Synthesis & characterization of quinoxalines Chapter-4

4. 1 Introduction to Quinoxaline
Quinoxaline derivatives are of significant interest from both academic and
industrial perspectives because they are noteworthy intermediates for the
manufacturing of pharmaceuticals and advanced materials [1, 2]. A number of
nitrogen-containing heterocycles show antimicrobial activity and have been
synthesized for medical use. Among various classes of heterocyclic units,
quinoxaline ring has frequently been used as a component of various antibiotic
molecules, such as levomycin and hinomycin, which inhibit the growth of Gram-
positive bacteria and are active against various transplantable tumors [3, 4].
Quinoxalines are very important compounds due to their wide spectrum of
biological activities such as anticancer [5], antibacterial [6], and activity as kinase
inhibitors [7]. They are well known for their application in rigid subunits in
macrocyclic receptor [8] elevtroluminescent materials [9], organic semi-
conductors [10] and DNA cleaving agents [11].
4. 2 Recent Literature Survey
Soleymani et al. [12] proposed mechanism for the formation of
quinoxalines from 1,2- diamine and 1, 2- dicarbonyl compounds by using Lewis
acid as the catalyst as shown in Scheme 4.1. Amino group because of non-
bonding electron pair on nitrogen atom makes nucleophilic attack on to carbonyl
carbon. This process is repeated twice until the removal of two water molecules
to yield quinoxalines.

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Considering the significant applications in the fields of medicinal, industrial and

synthetic organic chemistry, there has been tremendous interest in developing
efficient methods for the synthesis of quinoxalines. Improved methods have been
reported by using different catalyst such as Pd (OAc)2 [13], MnO2 [14], CAN [15],
manganese octahedral molecular sieves [16], task-specific ionic liquid [17] and
bismuth (III) [18]. Although great success has been obtained in some efforts,
many of these methodologies suffer one or more drawbacks such as drastic
reaction conditions, low yields, and tedious work-up procedures, using toxic
metal salts as catalysts, long reaction time and relatively expensive reagents. A
number of synthetic strategies have been developed for the preparation of
substituted quinoxalines [8, 15, 19-25]. The most common method involves the
condensation of an aryl-1, 2-diamine with a 1, 2-dicarbonyl compound in
refluxing ethanol or acetic acid for 2–12 h, and this typically gives yields of 34–
70%. Hence, the search for the better method, especially the readily available
and green catalysts, is still being demanded and actively pursued.
Krishnakumar et al. [26] synthesized quinoxaline from o-
phenylenediamine and benzil by using TiO2-P25-SO4-2 as the catalyst using
ethanol as the solvent at room temperature. Ishikawa et al. [27] symthesized
derivatives of 2, 3-bis (bromomethyl)quinoxaline with substituents at the 6-
and/or 7-positions by using acidic catalyst, and evaluated their activities against
bacteria and fungi. Antoniotti et al. [23] synthesized 2, 3-susbstituted
quinoxaline derivatives from epoxides and o-phenylenediamine using
Bi(0)/O2/DMSO or Bi(III)/O2/. The use of Bi(0)/O2/DMSO or Bi(III)/O2/DMSO
as the catalytic system in the oxidative ring opening of epoxides have already
been reported [28, 29]. The Bi(0)-catalyzed reaction did not take place in the
absence of an additve. Heravi et al. [30] reported ferric perchlorate catalyzed the
three component condensation reaction of o-phenylenediamine, aromatic
aldehydes, and cyclohexyl isocyanide to afford the corresponding N-cyclohexyl-
3-aryl-quinoxaline-2-amines. Dhakshinamoorthy et al. [31] developed protocol
in which zinc chloride-exchanged K10-montmorillonite (clay zinc) was
employed as a Lewis acid catalyst in aqueous media at room temperature for the
synthesis of various quinoxalines from carbonyl compounds and o-
phenylenediamine. Padmavathy et al. [32] synthesized quinoxalines in two

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stages or as a one pot reaction, starting from ketones via their α-hydroxylimino
ketone derivatives, and condensation of the latter with 1, 2- diaminobenzene
under microwave irradiation. Bachhav et al. [33] synthesized quinoxaline from o-
phenylenediamine and 1,2 dicarbonyl compounds employing glycerol and water
the as the green solvent at 90 °C. Guirado et al. [34] developed an efficient
synthetic method for previously unattainable 4-alkoxy-6,9-dichloro [1,2,
4]triazolo[4,3-a] quinoxalines by reactions between 5,8-dichloro-2,3-
dicyanoquinoxaline and alcohols in the presence of triethylamine led to 3-
alkoxy-5,8-dichloro-2-cyanoquinoxalines. Bhosale et al. [20] synthesized
quinoxaline from o-phenylenediamine and 1, 2-dicarbonyl compounds by using
molecular iodine as a catalyst in DMSO as the solvent at room temperature.
Corona et al. [35] synthesized a series of 5, 7-diamino-3-phenyl-2-benzylamino,
2-phenoxy and 2-phenylthio substituted quinoxalines. These compounds were
evaluated for their in vitro antitumor activity towards cell lines of nine different
types of human cancers. Srinivas et al. [16] synthesized biologically important
quinoxaline derivatives from various 1,2-dicarbonyls and aromatic 1,2-diamines
in excellent yields using very low amount of reusable polyaniline-sulfate salt
catalyst. Zhang et al. [36] Chinese synthesized quinoxaline derivatives from of
1,2-diamines and 1,2-dicarbonyl compounds by using polyethylene glycol as a
catalyst. Chandrasekhar et al. [37] developed a methodology employing 5 mol %
of PdCl2/CuCl2 in PEG/H2O as a efficient recyclable catalytic system for the
oxidation of internal alkynes to 2, 3- disubstituted quinoxaline derivatives.

