Catalytic formation of N3-substituted quinazoline-2,4(1: H,3 H)-diones by Pd(ii)EN?GO composite and its mechanistic investigations through DFT calculations

Article abstract of DOI:10.1039/c9nj04288a

In the current era, the scientific community is very much interested to utilize the greenhouse gas, carbon dioxide, through chemical fixation in order to produce value-based fine organic chemicals. The chemical combination of atmospheric carbon dioxide, isocyanides, and 2-iodoaniline in a one-pot reaction for the synthesis of quinazoline-2,4(1H,3H)-dione derivatives is a straight forward and attractive methodology to avoid multi-step and more toxic reagent containing routes. In this study, a heterogeneous catalyst was designed and synthesized from aminically modified graphene oxide by the incorporation of palladium metal. The catalyst was characterized by FT-IR, XRD, ICP-AES, Raman spectroscopy, XPS, TEM, SEM, EDX, and N₂ absorption desorption studies. In this report, the formation of N3-substituted 2,4(1H,3H)-quinazolinediones was performed under mild and heterogeneous reaction conditions under 1 bar CO₂ pressure. The catalyst is very efficient to produce the quinazoline derivatives. For the investigation of the mechanistic route of the catalytic reaction, density functional theory (DFT) calculations were also monitored. We have checked the recyclability of the catalyst, the results indicated that the catalyst maintained its catalytic efficacy even after six cycles of use.

Full text of DOI:10.1039/c9nj04288a

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Catalytic formation of N3-substituted
quinazoline-2,4(1H,3H)-diones by Pd(II)EN@GO
composite and its mechanistic investigations
through DFT calculations†
Cite this: New J. Chem., 2020,
44, 141
a
a
b
a
Surajit Biswas, Resmin Khatun,‡ Malay Dolai, ‡ Imdadul Haque Biswas,
a
ac
a
a
Najirul Haque, Manideepa Sengupta, Md Sarikul Islam and Sk Manirul Islam
*
In the current era, the scientific community is very much interested to utilize the greenhouse gas, carbon
dioxide, through chemical fixation in order to produce value-based fine organic chemicals. The chemical
combination of atmospheric carbon dioxide, isocyanides, and 2-iodoaniline in a one-pot reaction for the
synthesis of quinazoline-2,4(1H,3H)-dione derivatives is a straight forward and attractive methodology to avoid
multi-step and more toxic reagent containing routes. In this study, a heterogeneous catalyst was designed and
synthesized from aminically modified graphene oxide by the incorporation of palladium metal. The catalyst was
characterized by FT-IR, XRD, ICP-AES, Raman spectroscopy, XPS, TEM, SEM, EDX, and N
desorption studies. In this report, the formation of N3-substituted 2,4(1H,3H)-quinazolinediones was performed
under mild and heterogeneous reaction conditions under 1 bar CO pressure. The catalyst is very efficient to
2
absorption
Received 19th August 2019,
Accepted 15th November 2019
2
produce the quinazoline derivatives. For the investigation of the mechanistic route of the catalytic reaction,
density functional theory (DFT) calculations were also monitored. We have checked the recyclability of the
catalyst, the results indicated that the catalyst maintained its catalytic efficacy even after six cycles of use.
DOI: 10.1039/c9nj04288a
rsc.li/njc
for the production of N-containing heterocyclic molecules.
Quiznazoline-2,4(1H,3H)-diones are a very important structural
Introduction
In the last two decades, the scientific community has given sub-moiety of many commercially available drugs and biologically
8
increasing attention to the use of non-toxic, renewable, abundant, active molecules. Anti-hypertensive drugs such as cloperidone,
9
10
and inexpensive carbon dioxide for manufacturing value-based pelanserin, ketanserin and anti-psychotic drugs including
1
11
12
organic compounds. Although a significant development has tioperidone and belaperidone all contain quinazoline-2,4-
already been in progress in the related field, mainly by d-block (1H,3H)-diones as the prime framework (Scheme 1). Not only that
metal-catalyzed reactions, the synthesis of heterocyclic compounds these compounds are important intermediates for the production of
such as phenyl-annulated heteroarenes through carbon dioxide bio-active N1,N3-disubstituted quinazoline-2,4(1H,3H)-diones and
2
13
insertion has been less explored.
Isocyanides have been largely used as important synthons in
N3-substituted quinazoline-4(3H)-ones (Scheme 2).
Traditionally, the synthesis of quinazoline-2,4(1H,3H)-diones
modern synthetic organic chemistry, particularly for N-containing involved more poisonous reagents [such as carbon monoxide,
heterocyclic compounds synthesis via chemical conversions,
3
–7
including multi-component reactions.
