Synthesis of 2-hydroxy-1,4-naphthoquinone derivatives via a three-component reaction catalyzed by nanoporous MCM-41

Article abstract of DOI:10.1016/j.dyepig.2015.06.013

A one-pot procedure for synthesis of hydroxyl naphthalene-1,4-dione derivatives via a three-component reaction of 2-hydroxynaphthalene-1,4-dione, aromatic aldehydes and heterocyclic or carbocyclic amines is developed. MCM-41 nanoporous catalyst is effective, easy recovery, reusable and makes work-up easy. This approach is clean and environmentally friendly. The structures of the new compounds were confirmed by FT-IR, ¹H NMR, ¹³C NMR, and elemental analysis.

Full text of DOI:10.1016/j.dyepig.2015.06.013

Accepted Manuscript
Synthesis of 2-hydroxy-1,4-naphthoquinone derivatives via a three-component
reaction catalyzed by nanoporous MCM-41
Soroush Shaabani, Mohammad Reza Naimi-Jamal, Ali Maleki
PII:
S0143-7208(15)00231-4
10.1016/j.dyepig.2015.06.013
DYPI 4815
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 7 March 2015
Revised Date: 11 June 2015
Accepted Date: 13 June 2015
Please cite this article as: Shaabani S, Naimi-Jamal MR, Maleki A, Synthesis of 2-hydroxy-1,4-
naphthoquinone derivatives via a three-component reaction catalyzed by nanoporous MCM-41, Dyes
and Pigments (2015), doi: 10.1016/j.dyepig.2015.06.013.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Synthesis of 2-hydroxy-1,4-naphthoquinone derivatives via a three-
component reaction catalyzed by nanoporous MCM-41
Soroush Shaabani, Mohammad Reza Naimi-Jamal, Ali Maleki

