Yttrium nitrate catalyzed synthesis, photophysical study, and TD-DFT calculation of 2,3-dihydroquinazolin-4(1H)-ones

Article abstract of DOI:10.1002/hc.21379

We have developed an efficient method of the synthesis of 2,3-dihydroquinazolin-4(1H)-one (DHQ) using yttrium nitrate catalyst at room temperature. The synthetic method is simple, convenient, and easy product isolation. Best results obtained in CH₃CN, DMF, or water. The synthesized DHQ derivatives are found to be good fluorophores, and their characteristic photoluminescence properties are measured. Absorption and emission spectra of DHQ derivatives were recorded in CH₃CN. Calculated emission and absorption bands are in excellent agreement with experimentally observed values.

Full text of DOI:10.1002/hc.21379

Received: 17 March 2017
DOI: 10.1002/hc.21379
Revised: 29 June 2017
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R E S E A R C H A R T I C L E
Yttrium nitrate catalyzed synthesis, photophysical study, and
TD-DFT calculation of 2,3-dihydroquinazolin-4(1H)-ones
Abdul Ashik Khan1
Mohabul A. Mondal1
Kanchan Mitra1
Abhijit Mandal1
Nabajyoti Baildya2
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1Department of Chemistry, University of
Gour Banga, Malda, India
2Department of Chemistry, University of
Kalyani, Kalyani, Nadia, India
Abstract
We have developed an efficient method of the synthesis of 2,3-dihydroquinazolin-
4(1H)-one (DHQ) using yttrium nitrate catalyst at room temperature. The synthetic
method is simple, convenient, and easy product isolation. Best results obtained in
CH3CN, DMF, or water. The synthesized DHQ derivatives are found to be good
fluorophores, and their characteristic photoluminescence properties are measured.
Absorption and emission spectra of DHQ derivatives were recorded in CH3CN.
Calculated emission and absorption bands are in excellent agreement with
experimentally observed values.
Correspondence
Mohabul A. Mondal, Department of
Chemistry, University of Gour Banga,
Malda, India.
Email: mohabul.mondal@gmail.com
Funding information
DST New Delhi, Grant/Award Number:
EMR/2014/000542
K E Y W O R D S
Yttrium Nitrate, 2,3-dihydroquinazolin-4(1H)-ones, Photophysical properties, TD-DFT,
method is the cyclocondensation of 2-aminobenzamide
with aldehyde or ketone as shown in Scheme 1. The direct
1
INTRODUCTION
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2,3-Dihydroquinazolin-4(1H)-one (DHQ) is an important
class of heterocyclic moiety present in the many pharmaceu-
ticals, bio-active natural products, and synthetic drugs and
used as an important precursor for the synthesis of many
quinazoline derivatives. DHQ derivatives are evaluated as
potent and selective tankyrase inhibitors,[1]Bruton’s Tyrosine
Kinase inhibitors (BTK),[2] anticancer,[3] analgesic and anti-
inflammatory reagents,[4] and “turn-off” fluorescence sen-
sors for detection of Cu2+ ions.[5] Moreover, DHQ derivatives
can be easily converted to quinazolinone and quinazoline and
used as a starting material in many heterocyclic compounds
of medicinal importance. Because of diverse application of
the probe as pharmaceuticals and having interesting photo-
physical properties, DHQs are an important target for the
synthetic chemists developing convenient methods of synthe-
sis. Over last few decades a number of methods have been
developed for the synthesis of the DHQ derivatives.
cyclocondensation of 2-aminobenzamide with aldehydes
requires harsh condition.[8] However, the use of suitable cat-
alysts makes the process easier. The catalytic methods in-
volve use of tetrabutylammonium bromide in the presence
of CuCl2,[9] cyanuric chloride in anhydrous CH3CN at room
temperature (RT),[10] β-cyclodextrin in water at 60°C,[11]
β-cyclodextrine-SO3H in water in RT,[12] Amberlyst-15®
in CH3CN at 20°C,[13] graphene oxide nanosheets in aque-
ous medium at RT,[14] InBr3 in CH3CN at RT,[15] SbCl3 in
MeOH,[16] molecular iodine under solvent-free condition,[17]
silica-supported preyssler nanoparticles heteropolyacid,[18]
and CuI/L-proline/Cs2CO3/100°C.[19] Catalyst-free condi-
tions have been also reported; under heating in PEG-400 at
110°C,[20] in water at 90°C,[8] and in acetic acid under irradi-
ation of visible light (hv >390 nm).[21] Asymmetric version
of the method was also reported. In 2013, Huang et al.[22] re-
ported a chiral SPINOL-phosphoric acids-mediated synthe-
sis of optically active DHQs under anhydrous conditions. The
reported methods require either expensive catalyst systems,
heating at high temperatures, or organic reaction mediums.
