Synthesis of 2,3-dihydroquinazolin-4(1H)-ones from anthranilamide and ketones over Hβ zeolite in aqueous media*

Article abstract of DOI:10.1080/00397911.2018.1506033

The synthesis of 2,3-dihydroquinazolin-4(1H)-ones by cyclocondensation of anthranilamide with ketones in aqueous media using Hβ zeolite is reported. The scope of the reaction was explored by various ketones such as aromatic, aliphatic and cyclic ketones. Based on the preliminary mechanistic results, a tentative mechanism for the formation of 2,3-dihydroquinazolin-4(1H)-ones using zeolite catalyst (Hβ) is predicted. The reusability study, large-scale experiment and water as solvent showed significant benefits of this catalytic protocol in comparing to earlier methods.

Full text of DOI:10.1080/00397911.2018.1506033

Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic
Chemistry
ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: http://www.tandfonline.com/loi/lsyc20
Synthesis of 2,3-dihydroquinazolin-4(1H)-ones
from anthranilamide and ketones over Hβ zeolite
in aqueous media*
Krishna Sai Gajula, Naresh Mameda, Srujana Kodumuri, Durgaiah Chevella,
Rammurthy Banothu, Vasu Amrutham, Boris Ivanovich Kutepov & Narender
Nama
To cite this article: Krishna Sai Gajula, Naresh Mameda, Srujana Kodumuri, Durgaiah Chevella,
Rammurthy Banothu, Vasu Amrutham, Boris Ivanovich Kutepov & Narender Nama (2018):
Synthesis of 2,3-dihydroquinazolin-4(1H)-ones from anthranilamide and ketones over Hβ zeolite in
aqueous media*, Synthetic Communications, DOI: 10.1080/00397911.2018.1506033
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https://doi.org/10.1080/00397911.2018.1506033
Synthesis of 2,3-dihydroquinazolin-4(1H)-ones from
anthranilamide and ketones over Hb zeolite in
ꢀ
aqueous media
Krishna Sai Gajulaa,b, Naresh Mamedaa,b, Srujana Kodumuria, Durgaiah Chevellaa,
Rammurthy Banothua,b, Vasu Amruthama,b, Boris Ivanovich Kutepovc, and
Narender Namaa,b
b
aC&FC Division, CSIR-Indian Institute of Chemical Technology, Hyderabad, Telangana, India; Academy
of Scientific and Innovative Research, CSIR-Indian Institute of Chemical Technology, Hyderabad,
Telangana, IndiacIPC RAS, Oktyabrya, Russian Federation Ufa
ABSTRACT
ARTICLE HISTORY
Received 30 May 2018
The synthesis of 2,3-dihydroquinazolin-4(1H)-ones by cyclocondensa-
tion of anthranilamide with ketones in aqueous media using Hb zeo-
lite is reported. The scope of the reaction was explored by various
ketones such as aromatic, aliphatic and cyclic ketones. Based on the
preliminary mechanistic results, a tentative mechanism for the forma-
tion of 2,3-dihydroquinazolin-4(1H)-ones using zeolite catalyst (Hb) is
predicted. The reusability study, large-scale experiment and water as
solvent showed significant benefits of this catalytic protocol in com-
paring to earlier methods.
KEYWORDS
Aqueous media;
cyclocondensation; 2,3-
dihydroquinazolin-4(1H)-
ones; ketones; zeolites
GRAPHICAL ABSTRACT
Introduction
The synthesis of nitrogen-containing heterocycles has gained much attention for its
chemical, biological, and technical significance.[1–5] Among the various well-known
heterocyclic compounds, 2,3-dihydroquinazolin-4(1H)-ones are an important class of
heterocycles, which show a broad spectrum of biological and pharmaceutical activities
CONTACT Nama Narender
nama.iict@gov.in, narendern33@yahoo.co.in
C&FC Division, CSIR-Indian Institute of
Chemical Technology, Hyderabad, Telangana 500007, India.
ꢀ
IICT communication no. IICT/Pubs./2018/175
Supplemental data for this article can be accessed on the publisher’s website
ß 2018 Taylor & Francis Group, LLC

2
K. SAI GAJULA ET AL.
O
O
HN
N
NH
NH
N
H
N
H
O
N
O
Benzouracil
NCI substance T1D19143
(Anti cancer)
Evodiamine
O
O
O
O
O
H2N
N
H2N
S
S
NH
N
NH
O
O
Cl
N
H
Cl
N
H
Proquazone
Quinethazone
Fenqizone
Figure 1. Illustrative examples of drugs possessing quinazolinone skeleton.
