Green and catalyst-free synthesis of aminoanthraquinone derivatives in solvent-free conditions

Article abstract of DOI:10.1007/s11164-021-04485-9

In this study, new derivatives of aminoanthraquinone have been synthesized via one-pot three-component condensation reaction of 1- and 2-amino anthraquinones, triethyl orthoformate and CH-acid compounds without using any solvent or catalyst in mild temper

Full text of DOI:10.1007/s11164-021-04485-9

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-021-04485-9
Green and catalyst‑free synthesis of aminoanthraquinone
derivatives in solvent‑free conditions
Arezoo Sardashti‑Birjandi1 · Ebrahim Mollashahi1 ·
Malek Taher Maghsoodlou1 · Afshin Yazdani‑Elah‑Abadi2
Received: 27 December 2020 / Accepted: 7 May 2021
© The Author(s), under exclusive licence to Springer Nature B.V. 2021
Abstract
In this study, new derivatives of aminoanthraquinone have been synthesized via one-
pot three-component condensation reaction of 1- and 2-amino anthraquinones, tri-
ethyl orthoformate and CH-acid compounds without using any solvent or catalyst
in mild temperature (50 °C). This simple and efcient method yields the desired
products in short reaction time (14–50 min) and good to excellent yields (85–96%).
Moreover, chemical structures of synthesized products have been entirely confrmed
by FT-IR, 1H and 13CNMR and mass spectroscopy and melting points.
Keywords Multicomponent reactions · Anthraquinone · Catalyst-free · Triethyl
orthoformate
Introduction
Environmental pollution is one of the most severe problems that afects human
health worldwide by contaminating air, soil and water. Water is the most essential
resource in the world, as the existence of life is not possible without it. Water qual-
ity is an essential factor for human beings, plants, animals, and all living organisms.
Nowadays, the increase in using organic pollutants in various industries causes
harmful efects to humans and ecological systems at a fast-growing rate. The waste-
water from industries is directly released into the water, thus contaminating the
entire fresh water resources. Hence, water pollution has attracted the attention of
various researchers and scientists around the world and several solutions have been
ofered. One of the solution ways of this problem is to use a clean process or the
laws of green chemistry [1–9].
*
Ebrahim Mollashahi
mollashahi39@chem.usb.ac.ir
1
2
Department of Chemistry, Faculty of Science, University of Sistan and Baluchestan,
P.O. Box: 98135-674 Zahedan, Iran
Young Researchers and Elite Club, Yazd Branch, Islamic Azad University, Yazd, Iran
Vol.:(0123456789)
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A. Sardashti-Birjandi et al.
Green chemistry is one of the most important branches of chemistry which
deals with sustainable and environmentally friendly materials to achieve better
human life. This new emerging feld has attracted vast interest these days due to
the decrease and removal of hazardous materials and introduces sustainable and
useful processes. It is also defned as the careful and accurate planning for molec-
ular design and organic synthesis to eliminate adverse consequences and improve
human health and the environment [10–12]. Green Chemistry has a framework of
a cohesive set of twelve principles which the use of green conditions is the most
important one [13–15]. Solvents and catalysts undoubtedly are the main part of
green chemistry, because many of them are fammable, toxic and corrosive and
the use of solvents and catalysts in organic reactions and after the reaction, their
separation procedures are a huge challenge [16–19]. Certainly, the catalyst- and
solvent-free conditions are the safe and useful conditions that are in accordance
with principles of green chemistry [20–24]. Thus, it is of supreme importance to
employ these conditions in organic synthesis [25–29].
Nowadays, multicomponent reactions (MCRs) have received considerable
attention in modern organic chemistry because they combine three or more com-
pounds in a single step to produce a high yield of product, without formation
any intermediate or separation procedure [27, 30–34]. Recently, this strategy for
drug discovery using the synthesis of biologically active compounds has attracted
widespread attention in organic and pharmaceutical chemistry research [35]. It
has been generally employed due to its high yields and reduced reaction time
compared to conventional multistage reactions [36–39].