The method describing the synthesis of DHQs at RT in water
with easy isolation of product is relatively less common. In
Dihydroquinazoline derivatives can be prepared from isa-
toic anhydrides[6] or 2-aminobenzonitrile.[7] A most common
Contract grant sponsor: DST New Delhi.
Contract grant number: EMR/2014/000542.
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Heteroatom Chemistry. 2017;28:e21379.
https://doi.org/10.1002/hc.21379
wileyonlinelibrary.com/journal/hc
© 2017 Wiley Periodicals, Inc.
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KHAN et Al.
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O
CN
R3
NH2
NH2
R3
NH2
O
R
1CHO
2-aminobenzonitrile
R2
R
2-aminobenzamide
Derivative
N
R3
Derivative
N
H
1 1
2,3-dihydroquinazolin-4(1H)-one derivative
R1CHO
R2NH2
O
O
R3
N
H
O
SCHEME 1 Synthetic approaches
Isatoic anhydride
Derivative
toward 2,3-dihydroquinazolin-4(1H)-one
derivatives
continuation of our present interest on Lewis acidic prop-
erties of Y3+ ion, we found Y(NO3)3·6H2O as an efficient
catalyst for the synthesis of DHQs by cyclocondensation of
2-aminobenzamide with aldehyde or ketone in water. In this
article, we described the easy synthesis of DHQs and their
absorption and emission properties.
N,N-dimethylformamide (DMF) as shown in Table 1. In
CHCl3, the reaction was incomplete after 24 hours, and the
desired product was isolated in 20% yield.
The best result can be obtained in either CH3CN or DMF.
The product was isolated from the homogeneous reaction mix-
ture by dilution with water followed by filtration of the white
precipitate. Water was found to be a potential medium for
conducting the cyclocondensation reaction (Table 1, Entry 5).
However, because of poor solubility of the aromatic aldehyde
in water, the reaction requires 20 mol% catalyst loading, take
relatively longer time, and the isolated solid product require
further purification. Although the reaction is facile in CH3CN,
DMF, EtOH, and water, we have carried out the synthesis of
all the DHQs in CH3CN with 10 mol% catalyst loading at RT
because it did not require the extra effort for purification.
After optimizing reaction condition, we stud-
ied the further scope of the method for structurally
2
RESULTS AND DISCUSSION
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Initially, we carried out the reaction of 2-aminobenzamide
with benzaldehyde in EtOH at RT in the presence of 10 mol%
of Y(NO3)3·6H2O. After 5 hours, 2-phenyl-2,3-dihydroquina
zolin-4(1H)-one was isolated as white precipitate, collected
by filtration in 48% isolated yield. The poor isolated yield
is because of significant solubility of the product in EtOH.
The reaction was also carried out in CHCl3, CH3CN, and
TABLE 1 Y(NO3)3-catalyzed
O
cyclocondensation of 2-aminobenzanilide
with benzaldehyde in different solvents
O
NH2
NH2
10 mol% Y(NO3)3.6H2O
Solvent, RT
NH
Ph
PhCHO
N
H
1a
Entry
Y(NO3)3·6H2O (mol%)
Solvent
Time (h)
Yielda (%)
1
2
3
4
5
10
10
10
10
20
EtOH
CH3CN
CHCl3
DMF
10
5
24
5
48
98
20
97
86
H2O
24
aIsolated yield.

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TABLE 2 Synthesis of DHQs from different aldehydes
O
O
O
N
O
N
NH
NH2
NH2
R
10 mol% Y(NO3)3.6H2O
NH
Or
RCHO
Or
CH3CN, RT
NH2
R
N
H
R
1
2
3
Entry
RCHO
Product
Time (h)
Yielda (%)
1
2
3
4
5
6
7
8
Benzaldehyde
4-fluorobenzaldehyde
4-chlorobenzaldehyde
4-bromobenzaldehyde
4-methylbenzaldehyde
4-methoxybenzaldehyde
3-nitrobenzaldehyde
4-hydroxy-3-methoxybenzaldehyde
2-hydroxy-3-methoxybenzaldehyde
2-hydroxybenzaldehyde
Ethyl 2-(2-formylphenoxy)acetate
Furan-2-carbaldehyde
1a
1b
1c
1d
1e
5
5
5
5
5
5
5
14
14
14
14
5
98
95
97
97
96
98
97
94
88
98
96
86
85
95
1f
2g
1h
3i
1j
1k
1l
9
10
11
12
13
14
2-(anthracen-9-ylmethoxy)benzaldehyde
Cinnamaldehyde
1m
1n, 1o
14
5
aIsolated yield.
