An efficient method for the synthesis of quinoxaline derivatives catalyzed by titanium silicate-1

Article abstract of DOI:10.1007/s11164-020-04258-w

Abstract: A series of quinoxaline derivatives were efficiently synthesized by convenient and simple procedure in excellent yields using 1 wt.% of titanium silicate (TS-1) catalyzed reaction of 1,2-diamines and 1,2-diketones in methanol at room temperature

Full text of DOI:10.1007/s11164-020-04258-w

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-020-04258-w
An efcient method for the synthesis of quinoxaline
derivatives catalyzed by titanium silicate‑1
Pranav S. Chandrachood1,2 · Amol R. Jadhav2 · Dinesh R. Garud2
·
Nirmala R. Deshpande1 · Vedavati G. Puranik3 · Rajashree V. Kashalkar1,2
Received: 24 April 2020 / Accepted: 26 August 2020
© Springer Nature B.V. 2020
Abstract
A series of quinoxaline derivatives were efciently synthesized by convenient and
simple procedure in excellent yields using 1 wt.% of titanium silicate (TS-1) cata-
lyzed reaction of 1,2-diamines and 1,2-diketones in methanol at room temperature.
This reaction is scalable to multigram scale and the catalyst is recyclable.
Graphic abstract
R'
R'
N
N
NH2
NH2
O
TS-1Catalyst (1 wt%)
MeOH, rt
R
R
+
O
R'
R'
Keywords Quinoxaline · Titanium silicate-1 · o-phenylenediamine · Aromatic
1,2-diketones · Room temperature
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s1116
4-020-04258-w) contains supplementary material, which is available to authorized users.
* Dinesh R. Garud
ddgarud@gmail.com
Extended author information available on the last page of the article
Vol.:(0123456789)
1 3

P. S. Chandrachood et al.
Introduction
In recent years, N-containing heterocyclic compounds are the most valuable
group of scafolds in pharmaceuticals and bioactive natural products [1]. In this
regard, quinoxalines [2, 3] are a versatile class of nitrogen-containing heterocy-
clic compounds of pharmacological importance due to its interesting biological
activities (Fig. 1) such as antiviral, antibiotic, anti-infammatory, antiprotozoal,
antihelmintic, antimalarial, antitubercular, antidepressant, kinase inhibitors, anti-
cancer and also active against AIDS. Besides the biological activities, quinoxa-
line derivatives have been reported for their applications in synthesis of organic
semiconductors [4–6], dyes [7], and electroluminescent materials [8]. Due to
their enormous applications in various felds, a number of synthetic strategies
have been developed for the preparation of substituted quinoxalines. Most sig-
nifcant method for the synthesis of quinoxaline includes the condensation of an
aryl 1,2-diamine with a 1,2-diketone in the presence of catalysts (or reagents)
such as in refuxing ethanol or acetic acid [9], in MeOH=AcOH under micro-
wave irradiation [10], in the presence of catalysts such as molecular iodine [11,
12], cerium ammonium nitrate [13–15], glycerine–cerium chloride [16], sulfamic
acid [17], polymer-supported sulphanilic acid [18], Yb(OTf)3 [19], oxalic acid
[20], o-iodoxybenzoic acid (IBX) [21], H6P2W18O62.24H2O [22], KHSO4 [23],
Ni-nanoparticles [24], nano-Y-Fe2O3-SO3H [25], nanostructured Na2PdP2O7 [26],
polyaniline-sulfate salt [27], InCl3 [28], MnCl2 [29], CuSO4.5H2O [30], Zn=L-
proline [31], tween 40 [32], HClO4.SiO2 [33], ZnO-loaded mesoporous silica
(KIT-6) [34], graphite [35], montmorillonite K-10 [36], Yb-modifed NaY zeolite
OH
H3C
S
CH3
COOH
HO
O
OH
O
N
N
O
O
N
OH
N
N
O
H3C
H3C
N
N
N
N
H
N
H
O
NH
COOH
NCG555879-01
O
Quinacillin
Riboflavin
N
H
O
S
N
N
N
O
N
N
N
O
H3C
O
CH3
O
NH
CH3 CH3
N
NH2
Cl
HN
O
N
N
CH3
Varenicline
H
Chlorosulfaquinoxaline
O
O
CH3
S
S
CH3
N
O
O
Br
H
H
N
H
N
N
O
CH3
COOH
N
N
N
O
N
NH
O
O
CH3 CH3
O
N
N
Cl
N
O
H3C
CH3
Brimonidine
XK 469 (NSC697887)
Quinomycin A
N
Fig.1 Biologically important quinoxaline derivatives
1 3