4. 3 Objectives
1. To find out new synthetic pathway for well-known condensation reactions
of 1,2- diketone and o-phenylenediamines to affords various quinoxalines by
employing polymer supported sulphanilic acid (ENPFSA) as the
heterogeneous catalyst under different energy source such as conventional
method, ultrasound irradiation and at room temperature.
2. To optimize the conditions under conventional method and ultrasound
irradiation to get maximum yield in shorter duration.
3. To check the substrate scope of the novel protocol for synthesizing a good
library of quinoxaline derivatives.

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4. To characterize all the synthesized compounds by 1H NMR, 13C NMR, APT, IR,
MASS spectroscopic techniques.
4. 4 Result and Discussion
4. 4. 1 Scheme
The synthesis of 3 (Scheme 4.2) was carried out by one pot condensation
of o-phenylenediamines 1 with 1, 2 diarylketone 2 by using 5% w/w ENPFSA
with respect to o-phenylenediamines employing ethanol as the solvent by using
two different energy source such as conventional and and ultrasound irradiation
and also at room temperature.

4. 4. 2 Optimization
The cyclocondensation reaction between o-phenylenediamine (0.0105
mole) and benzil (0.01 mole) in ethanol (10 mL) under reflux to afford quinoxaline
4a (Scheme 4.2) was chosen as the model reaction for optimization.
The amount of ENPFSA was used in the ratio of % w/w with respect to o-
phenylenediamine. The optimization was carried out with respect to the amount of
catalyst and duration of reaction leading to the maximum yield. The progress of the
reaction was continuously monitored by thin layer chromatography (TLC) using
aluminum sheets precoated with silica gel 60 F254 (Merck) under ethylacetate: n-
hexane in the ratio 50:50. The characteristic data are shown in Table 4.1.
A variety of different catalyst and ENPFSA were employed for the
synthesis of quinoxaline 4a (Table 4.1, entries 1–13). The reaction was studied at
reflux temperature as well as at room temperature. Increase in the reaction
temperature to reflux had only marginal effect on % yield (Table 4.1). Reaction
was also optimized by varying amount of ENPFSA (Table 4.1, entries 8–13). It
was observed that 5% w/w amount of catalyst on the basis of o-
phenylenediamine is suitable to complete the reaction in moderate time with
high yield. Higher amount of the catalyst did not increase the yield noticeably.

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Model reaction was carried out by using different catalysts such as HCl,
CH3COOH, H2SO4, ZnCl2, CoCl2, NiCl2 and PEG-600. It was found that by using HCl,
CH3COOH and H2SO4 as the catalysts, reaction was completed in 85 minute with
80% yield under reflux and in 100 min with 75% yield at room temperature
(Table 4.1, entries 1- 3). By using ZnCl2, CoCl2, NiCl2 as the catalysts, reaction got
completed in 90 minutes with 80% yield under reflux and 110 min. with 75%
yield at room temperature (Table 1, entry 4-6). Thus the reaction was completed
in shorter time with high yield by using acid catalysts as compared to metal
chloride catalysts. Using PEG-600 as the catalyst, reaction was completed in 80
min. with 85% yield under reflux and 85 min. with 80% yield at room
temperature (Table 4.1, entry 7). Model reaction was performed by using 5%
ENPFSA as the catalyst, reaction was completed in 35 min. with 90% yield under
reflux and 40 min. with 88% yield at room temperature (Table 4.1, entry 12).
Table 4.1 Effect of different catalyst on the condensation of benzil and o-
phenylenediamine in ethanol as the solvent at room temperature and at reflux.
Entry Catalyst At room temp. Reflux
Timea Yieldsb Timea Yieldsb
(min) (%) (min) (%)
1 1mmol % HCl 100 80 85 75
2 1mmol % CH3COOH 100 80 85 75
3 1mmol % H2SO4 100 80 85 75
4 1mmol % ZnCl2 110 80 90 75
5 1mmol % CoCl2 110 80 90 75
6 1mmol % NiCl2 110 80 90 75
7 1mmol % PEG-600 85 85 80 80
8 1 % ENPFSA 45 70 40 65
9 2 % ENPFSA 45 72 40 70
10 3 % ENPFSA 45 75 40 73
11 4 % ENPFSA 45 80 40 75
12 5 % ENPFSA 40 90 35 88
13 6 % ENPFSA 50 85 40 83
a5% w/w ENPFSA with respect to o-phenylenediamine was used.; b Reaction was monitored by
TLC.; c Isolated yields.