Anthraquinones derivatives are polycyclic compounds containing two carbonyl
groups in the central ring based on the 9, 10-anthraquinonoid framework [40].
Natural and synthetic anthraquinones are widely used in industry and medicine
[41–43]. The importance of studies on anthraquinones in the industry is due to
their diferent applications in many felds, especially in the feld of colors, and it
has attracted the attention of the paint industry in the felds of food [44], indus-
trial dyes [45], clothing [46] and cosmetics [47]. On the other hand, anthraqui-
nones and their derivatives have received a great deal of attention for specifc
therapeutic uses such as antimicrobial [48], antibacterial [49], antiviral [50],
antioxidant [51], anticancer [52], and antidiabetes activities [53]. For example,
anthraquinones derivatives such as idarubicin, mitoxantrone and pixantrone are
the members of this class of compounds that are approved by the Food and Drug
Administration (USA), for clinical uses (Fig. 1) [42].
Due to the widespread applications of anthraquinone derivatives in industry
and their unique biological activity and therapeutic efects. Our research group
has been excited to study and synthesis of this fantastic class of organic com-
pounds [54–56]. In our previous research, anthraquinone-scafold based-enami-
nodiones (2, 2-diacylethenamines) compounds have been synthesized via one-pot
three-component reaction of amino anthraquinones, triethyl orthoformate and 1,
3-dicarbonyl compounds at room temperature and the presence of acetic acid as
an acidic catalyst [56]. In this study, a new and green method has been developed
to synthesize anthraquinone derivatives via three-component reaction of 1- and
1 3

Green and catalyst-free synthesis of aminoanthraquinone…
Fig. 1 Clinically approved anthraquinone derivatives
2-amino anthraquinones, triethyl orthoformate and CH-acid compounds in cata-
lyst- and solvent-free conditions (Scheme 1).
1HNMR and 13CNMR spectroscopy, mass, IR spectra, and the melting point have
been exploited to determine the chemical structures of new compounds.
Results and discussion
The reaction of 1-amino anthraquinone, triethyl orthoformate and barbituric acid has
been selected as a model reaction (Table 1). Then, to fnd the best solvent, the efects
of diferent polar and nonpolar solvents such as H2O, ethanol, acetone, diethyl ether,
methanol and solvent-free condition (entries 1–10) have been examined for the syn-
thesis of anthraquinone derivative 5a. Interestingly, the yield of the model reaction
was not satisfying in the presence of diferent solvents, while, in solvent-free condi-
tion, only after 16 min, the yield of the reaction was 96% (entry 9). Thus, the best
condition was selected solvent-free condition. After obtaining the optimized condi-
tion, the synthesis of anthraquinone derivative 5a was investigated at diferent tem-
peratures (entries 8–10). The best temperature was 50 °C, and with increasing the
Scheme 1 Synthesis of anthraquinone derivatives in catalyst- and solvent-free conditions
1 3

A. Sardashti-Birjandi et al.
Table 1 Optimization of the reaction condition for the synthesis of 5aa
Entry
Solvent
Temperature (oC)
Time (min)
Yield (%)b
1
2
3
4
5
6
7
8
9
Lactic acid
H2O
Ethanol
Methanol
Acetone
Diethyl ether
Ethanol
Solvent-free
Solvent-free
Solvent-free
RT
RT
RT
RT
RT
RT
Refux
RT
50
180
180
180
180
180
180
180
180
16
–
–
63
60
42
38
77
61
96
96
10
100
20
aMixture of 1-amino anthraquinone (1.0 mmol), triethyl orthoformate (1.0 mmol) and barbituric acid
(1.0 mmol) in the presence of diferent solvents and temperatures
bIsolated Yield
temperature above this temperature, the yield of the reaction was unchanged (entry
10). Therefore, the highest amount of compound 5a was obtained in solvent-free
condition at 50 °C after only 16 min running the reaction (entry 9).