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Synthesis of 2-hydroxy-1,4-naphthoquinone derivatives via a three-
component reaction catalyzed by nanoporous MCM-41
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Soroush Shaabani1, Mohammad Reza Naimi-Jamal*,1, Ali Maleki2
1 Research Laboratory of Green Organic Synthesis and Polymers, Department of
Chemistry, Iran University of Science and Technology, 16846-13114 Tehran, Iran
2 Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran
University of Science and Technology, Tehran 16846-13114, Iran.
E-mail: naimi@iust.ac.ir; Fax: +98-21-77491204
Abstract
A one-pot procedure for synthesis of hydroxyl naphthalene-1,4-dione derivatives via a three-
component reaction of 2- hydroxynaphthalene-1,4-dione, aromatic aldehydes and heterocyclic or
carbocyclic amines is developed. MCM-41 nanoporous catalyst is effective, easy recovery,
reusable and makes work-up easy. This approach is clean and environmentally friendly. The
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structures of the new compounds were confirmed by FT-IR, H NMR, C NMR, and elemental
analysis.
Keywords: Naphthoquinone pigment, 2-Hydroxynaphthalene-1,4-dione, Nanoporous MCM-41,
Environmentally friendly, Multicomponent reaction, One-pot synthesis.
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1. Introduction
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Multicomponent reactions (MCRs) are an important class of convergent organic reactions, in
which three or more starting materials react together to form a unique product [1,2]. They have
recently received special interest, because of the ability of the formation of multi-bonds in a one-
pot reaction with high atom efficiency and mild and environmentally benign conditions [3]. Due
to this important ability, researches on MCRs have received a rapidly increasing attention in both
academic and industrial researches [4].
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On the other hand, in recent years, the use of heterogeneous catalysts has been widely
studied; because, they are easily removable from the reaction media by simple filtration after
completion of the reaction and in many cases they are reusable [5]. In order to overcome the
lower reaction rate of heterogeneous catalysts compared to homogeneous ones, the use of high
surface area materials such as nanoporous MCMs, SBAs, and zeolites have been widely
investigated [6-9].
Molecules with the napthoquinone structure constitute one of the most interesting classes of
compounds in organic chemistry. They may possess different biological properties, industrial
applications (such as pigments) and can be used as potential intermediates in the synthesis of
heterocycles [10]. A series of related naphthoquinone pigments from streptocarpus dunnii have
been isolated and characterized (Fig. 1) [11,12].
Fig. 1.
2-Hydroxy-1,4-naphthoquinone (HNQ; Lawsone) exists in the leaves of henna as the
principal natural dye (1.0–1.4%). Henna (Lawsonia inermis, also called mignonette tree) is a
flowering plant, which has been used since the Bronze Age to dye hair, skin (including body art),
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fingernails, leather, silk and wool. In various festivals and celebrations, it is used as a natural
colorant [13,14].
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Herein, we wish to report an easy and efficient methodology for the one-pot synthesis of
hydroxyl naphthalene-1,4-dione derivatives 4a-t from 2-hydroxynaphthalene-1,4-dione 1,
aromatic aldehydes 2 and heterocyclic or carbocyclic amines 3 in the presence of MCM-41 as an
efficient heterogonous catalyst at room temperature in short reaction times, high yields and
simple work-up procedure (Scheme 1).
Scheme 1.
2. Experimental
2.1. General
All chemicals were purchased from Merck or Aldrich and have been used as received,
except for liquid aldehydes, which have been freshly distilled prior to use. MCM-41 was
synthesized according to the literature [15]. Analytical thin layer chromatography (TLC) for
monitoring reactions was performed using Merck 0.2 mm silica gel 60 F-254 Al-plates. Melting
points were determined using an Electrothermal 9100 apparatus and uncorrected. FT-IR spectra
were recorded as KBr pellets on a Shimadzu FT-IR- 8400S spectrometer. BET apparatus was a
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Micromeritics ASAP 2020, USA. H NMR spectra were obtained using Bruker DRX-500
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Avance spectrometer at 500.13 MHz. C NMR spectra were obtained using Bruker DRX-400
Avance spectrometer at 100.63 MHz or Bruker DRX-500 Avance spectrometer at 125.76 MHz.
Microanalysis of the products was carried out by a CHN analyzer (Perkine Elmer Series II,
2400).
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2.2. General procedure for the preparation of MCM-41
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To 42 mL deionized water in a 500 mL beaker, 2.7 g diethylamine was added at ambient
temperature and stirred. Then, 1.47 g cetyltributylammonium bromide (CTAB) was gradually
added to the above mixture until a clear solution was obtained. Tetraethyl orthosilicate (2.1 g)
was added drop-wise to the solution and the pH was fixed at 8.5 by addition of 1 M HCl