different aldehydes. Most common aldehydes such as benz-
aldehyde, 4-fluorobenzaldehyde, 4-chlorobenzaldehyde,
Figure 1 and 1H-NMR spectra of the mixture. Presumably at-
mospheric oxygen plays crucial role in the oxidation.
4-bromobenzaldehyde, 4-methylbenzaldehyde, and 4-me-
thoxybenzaldehyde were easily converted to their respective
2,3-dihydroquinazolin-4-one derivatives under this method
(Entries 1-6, Table 2). The presence of electronically different
functional groups in aldehydes did not make much difference
in the reactivity toward 2,3-dihydroquinazolin-4-one forma-
tion with 2-aminobenzamide. Reaction of 3-nitrobenzaldehyde
under this condition gave imine product 2g and fails to give
cyclic product 1, even under prolong reaction time. The struc-
3
PHOTOPHYSICAL STUDY
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Photoluminescence study of the synthesized DHQs was also
carried out. When excited at wavelength 334 nm, the emis-
sion spectra of compounds 1a-m showed emission bands near
400 nm (Table 3, Figure 2), and little effect on the nature of R
group was observed. This is further supported by theoretical
calculations (Table 4). The calculated absorption and emission
bandsareinexcellentagreementwithexperimentallyobserved
values. Quantum yields (φF) of the probes 1a-m were meas-
ured using quinine sulfate in 1 N H2SO4 as the standard.[23]
The highest φF was observed for 1f, and the lowest one was
observed for 1i (Figure 3). The emission bands of compound
1i (λem=402 and 360 nm) are due to the quinazolin-4(3H)-one
moiety and 2-hydroxy-3-methoxyphenyl groups, respectively,
the latter of which as a chromophore shows a significant ab-
sorption at 334 nm (Figure 3, spectrum 1i). The emission of
compound 1n is characteristic from the anthracene moiety
and exhibits an intramolecular fluorescence resonance energy
transfer (FRET) from 2,3-dihydroquinazolin-4(1H)-one to
the anthracene moiety. Existence of FRET in compound 1n
is clearly indicated in Figure 4. There is significant overlap
1
ture of 2g was confirmed by H and 13C NMR, LC-MS. All
compounds reported here are solid, isolated by filtration, and
1
used for characterization without further purification. H-
NMR data of the products are in agreement with the reported
data,[10] and the LC-MS is according to the structure. Electron-
rich aldehyde vanillin (Entry 8, Table 2) and the sterically
hindered aldehydes (Entries 9,10,11, and 13, Table 2) reacted
slowly under this condition. 2-hydroxy-3-methoxybenzalde-
hyde gave oxydised product 3i. Compound 1m containing an
anthracene moiety was successfully synthesized and character-
ized. The DHQ derivatives isolated by the method described
here were sufficiently pure as indicated by the LC-MS and 1H-
NMR spectra. Cinnamaldehyde reacted with anthranilamide
smoothly but it gave an inseparable mixture of the desired DHQ
(1n) with the oxidized product (1o) as suggested by LC-MS in

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FIGURE 1 LC-MS of the product obtained from cinnamaldehyde and 2-aminobenzamide A, Chromatogram using ZORBAX EXT
(4.6×50 mm, 5μ) column, NH4OAc (10 mmol L−1):CAN::90:10. B, Mass spectra of the fraction eluted at 2.89 min. C, Mass spectra of the fraction
eluted at 3.04 min
between the absorption spectrum of 1n and the emission
spectrum of 1a excited at 334 nm. Low quantum yield of 1d
is because of heteroatom effect. As the absorption and emis-
sion bands of all the compounds are very close (~400 nm), we
have selected only five compounds (1a, 1b, 1f, 1j, and 1l) for
calculation. Apart from slight change in ground sate geom-
etry, there is no significant effect on absorption and emission
band on the nature of R in structure 1 (Table 1).
emission spectra, we optimized the excited state (S1) geom-
etry in B3LYP functional and in 6-311+g(d,p) basis set.
