26.92-29.11
31.27
MP2/6-311 + G**
26.90-29.01
31.37
2CH3
26.93-29.04
31.38
C
CH2
32.30
32.63
33.73
32.45
34.99
CH2
50.40
50.01
50.31
50.44
50.39
CH
63.34
64.98
64.19
64.42
64.47
aromatic and olefinic carbons
114.40
114.65
128.27
128.96
129.34
129.54
130.36
130.47
131.23
133.05
136.48
143.69
161.04
163.52
199.54
114.88
114.99
128.08
128.39
129.22
129.78
130.84
130.65
131.10
133.79
137.78
139.46
160.11
162.37
170.11
114.52
114.69
114.70
115.58
128.42
128.25
129.24
129.26
129.99
130.30
131.89
133.01
135.44
148.45
160.88
163.99
199.11
114.93
114.60
128.31
128.40
129.07
128.71
129.05
129.18
129.66
129.38
130.08
130.81
130.65
130.25
131.40
131.69
133.27
133.64
135.01
135.68
141.11
142.57
C═O (1)
C═O (2)
C═O (3)
160.51
161.25
162.27
163.11
199.32
199.50
Abbreviations: EXP, Experimental; NMR, Nuclear Magnetic Resonance spectroscopy; TMS, Tetramethylsilane.
TABLE 7 Experimentally measured and calculated 1H chemical shifts δ (ppm, vs TMS) using G3MP2, LC-ωPBE/6-311 + G**,
B3LYP/6-311 + G**, and MP2/6-311 + G** for compound 5c
Calculated
1H NMR
EXP
G3MP2
1.08
LC-ωPBE/6-311 + G**
B3LYP/6-311 + G**
MP2/6-311 + G**
1.05
3H, s, CH3
1.02
1.02
1.01
3H, s, CH3
1.03
1.18
1.20
1.11
1.11
4H, m, 2CH2
1H, s, CH
2.26-2.34
4.51
2.31-2.48
4.49
2.30-2.44
4.53
2.28-2.45
4.57
2.29-2.38
4.48
7H, m, aromatic CHs
6.95-7.81
7.00-7.99
6.91-7.87
6.90-7.79
6.99-7.98
Abbreviations: EXP, Experimental; NMR, Nuclear Magnetic Resonance spectroscopy; TMS, Tetramethylsilane.
and 199.32 ppm and 160.88, 163.99, and 199.11 ppm,
respectively.
amounts at LC-wPBE/6-311 + G** and B3LYP/6-311
+ G** basis set levels are 1.02 and 1.20 ppm and 1.01 and
1.11 ppm, respectively. Also, chemical shifts of three car-
bonyl groups appear at δc 163.82, 168.09, and 196.35 ppm,
the calculated amounts at LC-wPBE/6-311 + G** and
B3LYP/6-311 + G** levels are 163.42, 167.88, and
196.31 ppm and 163.41, 167.99, and 196.32 ppm,
respectively.
Based on Tables 7 and 8, for the compound (5c), the
aromatic CH protons appear at δH 6.95-7.81 ppm, the cal-
culated amounts at LC-wPBE/6-311 + G** and
B3LYP/6-311 + G** basis set levels are 6.91 to 7.87 and
6.99 to 7.98 ppm, respectively. Protons of two methyl
groups appear at δH 1.02 and 1.03 ppm, the calculated

SABERI BIROON ET AL.