An efcient method for the synthesis of quinoxaline derivatives…
[37], NH4X [38], p-toluenesulfonic acid [39] as catalyst and solid-phase synthesis
[40–43]. Also, the synthesis of quinoxalines via the Ugi reaction is reported by
Ayaz et al. [44] Numerous other methods have been reported for synthesis of qui-
noxaline derivatives including the Pd(OAc)2 [45] or MnO2 [46–48] catalyzed tan-
dem oxidation of α-hydroxyl ketones, ruthenium catalyzed synthesis of quinoxa-
lines from diols and ortho-diamines [49–52], Bi-catalyzed oxidative coupling
of epoxides and ene-1,2-diamines [53], cyclization of α-arylimino oximes of
α-dicarbonyl compounds under refux in acetic anhydride [54], cyclization–oxi-
dation of phenacyl bromides [55], heteroannulation of nitroketene N,S-arylimi-
noacetals with POCl3 [56] and modifed HY zeolite [57] catalyzed synthesis of
2-methylquinoxaline from 1,2-phenylenediamine and 1,2-propanediol at 350 °C.
Recently, a copper-catalyzed tandem oxidative cycloamination of N-arylenamines
or ketimines with sodium azide provided an efcient access to quinoxalines [58,
59]. Pardeshi et al. reported the one‐pot reaction of styrenes with o‐phenylenedi-
amines catalyzed by N‐bromosuccinimide for the synthesis of quinoxalines [60].
Further, oxalic acid was used as building block for the synthesis of quinoxalines
from o-phenylenediamine [19, 61, 62].
Most of these methods for the preparation of quinoxaline derivatives are asso-
ciated with one or more of the following drawbacks: (1) use of expensive cata-
lysts, (2) need for anhydrous conditions, (3) unsatisfactory yields, (4) harsh reac-
tion conditions and (5) inefciency of the method with electron-withdrawing aryl
1,2-diamines substituents. Therefore, development of an efcient, simple, cheap,
safe, and green method for the preparation of quinoxalines is desirable. Recently,
zeolites as a catalyst in organic synthesis and transformations are becoming more
popular due to their greener approach, catalytic loadings and high selectivity. In
this regard, zeolite such as titanium silicate (TS-1) [63–74] is being extensively
used as a heterogeneous catalyst in various organic transformations. It has sev-
eral advantages, including being environmentally friendly, nontoxic, inexpensive,
recoverable, and reusable. Therefore we decided to explore the catalytic suitabil-
ity of TS-1 catalyst for the synthesis of quinoxalines. Herein we report, TS-1 (1
wt.%) catalyzed, a simple, efcient and practical method for the preparation of
quinoxaline derivatives by the reaction of substituted o-phenylenediamine with
aromatic 1,2-diketones.
Experimental
General procedure for the synthesis of quinoxalines
A mixture of 1,2-diamine 1 (1.05 mmol), 1,2-diketone 2 (1.00 mmol), and TS-1 (1
wt.%) in methanol (5 ml) was stirred at room temperature. The reaction progress was
monitored by TLC. After the completion of reaction, solvent was evaporated under
reduced pressure to provide crude product, which was further purifed using silica
gel column chromatography (hexane -ethyl acetate; 10:1) to obtain pure product 3.
1 3