The optimized geometries of 1a, 1b, 1f, 1j, and 1l and
MO’s are given in Figure 5. And the theoretical absorption
and emission wave lengths (in nanometer) in comparison
with experimental values are given in Table 4.
5
CONCLUSIONS
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4
COMPUTATIONAL DETAILS
In conclusion, a series of 2,3-dihydroquinazolin-4(1H)-one
derivatives having different aromatic functionalities have
been synthesized by the yttrium nitrate catalyzed cyclo-
condensation between 2-aminobenzamide and aromatic
aldehydes at ambient temperature. The method is easy
from practical points of view and product isolation. The
2,3-dihydroquinazolin-4(1H)-one derivatives were char-
acterized by LC-MS and NMR. Emission and absorption
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The selected structures of molecules 1a, 1b, 1f, 1j, and 1l
(shown in Table 2) are optimized in DFT formalism using
Gaussian 09 programs using basis sets 6-31 g(d)[24] and
B3LYP functional[25] in CH3CN solvent using Onsager’s
self-consistent reacting field (SCRF) method[26] for the
calculation of HOMO-LUMO plot. For the calculation of

KHAN et Al.
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TABLE 3 Emission and absorption
band of 1a-n in CH3CN
Experimental
λabs (nm)
Experimental
λem (nm)
Δγ Stokes
Molecule
ε (M−1 cm−1
)
φF
(cm−1
)
1a
1b
1c
1d
1e
1f
2g
1h
1i
335
333
335
336
335
332
328
334
335
332
335
328
684
535
503
377
596
579
633
423
411
488
492
797
405
400
401
402
405
404
392
405
402
406
404
398
0.54
0.44
0.59
0.10
0.58
0.71
0.05
0.53
0.02
0.41
0.55
0.32
0.05
5159
5030
4913
4886
5159
5368
4977
5248
4975
5490
5098
5362
-
1j
1k
1l
1m
346, 365, 385
648, 817, 717
391, 412, 345
Absorption spectra of 1a-m in CH3CN with concentration c=1×10−3 (mol L−1).
Fluorescence spectra of the probe 1a-n in CH3CN with Probe concentration c=4×10−5 (mol L−1), excitation
wavelength 334 nm.
Measurement of quantum yield: Quinine sulfate in 1 N H2SO4 (quantum yield of 0.546) was used as the refer-
ence. Refractive index of 1 N H2SO4 and CH3CN are 1.346 and 1.44, respectively, used for calculation.
φF measured by the single point method.
λabs are the experimentally observed λmax at concentration 1×10−3 mol L−1 in CH3CN.
O
O
O
NH
NH
NH2
Ar
1a
1c
1f
1d
2g
1h
3i
1j
1k
1l
1b
1e
1m
6
EXPERIMENTAL
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N
H
Ar
N
H
Ar
N
1a-f, 1h, 1j-m
2g
3i
1.0
0.5
0.0
6.1
Instrumentation and material
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All commercially available reagents were used without
any further purification, and the reactions were moni-
1
tored by TLC. H-NMR was obtained using a Bruker
400 MHz spectrometer in DMSO-d6 solution. Melting
points were measured on an Instrument India melting
point apparatus using an open capillary tube and are cor-
rected with standard benzoic acid. Mass Spectrometry
was performed on an LC-MS (Liquid chromatogram
using ZORBAX EXT [4.6×50 mm, 5μ] column, NH4OAc
[10 mmol L−1]:CAN::90:10]). UV-Vis spectra were re-
corded at room temperature in quartz cuvettes using a
Shimadzu UV1800 spectrophotometer in CH3CN solu-
tions of the synthesized compounds. Fluorescence spectra
were obtained from a Shimadzu RF 6000 spectrofluorom-
eter in the above-mentioned solvents. The quantum yields
of fluorescent compounds were calculated by following
standard procedure of the single point method and using
quinine sulfate as the reference standard (φF(s)=0.546 in
1 N 25°C) using the following equation;
400
500
600
λ (nm)
FIGURE 2 Normalized fluorescence spectra of the probes
1a-m in CH3CN with concentration c=4×10−5 (mol L−1), excitation
wavelength 334 nm
properties were also studied. Among the 4-halophenyl
groups, 1d showed a low φF because of heteroatom effect.