(Fig. 1).[6–14] Moreover, 2,3-dihydroquinazolinones are key synthetic intermediates for
the preparation of biologically active 4(3H)-quinazolinones by oxidation, which exhibit
many central nervous system effects, cardiovascular and anti-inflammatory activity and
act as psychotropic, hypnotic, cardiotonic, and antihistamine agents.[15] Owing to their
diverse pharmacological activities and synthetic utility, development of a modest and
clean process for the production of 2, 3-dihydroquinazolin-4(1H)-ones is still in
demand. Numerous strategies for their synthesis have been reported using several cata-
lysts such as Ga(OTf)3,[16] thiamine hydrochloride (VB1),[17] ionic liquid,[18]
KAI(SO4)2ꢁ12H2O,[19] ethylenediamine diacetate,[20] b-Cyclodextrin (b-CD),[21] nano-
In2O3,[22] CuO nanoparticles,[23] microwave (MW) irradiation,[24] ZrCl4,[25] amberlyst-
15,[26] propylphosphonic anhydride,[27] 2-morpholinoethanesulfonic acid,[28] magnetic
nanoparticles,[29] b-Cyclodextrin-SO3H,[30] lactic acid,[31] and dodecylbenzenesulfonic
acid.[32] Despite formidable advances, most of the methods suffer from one or more
shortcomings, such as using hazardous organic solvents, moisture sensitive catalysts,
strongly acidic conditions, high reaction temperatures, and tedious work-up procedures.
Moreover, most of the methods limited to aldehydes, ketones have been less investi-
gated. Owing to their diverse pharmacological activities and synthetic utility, the devel-
opment of a general, green and environmentally benign synthetic protocol for the
synthesis of 2,3-dihydroquinazolinones from ketones is highly desirable.
Lately, the development of novel methods that decrease pollution in the chemical
industry has established an important consideration because of increasing environmen-
tal concerns. In this context, heterogeneous catalysis has seemed like an appropriate
tool to reduce the waste production, lower contamination of the products, and recycling
of the catalysts.[33–36] Also, pursuing organic reactions in aqueous media under mild
conditions is of great importance in modern synthetic chemistry and paves the way to
design green, safe, and economically viable processes.
Zeolite materials have a wide range of applications in petroleum and fine chemical
industries,[37–40] this is mostly because zeolites have uniform channel size, unique
molecular shape selectivity, firm acidity, and thermal/hydrothermal stability. The

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Scheme 1. The synthesis of 2,3-dihydroquinazolinones from anthranilamide and ketones.
Table 1. Optimization for the synthesis of 2-methyl-2-phenyl-2,3-dihydroquinazolin-4(1H)-one
from acetophenone and anthranilamidea
Entry
Catalyst
Yield 3a (%)b
1
2
3
4
5
6
7
8
Hb
NaY
75
20
34
35
41
23
29
1
HZSM-5 (150)
H-Mordenite
HY
Montmorillonite K10
HMCM-41
Silica
9
Silica-alumina
Absence of catalyst
Hb
3
10
11
12
00
77c
98d
Hb
aReaction conditions: 1a (1 mmol), 2a (1 mmol), H2O (1 mL), catalyst (50 mg), 80 ꢂC, 2 h, sealed
b
c
tube; Isolated yields; 100 ꢂC, Hb (50 mg). dHb (100 mg).
accessible substantial micropore volume, large-pore channel system and the presence of
active sites in different concentrations make the BEA-type of zeolite (zeolite beta) as an
alternative and promising candidate for an extensive array of diverse chemical reac-
tions.[41–45] As part of our ongoing research interest to develop eco-friendly synthetic
protocols using zeolites and modified zeolites,[46–53] herein we report a simple, green
and environmentally benign approach for the synthesis of 2,3-dihydroquinazolinones
from anthranilamide and ketones over Hb zeolite in aqueous media (Scheme 1).
Results and discussion
The reaction between acetophenone (1a) (1 mmol) and anthranilamide (2a) (1 mmol)
was chosen as a model system to govern the optimal conditions for the synthesis of 2-
methyl-2-phenyl-2,3-dihydroquinazolin-4(1H)-one (3a). The reaction was carried out
over zeolites, MCM-41, montmorillonite K10, SiO2 and SiO2-Al2O3 to find out the best
catalyst for this transformation (Table 1, entries 1–9). Among the catalysts examined,
Hb zeolite exhibited the higher catalytic activity and gave the corresponding product
(3a) in 75% yield that attributed strong acidic sites and unique three-dimensional large

4
K. SAI GAJULA ET AL.
Table 2. The scope of the condensation reaction of anthranilamide with various ketones over Hb zeolitea.