P. S. Chandrachood et al.
Spectral data for selected compounds
Methyl 2,3‑diphenylquinoline‑6‑carboxylate (3f)
Yield=98%; M. P. 144–146 °C; FTIR (KBr): 2935, 1726, 1546, 1498, 1442,
1
1261 cm−1; H NMR (CDCl3, 400 MHz): δ 4.02 (s, 3H), 7.28–7.41 (m, 6H),
7.50–7.58 (m, 4H), 8.20 (d, J=8 Hz, 1H), 8.35 (dd, J=2 and 8 Hz, 1H), 8.90 (d,
J=2 Hz, 1H); 13C NMR (CDCl3, 100 MHz): δ52.4, 128.2, 128.99, 129.1, 129.3,
129.7, 131.0, 131.8, 138.5, 140.3, 142.99, 154.2,154.9, 166.1; MS: m/z=339
[M-1]+.
2,3‑Bis‑(4‑fuorophenyl)‑6‑chloro‑quinoxaline (3i)
Yield=98%; M. P. 132–133 °C; FTIR (KBr): 2920, 1732, 1519, 1230, 839, 702,
1
678 cm−1; H NMR (CDCl3, 400 MHz): δ 7.07 (t, J=9.1 Hz, 4H), 7.53 (dd,
J=8.8 & 5.6 Hz, 4H),7.72 (dd, J=2 and 8.8 Hz, 1H), 8.10 (d, J=8.8 Hz, 1H),
8.15 (d, J=2 Hz, 1H); 13C NMR (CDCl3, 100 MHz): δ 115.6 (2JC-F =23.0 Hz),
127.98, 130.3, 131.2, 131.8 (3JC-F =9.0 Hz), 134.6 (4JC-F =3.0 Hz),135.9, 139.6,
141.4, 152.3, 152.95, 163.4 (1JC-F =249.0 Hz); MS: m/z=353 [M+1]+; HRMS:
m/z=353.0657, calcd. for C20H12ClF2N2, found 353.0652[M+H]+.
Methyl 2,3‑Bis‑(4‑fuorophenyl)quinoxaline‑6‑carboxylate (3 l)
Yield=97%; M. P.187–189 °C; FTIR (KBr): 3645, 1742, 1558, 1512, 1230,
1
848, 457 cm−1; H NMR (CDCl3, 400 MHz): δ 4.03 (s, 3H), 7.06 (t, J=10 Hz,
4H), 7.50–7.60 (m, 4H), 8.18 (d, J=8 Hz, 1H), 8.3 (dd, J=2 & 8 Hz, 1H), 8.88
(d, J=2 Hz, 1H); 13C NMR (CDCl3, 100 MHz): δ 52.6, 115.6 (2JC-F =22.0 Hz),
129.3, 129.7, 131.4, 131.8 (3JC-F =9.0 Hz), 134.5 (4JC-F =3.0 Hz),140.4, 143.1,
152.1, 153.8, 163.4 (1JC-F =256.0 Hz), 166.2; MS: m/z=377 [M+1]+; HRMS:
m/z=377.1102, calcd. for C22H15F2N2O2, found 377.1094 [M+H]+.
2,3‑Bis‑(4‑bromophenyl)‑6‑bromo‑quinoxaline (3p)
Yield=95%; M. P.195–196 °C; FTIR (KBr): 3850, 3070, 1664, 1593, 1473,
1
1342, 820, 410 cm−1; H NMR (CDCl3, 400 MHz): δ 7.41 (d, J=8 Hz, 4H), 7.51
(d, J=8 Hz, 4H), 7.85 (dd, J=2.4 & 8 Hz, 1H), 8.00 (d, J=8 Hz, 1H), 8.33 (d,
J=2.4 Hz, 1H); 13C NMR (CDCl3, 100 MHz): δ 123.95, 124.1, 124.3, 130.4,
131.3, 131.4, 131.7, 133.9, 137.2, 137.3, 139.9, 141.7, 152.1, 152.6; MS: m/z=520
[M+1]+; HRMS: m/z=518.8530, calcd. for C20H12Br3N2, found 518.8527
[M+H]+.
Methyl 2,3‑Bis‑(4‑bromophenyl)quinoxaline‑6‑carboxylate (3r)
Yield=94%; M. P.191–192 °C; FTIR (KBr): 2922, 1730, 1448, 1257, 1217, 974,
1
833 cm−1; H NMR (CDCl3, 400 MHz): δ H), 4.03 (s, 3H), 7.40–7.47 (m, 4 H),
7.50–7.57 (m, 4 H), 8.18 (d, J=8 Hz, 1 H), 8.37 (dd, J=2 & 8 Hz, 1H), 8.86 (d,
1 3