Emission spectrum of 1m is characteristic of the emission
band of anthracene moiety, hence suggesting FRET with 2,3
-dihydroquinazolin-4(1H)-one. Thus, 1m is a potential probe
for developing FRET-based fluorescence probes. Effort in
this direction is under process.
AsFin2s
ꢀF(i)
=
ꢀF(s)
AiFsn2
i

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TABLE 4 Calculated absorption and
Experimental λabs Calculated λabs Experimental λem
Calculated
λem (nm)
emission wavelengths of 1a, 1b, 1f, 1j, and
Molecule
(nm)
(nm)
(nm)
1l
1a
1b
1f
1j
1l
335
333
332
332
328
325
326
326
338
323
405
400
404
406
398
392
391
393
394
391
2
1
0
6.2
Procedure for the synthesis of
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O
O
O
N
compound 1a
1a
1c
1f
1d
2g
1h
3i
1j
1k
1l
1b
1e
1m
NH
Ar
NH
Ar
NH2
Ar
N
H
N
H
1a-f, 1h, 1j-m
2g
3i
Yttrium nitrate hexahydrate (42 mg, 0.11 mmol) was added
to a mixture of 2-aminobenzamide (150 mg, 1.1 mmol) and
benzaldehyde (128 mg, 1.2 mmol) in 5 mL acetonitrile, and
the mixture was stirred at RT for 5 hours. After completion
of the reaction, as indicated by TLC, the reaction mass was
diluted with water (20 mL) and white solid product separated
out from the mixture. Isolation of the solid by filtration re-
sulted in analytically pure product (242 mg, 98%) in 98%
yield, white powder, m.p. 216-218°C (lit.[10] 218-219°C). 1H-
NMR (400 MHz, DMSO-d6) δ: 8.29 (s, 1H), 7.61 (d, J=8 Hz,
1H), 7.49 (m, 2H), 7.40-7.34 (m, 3H), 7.24 (t, J=8 Hz, 1H),
7.11 (s, 1H), 6.74 (d, J=8 Hz, 1H), 6.67 (t, J=8 Hz, 1H), 5.75
(s, 1H). LC-MS: calculated for C14H12N2O is 224.1, found
[M+H]+ 224.6.
300
400
λ(nm)
FIGURE 3 Absorption spectra of 1a-m in CH3CN [c=1×10−3
(mol L−1)]
6.3
Synthesis of the compounds 1b-1n[10,27]
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Compounds 1b-1n are synthesized following the same pro-
1
cedure as described for 1a. H-NMR, LC-MS, and m.p. are
described below.
1.0
Absorption of 1m
6.3.1
2-(4-Fluorophenyl)-2,3-
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Emission of 1a
dihydroquinazolin-4(1H)-one (1b)
0.5
The title compound was prepared according to the procedure
for 1a using 2-aminobenzamide and 4-fluorobenzaldehyde,
and Y(NO3)3·6H2O in 82% yield; white powder, m.p. 186-
187°C. 1H-NMR (400 MHz, DMSO-d6) δ: 8.22 (s, 1H), 7.63
(d, J=8 Hz, 1H), 7.53 (t, J=8 Hz, 1H), 7.43-7.38 (m, 1H),
7.26-7.20 (m, 3H), 7.03 (s, 1H), 6.74-6.67 (m, 2H), 6.04 (s,
1H). LC-MS: calculated for C14H11FN2O is 242.1, found
[M+H]+ 242.9.
0.0
300
350
400
450
λ (nm)
FIGURE 4 Absorption spectrum of 1m and emission spectrum
of 1a excited at 334 nm
6.3.2
2-(4-Chlorophenyl)-2,3-
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dihydroquinazolin-4(1H)-one (1c)
The title compound was prepared according to the procedure
for 1a using 2-aminobenzamide, 4-chlorobenzaldehyde, and
Y(NO3)3·6H2O in 97% yield; white powder, m.p. 207-208°C
(lit.[10] 205-206).1H-NMR (400 MHz, DMSO-d6) δ: 8.32 (s,
where A is the absorbance at the excitation wavelength, F the
area under the fluorescence curve, and n the refraction index.
Subscripts s and i refer to the standard and to the sample of
unknown quantum yield, respectively.