Thus, it was found that the condensation reaction carried out in the
presence 5% w/w ENPFSA at room temperature showed the highest conversion
rate and this was chosen as the optimized condition to perform a series of
reactions to check substrate dependency of the protocol.

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Reaction was also optimized by using ultrasound irradiation. First the

reaction was carried out without taking catalyst at room temperature under
ultrasound irradiation (Table 4.2, entry 1), it was observed that after 80 min.
reaction did not proceed. Reaction was carried out by taking 5% w/w with
respect to amount of o-phenylenediamine at room temperature (28 °C)
produced 90% yield in 30 min. ((Table 4.2, entry 2)). Same reaction was
performed under ultrasound irradiation at higher temperature at 50 °C (Table
4.2, entry 3), no significant increase in the yield was observed.
Table 4.2 Optimization data for the synthesis of 1, 2-diphenylquinoxaline under
ultrasound irradiationa.
Entry Catalyst Reaction condition Time (min)b Yieldc
1 No ENPFSA RT, ))) 80 0
2 5 % ENPFSA RT, ))) 30 88 %
3 5 % ENPFSA 50 °C, ))) 30 90 %
a5% w/w ENPFSA with respect to o-phenylenediamine was used.; b Reaction was monitored by
TLC.; c Isolated yields.

4. 4. 3 Characteristics Data Showing the Synthesis of Benzimidazoles

By using these optimized conditions, various quinoxaline derivatives
were synthesized in shorter time as well as in high yields. It was observed that
diketone having phenyl ring as the substituents underwent the conversion
smoothly in short time as compared to diketone having furyl and thenyl ring as
the substituents. The diamine component carrying electron withdrawing group
(Table 4.3, 4k-4o) underwent the reaction in shorter time with high yield as
compared to diamines carrying electron donating group (Table 4.3, 4a-4j and 4p-
4t).

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Table 4. 3 The characteristic data showing the synthesis of quinoxalines a, b.

Code R R1 Ultrasound Thermal At room
Irradiation Conditions temp.
at room temp. at reflux
temp.
Time c Yield Timec Yield Timec Yield
(min) (%)d (min) (%)d (min) (%)d
4a H C6H5 30 88 35 88 40 90
4b H p-CH3C6H4 30 85 35 87 45 85

4c H Phenanthrene- 32 85 30 87 45 85
9,10-dionee
4d H 2-furyl 40 80 44 80 50 80
4e H 2-thenyl 40 80 42 80 50 82
4f CH3 C6H5 38 85 40 87 45 84
4g CH3 p-CH3C6H4 39 85 40 85 48 80
4h CH3 Phenanthrene- 35 80 35 85 48 84
9,10-dionee
4i CH3 2-furyl 41 80 45 80 52 80
4j CH3 2-thenyl 40 80 46 82 52 80
4k NO2 C6H5 28 88 35 90 38 88
4l NO2 p-CH3C6H4 30 82 30 82 41 86
4m NO2 Phenanthrene- 30 85 31 90 41 86
9,10-dionee
4n NO2 2-furyl 42 88 42 88 45 85
4o NO2 2-thenyl 37 85 44 88 45 85
4p Cl C6H5 31 85 32 85 42 84
4q Cl p-CH3C6H4 33 80 35 80 45 84
4r Cl Phenanthrene- 37 85 38 85 45 85
9,10-dionee
4s Cl 2-furyl 40 80 44 85 48 82
4t Cl 2-thenyl 41 80 45 85 48 82
aSolvent ethanol as a medium of reaction.; b 5% w/w amount of catalyst with respect to o-
phenylenediamine.; c Reaction was monitored by TLC.; d Isolated yield.; eName of the diketone

4. 4. 4 Mechanism
The formation of quinoxaline derivatives is outlined in the following
mechanism (Scheme 4.3). 1, 2-Diketone stabilized in the interlayer of ENPFSA via
interaction with H+ by partial polarization of carbonyl group reacts readily with
o-phenylenediamine. The resultant amino-1, 2-diol undergoes dehydration to
give quinoxaline as the end product.

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4. 5 Recyclability of Catalyst
Recyclability of the catalyst was studied by using the ENPFSA recovered
from the previous batch. Reaction between benzil and o-phenylenediamine was
taken as the model reaction. The reaction proceeded smoothly yielding 88–85%
of product (Table 4.4) at room temperature for five successive turns. This result
indicates that the activity of catalyst was not getting much affected upon
recycling at least for five times.
Table 4.4 Recyclability of catalyst
No. of cycle Reaction timea Yield ( % )b
1 40 88
2 40 88
3 40 86
4 40 86
5 40 85
a Reaction was monitored by TLC.; b Isolated yields.

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4. 6 Conclusions
High yielding, one pot synthesis of quinoxaline derivatives from readily
available o-phenylenediamines and 1,2-diaryl ketones under ultrasound
irradiation, room temperature and thermal condition has been developed. The
conditions are mild, and a wide range of functional groups can be tolerated.
NEPFSA as catalyst offers advantages including simplicity of operation, easy
workup procedure, product obtained in high yields with excellent purity, less
time consuming and the recyclability of the catalyst.