aReaction conditions: 1 (1 mmol), 2 (1 mmol), H2O (1 mL), Hb zeolite (100 mg), 80 ꢂC, Isolated yields.
size porous structure of Hb zeolite catalyst (Table 1, entry 1). The reaction did not pro-
ceed in the absence of a catalyst, thus supporting the role of catalyst in the reaction
(Table 1, entry 10). Increase in reaction temperature could not help to improve the
yield of 3a (Table 1, entry 11), whereas increasing the amount of Hb zeolite catalyst
(50–100 mg) leads to a higher yield of 3a (Table 1, entry 12). From Table 1, 100 mg of
Hb was ideal to get the maximum yield of the desired product in H2O (1 mL) at 80 ꢂC
(Table 1, entry 12).
We then motivated our attention on evaluating the scope of the Hb zeolite-catalyzed
strategy by testing the reaction of anthranilamide with various ketones such as aralkyl,
acyclic, and cyclic ketones under optimized reaction conditions (Tables 2 and 3). As
showed in Tables 2 and 3, all the ketones reacted well with anthranilamide (2a) to
afford moderate to excellent yields of the corresponding 2,3-dihydro-4(1H)-

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Table 3. The scope of the condensation reaction of cyclic ketones with anthranilamide over Hb zeolitea.
aReaction conditions: 1 (1 mmol), 2 (1 mmol), H2O (1 mL), Hb zeolite (100 mg), 80 ꢂC, 2 h, Isolated yields.
quinazolinone products. To find out the effect of substitution on the aromatic ring of
acetophenone on the reaction path with this catalytic system, considered the condensa-
tion reaction with different substitutions. Activating groups present on the aromatic
ring of acetophenone were efficiently transformed into the respective 2,3-dihydro-
4(1H)-quinazolinone derivatives in 53–99% yields (Table 2, 3b–3h). However, the bulky
alkyl group-substituted acetophenone exhibited lower activity and presented the corre-
sponding product in 53% yield (Table 2, 3g). A highly deactivating group bearing aceto-
phenones and halo-substituted acetophenones also participated well in this reaction to
provide the desired products in 55–99% yields (Table 2, 3i-3p). It is noteworthy that
acetophenone having the same substituent at different positions on the phenyl ring had
an influence on the reaction yield (Table 2, 3e, 3f, 3i, 3j, 3k, 3m, 3n, 3o, and 3p). Next,
performing the reaction with acyclic ketones and furnished the respective products in
93% and 94% yields, respectively (Table 2, 3q and 3r).
Finally, we investigated the effectiveness of this present catalytic system with cyclic
ketones such as cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone
(Table 3). The outcome indicates that cyclic ketones efficiently underwent the reaction
with anthranilamide and the corresponding 2,3-dihydro-4(1H)-quinazolinones products
were obtained in excellent yields (Table 3, 3aa-3ad).
To illustrate the practical usefulness of this catalytic protocol, we have performed the
reaction at gram scale process under the optimized conditions and the corresponding
2,3-dihydro-4(1H)-quinazolinone product 3a was isolated in 70% yield (Scheme 2). It
shows that there was a deviation in the yield of the respective product when compared
to the small-scale reaction. However, a higher yield (92%) of 3a was obtained with 1 g
(or 1.5 g) of catalyst in 4 h.
To prove the potential recycling ability of Hb by performing the cyclocondensation
reaction with acetophenone (1a) and anthranilamide (2a) under similar reaction condi-
tions. After the reaction, the catalyst (Hb) was easily separated from the reaction mix-
ture by filtration, and the recovered catalyst was calcined at 450 ꢂC to use in the next
cycle. A similar protocol was maintained for other cycles, and no noticeable loss of cata-
lytic activity was detected even after five cycles (Fig. S1, See in ESI). The XRD analysis
suggests that catalyst was crystalline before and after the reaction (Fig. S2, See in ESI).

6
K. SAI GAJULA ET AL.
Scheme 2. Large-scale experiment for the synthesis of 2-methyl-2-phenyl-2,3-dihydroquinazolin-4(1H)-
one from anthranilamide and acetophenone.
Figure 2. The dependence of the reaction yield of 3a on the amount of 2,6-lutidine added to the
Hb-catalyzed cyclocondensation reaction between 1a and 2a. Reaction conditions: 1a (1 mmol), 2a
a
(1 mmol), H2O (1 mL), Hb (100 mg), 80 ꢂC, 2 h, 2,6-Lutidine (X mmol gꢄ1), sealed tube. Isolated yields.
There was no leaching of aluminum or silicon from zeolite (Hb) was observed by elem-
ental analysis.