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1a HOMO
1a LUMO
1a Opꢀmized Geometry
1b LUMO
1b HOMO
1f HOMO
1b Opꢀmized Geometry
1f LUMO
1f Opꢀmized Geometry
1j HOMO
1j LUMO
1j Opꢀmized Geometry
1l LUMO
1l HOMO
1l Opꢀmized Geometry
FIGURE 5 Optimized geometries and MO’s of 1a, 1b, 1f, 1j, and 1l

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1H), 7.60 (d, J=8 Hz, 1H), 7.50 (d, J=8 Hz, 2H), 7.45 (d,
J=8 Hz, 2H), 7.26 (t, J=8 Hz, 1H), 7.14 (s, 1H), 6.74 (d,
J=8 Hz, 1H), 6.68 (t, J=8 Hz, 1H), 5.76 (s, 1H). LC-MS:
calculated for C14H11ClN2O is 258.1, found [M+H]+ 258.8.
130.3, 127.5, 126.5, 126.5, 123.7, 118.6. LC-MS: calculated
for C14H11N3O3 is 269.1, found [M+H]+ 270.0.
6.3.7
2-(4-Hydroxy-3-methoxyphenyl)-2,3-
|
dihydroquinazolin-4(1H)-one (1h)
6.3.3
2-(4-Bromophenyl)-2,3-
|
The title compound was prepared according to the procedure
for 1a using 2-aminobenzamide, 4-hydroxy-3 methoxyben-
zaldehyde, and Y(NO3)3·6H2O in 94% yield; white powder,
m.p. 203-205°C; 1H-NMR (400 MHz, DMSO-d6) δ: 9.05 (s,
1H), 7.60 (d, 1H, J=8 Hz), 7.23 (t, 1H, J=8 Hz), 7.08 (s, 1H),
6.94 (s, 1H), 6.88 (d, 1H, J=8 Hz), 6.76-6.73 (m, 2H), 6.67 (t,
1H, J=8 Hz), 5.6 (s, 1H), 3.76 (s, 3H). LC-MS: calculated for
C15H14N2O3 is 270.1, found [M+H]+ 270.8.
dihydroquinazolin-4(1H)-one (1d)
The title compound was prepared according to the procedure
for 1a using 2-aminobenzamide, 4-bromobenzaldehyde, and
Y(NO3)3·6H2O in 97% yield; white powder, m.p. 230-232°C.
1H-NMR (400 MHz, DMSO-d6) δ: 8.31 (s, 1H), 7.60-7.57
(m, 3H), 7.43 (d, J=8 Hz, 2H), 7.24 (t, J=8 Hz, 1H), 7.13
(s, 1H), 6.73 (d, J=8 Hz, 1H), 6.67 (t, J=8 Hz, 1H), 5.74 (s,
1H). LC-MS: calculated for C14H11BrN2O is 302.0, found
[M+H]+ 304.9.
6.3.8
2-(2-hydroxy-3-methoxyphenyl)
|
quinazolin-4(3H)-one (3i)
6.3.4
2-(p-Tolyl)-2,3-dihydroquinazolin-
|
The title compound was prepared according to the procedure
for 1a using 2-aminobenzamide, 2-hydroxy-3-methoxybenz
aldehyde, and Y(NO3)3·6H2O; Yield: 88% yield, light yel-
low solid, m.p. 196-198°C. 1H-NMR (400 MHz, DMSO-d6)
δ: 13.94 (s, 1H), 12.44 (s, 1H), 8.16 (d, J=4 Hz, 1H), 7.86 (t,
J=8 Hz, 1H,), 7.81 (d, J=8 Hz, 1H), 7.76 (d, J=8 Hz, 1H),
7.55 (t, J=8 Hz, 1H), 7.16 (d, J=8 Hz, 1H), 6.89 (t, J=8 Hz,
1H), 3.83 (s, 3H). LC-MS: calculated for C15H12N2O3 is
268.1, found [M+H]+ 268.7.
4(1H)-one (1e)
The title compound was prepared according to the procedure
for 1a using 2-aminobenzamide, 4-methylbenzaldehyde, and
Y(NO3)3·6H2O in 96% yield; white solid, m.p. 232-234°C
(lit.[10] 233-234°C). 1H-NMR (400 MHz, DMSO-d6) δ: 8.22
(s, 1H), 7.59 (d, J=8 Hz, 1H), 7.36 (d, J=8 Hz, 2H), 7.24-
7.17 (m, 3H), 7.04 (s, 1H), 6.73 (d, J=8 Hz, 1H), 6.66 (t,
J=8 Hz, 1H), 5.70 (s, 1H), 2.29 (s, 3H). LC-MS: calculated
for C15H14N2O is 238.1, found [M+H]+ 239.2.