4. 7 Experimental
The reaction was performed in D compact ultrasonic cleaner with a
frequency of 30 kHz and power 230 W. Melting points were determined using
µThermoCal10 (Analab scientific Pvt. Ltd.) melting point apparatus and are
uncorrected. TLC was carried out using aluminum sheets precoated with silica
gel 60 F254.

4. 7. 1 Chemicals and Reagents

All chemicals used were of laboratory reagent grade and used without
further purification. o-phenylenediamines, was obtained from Samir Tech Chem.
Pvt. Ltd., Vadodara, India. Various 1, 2- diketone were used as received from
Merck, Mumbai, India. All the solvents were supplied by Sisco Chem. Pvt. Ltd.,
Mumbai, India.

4. 7. 2 General Procedure for Synthesis of Quinoxalines

To a mixture of an o-phenylenediamine (1 mmol) and benzil (1 mmol) in
ethanol (5mL), 5% w/w ENPFSA with respect to benzil was added and the
mixture was stirred at room temperature. The progress of the reaction was
monitored by TLC. After completion of the reaction, ethyl acetate was added to
the solidified mixture and the insoluble catalyst was separated by filtration. The
filtrate was dried over anhydrous Na2SO4. The solvent was evaporated with care
and the pure product was obtained. The product obtained had been
characterized by FT-IR, 1HNMR, 13CNMR and LC-MS analysis. A variety of
substituted o-phenylenediamines were condensed with benzil. The recovered
catalyst was washed with ethanol, chloroform, diethyl ether and subsequently

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dried at 80 °C to recycle in the subsequent model reaction. Compounds 4b-t were

synthesized by taking properly substituted 1, 2-dicarbonyl component in the
reaction mixture.

4. 8 Characterization
Melting points were determined using µThermoCal10 (Analab scientific
Pvt. Ltd.) melting point apparatus and are uncorrected. 1H NMR and 13C NMR
spectra were recorded on a Bruker Avance 400 spectrometer operating at 400
MHz for 1H NMR, and 100 MHz for 13C NMR, as solutions in DMSO-d6. Chemical
shifts (δ) are in ppm and referenced to the residual protic solvent. FT-IR spectra
were recorded on Shimadzu FT-IR 8401 spectrometer using KBr disc, and are
expressed in wavenumbers (cm-1). The mass spectra (ESI-MS) were recorded on
Shimadzu LCMS-2010 spectrometer.
For 4n & 4q compounds of the series, the representative spectra are
included at the end of the section for perusal. 1H NMR spectrum for 4n & 4q are
given in Figure 4.1 & Figure 4.6 respectively, 13C NMR spectrum are given Figure
4.2 & Figure 4.7. APT spectrum of 4n & 4q are given in Figure 4.3 & Figure 4.8
respectively. The infrared spectrum is shown in Figure 4.4 for 4n and Figure 4.9
for 4q. The mass spectrum obtained for the same compounds are given in Figure
4.5 & Figure 4.10 respectively. The molecular structures and characterization of
all the synthesized quinoxalines are given below.

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4a. 2, 3-diphenylquinoxaline
Molecular Formula C20H14N2
Molecular Weight (g· mol-1) 282.12
Melting Point (°C) 126
1H NMR (400 MHz, DMSO, δ ppm): 7.85-7.60 (m, 4H, Ar-H), 7.60- 7.45 (m, 10H,
Ar-H)
13C NMR (100 MHz, DMSO, δ ppm): 155.2, 142.4, 138.4, 129.8, 129.6, 129.4, 127.8
DEPT-135: Up peaks: 155.2, 142.4, 138.4
Down peaks: 129.8, 129.6, 129.4, 127.8
IR (KBr): 1608,1467, 1335, 1242, 1185, 1065, 980, 818, 726, 612 cm-1
LC-MS: 322.1
% C, H, N Analysis: Calculated: C, 85.05; H, 5.00; N, 9.9
Observed: C, 85.10; H, 5.06; N, 9.98

4b. 2,3-dip-tolylquinoxaline
Molecular Formula C22H18N2
Molecular Weight (g· mol-1) 310.15
Melting Point (°C) 147
1H NMR (400 MHz, DMSO, δ ppm): 7.85-7.60 (m, 4H, Ar-H), 7.60- 7.20 (m, 8H, Ar-
H), 2.35 (s, 6H)
13C NMR (100 MHz, DMSO, δ ppm): 155.2, 142.4, 135.4, 131.4, 129.9, 129.8, 129.6,
21.4
DEPT-135: Up peaks: 155.2, 142.4, 135.4, 131.4
Down peaks: 129.9, 129.8, 129.6, 21.4
IR (KBr): 1608,1464, 1335, 1244, 1180, 1069, 980, 819, 725, 603 cm-1
LC-MS: 311.2
% C, H, N Analysis: Calculated: C, 85.13; H, 5.85; N, 9.03
Observed: C, 85.16; H, 5.91; N, 9.08