solution. After 2 h, the resulting solid product was filtered and washed several times with
deionized water, and dried at 45 °C for 12 h. The obtained MCM-41 was calcined at 550 °C for 5
h to remove all the surfactant [7]. FT-IR spectra showed the characteristic peak of Si-O-Si at
1100 cm-1, while the broad peak around 3413 cm-1 belongs to the terminal silanol groups of
MCM-41. A sample of the prepared MCM-41 was investigated by SEM and BET tests.
According to the SEM micrograph, the particle sizes were around 35 nm in diameter. The
adsorption/desorption isotherms of the synthesized MCM-41 were recorded by BET apparatus
and the BET surface area was measured as 1261 m2g-1, while BJH adsorption average pore width
(4 V/A) was measured as 2.3 nm. These confirm the nanoporous structure of the synthesized
MCM-41.
2.3. General procedure for the preparation of 2-hydroxyl naphthalene-1,4-diones 4
A mixture of 2-hydroxynaphthalene-1,4-dione (1 mmol), amine (1 mmol), aldehyde (1
mmol), MCM-41 (5 mg) was stirred in EtOH (3 mL) at room temperature for appropriate time
(as indicated in Table 4). After completion of the reaction, as indicated by TLC, the mixture was
diluted with CH2Cl2 and the catalyst was separated by filtration. The solvent was evaporated
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under reduced pressure. The structures of all known products were determined on the basis of
their analytical and/or spectral data comparing with the literature data. The spectral data of the
new products are as following.
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2.4. Characterization of the new compounds
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Despite of heating the samples in CDCl3 prior to C NMR measurement, the low solubility of
such compounds makes it difficult to receive a clean 13C NMR spectrum (please see also section
2.2 in ref. 14). As a result, although the following data have been carefully taken from the
spectra, wherever possible, they could be inaccurate.
2.4.1. 2-((2,4-Dichlorophenyl)(phenylamino)methyl)-3-hydroxynaphthalene-1,4-dione (4d)
Yellow powder (yield 90%); mp 147 °C. IR (KBr) (vmax/cm-1): 3338 (br, OH and NH), 3095
(Ar), 1676 (C=O). 1H NMR (500 MHz, CDCl3):  (ppm) 6.13 (1H, s, CH), 6.50-6.53 (3H, m, H-
Ar), 6.91-6.97 (2H, m, H-Ar), 6.97-6.99 (1H, dd, J = 10.0, 2.1 Hz, H-Ar), 7.12-7.14 (1H, m, H-
Ar), 7.45-7.54 (3H, m, H-Ar), 7.83-7.84 (2H, m, H-Ar). Anal. Calcd. for C23H15Cl2NO3: C,
65.11; H, 3.56; N, 3.30%. Found: C, 65.19; H, 3.53; N, 3.11%.
2.4.2. 2-((4-Chlorophenyl)(p-tolylamino)methyl)-3-hydroxynaphthalene-1,4-dione (4o)
Orange powder (yield 90%); mp 147 °C. IR (KBr) (vmax/cm-1): 3369 (br, OH and NH), 3084
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(Ar), 2920 (CH3), 1670 (C=O). H NMR (500 MHz, CDCl3): (ppm) 2.04 (3H, s, CH3), 5.97
(1H, s, CH), 6.53 (2H, d, J = 8.1 Hz, H-Ar), 6.80 (2H, d, J = 8.0 Hz, H-Ar), 7.09 (2H, d, J = 8.2
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Hz, H-Ar), 7.32 (2H, d, J = 8.2 Hz, H-Ar), 7.48-7.70 (2H, m, H-Ar), 7.87 (2H, d, J = 7.5 Hz, H-
Ar). 13C NMR (100 MHz, CDCl3):  (ppm) 21.0, 54.4, 116.0 (2C), 120.9, 126.8 (2C), 127.1
(2C), 127.6, 129.5 (2C), 129.8 (2C), 130.4 (2C), 130.5, 132.8, 133.6, 134.3, 137.3, 143.8, 181.4,
184.2. Anal. Calcd. for C24H18ClNO3: C, 71.38; H, 4.49; N, 3.47%. Found: C, 71.31; H, 4.43; N,
3.53%.
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2.4.3. 2-((Benzylamino)(2,4-dichlorophenyl)methyl)-3-hydroxynaphthalene-1,4-dione (4t)
Orange powder (yield 90%); mp 158 °C. IR (KBr) (vmax/cm-1): 3440 (br, OH and NH), 3064
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(Ar), 1674 (CO), 1591 (CO). H NMR (500 MHz, CDCl3): (ppm) 3.86 (1H, d, J = 7.7 Hz,
CH2), 4.11 (1H, d, J = 7.7 Hz, CH2), 5.96 (1H, s, CH), 6.96-6.99 (1H, dd, J = 10.0, 2.1 Hz, H-
Ar), 7.18-7.22 (4H, m, H-Ar), 7.25-7.28 (2H, m, H-Ar), 7.40-7.44 (1H, m, H-Ar), 7.49-7.52 (2H,
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m, H-Ar), 7.85-7.87 (2H, m, H-Ar). C NMR (100 MHz, CDCl3):  (ppm) 50.8, 56.2, 125.6,
126.0, 126.2, 127.1, 127.8, 128.0, 128.9, 129.0 (2C), 129.3, 129.7 (2C), 131.3, 131.3, 131.8,
133.0, 133.6, 134.3, 135.1, 135.6, 181.9, 184.4. Anal. Calcd. for C24H17Cl2NO3: C, 65.77; H,
3.91; N, 3.20%. Found: C, 65.73; H, 3.91; N, 3.23%.
3. Results and discussion
To optimize the reaction conditions, the reaction of 2-hydroxy-1,4-naphthoquinone 1,
benzaldehyde and aniline as model reactants (1.0 mmol each) was studied at room temperature
(Table 1). Different solvents and catalysts were screened in the model reaction. After screening a
number of catalysts such as InCl3, ZnCl2, p-TSA, MCM-41, and MCM-41-SO3H, it has been
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found that mesoporous catalysts MCM-41 and MCM-41-SO3H promote the reaction in very
good yields, while other catalysts formed the product in lower yields. MCM-41 has been used for
further investigations, due to its more mildness and easier preparation method in comparison to
MCM-41-SO3H.
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Table 1.
In order to examine the rule of different solvents on the yield of hydroxyl naphthalene-1,4-
dione derivatives, we investigated the model reaction in various solvents such as CH3CN,