It is a well-known fact that apart from Bronsted acidity, there could be Lewis acidity
exists in Hb zeolite. It is known that 2,6-lutidine selectively interacts with Brꢃnsted
acid sites instead of Lewis acid sites due to the steric hindrance caused by its methyl
groups.[54] The model reaction was performed under optimized condition by the add-
ition of various amounts of 2,6-lutidine to elucidate the nature of the active sites for the
cyclocondensation reaction. As can be seen in Figure 2, the yield of 3a was gradually
reduced by 2,6-lutidine and no yield of 3a was observed over the 12 mmolgꢄ1 addition
of 2,6-lutidine to the reaction mixture. This observation revealed that the condensation
reaction is mainly promoted by the Brꢃnsted acid sites of the Hb catalyst.
Based on the above observation study, a tentative reaction mechanism for the forma-
tion of 2,3-dihydroquinazolin-4(1H)-ones from anthranilamide and ketones over Hb is
outlined in Scheme 3. It is hypothesized that the reaction is initiated by adsorption of
ketone on the acid sites of Hb zeolite (Bronsted acid sites activates the carbonyl group
of the ketone, and weak conjugate base [framework oxygen] activates the amine group
of the anthranilamide), which subsequently reacts with anthranilamide (2a) to provide
the intermediate (A) after loss of a water molecule. Then, an intramolecular

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7
Scheme 3. The plausible reaction mechanism for the formation of 2,3-dihydroquinazolin-4(1H)-ones
over Hb zeolite.
nucleophilic attack of intermediate (A), followed by 1,5-hydrogen shift yields the 2,3-
dihydroquinazolin-4(1H)-ones (3).
Experimental section
General information
All chemicals were obtained and used as received from Sigma–Aldrich. The Hb zeolite
1
(Si/Al ¼ 12.5) was acquired from Alfa Aesar, England. HNMR spectra were recorded at
300, 400, or 500 MHz and 13CNMR spectra at 100 or 125 MHz in CDCl3. The chemical
shifts (d) are described in ppm units relative to TMS as an internal standard for
1HNMR and CDCl3 for 13CNMR spectra. Coupling constants (J) are reported in hertz
(Hz) and multiplicities are indicated as follows: s (singlet), br s (broad singlet), d (doub-
let), dd (doublet of doublet), t (triplet), m (multiplet). The mass spectrometric analysis
was performed by using high-resolution Q-TOF Mass Spectrometer. The GC analysis
was carried out using GC Shimadzu (GC-2014) gas chromatograph equipped with FID
detector and capillary column (EB-5, length 30 m, inner diameter 0.25 mm, film
0.25 mm). TLC inspections were carried out on Silica gel 60 F254 plates. Column chro-
matography was performed on silica gel (100–200 mesh) using n-hexane-EtOAc as elu-
ent. The XRD patterns of the zeolites were obtained on a Regaku miniflex X-ray
Diffractometer using Ni-filtered CuKa radiation at 2h ¼ 2–80ꢂ with a scanning rate of
2ꢂ minꢄ1 and the beam voltage and currents of 30 kV and 15 mA, respectively. ESI-
HRMS were performed on Exactive orbitrap (Thermo scientific), mass accur-
acy <1 ppm.
General procedure
Hb zeolite (100 mg) was added to the well-stirred solution of anthranilamide (1 mmol),
ketone (1 mmol), and water (1 mL) in a 15 mL sealed tube and the reaction mixture was
allowed to stir at 80 ꢂC. After the disappearance of the anthranilamide (monitored by
TLC) or after an appropriate time, the reaction mixture was cooled to room

8
K. SAI GAJULA ET AL.
temperature and diluted with ethyl acetate (3 ꢅ 10 mL). Simple filtration separated the
catalyst (Hb zeolite), and the removal of solvent in vacuo yielded crude. The crude was
purified by column chromatography using silica gel (100–200 mesh) to afford pure
1
products and these identified based on H, 13C NMR, and mass spectral data.
Conclusions
In summary, a green and straightforward method for the synthesis of 2,3-dihydroquina-
zolin-4(1H)-ones involving the condensation of anthranilamide with ketones over Hb
zeolite in aqueous media was successfully developed. Broad substrate scope, water as a
solvent, use of non-hazardous and reusable catalysts, higher yields of the desired prod-
ucts, and simple workup procedures are prominent advantages of this catalytic strategy.
These findings highlight the potential of this protocol as an inexpensive and environ-
mentally benign method.
Funding
We thank the DST, New Delhi for financial support under Indo-Russia (DST-RSF) (No. INT/
RUS/RSF/P-7) program. G. K., M. N. and Ch. D. acknowledge the CSIR, India and K. S. and B.