9
TABLE 8 Experimentally measured and calculated 13C chemical shifts δ (ppm, vs TMS) using G3MP2, LC-ωPBE/6-311 + G**,
B3LYP/6-311 + G**, and MP2/6-311 + G** for compound 5c
Calculated
13C NMR
2CH3
C
EXP
G3MP2
25.74-28.11
31.78
LC-ωPBE/6-311 + G**
25.83-28.28
31.78
B3LYP/6-311 + G**
26.89-28.31
32.78
MP2/6-311 + G**
25.99-28.38
31.89
26.91-28.22
32.61
CH2
42.46
41.59
42.39
42.58
42.45
CH2
50.48
53.13
50.11
51.02
50.07
CH
63.56
64.61
63.11
63.61
62.11
aromatic
and olefinic carbons
113.94
123.36
126.37
127.22
128.28
128.63
129.14
129.83
132.17
132.82
133.39
134.75
163.82
168.09
196.35
118.90
123.30
127.32
127.99
128.11
128.48
129.10
129.98
132.07
132.59
133.24
134.96
160.22
162.12
193.99
113.49
113.95
113.55
123.88
127.01
127.57
128.11
128.58
129.10
129.91
132.10
132.88
133.04
134.85
163.41
167.99
196.32
123.75
123.31
127.21
127.11
127.66
127.45
128.24
128.21
128.68
128.64
129.05
129.14
129.73
129.82
132.11
132.11
132.76
132.80
133.16
133.41
134.58
134.65
C═O (1)
C═O (2)
C═O (3)
163.43
163.55
167.88
168.12
196.31
195.99
Abbreviations: EXP, Experimental; NMR, Nuclear Magnetic Resonance spectroscopy; TMS, Tetramethylsilane.
The synthesis of organic compounds increasingly
makes use of computational chemistry approaches for
modeling and understanding molecular phenomena. Cal-
culations are employed to rationalize reaction outcomes,
predict how a new system will perform, and inform syn-
thetic plan. As a result, new insights into the interactions
of fundamental chemical forces have emerged that
advance the field of complex small and large molecule
synthesis. This review presents four examples of compu-
tational techniques used in the synthesis of organic com-
pounds, and discusses the unique perspectives afforded
by these quantitative analyses.
graphic based on the theoretical and experimental data
was investigated. The correlation value (R2) for com-
pounds are represented in Table 9. As can be seen, there is
a great agreement between experimental and theoretical
results.[46] A small difference between the experimental
and calculated vibrational modes was observed. This dif-
ference might have been due to the intermolecular hydro-
gen bonding formation. Furthermore, the experimental
results belonged to a solid phase, while the theoretical cal-
culations belong to the isolated gaseous phase.[50]
We use mathematical algorithms, statistics, and large
databases to integrate chemical theory. In addition, a
thorough understanding of the synthesized products can
be achieved by a careful examination of the structure and
reactivity of the compounds through HOMO and LUMO
orbitals investigations and molecular softness and
hardness.
3.2.3 | Electronic properties
Quantum chemical methods are significant in obtaining
information about molecular structure and electrochemi-
cal behavior. A frontier molecular orbital (FMO) analysis
was carried out for the compounds using the
B3LYP/6-311 + G** level. FMO results such as EHOMO
,
There was an excellent agreement between experimen-
tal and theoretical results for all the methods employed.
In order to compare this agreement, the correlation
ELUMO, and the HOMO-LUMO energy gap (ΔE) of the
title compounds are summarized in Table 10. The energy
of the LUMO, and HOMO and their energy gaps reflect

10
SABERI BIROON ET AL.
TABLE 9 Correlation of calculated and experimental 1H NMR, 13C NMR, and IR of the compounds
Compounds
G3MP2
0.9983
0.9986
0.9953
0.9986
0.9970
0.9975
0.9986
0.9996
0.9977
LC-ωPBE/6-311 + G**
0.9999
B3LYP/6-311 + G**
0.9990
MP2/6-311 + G**
0.9998
5a
5b
5c
5a
5b
5c
5a
5b
5c
IR
0.9998
0.9998
0.9999
0.9995
0.9995
0.9978
13C NMR
1H NMR
0.9999
0.9988
0.9990
0.9997
0.9983
0.9991
0.9999
0.9991
0.9974
0.9999
0.9985
0.9997
0.9995
0.9990
0.9998
0.9995
0.9992
0.9975
TABLE 10 Absolute energy (a.u), dipole moment (μ, Debye), frontier orbital energies (HOMO and LUMO, eV), hardness (η, eV),
chemical potential (μ, eV), and electrophilicity (ω, eV) of the 5a, 5b, and 5c molecules
EHOMO
ELUMO
0.01449
0.00516
0.01002
I
A
μ
η
ω
μD
Point group
5a
5b
5c
−0.12044
−0.13041
−0.12564
0.12044
0.13041
0.12564
−0.01449
−0.00516
−0.01002
−0.052975
−0.062625
−0.05781
0.127685
0.13299
0.13065
0.00018
0.00026
0.00021
2.6389
5.8185
3.8630
C1
C1
C1
Abbreviations: HOMO, highest occupied molecular orbital; LUMO, lowest unoccupied molecular orbital.