Nowadays, various
3
4
5
6
7
transition metal (such as Pd , Cu , Ag , Co and Ni ) catalyzed
reactions have been reported, where isocyanides are employed
a
Department of Chemistry, University of Kalyani, Kalyani, Nadia 741235,
West Bengal, India. E-mail: manir65@rediffmail.com; Fax: +91-33-2582-8282;
Tel: +91-33-2582-8750
b
Department of Chemistry, Prabhat Kumar College, Purba Medinipur 721401, India
c
Refinery Technology Division, CSIR-Indian Institute of Petroleum, Dehradun,
2
48005, Uttarakhand, India
†
‡
Electronic supplementary information (ESI) available. See DOI: 10.1039/c9nj04288a
These authors contributed equally.
Scheme 1 Quiznazoline-2,4(1H,3H)-diones moiety in some drug molecules.
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Scheme 3 Comparison between previous reports with the present study
for the catalytic synthesis of N3-substituted quinazoline-2,4(1H,3H)-
diones via carboxylation–cyclization–insertion reaction.
Experimental
Graphene oxide (GO) synthesis
1
8
Previously reported procedure was followed to synthesize
graphene oxide. Concentrated H PO (20 ml) and H SO (180 ml)
Scheme 2 Some examples of biologically active N1,N3-subsituted quinazo-
line-2,4(1H,3H)-diones, and N3-substituted quinazoline-4(3H)-ones.
3
4
2
4
were taken in a 500 ml RB flask. 1.5 g of graphite flakes were added
slowly to the solution. Then, potassium permanganate (9 g) was
added pinch by pinch to the mixture. The resultant mixture was
stirred at 50 1C for 16 hours. After completing the reaction, the
mixture was cooled at RT. 30% H O (3 ml) was added to the
reaction solution and ice-cooled for a few hours until a brown
coloration appeared. The obtained brown-colored solution was
centrifuged and washed thoroughly by a 10% solution of hydro-
azides, phosgene/phosgene derivatives (di-tert-butyl dicarbonate,
1
4–16
chloroformates, and isocyanates)]
and multiple steps. Con-
2
2
sequently, the low atom economy and the variation in the sub-
stituent in the arene ring were found to be very difficult. Thus, those
synthetic procedures were not desirable from the point of both
economical as well as environmental aspects, and hence an effective
single-step low-cost route for the access of such an important
skeleton molecule was highly demandable.
2
chloric acid, H O (de-ionized), and MeOH sequentially. Finally,
the solid brown graphene oxide was desiccated in a vacuum.
The combination of carbon dioxide and isocyanides via a
multi-component reaction to manufacture N3-substituted
Preparation of GO-EN
In toluene (80 ml), 1 g of GO powder was dispersed through
sonication for 3 hours using an ultrasonic bath. Then, 25 ml of
ethylenediamine and 4 ml of triethylamine were added, in
sequence, to this solution. The resultant solution was heated
2,4(1H,3H)-quinazolinedione derivatives would be an attractive
way, but in the participation of transition metal catalysts, this
17
type of a multi-component reaction is still under development.
This is because carbon dioxide is a gas and its solubility is very
poor in organic solvents, and again with increasing temperature,
the solubility decreases. Moreover, isocyanides are solids or
liquids and completely soluble in organic solvents. As a result,
2
to reflux under a N atmosphere for 48 hours. Finally, the
reaction mixture was cooled, filtered and washed successively
using anhydrous toluene and MeOH to eliminate excess ethy-
lenediamine and dried under vacuum.
2
the combination of both reactants (i.e. CO and isocyanides) in
the multi-component reaction becomes very challenging.
Herein, we reveal the design, synthesis, and characterizations
Pd(II)EN@GO catalyst preparation
of ethylenediamine-grafted GO-based palladium, Pd(II)EN@GO The obtained material (GO-EN) (1 g) was suspended in 60 ml of
composite and its potential catalytic ability in a carboxylation– EtOH via sonication for 1 h. Then, 5 ml PdCl solution (5% w/v)
2
cyclization–insertion reaction to prepare N3-substituted 2,4(1H,3H)- was added drop-wise to the solution and refluxed for 20 hours
quinazolinediones via a multi-component coupling of o-halo under stirring conditions. The final reaction mixture was centri-
anilines, CO
methodology for the manufacture of N3-substituted 2,4(1H,3H)- un-reacted PdCl
quinazolinediones through the use of atmospheric CO
under under vacuum (Scheme 4).
2
and isocyanides. The catalytic reaction offers a fuged and washed using ethanol several times to eliminate the
, and finally Pd(II)EN@GO composite was dried
2
2
mild reaction conditions (Scheme 3). Previously reported protocols
regarding this synthesis involved homogeneous catalysts as well as
the requirement of high pressure CO . Also, those protocols
2
General preparation of N3-substituted 2,4(1H,3H)-
quinazolinediones
required the presence of some co-catalyst/ligand (Scheme 3). Again A mixture of 2-iodoaniline/derivatives (0.6 mmol, 1 equiv.), tert-
first-time density functional theory calculations were performed to butyl isocyanides/cyclohexyl isocyanides (0.72 mmol, 1.2 equiv.),
investigate the mechanistic pathway of the catalytic reaction cycle. 1,8-diazabicyclo[5.4.0]undec-7-ene (1.2 mmol, 2 equiv.) and
Moreover, the catalysis process occurred via a heterogeneous 50 mg of Pd(II)EN@GO were taken in 4 ml of anhydrous MeCN
pathway and the catalyst was effective even after sixth con- in a 25 ml RB flask. The mixture was stirred under 1 atm of CO
secutive cycles of utilization. using a balloon set up that was maintained at 80 1C temperature.