R. acknowledge the UGC, India for financial support in the form of fellowship.
References
[1] Su€zen, S. Antioxidant Activities of Synthetic Indole Derivatives and Possible Activity
Mechanisms. In Khan, M.T.H., Eds.; Bioactive Heterocycles V; Springer Berlin Heidelberg:
Berlin, Heidelberg, 2007; pp. 145–178.
[2] Eicher, T.; Hauptmann, S. The Chemistry of Heterocycles: Structure, Reactions, Synthesis,
and Applications; Wiley-VCH: Weinheim, 2003.
[3] Joule, J. A.; Mills, K. Heterocyclic Chemistry; Blackwell Science: Oxford, 2013.
[4] Vitaku, E.; Smith, D. T.; Njardarson, J. T. Analysis of the Structural Diversity, Substitution
Patterns, and Frequency of Nitrogen Heterocycles among U.S. FDA Approved
Pharmaceuticals. J. Med. Chem. 2014, 57, 10257–10274. DOI: 10.1021/jm501100b.
ꢀ
[5] Gonzalez, M.; Cerecetto, H.; Monge, A. Quinoxaline 1,4-Dioxide and Phenazine 5,10-
Dioxide. Chemistry and Biology. In Khan, M.T.H., Eds.; Topics in Heterocyclic Chemistry;
Springer: Berlin, Heidelberg, 2007; Vol. 11, pp. 179–211.
[6] Yale, H. L.; Kalkstein, M. Substituted 2, 3-Dihydro-4(1H)-Quinazolinones. A New Class of
Inhibitors of Cell Multiplication. J. Med. Chem. 1967, 10, 334–336. DOI: 10.1021/
jm00315a010.
[7] Peet, N. P.; Sunder, S.; Cregge, R. J. Preparation and Utility of 1-Acetyl-1-
Methylhydrazine. J. Org. Chem. 1976, 41, 2733–2736. DOI: 10.1021/jo00878a018.
[8] Ozaki, K. I.; Yamada, Y.; Oine, T.; Ishizuka, T.; Iwasawa, Y. Studies on 4(1H)-
Quinazolinones. 5. Synthesis and Antiinflammatory Activity of 4(1H)-Quinazolinone
Derivatives. J. Med. Chem. 1985, 28, 568–576. DOI: 10.1021/jm50001a006.
[9] Jiang, J. B.; Hesson, D. P.; Dusak, B. A.; Dexter, D. L.; Kang, G. J.; Hamel, E. Synthesis
and Biological Evaluation of 2-Styrylquinazolin-4(3H)-Ones, a New Class of Antimitotic
Anticancer Agents Which Inhibit Tubulin Polymerization. J. Med. Chem. 1990, 33,
1721–1728. DOI: 10.1021/jm00168a029.
[10] El-Naser Ossman, R.; El-Sayed Barakat, S. Synthesis and Anticonvulsant Activity of Some
New 3-(p-Sulfamoylphenyl)-4(3H)-Quinazolinones. Arzneimittelforschung. 1994, 44,
915–919. DOI: 10.1021/jm00163a027.

R
SYNTHETIC COMMUNICATIONSV
9
[11] Bridges, A. J.; Zhou, H.; Cody, D. R.; Rewcastle, G. W.; McMichael, A.; Showalter,
H. D. H.; Fry, D. W.; Kraker, A. J.; Denny, W. A. Tyrosine Kinase Inhibitors. 8. An
Unusually Steep Structure-Activity Relationship for Analogues of 4-(3-Bromoanilino)-6,7-
Dimethoxyquinazoline (PD 153035), a Potent Inhibitor of the Epidermal Growth Factor
Receptor. J. Med. Chem. 1996, 39, 267–276. DOI: 10.1021/jm9503613.
[12] Osborne, D.; Stevenson, P. J. A Concise Formal Synthesis of Luotonin A. Tetrahedron
Lett. 2002, 43, 5469–5470. DOI: 10.1016/S0040-4039(02)01049-3.
[13] Shi, D. Q.; Rong, L.; Wang, J.; Zhuang, Q.; Wang, X.-S.; Hu, H. Synthesis of Quinazolin-
4(3H)-Ones and 1,2-Dihydroquinazolin-4(3H)-Ones with the Aid of a Low-Valent
Titanium Reagent. Tetrahedron Lett. 2003, 44, 3199–3201. DOI: 10.1016/S0040-4039(03)
00449-0.