FIGURE 2 Molecular electrostatic potential (MEP) maps of the title compounds calculated using the B3LYP/6-311 + G** level
the chemical reactivity of the molecule.[51] In addition,
the HOMO can act as an electron donor and the LUMO
and 5c are 0.14, 0.13, and 0.15 eV, respectively. Density
of states (DOS) plots[53] also demonstrate the calculated
energy gaps (ΔE) for the compounds 5a, 5b, and 5c (see
Figure 2). It is obvious that the energy gap of the com-
pound 5c is the highest (0.15 eV), and therefore it is less
reactive than the other structures. Meanwhile, the energy
gap of the compound 5b is the lowest (0.13 eV), which
indicates that it is the most reactive. As presented in
Figure 2 charge transfer can take place within the three
molecules.
as an electron acceptor. Higher HOMO energy (EHOMO
)
for the molecule indicates a higher electron-donating
ability to an appropriate acceptor molecule with a low-
energy empty molecular orbital.[52] As shown in Figure 1.
The HOMO energy of the compound 5a has the highest
value (−0.12044 eV). A large energy gap implies the high
stability for the molecule. The calculated values of the
HOMO-LUMO energy gap (ΔE) for the structures 5a, 5b,

SABERI BIROON ET AL.
11
TABLE 11 Thermodynamic parameters of the 5a, 5b, and 5c molecules using the B3LYP/6-311 + G** level
5a
5b
5c
Zero-point correctiona
0.406036
0.429319
0.430263
0.351336
−1207.858982
−1207.835699
−1207.834755
−1207.913682
269.402
0.395624
0.419784
0.420728
0.340837
−1662.458578
−1662.434418
−1662.433474
−1662.513366
263.418
0.384774
0.410552
0.411496
0.326996
−2117.050471
−2117.024693
−2117.023749
−2117.108248
257.625
Thermal correction to energya
Thermal correction to enthalpya
Thermal correction to Gibbs free energya
Sum of electronic and zero-point energiesa
Sum of electronic and thermal energiesa
Sum of electronic and thermal enthalpiesa
Sum of electronic and thermal free energiesa
E (thermal)b
heat capacity at constant volume (Cv)c
Sc
90.082
93.667
97.990
166.116
168.145
177.844
aHartree/Particle.
bKCal/Mol.
cCal/Mol-Kelvin.
Detailed information about quantum molecular
descriptors of title compounds such as ionization poten-
tial, electron affinity, global hardness, electronic chemical
potential, and electrophilicity are calculated and listed in
Table 10. The first ionization potential (I) and electron
affinity (A) can be expressed through HOMO and LUMO
orbital energies by connecting it with HartreeFock SCF
theory and invoking Koopmans' theorem[54] as
I = −EHOMO, A = −ELUMO. Chemical hardness (η = I _
A/2) is an important property that indicates the molecular
stability and reactivity.[55] A hard molecule has a large
energy gap (ΔE) and a soft molecule has a small energy
gap (ΔE).[56] The chemical hardness (η) values of the com-
pounds 5a, 5b, and 5c are 0.127, 0.130, and 0.132 eV,
respectively. Compound 5c has the highest chemical hard-
ness (η = 0.132 eV), and therefore, it is a hard and less
reactive molecule with a high energy gap (ΔE = 0.15 eV).