6.3.9
2-(2-Hydroxyphenyl)-2,3-
|
6.3.5
2-(4-Methoxyphenyl)-2,3-
dihydroquinazolin-4(1H)-one (1j)
|
dihydroquinazolin-4(1H)-one (1f)
The title compound was prepared according to the procedure
for 1a using 2-aminobenzamide, 2-hydroxybenzaldehyde,
and Y(NO3)3·6H2O in 98% yield; white powder, m.p. 176-
The title compound was prepared according to the procedure
for 1a using 2-aminobenzamide, 4-methoxybenzaldehyde,
and Y(NO3)3·6H2O in 98% yield; white powder, m.p. 194-
1
178°C. H-NMR (400 MHz, DMSO-d6) δ: 9.84 (S, 1H),
195°C (lit.[10] 192-193°C). H-NMR (400 MHz, DMSO-d6)
7.92 (s, 1H), 7.61 (d, J=8 Hz, 1H), 7.33 (d, J=8 Hz, 1H),
7.21 (t, J=4 Hz, 1H), 7.14 (t, J=4 Hz, 1H), 6.85 (d, J=8 Hz,
1H), 6.81-6.74 (m, 3H), 6.66 (t, J=8 Hz, 1H), 5.99 (s, 1H).
LC-MS: calculated for C14H12N2O2 is 240.1, found [M+H]+
240.9.
1
δ: 8.17 (s, 1H), 7.60 (d, J=8 Hz, 1H), 7.41 (d, J=8 Hz, 2H),
7.23 (t, J=8 Hz, 1H), 6.99 (s, 1H), 6.94 (d, J=8 Hz, 2H), 6.73
(d, J=8 Hz, 1H), 6.66 (t, J=8 Hz, 1H), 5.69 (s, 1H), 3.74
(s, 3H). LC-MS: calculated for C15H14N2O2 is 254.1, found
[M+H]+ 254.8.
6.3.10
Ethyl 2-[2-(4-Oxo-1,2,3,4-
|
6.3.6
(E)-2-((3-nitrobenzylidene)amino)
tetrahydroquinazolin-2-yl)phenoxy]acetate (1k)
|
benzamide (2g)
The title compound was prepared according to the procedure
for 1a using 2-aminobenzamide, ethyl 2-(2-formylphenoxy)
acetate, and Y(NO3)3·6H2O in 96% yield; white powder,
m.p. 143-145°C. 1H-NMR (400 MHz, DMSO-d6) δ: 8.01 (s,
1H), 7.61 (d, J=8 Hz, 1H), 7.37 (d, J=8 Hz, 1H), 7.30-7.21
(m, 2H), 6.96-7.04 (m, 2H), 6.84 (s, 1H), 6.74 (d, J=8 Hz,
1H), 6.67 (t, J=8 Hz, 1H), 6.07 (s, 1H), 4.90 (s, 2H), 4.20 (q,
J=8 Hz, 2H), 3.01 (t, J=8 Hz, 3H). LC-MS: calculated for
C18H18N2O4 is 326.1, found [M+H]+ 326.8.
The title compound was prepared according to the procedure
for 1a using 2-aminobenzamide, 3-nitrobenzaldehyde, and
Y(NO3)3·6H2O in 97% yield; white powder, m.p. 163-165°C.
1H-NMR (400 MHz, DMSO-d6) δ: 8.76 (s, 1H), 8.74 (s, 1H),
8.40 (t, J=8 Hz, 2H), 7.94 (bs, 1H), 7.85 (t, J=8 Hz, 1H), 7.81
(d, J=8 Hz, 1H), 7.59 (bs, 1H), 7.55 (t, J=8 Hz, 1H), 7.37 (t,
J=8 Hz, 1H), 7.25 (d, J=8 Hz, 1H). 13C-NMR (150 MHz,
CDCl3) δ: 167.6, 159.1, 148.9, 136.8, 134.1, 132.9, 131.7,

KHAN et Al.
9 of 9
|
[6] S. Y. Abbas, K. A. M. El-Bayouki, W. M. Basyouni, Synth.
Commun. 2016, 46, 993.
6.3.11
2-(Furan-2-yl)-2,3-
|
dihydroquinazolin-4(1H)-one (1l)
[7] A. V. Narender Reddy, A. Kamal, P. B. Sattur, Synth. Commun.