2
1
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ꢀ
1
(
–N–H stretching vibration of amine), 2904 cm (–CH stretching),
ꢀ
1
20
and 1527 cm (–N–H bending vibration of amine) clearly
confirm the grafting of ethylenediamine onto the GO surface. In
the case of the Pd(II)EN@GO composite, the position of all those
peaks shifted to a higher wavenumber.
Powder X-ray diffraction studies. The PXRD studies of the
graphene oxide and Pd(II)EN@GO composite is shown in Fig. 2.
Two characteristics diffraction peaks at 2y = 10.0011 and
42.3751 appeared in the PXRD spectra of graphene oxide. The
peak at 2y = 10.0011 is because of the (002) plane of GO and the
other peak at 2y = 42.3751 is due to the (100) plane of carbon
hexagonal structure in GO. The (002) plane of graphene oxide
Scheme 4 Scheme for preparation of the Pd(II)EN@GO composite.
2
1
The progress of the reaction was monitored by thin-layer shifted to a slightly higher angle of 2y = 11.3481 after the
chromatography, and after completing the reaction, the solution incorporation of both ethylenediamine and Pd metal on the
was cooled and evaporated using a rotary evaporator. The GO surface. This plane shifting occurred due to the sonication
separated pure product (via column chromatography) was iden- and intercalation of molecules. There are also two new peaks
1
tified by FT-IR and H NMR spectroscopies.
that appeared in the spectra of Pd(II)EN@GO at 2y = 40.5121
and 46.3271, which correspond to the (111) and (200) planes
of palladium. Therefore, it was confirmed that the Pd metal
was incorporated on the surface of ethylenediamine modified
graphene oxide sheets.
2
2
Results and discussion
Ethylenediamine-modified graphene oxide-based palladium,
Pd(II)EN@GO, composite was synthesized and characterized.
In the first step, GO was produced by a previously reported
method, and then it has been aminated by ethylenediamine
molecules. Finally, the PdCl2 solution (5% w/v) was used in
order to get the Pd(II)EN@GO composite.
Raman spectra. In order to study the structural variation that
arises during the course of a chemical reaction from graphene oxide
to the Pd(II)EN@GO composite formation, Raman spectroscopy was
performed. In the Raman spectrum of pure GO two characteristic
ꢀ
1
peaks are observed, one is at 1598 cm , which signifies the G band,
ꢀ1
and the other was at 1355 cm , which implies the D band (Fig. 3).
The D band is associated with structural deficiency and dis-
orders, while the G band was connected to the E phonon of
Characterization
ꢀ
1
2
g
FTIR spectra. A broadband is exhibited in the 2800–3750 cm
2
23
ꢀ1
sp -C atoms stretching frequency in the graphene sheets.
range. The midpoint at 3400 cm in the FTIR spectra of graphene
oxide was attributed to the –OH group stretching in the carboxylic
acid functional groups, alcohol, and/or adsorbed water molecules
Fig. 1). Another four characteristics peaks of GO also appeared at
740 cm (due to the stretching frequency of CQO present in the
aldehyde, ketone, and carboxyl groups), 1626 cm (because of sp
CQC), 1058 and 1228 cm (for the stretching frequency of C–O
associated with the epoxy and phenolic groups, respectively).
In the GO-EN spectra, the band at 1740 cm of GO disappeared,
The appearance of both D and G bands in the Pd(II)EN@GO
composite’s Raman spectrum confirmed the existence of the
graphitic carbon in the composite. It was found from the previous
reports that the intensity ratio of D and G bands (I /I ) typically
(
1
ꢀ
1
D
G
ꢀ1
2
enhanced the interactions of electrons between metal nanoparticles
or metal and graphene oxide when metal nanoparticles or metal are
ꢀ1
24
1
9
grafted on the graphene oxide surface.
ꢀ
1
ꢀ
1
and the intensity of the band in the 2800–3750 cm range
decreased. Moreover three new peaks observed at 3080 cm
ꢀ1
Fig. 1 Fourier-transform infrared spectra of graphene oxide, GO-EN, and
Pd(II)EN@GO.
Fig. 2 X-ray powder diffraction spectra of graphene oxide and Pd(II)EN@GO.
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Fig. 3 Raman spectra of graphene oxide and Pd(II)EN@GO composite.