Electronic chemical potential (μ = −[I + A]/2)is a form of
potential energy that can be absorbed or released during a
chemical reaction and that may also change during a
phase transition.[57] Electrophilicity (ω) measures the sta-
bilization in energy when the system acquires an addi-
tional electronic charge from the environment. The
electrophilicity index (ω = μ2/2η) contains information
about both electron transfer (chemical potential) and sta-
bility (hardness) and is a better descriptor of global chemi-
cal reactivity.[58] The higher the value of the
electrophilicity index, the higher the capacity of the mole-
cule to accept electrons. The electrophilicity index for the
compounds 5a, 5b, and 5c is 0.00018, 0.00021, and
0.00026 eV, respectively. The compound 5c has the
highest electrophilicity index; therefore, it has a high
capacity for accepting electrons. The dipole moment (μD)
is a good measure of the asymmetric nature of a molecule.
The size of the dipole moment depends on the composi-
tion and dimensionality of the 3D structures. As shown in
Table 10, all structures have a high value of dipole
moment and point group of C1, which indicates that there
is no symmetry in the structures. The dipole moment of
the compound 5b (B3LYP/6-311 + G** = 5.8185 Debye) is
higher than those of the compounds 5a and 5c (2.6389
and 3.8630 Debye, respectively). The high value for 5c is
due to its asymmetric character.
3.2.4 | Thermodynamic analysis
The total energy of a molecule consists of the sum of
translational, rotational, vibrational, and electronic ener-
gies. The statistical thermochemical analysis of title com-
pounds is carried out, making sure that the molecule is at
room temperature of 25ꢀC and under 1 atmospheric pres-
sure. The thermodynamic parameters, such as zero-point
vibrational energy, rotational constant, heat capacity (C),
and the entropy (S) of the title compound by
B3LYP/6-311 + G** level are listed in Table 11.
According to this table, the calculated values for com-
pounds 5a and 5b are larger than those for compound 5c;
therefore, compounds 5a and 5b have maximum stability
compared with compound 5c, due to the formation of the
intramolecular hydrogen bonding.
3.2.5 | Molecular electrostatic potential
MEP was calculated by the B3LYP/6-311 + G** level.
MEP is pertinent to the electronic density and is a very
beneficial descriptor in identification of the locations for

12
SABERI BIROON ET AL.
electrophilic attacks and nucleophilic reactions, as well
as hydrogen bonding interactions.[53] The negative
regions (red color) of the MEP are related to electrophilic
reactivity and the positive (blue color) region is related to
nucleophilic reactivity, as shown in Figure 2.
ACKNOWLEDGMENTS
The authors are thankful to the Zanjan Branch, Islamic
Azad University, for partial support of this work.
ORCID
MEP surfaces aim at locating the positively and nega-
tively charged electrostatic potentials in molecules. In
each MEP surface, there is a color scale which indicates
the negative and positive values. The red color is a sign of
the negative extreme and the blue color depicts the posi-
tive extreme. The red color with a negative sign indicates
the minimum electrostatic potential (which means it is
bound loosely or has excess electrons) and it acts as an
electrophilic attack. The blue color also indicates the
maximum of electrostatic potential, and it acts the
opposite.
According to the above, if we plot all MEP surfaces
with all iso-surface values, we see only the top surface. It
can be observed from the MEP map in Figure 2 that the
nitrogen-bonded nitrogen atoms in the N─N group and
the oxygen atoms in the carbonyl groups (C═O) of the
rings are negative regions in all compounds, since in the
resonance form of the nitro group, the oxygen atoms
have a negative charge and the nitrogen atom has a posi-
tive charge, and in the resonance form of the carbonyl
groups, the oxygen atoms have a negative charge and the
carbon atom has a positive charge. Thus oxygen atoms
are sites for electrophilic activity. The nitrogen atoms in
the ring, which are attached to carbonyl lethal electron
groups, are also positively, charged, and therefore, nitro-
gen atoms are sites for nucleophilic attraction. As such
these sites provide information about the regions where
the compounds can have strong intermolecular
interactions.
Nahid Shajari https://orcid.org/0000-0001-6416-8644
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How to cite this article: Saberi Biroon S,
Shajari N, Yahyaei H. Green and efficient synthesis
of 1H-indazolo[1,2-b] phthalazine-1,6,11(13H)-
triones using ZrO(NO3)2.2H2O as a novel catalyst
and theoretical study of synthesized compounds.
J Heterocyclic Chem. 2020;1–13. https://doi.org/10.
1002/jhet.3959
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