[14] Masamune, T.; Takasugi, M.; Mori, Y. The C-9 Configuration of Jervine and Related
Alkaloids. Tetrahedron Lett. 1965, 6, 489–495. DOI: 10.1016/S0040-4039(00)89985-2.
[15] He, L.; Li, H.; Chen, J.; Wu, X.-F. Recent Advances in 4(3H)-Quinazolinone Syntheses.
RSC Adv. 2014, 4, 12065–12077. DOI: 10.1039/C4RA00351A.
[16] Chen, J.; Wu, D.; He, F.; Liu, M.; Wu, H.; Ding, J.; Su, W. Gallium(III) Triflate-Catalyzed
One-Pot Selective Synthesis of 2,3-Dihydroquinazolin-4(1H)-Ones and Quinazolin-4(3H)-
Ones. Tetrahedron Lett. 2008, 49, 3814–3818. DOI: 10.1016/j.tetlet.2008.03.127.
[17] Chen, Y.; Shan, W.; Lei, M.; Hu, L. Thiamine Hydrochloride (VB1) as an Efficient
Promoter for the One-Pot Synthesis of 2,3-Dihydroquinazolin-4(1H)-Ones. Tetrahedron
Lett. 2012, 53, 5923–5925. DOI: 10.1016/j.tetlet.2012.08.090.
[18] Davoodnia, A.; Allameh, S.; Fakhari, A. R.; Tavakoli-Hoseini, N. Highly Efficient Solvent-
Free Synthesis of Quinazolin-4(3H)-Ones and 2,3-Dihydroquinazolin-4(1H)-Ones Using
Tetrabutylammonium Bromide as Novel Ionic Liquid Catalyst. Chin. Chem. Lett. 2010, 21,
550–553. DOI: 10.1016/j.cclet.2010.01.032.
[19] Dabiri, M.; Salehi, P.; Otokesh, S.; Baghbanzadeh, M.; Kozehgary, G.; Mohammadi, A. A.
Efficient Synthesis of Mono- and Disubstituted 2,3-Dihydroquinazolin-4(1H)-Ones Using
KAl(SO4)2ꢁ12H2O as a Reusable Catalyst in Water and Ethanol. Tetrahedron Lett. 2005,
46, 6123–6126. DOI: 10.1016/j.tetlet.2005.06.157.
[20] Narasimhulu, M.; Lee, Y. R. Ethylenediamine Diacetate-Catalyzed Three-Component
Reaction for the Synthesis of 2,3-Dihydroquinazolin-4(1H)-Ones and Their Spirooxindole
Derivatives. Tetrahedron. 2011, 67, 9627–9634. DOI: 10.1016/j.tet.2011.08.018.
[21] Ramesh, K.; Karnakar, K.; Satish, G.; Reddy, K. H. V.; Nageswar, Y. V. D. Tandem
Supramolecular Synthesis of Substituted 2-Aryl-2,3- Dihydroquinazolin-4(1H)-Ones in the
Presence of b-Cyclodextrin in Water. Tetrahedron Lett. 2012, 53, 6095–6099. DOI:
10.1016/j.tetlet.2012.08.141.
[22] Santra, S.; Rahman, M.; Roy, A.; Majee, A.; Hajra, A. Nano-Indium Oxide: An Efficient
Catalyst for One-Pot Synthesis of 2,3-Dihydroquinazolin-4(1H)-Ones with a Greener
Prospect. Catal. Commun. 2014, 49, 52–57. DOI: 10.1016/j.catcom.2014.01.032.
[23] Zhang, J.; Ren, D.; Ma, Y.; Wang, W.; Wu, H. CuO Nanoparticles Catalyzed Simple and
Efficient Synthesis of 2,3-Dihydroquinazolin-4(1H)-Ones and Quinazolin-4(3H)-Ones
under Ultrasound Irradiation in Aqueous Ethanol. Tetrahedron. 2014, 70, 5274–5282.
DOI: 10.1016/j.tet.2014.05.059.
[24] Safari, J.; Gandomi-Ravandi, S. Efficient Synthesis of 2-Aryl-2,3-Dihydroquinazolin-4(1H)-
Ones in the Presence of Nanocomposites under Microwave Irradiation. J. Mol. Catal. A
Chem. 2014, 390, 1–6. DOI: 10.1016/j.molcata.2014.02.013.
[25] Abdollahi-Alibeik, M.; Shabani, E. Synthesis of 2,3-Dihydroquinazolin-4(1H)-Ones
Catalyzed by Zirconium (IV) Chloride as a Mild and Efficient Catalyst. Chinese Chem.
Lett. 2011, 22, 1163–1166. DOI: 10.1016/j.cclet.2011.05.011.