acetone, H2O and EtOH (96%) and also under solvent-free condition at room temperature. It was
found that the best results were obtained in EtOH in the presence of MCM-41 (Table 2).
Table 2.
In order to optimize the amount of the catalyst loading, the model reaction was also studied
in the presence of less amounts of MCM-41 at room temperature (Table 3). The best results were
obtained when 5 mg of the catalyst was used. It is notable that by using excess amounts of the
catalyst, the yield of the desired product was decreased.
Table 3.
After developing the optimized reaction conditions, a variety of aromatic aldehydes and
amines were employed under similar circumstances to evaluate the substrate scope of this
methodology. The results are summarized in Table 4. The aromatic aldehydes carrying both
electron-withdrawing and electron-releasing substituents were converted to their corresponding
2-hydroxyl naphthalene-1,4-diones derivatives in high yields.
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In addition, due to various biological properties of polyfunctionalized heterocyclic
compounds, a few 2-hydroxy-1,4-naphtoqionin derivatives were also synthesized by starting
from heterocyclic amines such as 2-aminopyridine, 2-aminobenzimidazole and benzyl amine in
high yields under the same reaction conditions (Table 4, entries 16-20).
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Table 4.
The reusability of the catalyst was also investigated in the model reaction. After each run, the
filtered catalyst was washed several times with acetone and ethanol, and dried in an oven at 80°C
for 5 h [15] and re-used in consecutive runs. The results of catalyst recyclability have been
summarized in Fig. 2. As it is shown, after 4 consecutive runs the catalyst remained still intact.
Fig. 2.
4. Conclusions
In summary, we have developed a simple, efficient and green methodology for the synthesis
of hydroxyl naphthalene-1,4-dione derivatives under heterogeneous catalysis conditions. The
simple experimental procedure at room temperature, short reaction times, high yields, simple
work-up, easy recovery and reusability of the catalyst and environmentally acceptable solvent
are the advantages of the present method.
Acknowledgements
The authors gratefully acknowledge the partial support from the Research Council of the
Iran University of Science and Technology.
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Supplementary data
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Supplementary data associated with this article can be found, in the online version, at
www.elsevier.com/locate/dyepig.
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[5] Smith GV, Notheisz F. Heterogeneous Catalysis in Organic Chemistry, 1st ed., Academic
Press, NY, 1999.
[6] Ali E, Naimi-Jamal MR, Dekamin MG. Scientia Iranica 2013; 20: 592-597.
[7] Dekamin MG, Mokhtari Z. Tetrahedron 2012; 68: 922-930.
[8] Kalbasi RJ, Massah AR, Shafiei A. J Mol Catal A: Chem 2011, 335: 51-59.
[9] Massah AR, Kalbasi RJ, Shafiei A. Monatsh Chem 2012; 143: 643-652.
[10] Tisseh ZN, Azimi S, Mirzaei P, Bazgir A. Dyes Pigments 2008; 79: 273-275.
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[11] Tisseh ZN, Bazgir A. Dyes Pigments 2009; 83: 258-261.
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[12] Dabiri M, Tisseh ZN, Bazgir A. Monatsh Chem 2012; 143: 139-143.
[13] Ashnagar A, Shiri A. Int J Chem Tech Res 2011; 3: 1941-1944.
[14] Dabiri M, Tisseh ZN, Bazgir A. Dyes Pigments 2011; 89: 63-69.
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[15] Tourani H, Naimi-Jamal MR, Dekamin MG, Amirnejad M. CR Chimie 2012; 15: 1072-
1076.
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Captions
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Fig. 1. Examples of naphthoquinone pigments.
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Scheme 1. Synthesis of hydroxyl naphthalene-1,4-dione derivatives 4a-t.
Table 1. Screening of different catalysts in the model reaction.
Table 2. Screening of the different solvents in the model reaction.
Table 3. Optimization of the amount of the catalyst loading in the model reaction.
Table 4. Synthesis of 2-hydroxy(aryl(arylamino)methyl)naphthalene-1,4-diones 4a-t.
Fig. 2. Reusability study of the catalyst in the model reaction.
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Fig. 1.
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Scheme 1.
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Table 1.
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Entry
Catalyst
InCl3
Catalyst loading (mg)
Time (h)
Yielda (%)
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MCM-41-SO3H
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a Isolated yield.
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Table 2.
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Entry
Solvent
Time
10 h
Yielda (%)
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30
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32
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34
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38
39
40
41
42
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48
49
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1
32
27
CH3CN
2
CH3COCH3
12 h
3
8 h
70
H2O
4
80 min
48 h
90
EtOH (96%)
-
5
Trace
a Isolated yield.
15