1988, 18, 525.
The title compound was prepared according to the procedure
for 1a using 2-aminobenzamide, furan-2-carbaldehyde, and
Y(NO3)3·6H2O in 86% yield; white yellow powder, m.p.
146-148°C. 1H-NMR (400 MHz, DMSO-d6) δ: 8.37 (s, 1H),
7.59-7.60 (m, 2H), 7.25-7.19 (m, 2H), 6.74 (d, J=8 Hz, 1H),
6.67 (t, J=8 Hz, 1H), 6.37 (s, 1H), 6.24 (d, J=4 Hz, 1H), 5.73
(s, 1H). LC-MS: calculated for C12H10N2O2 is 214.1, found
[M+H]+ 215.1.
[8] Z.-B. Xie, S.-G. Zhang, G.-F. Jiang, D.-Z. Sun, Z.-G. Le, Green
Chem. Lett. Rev. 2015, 8, 95.
[9] A. Davoodnia, S. Allameh, A. R. Fakhari, N. Tavakoli-Hoseini,
Chin. Chem. Lett. 2010, 21, 550.
[10] M. Sharma, S. Pandey, K. Chauhan, D. Sharma, B. Kumar, P. M.
S. Chauhan, J. Org. Chem. 2012, 77, 929.
[11] K. Ramesh, K. Karnakar, G. Satish, K. Harsha Vardhan Reddy, Y.
V. D. Nageswar, Tetrahedron Lett. 2012, 53, 6095.
[12] J. Wu, X. Du, J. Ma, Y. Zhang, Q. Shi, L. Luo, B. Song, S. Yang,
D. Hu, Green Chem. 2014, 16, 3210.
[13] P. Vns Murthy, D. Rambabu, G. Rama Krishna, C. Malla Reddy,
K. R. S. Prasad, M. V. Basaveswara Rao, M. Pal, Tetrahedron
Lett. 2012, 53, 863.
6.3.12
2-(2-(anthracen-9-ylmethoxy)
|
phenyl)-2,3-dihydroquinazolin-4(1H)-one (1m)
The title compound was prepared according to the procedure
for 1a using 2-aminobenzamide, 2-(anthracen-9-ylmethoxy)
benzaldehyde, and Y(NO3)3·6H2O in 87% yield; light yellow
[14] N. Kausar, P. P. Ghosh, G. Pal, A. R. Das, RSC Adv. 2015, 5,
60199.
[15] L. Rajaka, N. R. Penumati, K. Nagaiah, Y. Poornachandra, C. G.
Kumar, Synth. Commun. 2015, 45, 1893.
1
solid, m.p. 194-195°C. H-NMR (400 MHz, DMSO-d6) δ:
[16] S. Ali Pourmousavi, A. Kanaani, H. Reza Fatahi, F. Ghorbani, D.
Ajloo, J. Phys. Chem. Solids 2017, 106, 82.
8.71 (s, 1H), 8.48 (d, J=8 Hz, 2H), 8.15 (d, J=8 Hz, 2H), 7.86
(s, 1H), 7.66-7.46 (m, 8H), 7.15 (m, 1H), 7.07 (m, 1H), 6.60-
6.55 (m, 2H), 6.44 (s,1H), 6.16-6.13 (m, 2H), 5.82 (s, 1H). LC-
MS: calculated for C29H22N2O2 is 430.2, found [M+H]+ 431.0.
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Shadjou, Synth. Commun. 2008, 38, 3567.
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Roshani, R. Safaee, Org. Chem. Int. 2013, 2013, 14.
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[21] K. Hemalatha, G. Madhumitha, C. S. Vasavi, P. Munusami, J.
Photochem. Photobiol. B 2015, 143, 139.
ACKNOWLEDGMENTS
Authors are thankful to head department of Chemistry, Visva-
Bhrati, and North Bengal University for providing analyti-
cal facility. Financial support for DST New Delhi (Grant no
EMR/2014/000542) is a grateful acknowledgement. Thanks
to Dr. Shubhamoy Chowdhury, department of Chemistry,
UGB, Malda for supporting theoretical calculation.
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2244.
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How to cite this article: Khan AA, Mitra K, Mandal
A, Baildya N, Mondal MA. Yttrium nitrate catalyzed
synthesis, photophysical study, and TD-DFT
calculation of 2,3-dihydroquinazolin-4(1H)-ones.
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