An efcient method for the synthesis of quinoxaline derivatives…
J=2 Hz, 1 H); 13C NMR (CDCl3, 100 MHz): δ 52.7, 124.1, 124.2, 129.4, 129.9,
131.4, 131.6, 131.7,131.8, 137.2,140.4,143.1, 152.8, 153.5, 166.1; MS: m/z=499
[M+1]+; HRMS: m/z=498.9480, calcd. for C22H15Br2N2O2, found 498.9477
[M+H]+.
Results and discussion
Optimization of reaction conditions
We frst studied the preparation of quinoxaline 3a using o-phenylenediamine, 1a and
a slight excess of benzil 2a as the model reaction (Scheme1, Table 1). When, the
reaction of o-phenylenediamine, 1a and benzil, 2a was carried out using 10 wt.% of
TS-1 under solvent-free conditions and in water, the reaction resulted in the forma-
tion of desired quinoxaline 3a in 15% and 40% yields, respectively (Table 1, entries
1 and 2). Even after stirring the reaction mixture for longer time, no substantial
increase in the yield was observed. We were delighted to observe the formation qui-
noxaline in excellent yields when the reaction was carried out using 10 wt.% of TS-1
in methanol (entry 3). Next, the eforts were directed towards the catalytic evalua-
tion of TS-1 and solvent selection to improve the yield of reaction (entries 4–17). It
is noteworthy that, the reaction was infuenced by the amount of TS-1 and loading
of 1 wt.% of TS-1 in methanol was found to be best condition for the synthesis of
quinoxaline 3a (entry 6).
With successful optimization results in hand, we moved on to investigate the
scope of the process for reactions of variety of 1,2-diamines with substituted benzils
(Scheme 2, Table 2). In the case of simple benzil 2a, substitution at 1,2-diamine part
is well tolerated and corresponding quinoxalines 3a-3f were obtained in excellent
yields (Table 2, entries 1–6). Next, when the substituted benzil 2b and 2c were used
in the reaction under optimized conditions, the corresponding quinoxaline deriva-
tives 3g-3r were also obtained in excellent yields (entries 7–18). The compounds
3k-l and 3q-r required longer reaction time as well as loading of 2 wt.% of the TS-1
catalyst (entries 7–10 and 13–16, respectively). A variety of functional groups were
well tolerated under the present reaction conditions. The structure of the quinoxa-
1
line derivatives 3 were confrmed by the studies of IR, H-, 13C-NMR and Mass
spectroscopy.
N
N
NH2
NH2
O
Catalyst, Solvent
Temperature
+
O
1a
2a
3a
Scheme 1 Synthesis of Quinoxaline 3a by the reaction of 1a with 2a using TS-1 catalyst
1 3

P. S. Chandrachood et al.
Table 1 The reaction of 1a with
2a using TS-1 catalyst under
diferent conditionsa
Entry
Solvent
TS-1 catalyst Time (min)
% Yieldb
(wt.%) (%)
1
2
3
4
5
6
7
8
–
10
10
10
5
2
1
1
1
1
1
1
1
1
1
1
–
–
6 h
6 h
30
40
60
60
60
60
60
15
40
99
99
99
99
91
89
80
83
92
31
87
29
18
86
42
Water
Methanol
Methanol
Methanol
Methanol
Ethanol
Dioxane
Acetonitrile
DCM
9
10
11
12
13
14
15
16
17
60
60
Chloroform
Water
THF
12 h
60
12 h
12 h
24 h
24 h
DMF
DMSO
Methanol
Ethanol
aAll the reactions were performed on 1.05 mmol of 1, 1.00 mmol
of 2 and 1 wt.% of TS-1 catalyst in methanol at room temperature
unless and otherwise stated
bIsolated yields after column chromatography
R'
R'
R'
R
NH2
NH2
O
O
R
N
N
TS-1Catalyst (1 wt%)
MeOH, rt
+
R'
1a-e
2a-e
3a-r
Scheme 2 Synthesis of Quinoxaline 3 by the reaction of 1 with 2 using TS-1 catalyst
In order to confrm the structure of methyl 2,3-diphenylquinoxaline-6-carbox-
ylate (3f), we carried out the X-ray analysis of this compound. Single crystals
of the compound 3f were grown by slow evaporation of the solution mixture
of hexane and ethyl acetate. An ORTEP drawing, depicted in Fig. 2, shows the
crystal structure of the 3f [84]. CCDC reference: 973,448, mp 144–146 °C. Pale
yellow colored crystal of approximate size 0.23 × 0.13 × 0.04 mm3, was used
for data collection on Bruker SMART APEX CCD difractometer using Mo Kα
radiation. Crystal, exposure/frame = 5.0 s/frame, θ range = 2.33°–24.49°, com-
pleteness to θ of 24.49° is 99.9%. SADABS correction applied, C22H16N2O2,
M = 340.37. Crystals belong to triclinic, space group P-1, a = 7.8345(4),
1 3