Here, the intensity ratio (I
D G
/I ) of the composite increased to
1
.01 from 0.85 (that of pure GO) and also shifting of the G band
ꢀ
1
ꢀ1
Fig. 5 HR-TEM images of the Pd(II)EN@GO composite.
from 1598 cm to 1594 cm was observed. These results
indicate the electronic interactions between Pd metal and
aminecally modified graphene oxide, thus confirming the
successful attachment of the Pd metal on GO-EN.
FE SEM and HR TEM analysis. The FE SEM and HR TEM
analyses were performed to predict the structure and morphology
of the catalyst. The SEM images of the Pd(II)EN@GO composite
metal. The EDX pattern obtained from HR TEM further con-
firmed the presence of carbon, nitrogen, oxygen, and palladium
on the GO surface.
2 2
N adsorption–desorption study. The N adsorption–desorption
study of the Pd(II)EN@GO catalyst was performed to investigate the
pore size as well as the surface area of the catalyst. The catalyst
isotherm depicts a typical type IV sorption isotherm, having a
(Fig. 4) disclosed a distinct 3D interconnected graphene sheet,
having a sponge-like porous arrangement. The EDX spectrum
coupled to the SEM established the presence of Pd in the catalyst
texture (Fig. S1, ESI†).
hysteresis loop nearly at a 0.8 o p/p o 1.0 pressure range
0
25
(
Fig. 7). From the BJH method, the pore size distribution curve
The HR-TEM images with various higher magnification of
the Pd(II)EN@GO composite are shown in Fig. 5. The images
exposed transparent films of modified GO with net-like appearances.
Fig. 5(b) image illustrated the magnification part (red box
part) of Fig. 5(a), whereas Fig. 5(c) pointed up that of Fig. 5(b)
was plotted, and the plot clearly indicates that the catalyst
contains typical pores with a size of 4.04 nm. Thus, the pore
size of the material representing Pd(II)EN@GO was a class of
mesoporous material. Again, from the BET analysis, we confirmed
2
ꢀ1
the catalyst surface area was 11.658 m g
.
(white box part). The black spots in those images indicate the
X-ray photoelectron spectroscopy. To know the oxidation
state of the palladium metal in the composite, X-ray photoelec-
tron spectroscopy analysis was performed. The XPS spectrum of
the 3d core–shell of palladium in the composite displays two
presence of the Pd metal particles, which are homogeneously
distributed over the modified graphene oxide surface. The
average particle size was around 3–4 nm.
Fig. 6 shows the elemental mapping of the composite. A
consistent allocation of elements C, N, O, and Pd on the whole
surface of GO indicates the steady attachments of the ethyle-
nediamine on GO and desirable incorporation of the palladium
Fig. 6 Elemental mapping and EDX of the Pd(II)EN@GO composite from
Fig. 4 FE-SEM images of the Pd(II)EN@GO composite.
HR-TEM.
1
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isocyanide (1a) under atmospheric CO
2
pressure in the presence
of the Pd(II)EN@GO catalyst as the model reaction. Initially, we
performed the reaction using 2-iodoaniline (0.6 mmol), tert-butyl
isocyanide (0.72 mmol, 1.2 equiv.), DBU (0.6 mmol, 1 equiv.) in
4
ml dry MeCN in the presence of a 40 mg catalyst at 80 1C under
a 1 atm carbon dioxide pressure. To our delight, the reaction gave
4% isolated yield of the desired product (P1) (Table 1, entry 1).
6
By changing the DBU amount from 1 equivalent to 2 or 3 equivalents
with respect to the substrate under the same reaction conditions
(Table 1, entries 2 and 3), we obtained a better yield (85%) of
the product with the use of 2 equivalents of DBU. Then, we
altered the base DBU with different organic bases, including
1
(
K
,4-diazabicyclo[2.2.2]octane (DABCO), N,N-diisopropylethylamine
DIPEA), t-BuOK, NEt or inorganic bases, including Cs CO
, (Table 1, entries 4–10) but did not get
3
2
3
,
2 3 3 4
CO , and K PO
improve results compared with the use of the DBU base. Now
the same reaction was monitored using 2 equiv. of DBU in
various solvents (Table 1, entries 11–16), the collective data
showed that MeCN was the most effective solvent for the catalytic
reaction. Next, we varied the amount of catalyst (Table 1, entries
Fig. 7
2
N adsorption–desorption isotherm of the Pd(II)EN@GO catalyst.
17–19), the highest yield of product (94%) was obtained after 10 h
of reaction when 50 mg of Pd(II)EN@GO was used in the reaction
(Table 1, entry 17).
Only 15% yield of the desired product was obtained in the
absence of the catalyst, but in the presence of DBU (Table 1,
entry 20) and without the base (DBU) in the presence of a
a
Table 1 Screening of reaction conditions
b
Base
(equiv.)
Amount of
catalyst (mg) (1C)
Temp.