More importantly, the scope and generality of the method have been studied for
the synthesis of a wide variety of amino anthraquinone derivatives through one-
pot three-component condensation reaction of 1- and 2-amino anthraquinone, tri-
ethyl orthoformate and various CH acids like barbituric acid, malononitirile, dime-
done, meldrum’s acid, 1, 3-dimethyl barbituric acid, methyl acetoacetate and ethyl
cyanoacetate (Table 2). It is worth mentioning that the barbituric acid had the most
active CH acid and it reacted better with amino anthraquinone and triethyl ortho-
formate and the highest amount of yield (96%) was obtained (entry 1). Taking into
account other CH-acid compounds, malononitrile was better compared to meldrum’s
acid with a 95% yield of product (entries 2 and 6). The lowest amount of product
was achieved with the use of meldrum’s acid as a CH-acid compound (85%) (entry
6). These observations showed that the most and least active CH-acid compounds
were barbituric acid and meldrum’s acid, respectively, for this method. The new
products have been identifed by FT-IR, 1H and 13CNMR and mass spectroscopy.
1 3

Green and catalyst-free synthesis of aminoanthraquinone…
Table 2 Synthesis of amino anthraquinone derivatives in solvent-free conditionsa
Entry CH acid
Product
Time (min) Yield (%)b Melting point (oC)
Found/reported [ref]
1
16
23
96
95
>360/this study
5a
2
320–322/this study
5b
3
4
25
24
90
93
250–252/this study
266–268/this study
5c
5d
5
50
90
258–260/257–259 [56]
5e
5f
6
7
14
14
85
94
256–258/256–257 [56]
>360/>330 [56]
5g
8
9
3293
35
310–312/this study
222–223/this study
6b
91
6c
1 3

A. Sardashti-Birjandi et al.
Table 2 (continued)
Entry CH acid
Product
Time (min) Yield (%)b Melting point (oC)
Found/reported [ref]
10
33
93
263–267/this study
6d
11
12
13
44
50
14
88
85
90
259–262/258–260 [56]
249–252/258–259 [56]
338–340/>330 [56]
6e
6f
6g
aMixture of amino anthraquinone (1.0 mmol), triethyl orthoformate (1.0 mmol) and CH-acid compounds
(1.0 mmol) in solvent-free condition at 50 °C temperatures
To better understanding product synthesis, the proposed mechanism was illus-
trated in Scheme 2. In the frst step, the CH-acid compound (A) attacks the triethyl
orthoformate (B) and then removes two molecules of EtOH, and the intermediate
(C) was formed consequently. Then, from the rapid Knoevenagel condensation reac-
tion of aminoanthraquinone (D) with the previous intermediate, the target anthraqui-
none-based enamino-dicarbonyl compound (E) was obtained.
The last experiment in this research was the comparison of our method with other
previously published approaches. After literature survey, only two published arti-
cles observed for the synthesis of amino anthraquinone derivatives. As shown in
Table 3, our method has some worthwhile advantages over previous approaches. For
Scheme 2 Proposed mechanism for the synthesis of amino anthraquinone derivatives
1 3

Green and catalyst-free synthesis of aminoanthraquinone…
Table 3 The comparison of our method with other approaches for the synthesis of product 5 g
Entry
Product
Conditions
Temp. ( °C)
Time (h)
Yield (%)a
Reference
[56]
1
Acetic acid
r.t
24
93
2
3
Formic acid
Solvent-free
refux
50
30
94
94
[57]
This work
14b
aIsolated yields
bMinutes
example, we synthesized amino anthraquinone derivatives in milder reaction condi-
tions without using any acidic or basic catalysts and also solvents. More importantly,
the product 5 g has been prepared after only 14 min. running the reaction, while in
previous methods, the synthesis of product 5 g was carried out in longer reaction
times (24 and 30 h) (Table 3, entries 1 and 2).
Experimental section
Materials and instruments
Melting points were analyzed on an Electrothermal type 9100 melting point appa-
ratus. The FT-IR spectra were performed on an Avatar 370 FT-IR Thermo-Nicolet
spectrometer. Proton and Carbon NMR spectra were obtained with a Bruker DRX-
300 Avance spectrometer at 300 MHz. All materials were purchased from Sigma-
Aldrich and Merck companies.