An efcient method for the synthesis of quinoxaline derivatives…
Table 2 Synthesis of Quinoxaline derivatives 3a–3r with 1 wt.% of TS-1 catalysta
Entry
R
R´
Time (min)
Product
Yield (%)c Mp (°C)
(observed) (reported)
Mp (°C)
Refer-
ences
1
2
3
4
5
6
7
8
–H
–CH3
–Cl
–H
–H
–H
–H
–H
–H
–F
–F
–F
–F
–F
–F
–Br 60
–Br 60
–Br 60
–Br 60
–Br
–Br
60
45
60
60
24 h
60
45
45
60
3a
3b
3c
3d
3e
3f
99
98
97
98
97
98
99
98
98
98
96
97b
98
98
95
95b
89b
94
128–129
104–106
104–106
122–123
193–194
144–146
135–136
165–166
132–133
168–169
175–176
187–189
138–141
175–176
166–168
195–196
166–167
191–192
126–127
115–116
122–123
[11]
[75]
[76]
–Br
123.5–123.6 [77]
–NO2
–CO2Me
–H
–CH3
–Cl
193–194
144–145
135–137
165–167
133–134
168–170
176–177
188–189
194–195
185–186
167–168
–
[30]
[78]
[21]
[21]
[79]
[80]
[31]
[78]
[81]
[81]
[82]
[83]
[77]
[78]
3 g
3 h
3i
9
10
11
12
13
14
15
16
17
18
–Br
60
24 h
3 h
3j
–NO2
–CO2Me
–H
–CH3
–Cl
–Br
–NO2
–CO2Me
3 k
3 l
3 m
3n
3o
3p
3q
3r
24 h
6 h
188–190
193–194
aAll the reactions were performed on 1.05 mmol of 1, 1.00 mmol of 2 and 1 wt.% of TS-1 catalyst in
methanol at room temperature unless and otherwise stated
bReactions were carried out using 1.05 mmol of 1, 1.00 mmol of 2 and 2 wt.% of TS-1 catalyst in metha-
nol at room temperature
cIsolated yields after column chromatography
b = 9.5425(5), c = 12.5293(6) Å, α = 91.285(1)°, β = 99.154(1)°, γ = 112.820(1)°,
V = 848.74(7) Å3, Z = 2, Dc = 1.332 mg m−3, T = 170(2) K, 7632refections
measured, 2814unique [I > 2σ(I)], R value 0.0683, wR2 = 0.1707. All the data
were corrected for Lorentzian, polarization and absorption efects. SHELX-97
(ShelxTL) [85] was used for structure solution and full matrix least squares
refnement on F2. Hydrogen atoms were included in the refnement as per the
riding model.
The four bond length of N(1)-C(2), N(4)-C(3),N(1)-C(9) and N(4)-C(10) in
3f were found to be 1.313(3) Å, 1.311(3) Å, 1.358(3) Å and 1.366(3) Å, respec-
tively, and clearly shows that nitrogen atoms are the part of aromatic ring. The
carbon–oxygen bond lengths in the ester groups were found to be 1.211(3)Å for
O(1)-C(23) double bond and 1.440(3)Å for O(2)-C(24) single bond. The torsion
angles for N(1)-C(9)-C(10)-N(4), N(4)-C(3)-C(2)-N(1) and C(17)-C(3)-C(2)-
C(11) were -6.2(4)°, -9.7(4)° and -13.8(4)°, respectively.
1 3