Yield
Time (h) (%)
Entry Solvent
1
2
3
4
5
6
7
8
9
1
1
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
DMSO
DMA
DBU (1)
DBU (2)
DBU (3)
DABCO (2) 40
DIPEA (2) 40
t-BuOK (2) 40
40
40
40
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
90
70
10
10
10
5
5
5
5
5
5
5
10
10
10
10
10
10
10
10
10
5
10
10
10
10
64
85
74
42
38
35
30
34
22
24
43
38
33
65
13
52
94
60
87
15
28
00
76
48
Fig. 8 X-ray photoelectron spectra of the Pd 3d level of the Pd(II)EN@GO
catalyst.
peaks at 337.4 and 342.7 eV, which can be assigned to the
NEt
Cs CO
3
40
(2) 40
40
5
/2
3/2
binding energies of Pd 3d and Pd 3d , respectively (Fig. 8).
2
3
2
+
K2CO
These values imply that the presence of the Pd species in the
Pd(II)EN@GO composite.
3
0
1
K PO
3 4
40
40
40
40
40
40
40
50
30
60
—
40
—
50
50
DBU (2)
DBU (2)
DBU (2)
DBU (2)
DBU (2)
The loading of the palladium(II) metal on the GO surface was 12
1
1
1
3
4
5
DCE
Toluene
THF
also determined through the ICP-AES analysis, and the result
suggested that about 7.13% of the palladium metal is present
in the GO-EN surface.
16
1,4-Dioxane DBU (2)
1
1
1
7
8
9
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
DBU (2)
DBU (2)
DBU (2)
DBU (2)
—
—
DBU (2)
DBU (2)
Catalytic performance of the Pd(II)EN@GO catalyst
Formation of N3-substituted 2,4(1H,3H)-quinazolinediones 20
2
2
2
1
2
3
via three component coupling of o-halo anilines, CO2 and
isocyanides by the Pd(II)EN@GO catalyst. To determine the
optimized reaction conditions, we varied various reaction factors 24
such as solvent, base, temperature, catalyst amount, and time by
performing the reaction of 2-iodoaniline (R1) with tert-butyl (0.72 mmol), solvent (4 ml), base, catalyst, CO
a
Reaction conditions: 2-iodoaniline, R1 (0.6 mmol), t-BuNC, 1a
b
2
balloon. Isolated yields.
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a
Table 2 Substrate scope
Table 2 (continued)
Yield (%) Entry Substrate
b
b
Entry Substrate
Isocyanides Product
Isocyanides Product
Yield (%)
1
94
1
2
64
58
2
3
4
95
93
88
1
3
a
Reaction conditions: substrate (0.6 mmol), isocyanide (0.72 mmol),
Pd(II)EN@GO (50 mg, 0.033 mmol based on the Pd metal), DBU
1.2 mmol), MeCN (4 ml), 80 1C, carbon dioxide balloon, 10 hours.
(
b
Isolated yields.
catalyst (40 mg) only B28% of the desired product was formed
Table 1, entry 21). Again in the absence of both catalysts and
(
base, no conversion of the substrate was observed (Table 1,
entry 22). Lastly, the temperature effect on the reaction was
checked (Table 1, entries 23 and 24), the results demonstrated
that 80 1C is the optimum temperature for the reaction. Therefore,
the optimized reaction condition for the reaction was: substrate
5
85
(
0.6 mmol), t-BuNC (0.72 mmol), Pd(II)EN@GO (50 mg, 0.033 mmol
based on the Pd metal), DBU (1.2 mmol, 2 equiv.), MeCN (4 ml),
0 1C, carbon dioxide (1 atm).
8
Under the optimized reaction conditions, we investigated
the substrate scope of various derivatives of o-iodoanilines
Table 2). An electron-donating group (such as methyl group)
containing 2-iodoanilines afforded 490% isolated yield of the
corresponding desired product through this reaction. When
mild electron-withdrawing groups such as cyano, chloro, or fluoro-
substituted o-iodoanilines were subjected to the reaction, we got
moderate to very good isolated yield (65–88%) of the respective
6
7
65
55
(
product., Moreover, strong electron-withdrawing –NO
-iodoaniline derivative also produced a 55% yield of the corres-
ponding quinazolinedione product.
Under the same optimized reaction conditions, all derivatives
of 2-iodoaniline furnished a mild to excellent isolated yield
2
substituted
2
8
9
92
(58–94%) when cyclohexyl isocyanide was used instead of tert-
butyl isocyanide (Table 2).
94
83
80
So far, only three protocols were developed for the catalytic
production of N3-substituted 2,4(1H,3H)-quinazolinediones via a
three-component coupling reaction of isocyanide, 2-haloaniline,
and carbon dioxide in the presence of a palladium metal
1
7
catalyst. All three protocols produced the desired products
with high yield under mild reaction conditions but in a homo-
geneous catalytic environment and in the presence of a co-catalyst/
ligand (Table 3). Therefore, the recyclability and reusability of the
catalyst remain problematic in those catalytic systems. In our
developed protocol, the catalytic reactions occurred in a hetero-
1
1
0
1
geneous condition under mild reaction conditions and 1 atm CO
2
pressure. Again no co-catalyst/ligand was required in this method.