General procedure for the synthesis of aminoanthraquinone derivatives
A mixture of 1- or 2-amino anthraquinone (1.0 mmol), triethyl orthoformate
(1.0 mmol) and CH-acid compounds (1.0 mmol) was stirred in an oil bath at 50 °C
for the time mentioned in Table 2. After fnalizing the reaction (monitored by TLC
(n-hexane: ethyl acetate 1:1), the obtained solid products were collected to give
desired products. The structures of the synthesized products described by their phys-
ical and spectral data (1H NMR, 13C NMR, and FT-IR spectra and mass).
5‑(((9,10‑Dioxo‑9,10‑dihydroanthracen‑1‑yl)amino)methylene)
pyrimidine‑2,4,6(1H,3H,5H)‑trione (5a)
Yield: 96%; in the form of yellow solid; mp>360 °C; FT-IR (cm−1) 3171, 3030,
2992, 2833, 1734, 1689, 1653, 1592, 1561, 1498, 1445, 1426, 1361, 1302,
1260, 1163, 1048, 1000, 859, 803, 781, 733, 705, 608, 524, 511, 492, 448, 408;
1 3

A. Sardashti-Birjandi et al.
1H NMR (300 MHz, DMSO-d6): 7.92–7.97 (m, 3H, 3CH arom), 8.07 (d, J=6.9,
1H, CH arom), 8.19 (d, J=9, 1H, CH arom), 8.23–8.28 (m, 2H, 2CH arom), 8.75
(d, J=13.5, 1H, CHNH), 11.01–11.10 (2S, 2H, 2 CONHCO), 14.11 (d, J=13.5,
CHNH); 13C NMR (300 MHz, DMSO-d6): 96.02, 119.94, 122.99, 124.19, 126.95,
127.41, 132.72, 134.17, 134.76, 135.08, 135.27, 136.13, 140.73, 150.34 (CHNH),
151.18 (HNCONH), 164.05 (CCONH), 165.32 (CCONH), 182.45, 185.28; Mass
(MALDI-TOF) m/z calcd for C19H11N3O5 [M]þ 361.07 found: 361.2.
2‑(((9,10‑Dioxo‑9,10‑dihydroanthracen‑1‑yl)amino)methylene)malononitrile (5b)
Yield: 95%; in the form of warm red solid; mp 320–322 °C; FT-IR (cm−1) 3067,
2229, 1670, 1650, 1614, 1584, 1572, 1494, 1400, 1364, 1341, 1261, 1232, 1162,
1
1076, 1001, 969, 887, 827, 793, 728, 700, 625, 610, 587, 555, 425; H NMR
(300 MHz,DMSO-d6): 7.95–8.05 (m, 4H, 4CH arom), 8.20–8.30 (m, 4H, 4CH
arom), 9.19 (d, J=9.9, 1H, CHNH), 12.87 (d, J=9.6, 1H, CHNH); 13C NMR
(300 MHz, DMSO-d6) 57.82, 113,42, 115,26 (CN), 118.27 (CN), 122.31, 123.78,
127.13, 127.68, 132.81, 133.87, 134.50, 135.43, 135.59, 136.47, 140.87, 156.31
(CHNH), 182.26, 187.26; Mass (MALDI-TOF) m/z calcd for C18H9N3O2 [M]þ
299.07 found: 299.1.