P. S. Chandrachood et al.
Fig.2 Crystal structure x-ray ORTEP diagram of compound 3f. Ellipsoids are drawn at 50% probability
O
O
O
O
O
Si
Ar
O
O
O
Ti
O
(I)
Ar
Ar
Ar
N
N
N
Ar
Ar
N
H
O
O
O
O
Si
H
N
H
H
(II)
O
O
O
Ti
O
NH2
(IV)
H2O
H2O
(III)
Fig. 3 Plausible reaction mechanism for quinoxaline formation in the presence of TS-1 catalyst
Proposed mechanism for the formation of quinoxaline derivatives
Figure 3 shows a plausible reaction mechanism for the formation of quinoxalines.
Firstly, the lone pair of one of the carbonyl oxygen of 1,2-diketone (I) interacts
with TS-1 catalyst to enhance electrophilicity and nucleophilic attack of nitro-
gen of o-phenylenediamine (II) takes place immediately. At the same time, the
TS-1 catalyst acts as a Bronsted base and accelerates the reaction by elimination
of water molecule to form a carbon–nitrogen double bond (C=N) (III). Respec-
tively, one more elimination of water molecule results in formation of second
carbon–nitrogen double bond (C=N) giving rise to the required target molecule
quinoxaline (IV).
1 3

An efcient method for the synthesis of quinoxaline derivatives…
Table 3 Reusability of TS-1
Reaction turn
Time (min)
% Yield (3a)b
catalysta
1st
2nd
3rd
4th
60
60
60
60
99
98
98
97
aReaction details: 1a (1.135 g, 10.5 mmol), 2a (2.102 g, 10.0 mmol),
TS-1 (2 wt.%), methanol, room temperature
bIsolated yields after column chromatography
Catalyst reusability
Recyclability of catalyst is the most important and salient feature of present reac-
tion. As shown in Table 3, the reusability of catalyst is checked at gram scale by
reaction of o-phenylenediamine, 1a (1.135 g, 10.5 mmol) with benzil, 2a (2.102 g,
10.0 mmol) using 2 wt% of TS-1 catalyst in methanol. The reactions resulted in for-
mation of required quinoxaline compound 3a in excellent yields after column chro-
matographic purifcation. The TS-1 catalyst could be reused at least fve times. Side
products were not observed in these reactions. Furthermore, the reaction can be
scaled up to a multigram scale.
Conclusion
In conclusion, we have developed a convenient and simple methodology for the
synthesis of quinoxaline derivatives using the reaction of 1,2-diamines and 1,2-dik-
etones with 1 wt.% of titanium silicate (TS-1) in methanol at room temperature.
Structure of the compound 3f was confrmed by x-ray analysis. This reaction is scal-
able to multigram scale and the catalyst is recyclable.
Supporting information
Full Experimental details with 1H-NMR and 13C-NMR spectra can be found via the
“Supplementary Content” section of this articles webpage.
Acknowledgements The authors are thankful to Principal, S. P. College for providing necessary facili-
ties. Authors are also thankful to CIF, Savitribai Phule Pune University, Pune for spectral analysis.
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Afliations
Pranav S. Chandrachood1,2 · Amol R. Jadhav2 · Dinesh R. Garud2
·
Nirmala R. Deshpande1 · Vedavati G. Puranik3 · Rajashree V. Kashalkar1,2
1
T. R. Ingle Research Laboratory, Department of Chemistry, Sir Parashurambhau College
(afliated to Savitribai Phule Pune University, formerly University of Pune), Tilak Road, Pune,
Maharashtra 411030, India
2
Department of Chemistry, Sir Parashurambhau College (afliated to Savitribai Phule Pune
1 3

P. S. Chandrachood et al.
University, formerly University of Pune), Tilak Road, Pune, Maharashtra 411030, India
3
Centre for Materials Characterisation, CSIR-National Chemical Laboratory, Pune,
Maharashtra 411 008, India
1 3