Moreover, the catalyst was easily recyclable and reusable.
1
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Table 3 Comparison table of the catalytic synthesis of 3-(tert-butyl)quinazoline-2,4(1H,3H)-dione (P1) via the coupling reaction of 2-iodoaniline,
carbon dioxide and tert-butyl isocyanide with other reported methods
Serial
no.
Catalytic
nature
Yield
T (h) (%)
Catalyst
Pd(CH CN)
Reaction conditions
Ref.
1
2
3
2
Cl
2
2-Iodoaniline (0.20 mmol), tert-butyl isocyanide (0.24 mmol), catalyst (10 mol%),
Homogeneous 12
Homogeneous
90
94
17a
SPhos (20 mol%), Cs
2-Iodoaniline (0.50 mmol), t-BuNC (0.60 mmol), catalyst (3 mol%),
diadamantylbutylphosphine (6 mol%), Cs CO (1.0 mmol),
,4-dioxane (1.0 ml), carbon dioxide (10 atm), 80 1C.
2 3 2
CO (0.40 mmol), CO (2 MPa), DMSO (4 ml), 90 1C
Pd(OAc)
2
7
17b
2
3
1
3
4
PdCl
2
2-Iodoaniline (0.30 mmol), tert-butyl isocyanide (0.45 mmol), catalyst (0.03 mmol), Homogeneous 12
DBU (0.6 mmol), triphenylphosphine (0.06 mmol), dry acetonitrile (2 ml),
carbon dioxide balloon, 80 1C
92
94
17c
Pd(II)EN@GO
2-Iodoaniline (0.6 mmol), tert-butyl isocyanide, (0.72 mmol), Pd(II)EN@GO
50 mg, 0.033 mmol based on Pd metal), DBU (1.2 mmol), MeCN (4 ml),
CO balloon, 80 1C
Heterogeneous 10
This
work
(
2
DFT calculation
To study and understand the mechanistic pathway of the current
catalytic study from the molecular level, the density functional
theory (DFT) computations were performed through GAUSSIAN
2
6
0
9. First, the stabilization energies of the Pd(II)EN@GO compo-
site (considering the GO composite as the methyl group) were
computed, since the XRD and XPS results confirmed the presence
of Pd(II) in the EN@GO composite, hence the DFT calculations
3
were performed with Pd(II)EN@CH as the active centre. The
individual roles of the catalyst and support have been studied. All
the ground state geometries were optimized without any symme-
try constraints. All calculations were performed using the B3LYP
27,28
29
function
and LanL2DZ basis because it was confirmed that
for the transition metal this combination yields proper geometries
and electronic properties. The stabilization of Pd(II)EN@GO
3
{–CH RGO} from the Pd(II)EN@GO composite was studied.
3
For this study, only a portion of the Pd(II)EN@CH was chosen
for the simplicity of computation.
ꢀ1
The absorption energy of Pd(II)EN@CH
3
was ꢀ237.765 kcal mol
and it was observed that Pd(II) was stabilized by the ethylene
diamine (EN group) of the EN@GO composite, and two
Fig. 9 Stabilization of Pd(II) metal coordination with EN@GO finally
resulted in the Pd(II)EN@GO{–CH RGO} composite.
ꢀ
3
chlorine (Cl ) atoms attained a square planar geometry
(
Fig. 9). To understand the mechanistic pathway of the reaction
along with the role of catalyst, reagent and base, a plausible Pd(0)EN@CH
mechanism for o-iodoaniline and t-BuNC cycloaddition with (Fig. 11b), which is very reactive and enforces to create inter-
CO in presence of the catalyst Pd(II)EN@CH , and a base DBU mediate-1 (Fig. 11c). The intermediate-1 is then attacked by tert-
3
through iodine and forms the transition state-1
2
3
has been represented in Fig. 10, which was further confirmed butyl isocyanide to form the transition state-2 (Fig. 11d). Due to
from the DFT calculations. From the systematic study, it was the strong repulsion of the ring electron, such transition states
clear that o-iodoaniline and tert-butyl isocyanide were not would not exist and the energy is very high so it is reactive.
reactive to CO
o-iodoaniline and then tert-butyl isocyanide accelerated the amine group to CO
catalysis of cycloaddition with CO ; however, the lone pair of the formation of the transition state-2 was very reactive to CO
coordinated aniline-catalyst moved towards the terminal carbon of first acted as a ligand and coordinated to Pd(II) via the O-atom,
CO , and ultimately provided the catalytic product (Z)-4-(tert- which enhanced the p-accepting capacity of the carbon dioxide’s
2
. However, the addition of the catalyst with
Thus, the coordination of the lone pair of nitrogen of the
was activated on the opposite side. The
. CO
2
2
2
2
2
butylimino)-1H-benzo[d][1,3]oxazin-2(4H)-one. Simultaneously, carbon and formed the intermediate-2 (Fig. 11e). The coordination
this catalytic product undergoes a specific rearrangement in the of CO to Pd(II) helps to push back the Pd–C(isocyanide) bond pair
2
presence of 1,8-diazabicyclo[5.4.0]undec-7-ene as a base to give towards oxygen, which assists the formation of the C–CO bond to
2
the desired product 3-(tert-butyl)quinazoline-2,4(1H,3H)-dione.