Methyl (E)‑2‑(((9,10‑dioxo‑9,10‑dihydroanthracen‑1‑yl)amino)methylene)‑3
oxobutanoate (5c)
Yield: 90%; in the form of dark orange solid; mp: 250–252 °C; FT-IR (cm−1) 3154,
3088, 3013, 2956, 1703, 1664, 1642, 1574, 1558, 1475, 1434, 1397, 1339, 1307,
1250, 1195, 1164, 1139, 1085, 1062, 1003, 968, 881, 832, 806, 730, 706, 659, 618,
1
571, 545, 496, 415; H NMR (300 MHz, DMSO-d6): 2.22 (s, 3H, CH3), 3.776 (s,
3H, CH3), 7.93–8.02 (m, 4H, 4CH arom), 8.16–8.24 (m, 3H, 3CH arom),8.67 (d,
J=12.9, 1H, CHNH), 14.34 (d, J=12.6, 1H,CHNH); 13C NMR (300 MHz, CDCl3)
31.478, 51.69, 120.65, 123.74, 127.06, 128.02, 134.38, 134.71, 135.29, 141.83,
148.79(CHNH), 167.41(CCOOCH3), 199.28 (H3CCOC); Mass (MALDI-TOF) m/z
calcd for C20H15NO5 [M]þ 349.1 found: 349.
Ethyl (E)‑2‑cyano‑3‑((9,10‑dioxo‑9,10‑dihydroanthracen‑1‑yl)amino)acrylate (5d)
Yield: 93%; in the form of yellow solid; mp: 266–268 °C; FT-IR (cm−1) 3076, 2980,
2905, 2218, 1707, 1673, 1613, 1573, 1381, 1339, 1268, 1230, 1184, 1165, 1112,
1
1028, 999, 971, 887, 829, 797, 728, 702, 656, 608, 537, 502, 423, 406; H NMR
(300 MHz, DMSO-d6): 1.34 (t, 3H, CH3), 4.33 (q, 2H, CH2), 7.83–7.94 (m, 4H,
4CH arom), 8.11–8.23 (m, 3H, 3CH arom) 8.708 (d, J=8.1, 1H, CHNH), 13.48 (d,
J=8.1,1H, CHNH); 13C NMR (300 MHz, DMSO-d6): 9.67, 10.35, 14.29, 29.58,
30.28, 60.93, 122.94 (CN), 134.81, 135.82 (CHNH); Mass (MALDI-TOF) m/z
calcd for C20H14N2O4 [M]þ 346.10 found: 346.
1 3

Green and catalyst-free synthesis of aminoanthraquinone…
1‑(((4,4‑Dimethyl‑2,6‑dioxocyclohexylidene) methyl) amino) anthracene‑9,10‑dione
(5e)
Yield: 90%; in the form of dark yellow solid; mp: 258–260 °C; FT-IR (cm−1) 3086,
2952, 2924, 1656, 1610, 1548, 1455, 1410, 1378, 1328, 1231, 1157, 1085, 988, 925,
870, 832, 800, 732, 703,
652, 624; 1H NMR (300 MHz, DMSO-d6): 1.07 (s, 6H, 2CH3), 2.46 (s,2H, CH2),
7.50–8.0 (m, 3H, 3CH arom), 8.11 (dd, J1=7.95, J2=0.9, 1H, CH arom), 8.20–8.31
(m, 3H, 3CH arom), 8.67 (d, J=13.2, 1H, CHNH), 14.47 (d, J=13.2, 1H, CHNH).
5‑(((9,10‑Dioxo‑9,10‑dihydroanthracen‑1‑yl)amino)
methylene)‑2,2‑dimethyl‑1,3‑dioxane‑4,6‑dione (5f)
Yield: 85%; in the form of safron yellow solid; mp: 256–258 °C; FT-IR (cm−1)
3118, 3076, 2986, 1730, 1676,1649, 1597, 1564, 1493, 1461, 1416, 1373, 1341,
1251, 1194, 1139, 1078, 1002, 933, 857, 807, 785, 737, 710, 673, 643, 546, 504,
1
483, 428; H NMR (300 MHz, DMSO d6): 1.74 (s, 6H, 2CH3), 7.97–8.01 (m, 3H,
3CH arom), 8.12 (d, J=7.5 1H, CH arom), 8.25 (dd, J1=20.4, J2=8.4, 2H, 2CH
arom), 8.35 (d, J=8.4, 1H, CH arom), 8.91 (d, J=13.8, 1H, CHNH), 13.84 (d,
J=14.1, 1H, CHNH); 13C NMR (300 MHz, DMSO): 27.12, 90.25, 104.90, 123.32,
124.63, 127.01, 127.57, 132.78, 134.16, 134.74, 135.25, 135.38, 136.17, 140.38,
152.72 (CHNH), 163.15 (CCOO), 163.57 (CCOO), 180.22, 182.47.