[26] Murthy, P. V. N. S.; Rambabu, D.; Krishna, G. R.; Reddy, C. M.; Prasad, K. R. S.;
Rao, M. V. B.; Pal, M. Amberlyst-15 Mediated Synthesis of 2-Substituted 2,3-
Dihydroquinazolin- 4(1H)-Ones and Their Crystal Structure Analysis. Tetrahedron Lett.
2012, 53, 863–867. DOI: 10.1016/j.tetlet.2011.12.023.

10
K. SAI GAJULA ET AL.
[27] Desroses, M.; Scobie, M.; Helleday, T.
A
New Concise Synthesis of 2,3-
Dihydroquinazolin-4(1H)-One Derivatives. New J. Chem. 2013, 37, 3595. DOI: 10.1039/
c3nj00618b.
[28] Labade, V. B.; Shinde, P. V.; Shingare, M. S. A Facile and Rapid Access towards the
Synthesis of 2,3-Dihydroquinazolin-4(1H)-Ones. Tetrahedron Lett. 2013, 54, 5778–5780.
DOI: 10.1016/j.tetlet.2013.08.037.
[29] Ghorbani-Choghamarani, A.; Norouzi, M. Synthesis of Copper (II)-Supported Magnetic
Nanoparticle and Study of Its Catalytic Activity for the Synthesis of 2,3-
Dihydroquinazolin-4(1H)-Ones. J. Mol. Catal. A Chem. 2014, 395, 172–179. DOI: 10.1016/
j.molcata.2014.08.013.
[30] Wu, J.; Du, X.; Ma, J.; Zhang, Y.; Shi, Q.; Luo, L.; Song, B.; Yang, S.; Hu, D. Preparation
of 2,3-Dihydroquinazolin-4(1H)-One Derivatives in Aqueous Media with b-Cyclodextrin-
SO3H as a Recyclable Catalyst. Green Chem. 2014, 16, 3210–3217. DOI: 10.1039/
c3gc42400f.
[31] Zhaleh, S.; Hazeri, N.; Maghsoodlou, M. T. Green Protocol for Synthesis of 2,3-
Dihydroquinazolin-4(1H)-Ones: Lactic Acid as Catalyst under Solvent-Free Condition.
Res. Chem. Intermed. 2016, 42, 6381–6390. DOI: 10.1007/s11164-016-2469-z.
[32] Chen, B. H.; Li, J. T.; Chen, G. F. Efficient Synthesis of 2,3-Disubstituted-2,3-
Dihydroquinazolin-4(1H)-Ones Catalyzed by Dodecylbenzenesulfonic Acid in Aqueous
Media under Ultrasound Irradiation. Ultrason. Sonochem 2015, 23, 59–65. DOI: 10.1016/
j.ultsonch.2014.08.024.
[33] Sheldon, R. A. Catalytic Oxidations in the Manufacture of Fine Chemicals. Stud. Surf. Sci.
Catal. 1990, 55, 1–32. DOI: 10.1016/S0167-2991(08)60130-5.
[34] Sheldon, R. Chemistry of Waste Minimisation; Blackie Academic & Professional: London,
1996; Vol. 4.
€
[35] Holderich, W. F.; Heitmann, G. Synthesis of Intermediate and Fine Chemicals on
Heterogeneous Catalysts with respect to Environmental Protection. Catal. Today. 1997,
38, 227–233. DOI: 10.1016/S0920-5861(97)00071-0.
[36] Anastas, P. T.; Bartlett, L. B.; Kirchhoff, M. M.; Williamson, T. C. The Role of Catalysis in
the Design, Development, and Implementation of Green Chemistry. Catal. Today. 2000,
55, 11–22. DOI: 10.1016/S0920-5861(99)00222-9.
[37] Stewart, A. An Introduction to Zeolite Molecular Sieves by Alan Dyer.Surf. Interface Anal.
1989, 14, 213–213. DOI: 10.1002/sia.740140410.
[38] Breck, D. W. Zeolite Molecular Sieves: Structure, Chemistry, and Use. J. Chromatogr. Sci.
1975, 13, 18A–18A. DOI: 10.1093/chromsci/13.4.18A-c.
[39] Cundy, C. S.; Cox, P. A. The Hydrothermal Synthesis of Zeolites: History and
Development from the Earliest Days to the Present Time. Chem. Rev. 2003, 103, 663–701.
DOI: 10.1021/cr020060i.
[40] Farneth, W. E.; Gorte, R. J. Methods for Characterizing Zeolite Acidity. Chem. Rev. 1995,
95, 615–635. DOI: 10.1021/cr00035a007.