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4c. dibenzo[a,c]phenazine
Molecular Formula C20H12N2
Molecular Weight (g· mol-1) 280.32
Melting Point (°C) 225
1H NMR (400 MHz, DMSO, δ ppm): 9.10- 7.88 (m, 8H, Ar-H), 7.85-7.60 (m, 4H, Ar-H)

13C NMR (100 MHz, DMSO, δ ppm): 142.4, 129.8, 129.2, 127.6, 126.8, 125.6, 122.6
DEPT-135: Up peaks: 142.4, 129.8, 127.6
Down peaks: 129.2, 126.8, 125.6, 122.6
IR (KBr): 1608,1467, 1336, 1242, 1181, 1065, 980, 817, 725, 605 cm-1
LC-MS: 281.3
% C, H, N Analysis: Calculated: C, 85.69; H, 4.31; N, 9.99
Observed: C, 85.72; H, 4.36; N, 10.03

4d. 2,3-di(furan-2-yl)quinoxaline
Molecular Formula C16H10O2N2
Molecular Weight (g· mol-1) 262.26
Melting Point (°C) 132
1H NMR (400 MHz, DMSO, δ ppm): 7.85-7.60 (m, 4H, Ar-H), 7.60- 6.90 (m, 6H, Ar-H)

13C NMR (100 MHz, DMSO, δ ppm): 157.9, 144.6, 142.6, 142.4, 129.8, 129.5, 112.4,
107.5
DEPT-135: Up peaks: 157.9, 144.6, 142.4
Down peaks: 142.6, 129.8, 129.5, 112.4, 107.5
IR (KBr): 1606,1467, 1332, 1240, 1180, 1065, 981, 817, 728, 609 cm-1
LC-MS: 263.3
% C, H, N Analysis: Calculated: C, 73.27; H, 3.84; N, 10.68
Observed: C, 73.32; H, 3.89; N, 10.71

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4e. 2,3-di(thiophen-2-yl)quinoxaline
Molecular Formula C16H10N2S2
Molecular Weight (g· mol-1) 294.39
Melting Point (°C) 140
1H NMR (400 MHz, DMSO, δ ppm): 7.85-7.60 (m, 4H, Ar-H), 7.62- 6.90 (m, 6H, Ar-H)

13C NMR (100 MHz, DMSO, δ ppm): 145.2, 139.8, 139.5, 129.4, 128.4, 128.1, 127.8
DEPT-135: Up peaks: 145.2, 139.8, 139.5
Down peaks: 129.4, 128.4, 128.1, 127.8
IR (KBr): 1600,1467, 1335, 1248, 1188, 1065, 985, 818, 725, 602 cm-1
LC-MS: 295.4
% C, H, N Analysis: Calculated: C, 65.28; H, 3.42; N, 9.52
Observed: C, 65.33; H, 3.49; N, 9.57

4f. 6-methyl-2,3-diphenylquinoxaline
Molecular Formula C21H16N2
Molecular Weight (g· mol-1) 296.37
Melting Point (°C) 116

1H NMR (400 MHz, DMSO, δ ppm): 8.10-7.50 (m, 3H, Ar-H), 7.50- 7.40 (m, 10H,
Ar-H), 2.35 (s, 3H)
13C NMR (100 MHz, DMSO, δ ppm): 155.4, 154.2, 142.4, 140.6, 138.9, 138.6, 134.6,
129.0, 128.9, 127.6, 127.2, 21.4
DEPT-135: Up peaks: 155.4, 154.2, 142.4, 140.6, 138.9, 138.6
Down peaks: 134.6, 129.0, 128.9, 127.6, 127.2, 21.4
IR (KBr): 1608,1467, 1339, 1242, 1180, 1065, 980, 818, 720, 606 cm-1
LC-MS: 297.4
% C, H, N Analysis: Calculated: C, 85.11; H, 5.44; N, 9.45
Observed: C, 85.15; H, 5.48; N, 9.49

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4g. 6-methyl-2,3-dip-tolylquinoxaline
Molecular Formula C23H20N2
Molecular Weight (g· mol-1) 324.42
Melting Point (°C) 137
1H NMR (400 MHz, DMSO, δ ppm): 8.10-7.50 (m, 3H, Ar-H), 7.52- 7.28 (m, 8H, Ar-
H), 2.35 (s, 9H)
13C NMR (100 MHz, DMSO, δ ppm): 155.4, 154.2, 142.2, 140.4, 138.8, 135.4, 134.6,
131.9, 129.6, 128.6, 127.8, 125.9, 21.4
DEPT-135: Up peaks: 155.4, 154.2, 142.2, 140.4, 138.8, 135.4, 134.6, 131.9
Down peaks: 129.6, 128.6, 127.8, 125.9, 21.4
IR (KBr): 1602,1465, 1332, 1242, 1180, 1062, 970, 818, 735, 612 cm-1
LC-MS: 325.4
% C, H, N Analysis: Calculated: C, 85.15; H, 6.21; N, 8.63
Observed: C, 85.19; H, 6.26; N, 8.68