5‑(((9,10‑Dioxo‑9,10‑dihydroanthracen‑1‑yl)amino)
methylene)‑1,3‑dimethylpyrimidine‑2,4,6(1H,3H,5H)‑trione (5 g)
Yield: 94%; in the form of light yellow solid; mp>360 °C; FT-IR (cm−1) 3116,
3081, 1722, 1668, 1636, 1595, 1568, 1503, 1464, 1431, 1357, 1307, 1268, 1240,
1177, 1085, 999, 984, 860, 830, 803, 780, 752, 732, 704, 655, 616, 545, 483, 415.
2‑(((9,10‑Dioxo‑9,10‑dihydroanthracen‑2‑yl)amino)methylene)malononitrile (6b)
Yield: 93%; in the form of dark goldenrod solid; mp 310–312 °C; FT-IR (cm−1)
3293, 3203, 3114, 3061, 2225, 1669, 1655, 1640, 1572, 1486, 1282, 1101, 977, 929,
862, 709, 659, 639, 582, 551, 472, 434; 1H NMR (300 MHz,DMSO-d6): 7.93–7.97
(m, 3H, 3CH arom), 8.17–8.24 (m, 4H, 4CH arom), 8.84 (s, 1H, CHNH), 11.57 (s,
1H, CHNH); 13C NMR (300 MHz, DMSO-d6) 55.73, 113.96, 115.85 (CN), 116.22
(CN), 122.86, 127.19, 127.27, 129.29, 129.58, 133.51, 133.54, 134.85, 134.94,
135.17, 144.74, 156.08 (CHNH), 181.79, 182.56; Mass (MALDI-TOF) m/z calcd
for C18H9N3O2 [M]þ 299.07 found: 299.1.
Methyl (Z)‑2‑(((9,10‑dioxo‑9,10‑dihydroanthracen‑2‑yl)amino)
methylene)‑3‑oxobutanoate (6c)
Yield: 91%; in the form of brown solid; mp: 222–223 °C; FT-IR (cm−1) 3376, 3203,
2943, 1712, 1670, 1643, 1585, 1563, 1432, 1403, 1376, 1356, 1319, 1286, 1237,
1 3

A. Sardashti-Birjandi et al.
1189, 1151, 1072, 978, 931, 844, 795, 713, 662, 641, 573, 552, 501, 430, 413;
1H NMR (300 MHz, DMSO-d6): 2.48 (s, 3H, CH3), 3.79 (s, 3H, CH3), 7.93–7.99
(m, 3H, 3CH arom), 8.13 (d, J=1.8 1H, CH arom) 8.23–8.26 (m, 3H, 3CH arom)
8.56 (d, J=30, 1H, CHNH), 12.56 (d, J=8.1. 1H, CHNH); 13C NMR (300 MHz,
CDCl3): 31.46, 51.70, 104.79, 114.20, 122.65, 127.47, 130.01, 133.47, 133.66,
134.23, 134.65, 135.45, 144.17, 150.24 (CHNH), 166.80 (CCOOCH3), 181.82,
182.74, 201.16 (CH3COC); Mass (MALDI-TOF) m/z calcd for C20H15NO5 [M]þ
349.10 found: 349.