form the intermediate of this reaction. Finally, the intermediate
cyclizes to give the product (Fig. 11f) after the completion of
At the beginning of the catalysis, catalyst Pd(II)EN@CH
3
becomes Pd(0)EN@CH
3
after the removal of two chlorine atoms catalysis. After that, this product was rearranged by the use of
as a Cl molecule. Then, o-iodoaniline coordinates with this DBU as the base to give intermediate-3 (Fig. 12b) and finally gives
2
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Fig. 10 Plausible mechanistic route for the preparation of 3-(tert-butyl)-
quinazoline-2,4(1H,3H)-dione from o-iodoaniline, tert-butyl isocyanide,
Fig. 12 The catalytic effect of the Pd(II)EN@GO composite in CO
cycloadditions with o-iodoaniline and tert-butyl isocyanide: yield as inter-
2
2
and atmospheric CO , via cycloaddition using the Pd(II)EN@GO composite
as catalyst and DBU as a base.
mediates (a) (Z)-4-(tert-butylimino)-1H-benzo[d][1,3]oxazin-2(4H)-one,
0
(
b) formed (Z)-N -tert-butyl-2-isocyanato-benzoxylimidate after treated
of (a) with base DBU, (c) desired product 3-(tert-butyl)quinazoline-
,4(1H,3H)-dione.
2
Fig. 11 (a) Reactant, (b) transition state-1, (c) intermediate-1, (d) transition
state-2, (e) intermediate-2 and (f) catalytic product (Z)-4-(tert-butylimino)-
1H-benzo[d][1,3]oxazin-2(4H)-one.
Fig. 13 Energy profile diagram for different transition states and inter-
mediates for the generation of (Z)-4-(tert-butylimino)-1H-benzo[d][1,3]-
the desired product (Fig. 12c). To compare the effect of the Pd(II)
ion, the reaction in the presence and absence of a catalyst was oxazin-2(4H)-one from o-iodoaniline, tert-butyl isocyanide and CO in the
2
presence of catalyst Pd(II)EN@GO composite.
studied. It was observed that without a catalyst no reaction
occurred.
The energy profile diagram for this reaction is shown in
From the DFT optimization, we found that the size of the
Fig. 13. The activation energy for the activation of o-iodoaniline
substrate (i.e. 2-iodoaniline) was 2.79 nm, which was smaller
than the pore size (4.04 nm) of the as-synthesized Pd(II)EN@GO
catalyst. Therefore, it is clear from the DFT analysis that the
substrate was completely incorporated into the pores of the
catalyst material and got efficiently activated. In addition, we
found that the size of the product (i.e. 3-tert-butylquinazoline-
ꢀ
1
to form TS-1 was 1.95 eV (45.40 kcal mol ). The free energy of the
ꢀ
1
formation of the intermediate-1 was ꢀ8.07 eV (ꢀ187.90 kcal mol ).
The activation energy for the attack of tert-butyl isocyanide to
intermediate-1 to form TS-2 was 2.90 eV (67.52 kcal mol ). The
free energy for the formation of the intermediate-2 from the reaction
ꢀ
1
ꢀ1
of TS-2 and CO
2
was ꢀ6.89 eV (ꢀ160.43 kcal mol ). The activation
2,4(1H,3H)-dione) was 4.67 nm, which is larger than the catalyst
ꢀ1
energy of cyclization was ꢀ9.17 eV (ꢀ213.52 kcal mol ). The
pore size. This observation suggests that the product material
does not block the pores of the catalyst material, which is in
line with the efficient recyclability of the Pd(II)EN@GO catalyst.
0
catalytic product was rearranged to give (Z)-N -tert-butyl-2-
isocyanato-benzoxylimidate (intermediate-3). The activation
ꢀ
1
energy for the intermediate-3 was ꢀ9.29 eV (ꢀ216.54 kcal mol
)
and finally, the free energy for the formation of the desired product
ꢀ1
Heterogeneity of catalyst
was ꢀ9.10 eV (ꢀ211.99 kcal mol ). From the energy profile
diagram, it was obvious that the first step was the rate- The life span in the industrial applications of a heterogeneous
determining step of this reaction.
catalyst is its most essential features. So, to check the
1
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heterogeneity of our synthesized catalyst, we performed a hot Recycling of catalyst
filtration test via the synthesis of 3-tert-butylquinazoline-
Recyclability, recoverability and easy separation are the prime
features of a heterogeneous catalyst. The catalyst recyclability was
tested in a three-component coupling reaction of 2-iodoaniline,
carbon dioxide, and tert-butyl isocyanide. From the reaction
mixture, the catalyst was separated via a simple filtration after
every catalytic cycle. Then, the separated catalyst was washed
2
,4(1H,3H)-dione from o-iodoaniline, tert-butyl isocyanide and
CO in the presence of the Pd(II)EN@GO composite catalyst.