4h. 11-methyldibenzo[a,c]phenazine
Molecular Formula C21H14N2
Molecular Weight (g· mol-1) 294.35
Melting Point (°C) 209
1H NMR (400 MHz, DMSO, δ ppm): 8.95-8.10 (m, 8H, Ar-H), 8.10-7.50 (m, 3H, Ar-
H), 2.35 (s, 3H)
13C NMR (100 MHz, DMSO, δ ppm): 142.3, 140.1, 138.8, 138.9, 134.6, 129.8, 128.6,
127.9, 127.8, 127.6, 126.8, 126.4, 125.9, 122.6, 21.4
DEPT-135: Up peaks: 142.3, 140.1, 138.8, 129.8, 127.6, 126.8
Down peaks: 138.9, 134.6, 128.6, 127.9, 127.8, 126.4, 125.9, 122.6, 21.4
IR (KBr): 1604,1462, 1332, 1240, 1179, 1061, 980, 818, 725, 610 cm-1
LC-MS: 295.4
% C, H, N Analysis: Calculated: C, 85.69; H, 4.79; N, 9.52
Observed: C, 85.73; H, 4.84; N, 9.58

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4i. 2,3-di(furan-2-yl)-6-methylquinoxaline
Molecular Formula C17H12N2O2
Molecular Weight (g· mol-1) 276.29
Melting Point (°C) 118
1H NMR (400 MHz, DMSO, δ ppm): 8.10-7.50 (m, 3H, Ar-H), 7.50- 6.90 (m, 6H, Ar-
H), 2.35 (s, 3H)
13C NMR (100 MHz, DMSO, δ ppm): 157.8, 144.3, 143.5, 142.8, 142.2, 140.4, 138.9,
134.8, 128.4, 127.8, 112.4, 107.2, 21.4
DEPT-135: Up peaks: 157.8, 144.3, 143.5, 142.2, 140.4, 138.9
Down peaks: 142.8, 134.8, 128.4, 127.8, 112.4, 107.2, 21.4
IR (KBr): 1610,1462, 1337, 1242, 1184, 1065, 984, 818, 726, 603 cm-1
LC-MS: 277.3
% C, H, N Analysis: Calculated: C, 73.90; H, 4.38; N, 10.14
Observed: C, 73.96; H, 4.44; N, 10.19

4j. 6-methyl-2,3-di(thiophen-2-yl)quinoxaline
Molecular Formula C17H12N2S2
Molecular Weight (g· mol-1) 308.42
Melting Point (°C) 110
1H NMR (400 MHz, DMSO, δ ppm): 8.10-7.50 (m, 3H, Ar-H), 7.50- 7.10 (m, 6H, Ar-
H), 2.35 (s, 3H)
13C NMR (100 MHz, DMSO, δ ppm): 144.7, 144.3, 142.2, 140.4, 140.8, 138.9, 134.6,
128.8, 128.6, 128.2, 128.1, 127.4, 21.4
DEPT-135: Up peaks: 144.7, 144.3, 142.2, 140.4, 140.8, 138.9
Down peaks: 134.6, 128.8, 128.6, 128.2, 128.1, 127.4, 21.4
IR (KBr): 1609,1467, 1338, 1242, 1180, 1055, 981, 817, 722, 605 cm-1
LC-MS: 309.4
% C, H, N Analysis: Calculated: C, 66.20; H, 3.92; N, 9.08
Observed: C, 66.28; H, 3.98; N, 9.13

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4k. 6-nitro-2,3-diphenylquinoxaline
Molecular Formula C20H13N3O2
Molecular Weight (g· mol-1) 327.34
Melting Point (°C) 192
1H NMR (400 MHz, DMSO, δ ppm): 9.10-7.90 (m, 3H, Ar-H), 7.60- 7.35 (m, 10H,
Ar-H)
13C NMR (100 MHz, DMSO, δ ppm): 159.2, 157.4, 144.8, 141.4, 138.4, 129.4, 128.9,
128.4, 127.6, 123.6, 122.8
DEPT-135: Up peaks: 159.2, 157.4, 144.8, 141.4, 138.4
Down peaks: 129.4, 128.9, 128.4, 127.6, 123.6, 122.8
IR (KBr): 1608,1467, 1338, 1242, 1180, 1065, 980, 816, 729, 612 cm-1
LC-MS: 328.4
% C, H, N Analysis: Calculated: C, 73.38; H, 4.00; N, 12.84
Observed: C, 73.38; H, 4.00; N, 12.84

4l. 6-nitro-2,3-dip-tolylquinoxaline
Molecular Formula C22H17N3O2
Molecular Weight (g· mol-1) 355.39
Melting Point (°C) 168
1H NMR (400 MHz, DMSO, δ ppm): 9.10-7.90 (m, 3H, Ar-H), 7.70- 7.25 (m, 8H, Ar-
H), 2.35 (s, 6H)
13C NMR (100 MHz, DMSO, δ ppm): 159.2, 157.4, 144.8, 141.3, 135.4, 131.9, 129.6,
128.4, 125.8, 123.6, 21.4
DEPT-135: Up peaks: 159.2, 157.4, 144.8, 141.3, 135.4, 131.9
Down peaks: 129.6, 128.4, 125.8, 123.6, 21.4
IR (KBr): 1610,1467, 1338, 1244, 1185, 1065, 987, 821, 730, 607 cm-1
LC-MS: 356.4
% C, H, N Analysis: Calculated: C, 74.35; H, 4.82; N, 11.82
Observed: C, 74.38; H, 4.86; N, 11.88