Ethyl (Z)‑2‑cyano‑3‑((9,10‑dioxo‑9,10‑dihydroanthracen‑2‑yl)amino)acrylate (6d)
Yield: 93%; in the form of greenish yellow solid; mp: 263–267 °C; FT-IR (cm−1)
3392, 3178, 3082, 2944, 2230, 1708, 1678, 1642, 1587, 1491, 1366, 1329, 1291,
1257, 1181, 1126, 1018, 977, 932, 909, 842, 760, 709, 660, 640, 608, 568, 545, 500;
1H NMR (300 MHz, DMSO-d6): 2.47 (t, 3H, CH3), 3.78 (q, 2H, CH2), 7.94–7.97
(m, 3H, 3CH arom), 8.11–8.26 (m, 4H, 4CH arom) 8.59 (s, 1H, CHNH), 12.56 (s,
1H, CHNH); 13C NMR (300 MHz, DMSO-d6): 10.29, 14.29, 60.75, 77.79, 114.95
(CN), 122.05, 126.72, 128.57, 128.89, 132.92, 134.26, 134.62, 151.35 (CHNH),
164.04, 181.14, 182.03; Mass (MALDI-TOF) m/z calcd for C20H14N2O4 [M]þ
346.10 found: 346.
2‑(((4,4‑Dimethyl‑2,6‑dioxocyclohexylidene)methyl)amino) anthracene‑9,10‑dione
(6e)
Yield: 88%; in the form of light brown solid; mp: 259–262 °C; FT-IR (cm−1) 3050,
2933, 2866, 2314, 1661, 1574, 1447, 1407, 1325, 1267, 1211, 1130, 1015, 972, 924,
1
897, 845, 791, 748, 710, 663, 621; H NMR (300 MHz, DMSO-d6): 1.05 (s, 6H,
2CH3), 2.44 (s, 2H, CH2), 7.96–8.0 (m, 2H, 2CH arom), 8.07 (dd, J1=8.4, J2=2.4
1H, CH arom), 8.20 (d, J=2.1, 1H, CH arom), 8.23–8.27 (m, 3H, 3CH arom), 8.62
(d, J=13.2, 1H, CHNH),12.67 (d, J=13.5, 1H, CHNH).
5‑(((9,10‑Dioxo‑9,10‑dihydroanthracen‑2‑yl)amino)
methylene)‑2,2‑dimethyl‑1,3‑dioxane‑4,6‑dione (6f)
Yield: 85%; in the form of cool brown solid; mp: 249–252 °C; FT-IR (cm−1) 3182,
2997, 1733, 1672, 1624, 1573, 1504, 1463, 1380, 1263, 1198, 1136, 1097, 1025,
987, 926, 858, 824, 782, 715, 640.
5‑(((9,10‑Dioxo‑9,10‑dihydroanthracen‑2‑yl)amino)
methylene)‑1,3‑dimethylpyrimidine‑2,4,6(1H,3H,5H)‑trione (6 g)
Yield: 90%; in the form of cool brown solid; mp: 338–340 °C; FT-IR(cm−1) 3108,
1716, 1656, 1585, 1498, 1469, 1425, 1297, 1205, 1176, 1151, 1094, 1052, 981, 933,
895, 802, 753, 710, 657; 1H NMR (300 MHz, DMSO-d6): 3.24 (s, 3H, CH3), 3.26 (s,
3H, CH3), 7.96–7.99 (m, 2H, 2CH arom), 8.10–8.13 (dd, 1H, CH arom), 8.23–8.29
(m, 4H, 4CH arom), 8.76 (d, 1H, CHNH); 8.81 (d, 1H, CHNH).
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Green and catalyst-free synthesis of aminoanthraquinone…
Conclusions
In summary, the new strategy has been introduced for the synthesis of diferent
derivatives of aminoanthraquinone through a one-pot three-component condensa-
tion reaction of amino anthraquinone, triethyl orthoformate and CH-acid com-
pounds. One of the most advantages of this method was the environmentally
friendly conditions without using any solvent or catalyst and in agreement with
the principles of green chemistry. Besides, this strategy was simple and rapid
to give the desired products with good to excellent yields with easy workup
procedure.
Supplementary Information The online version contains supplementary material available at https://doi.
org/10.1007/s11164-021-04485-9.
Acknowledgements We wish to express our thanks to the Research Council of the University of Sistan
and Baluchestan for the fnancial support of this work.
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