[41] Smith, K.; Musson, A.; DeBoos, G. A. A Novel Method for the Nitration of Simple
Aromatic Compounds. J. Org. Chem. 1998, 63, 8448–8454. DOI: 10.1021/jo981557o.
[42] Bellussi, G.; Pazzuconi, G.; Perego, C.; Girotti, G.; Terzoni, G. Liquid-Phase Alkylation of
Benzene with Light Olefins Catalyzed by b Zeolites. J. Catal. 1995, 157, 227–234. DOI:
10.1006/jcat.1995.1283.
[43] Camiloti, A. M.; Jahn, S. L.; Velasco, N. D.; Moura, L. F.; Cardoso, D. Acidity of Beta
Zeolite Determined by TPD of Ammonia and Ethylbenzene Disproportionation. Appl.
Catal. A Gen. 1999, 182, 107–113. DOI: 10.1016/S0926-860X(98)00418-9.
€
[44] Mintova, S.; Valtchev, V.; Onfroy, T.; Marichal, C.; Knozinger, H.; Bein, T. Variation of
the Si/Al Ratio in Nanosized Zeolite Beta Crystals. Microporous Mesoporous Mater. 2006,
90, 237–245. DOI: 10.1016/j.micromeso.2005.11.026.
[45] De Jong, K. P.; Mesters, C. M. A. M.; Peferoen, D. G. R.; Van Brugge, P. T. M.; De Groot,
C. Paraffin Alkylation Using Zeolite Catalysts in a Slurry Reactor: Chemical Engineering

R
SYNTHETIC COMMUNICATIONSV
11
Principles to Extend Catalyst Lifetime. Chem. Eng. Sci. 1996, 51, 2053–2060. DOI:
10.1016/0009-2509(96)00062-0.
[46] Narender, N.; Reddy, K. S. K.; Kumar, M. A.; Rohitha, C. N.; Kulkarni, S. J.
Tetrahydropyranylation of Alcohols over Modified Zeolites. Catal. Lett. 2010, 134,
175–178. DOI: 10.1007/s10562-009-0205-7.
[47] Mohan, K. V. V. K.; Narender, N.; Kulkarni, S. J. Liquid Phase Synthesis of Annelated
Pyridines over Molecular Sieve Catalyst. Microporous Mesoporous Mater. 2007, 106,
229–235. DOI: 10.1016/j.micromeso.2007.03.001.
[48] Mohan, K. V. V. K.; Narender, N.; Kulkarni, S. J. Zeolite Catalyzed Acylation of Alcohols
and Amines with Acetic Acid under Microwave Irradiation. Green Chem. 2006, 8, 368.
DOI: 10.1039/b600031b.
[49] Narender, N.; Mohan, K. V. V. K.; Reddy, R. V.; Srinivasu, P.; Kulkarni, S. J.; Raghavan,
K. V. Liquid Phase Bromination of Phenols Using Potassium Bromide and Hydrogen
Peroxide over Zeolites. J. Mol. Catal. A Chem. 2003, 192, 73–77. DOI: 10.1016/S1381-
1169(02)00131-0.
[50] Narender, N.; Srinivasu, P.; Kulkarni, S. J.; Raghavan, K. V. Intermolecular Cyclization of
Diethanolamine and Methylamine to N,N0-Dimethylpiperazine over Zeolites under High
Pressure. J. Catal. 2001, 202, 430–433. DOI: 10.1006/jcat.2001.3291.
[51] Narender, N.; Srinivasu, P.; Kulkarni, S. J.; Raghavan, K. V. Liquid Phase Acylation of
Amines with Acetic Acid over HY Zeolite. Green Chem. 2000, 2, 104–105. DOI: 10.1039/
b000227p.
[52] Reddy, M. M.; Kumar, M. A.; Swamy, P.; Naresh, M.; Srujana, K.; Satyanarayana, L.;
Venugopal, A.; Narender, N. N-Alkylation of Amines with Alcohols over Nanosized
Zeolite Beta. Green Chem. 2013, 15, 3474. DOI: doi:10.1039/c3gc41345d.
[53] Naresh, M.; Swamy, P.; Reddy, M. M.; Srujana, K.; Durgaiah, C.; Naresh, G.; Narender, N.
Solvent-Free Hydration of Alkynes over Hb Zeolite. Appl. Catal. A Gen. 2015, 505,
213–216. DOI: 10.1016/j.apcata.2015.07.038.
[54] Corma, A. Inorganic Solid Acids and Their Use in Acid-Catalyzed Hydrocarbon
Reactions. Chem. Rev. 1995, 95, 559–614. DOI: 10.1021/cr00035a006.