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4m. 11-nitrodibenzo[a,c]phenazine
Molecular Formula C20H11N3O2
Molecular Weight (g· mol-1) 325.32
Melting Point (°C) 245
1H NMR (400 MHz, DMSO, δ ppm): 9.10-7.90 (m, 3H, Ar-H), 9.0- 7.80 (m, 8H, Ar-H)

13C NMR (100 MHz, DMSO, δ ppm): 144.8, 141.4, 129.8, 128.4, 127.8, 126.8, 125.8,
123.6, 122.8, 122.6
DEPT-135: Up peaks: 144.8, 141.4, 129.8, 127.8, 126.8
Down peaks: 128.4, 125.8, 123.6, 122.8, 122.6
IR (KBr): 1604,1464, 1336, 1244, 1184, 1070, 980, 819, 730, 603 cm-1
LC-MS: 326.3
% C, H, N Analysis: Calculated: C, 73.84; H, 3.41; N, 12.92
Observed: C, 73.88; H, 3.45; N, 12.97

4n. 2,3-di(furan-2-yl)-6-nitroquinoxaline
Molecular Formula C16H9N3O4
Molecular Weight (g· mol-1) 307.26
Melting Point (°C) 165
1H NMR (400 MHz, DMSO, δ ppm): 8.77 – 8.20 (m, 3H, Ar-H), 7.98- 6.75 (m, 6H,
Ar-H)
13C NMR (100 MHz, DMSO, δ ppm): 150.1, 150.0, 148.0, 146.7, 146.2, 146.0, 144.5,
144.0, 142.8, 138.9, 130.8, 130.7, 124.9, 124.2, 113.0, 112.8
DEPT-135: Up peaks: 150.1, 150.0, 148.0, 146.7, 142.8
Down peaks: 146.2, 146.0, 144.5, 144.0, 138.9, 130.8, 130.7,
124.9, 124.2, 113.0, 112.8
IR (KBr): 1566,1520, 1474, 1342, 1011, 910, 887 cm-1
LC-MS: 308.1
% C, H, N Analysis: Calculated: C, 62.54; H, 2.95; N, 13.68
Observed: C, 62.63; H, 2.35; N, 20.94

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4o. 6-nitro-2,3-di(thiophen-2-yl)quinoxaline
Molecular Formula C16H9N3S2O2
Molecular Weight (g· mol-1) 339.39
Melting Point (°C) 220
1H NMR (400 MHz, DMSO, δ ppm): 9.90- 7.90 (m, 3H, Ar-H), 7.70- 7.50 (m, 6H, Ar-H)

13C NMR (100 MHz, DMSO, δ ppm): 149.2, 147.6, 144.8, 141.4, 140.1, 128.5, 128.4,
128.0, 127.8, 123.6, 122.8
DEPT-135: Up peaks: 149.2, 147.6, 144.8, 141.4, 140.1
Down peaks: 128.5, 128.4, 128.0, 127.8, 123.6, 122.8
IR (KBr): 1608,1462, 1335, 1242, 1183, 1064, 980, 819, 726, 600 cm-1
LC-MS: 340.4
% C, H, N Analysis: Calculated: C, 56.62; H, 2.67; N, 12.38
Observed: C, 56.68; H, 2.71; N, 12.44

4p. 6-chloro-2,3-diphenylquinoxaline
Molecular Formula C20H13ClN2
Molecular Weight (g· mol-1) 316.78
Melting Point (°C) 115
1H NMR (400 MHz, DMSO, δ ppm): 7.15- 7.11 (m, 3H, Ar-H), 7.50-7.40 (m, 10H,
Ar-H)
13C NMR (100 MHz, DMSO, δ ppm): 156.4, 155.4, 144.2, 142.4, 140.4, 138.4, 131.8,
130.9, 129.1, 128.9, 128.4, 127.6
DEPT-135: Up peaks: 156.4, 155.4, 144.2, 142.4, 140.4, 138.4
Down peaks: 131.8, 130.9, 129.1, 128.9, 128.4, 127.6
IR (KBr): 1568,1522, 1476, 1348, 1011, 910, 888, 625 cm-1
LC-MS: 317.8
% C, H, N Analysis: Calculated: C, 75.83; H, 4.14; N, 11.19
Observed: C, 75.86; H, 4.19; N, 11.24

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4q. 6-chloro-2, 3-dip-tolylquinoxaline

Molecular Formula C22H17ClN2
Molecular Weight (g· mol-1) 344.11
Melting Point (°C) 170
1H NMR (400 MHz, DMSO, δ ppm): 8.19- 7.85 (m, 3H, Ar-H), 7.37 (m, 4H, Ar-H),
7.17 (m, 4H, Ar-H), 2.30 (s, 6H);
13C NMR (100 MHz, DMSO, δ ppm): 154.4, 153.8, 141.1, 139.5, 139.1, 139.0, 136.1,
136.1, 134.8, 131.2, 131.1, 130.1, 129.6, 129.4, 129.2, 129.1, 128.9, 127.9, 127.8