2
Initially, the reaction was continued for 5 h under optimized
reaction conditions; 64% yield of the desired product was
obtained. Then, the catalyst was separated by filtration, and
the reaction mixture without catalyst was further put into the
same reaction environment for another 5 h. No significant
change in the product yield was observed. After performing
the filtration test, the filtrate was analyzed by ICP-AES but there
was no trace of the palladium metal found in the filtrate.
properly using distilled H O, hot MeOH, and acetone, and dried
2
using a vacuum desiccator. Fig. 14 shows that after the use of six
successive cycles, the catalyst maintains its efficiency.
Moreover, FE SEM, IR, and XPS analyses of the recycled catalyst Conclusion
were performed for additional clarification. The FE SEM images
Ethelenediamine-modified graphene oxide-based palladium metal-
containing catalyst was designed and synthesized. The characteriza-
tion of the catalyst was done via ICP-AES, PXRD, SEM, TEM, EDX,
2
XPS, N adsorption desorption, Raman and IR studies. The catalyst
was very much efficient for the synthesis of N3-substituted
quinazoline-2,4(1H,3H)-diones through a three-component coupling
reaction of o-halo anilines, CO2 and isocyanides. The catalytic
of the reused catalyst showed almost the same morphology as
that found in the fresh catalyst (Fig. S14, ESI†). No major change
was detected in the peak position of the palladium metal in the
XPS analysis of the recovered Pd(II)EN@GO catalyst (Fig. S15,
ESI†). Two distinct peaks at 337.8 and 343.1 eV, which were due
5
/2
3/2
to the binding energies of Pd 3d and Pd 3d clearly indicate
that the oxidation state of palladium i.e. +2 remains unchanged
3
0
reaction occurred in 1 bar CO pressure under heterogeneous
2
after finishing the catalysis process. The inferred spectrum
pattern of both the reused and fresh catalyst showed almost the
same nature (Fig. S16, ESI†). This result signifies that after the
catalytic reaction the nature of the catalyst remains unaltered.
Again the ICP-AES analysis results of the used catalyst after
the first cycle of the catalytic reaction gave the same result as the
synthesized catalyst. Furthermore, the same analysis of the
reused catalyst after the sixth cycle (Pd loading is 7.10%) did
not show a considerable loss of the palladium metal amount
and mild reaction conditions. All previously reported methods
regarding N3-substituted quinazoline-2,4(1H,3H)-diones synthesis,
was proceeded under homogeneous catalytic conditions. Again, the
2
high pressure of CO was used. A mechanistic route for the catalytic
cycles was reported here the first time via the DFT calculations.
Besides, our catalyst is very stable, easily separable and preserved its
catalytic efficiency after the use of six successive catalytic cycles.
from the GO-EN surface. The ICP analysis was also performed for Conflicts of interest
the product mixtures of catalysis reaction, and the result con-
firmed the absent of palladium metal in the mixture. All these
There are no conflicts to declare.
data confirm that the Pd metal was not leached from the catalyst
during the course of the catalytic cycle, and hence the catalyst was
conveyed in its heterogeneous nature throughout the reaction.
Acknowledgements
Prof. S. M. Islam acknowledges the Department of Science and
Technology (DST-SERB) (Project sanction No. EMR/2016/004956),
New Delhi, India, Board of Nuclear Science, (BRNS, project sanction
number; 37(2)/14/03/2018-BRNS/37003), Govt of India and Council
of Scientific and Industrial Research (CSIR, Project sanction No.
02(0284)/16/EMR-II, Dated 06-12-2016), and New Delhi, India for
financial support. Dr S. Biswas acknowledges University Grants
Commission (UGC) for financial support through D. S. Kothari
Post-Doctoral Fellowship (Award letter no. F.4-2/2006(BSR)/CH/
16-17/0026). R. Khatun also acknowledges UGC for providing the
financial support through the Maulana Azad National Fellowship
and the Department of Science and Technology (DST-INSPIRE) for
financial support (INSPIRE fellow Registration No. IF170931) grate-
fully acknowledged by Md S. Islam. We acknowledge UGC and DST
New Delhi, India for financial and instrumental support to the
Department of Chemistry, the University of Kalyani under PURSE,
FIST and SAP program. For providing Powder X-ray Diffraction
instrument facility, we are very grateful to Dr Arup Gayen, Depart-
ment of Chemistry, Jadavpur University, 188, Raja S. C. Mallick Rd,
Kolkata 700032, West Bengal, India.
Fig. 14 Recyclability of catalyst for the synthesis of 3-(tert-butyl)-
quinazoline-2,4(1H,3H)-dione (P1) via a three-component coupling of
2
2
-iodoaniline, CO and tert-butyl isocyanide.
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