DEPT-135: Up peaks: 154.4, 153.8, 141.1, 139.5, 139.1, 139.0, 136.1, 136.1, 134.8
Down peaks: 131.2, 131.1, 130.1, 129.6, 129.4, 129.2, 129.1, 128.9,
127.9, 127.8

IR (KBr): 1605,1466, 1335, 1242, 1180, 1065, 980, 818, 725, 602 cm-1
LC-MS: 345.2
% C, H, N Analysis: Calculated: C, 76.63; H, 4.97; N, 8.12
Observed: C, 76.93; H, 5.31; N, 8.25

4r. 11-chlorodibenzo[a,c]phenazine
Molecular Formula C20H11ClN2
Molecular Weight (g· mol-1) 314.77
Melting Point (°C) 225
1H NMR (400 MHz, DMSO, δ ppm): 7.15- 7.11 (m, 3H, Ar-H), 8.20-7.80 (m, 8H, Ar-H)

13C NMR (100 MHz, DMSO, δ ppm): 142.4, 144.2, 140.4, 131.8, 130.7, 129.8, 128.1,
127.7, 126.8, 126.6, 125.9, 122.5
DEPT-135: Up peaks: 142.4, 144.2, 140.4, 129.8, 127.7, 126.8, 126.6, 122.5
Down peaks: 131.8, 130.7, 128.1, 125.9
IR (KBr): 1569,1520, 1479, 1346, 1015, 910, 889, 610 cm-1
LC-MS: 315.8
% C, H, N Analysis: Calculated: C, 76.31; H, 3.52; N, 8.90
Observed: C, 76.37; H, 3.58; N, 8.95

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4s. 6-chloro-2,3-di(furan-2-yl)quinoxaline
Molecular Formula C16H9ClN2O2
Molecular Weight (g· mol-1) 296.71
Melting Point (°C) 133
1H NMR (400 MHz, DMSO, δ ppm): 7.15- 7.11 (m, 3H, Ar-H), 7.60- 6.90 (m, 6H, Ar-H)

13C NMR (100 MHz, DMSO, δ ppm): 167.2, 157.8, 145.6, 144.7, 142.7, 142.5, 141.6,
140.4, 131.9, 130.9, 128.4, 112.3
DEPT-135: Up peaks: 157.8, 145.6, 144.7, 142.5, 141.6, 140.4
Down peaks: 167.2, 142.7, 131.9, 130.9, 128.4, 112.3
IR (KBr): 1568,1522, 1474, 1345, 1019, 910, 805, 602 cm-1
LC-MS: 297.7
% C, H, N Analysis: Calculated: C, 64.77; H, 3.06; N, 9.44
Observed: C, 64.79; H, 3.10; N, 9.49

4t. 6-chloro-2,3-di(thiophen-2-yl)quinoxaline
Molecular Formula C16H9ClN2S2
Molecular Weight (g· mol-1) 328.84
Melting Point (°C) 190
1H NMR (400 MHz, DMSO, δ ppm): 7.15- 7.11 (m, 3H, Ar-H), 7.50- 7.70 (m, 6H, Ar-H)

13C NMR (100 MHz, DMSO, δ ppm): 146.7, 145.4, 142.5, 141.5, 140.6, 139.8, 130.4,
131.8, 128.4, 128.3, 128.2, 127.4
DEPT-135: Up peaks: 146.7, 145.4, 142.5, 141.5, 140.6, 139.8, 130.4
Down peaks: 131.8, 128.4, 128.3, 128.2, 127.4
IR (KBr): 1567,1522, 1476, 1348, 1018, 910, 887, 610 cm-1
LC-MS: 329.8
% C, H, N Analysis: Calculated: C, 58.44; H, 2.76; N, 8.52
Observed: C, 58.48; H, 2.78; N, 8.58

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Figure 4.1 1H NMR spectrum of 4n 2, 3-di(furan-2-yl)-6-nitroquinoxaline

Figure 4.2 13C NMR spectrum of 4n 2, 3-di(furan-2-yl)-6-nitroquinoxaline

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Figure 4.3 13C NMR spectrum of 4n 2, 3-di(furan-2-yl)-6-nitroquinoxaline

Figure 4.4 IR spectrum of 4n 2, 3-di(furan-2-yl)-6-nitroquinoxaline

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 Synthesis & characterization of quinoxalines Chapter-4

Figure 4.5 Mass spectrum of 4n 2, 3-di(furan-2-yl)-6-nitroquinoxaline

Figure 4.6 1H NMR spectrum of 4q 6-chloro-2, 3-dip-tolylquinoxaline

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Figure 4.7 13C NMR spectrum of 4q 6-chloro-2, 3-dip-tolylquinoxaline

Figure 4.8 APT spectrum of 4q 6-chloro-2, 3-dip-tolylquinoxaline

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Figure 4.9 IR spectrum of 4q 6-chloro-2, 3-dip-tolylquinoxaline

Figure 4.10 Mass spectrum of 4q 6-chloro-2, 3-dip-tolylquinoxaline

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