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Table 3.
6
7
8
Entry
Catalyst loading (mg)
Time (min)
Yielda (%)
9
10
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1
2
3
4
5
80
100
80
95
88
90
90
10
20
30
180
a Isolated yield.
16

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Table 4.
6
7
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Mp (°C)
Entry Product
X
Amine
Time (min) Yielda (%)
Obsd.
148
145
145
147
175
Lit.
1
2
3
4
5
H
80
150
25
95
95
95
90
90
143-145 [14]
145-148 [14]
145-148 [14]
-
4a
4b
4c
4d
4e
4-Me
4-NO2
2,4-di-Cl
4-OH
180
120
185-190 [14]
6
7
H
120
175
125
180
60
90
90
95
95
95
95
90
90
95
146
145
146
150
150
154
148
144
148
147-150 [14]
144-147 [14]
146-149 [14]
149-152 [14]
141-144 [14]
147-150 [14]
144-147 [14]
149-152 [14]
144-147 [14]
4f
4g
4h
4i
4-OMe
4-Me
8
9
4-OH
4-NO2
4-Br
10
11
12
13
14
4j
210
185
70
4k
4l
2,4-di-Cl
2-Cl
4m
4n
3-NO2
70
17

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4-Cl
H
95
60
90
90
147
145
-
4o
4p
4q
145-148 [14]
10
11
12
13
14
15
16
17
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19
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17
18
19
20
4-NO2
H
20
125
70
95
90
99
90
150
150
154
158
148-151 [14]
155-151 [14]
150-153 [14]
-
4r
4s
4t
4-NO2
2,4-di-Cl
60
a Isolated yield.
18

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Fig. 2.
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Highlights
 A green procedure was developed for the one-pot synthesis of
naphthalene-1,4-diones.
 The multicomponent reaction gave good to excellent yields from
simple precursors.
 The protocol includes important aspects like easy workup procedure
and high atom economy.
 An efficient and reusable nanocatalyst was introduced.

Supplementary data
ACCEPTED MANUSCRIPT
Synthesis of 2-hydroxy-1,4-naphthoquinone derivatives via a three-
component reaction catalyzed by nanoporous MCM-41
Soroush Shaabani1, Mohammad Reza Naimi-Jamal*,1, Ali Maleki2
1 Research Laboratory of Green Organic Synthesis and Polymers, Department of
Chemistry, Iran University of Science and Technology, 16846-13114 Tehran, Iran
2 Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran
University of Science and Technology, Tehran 16846-13114, Iran.
E-mail: naimi@iust.ac.ir; Fax: +98-21-77491204

Supplementary data
ACCEPTED MANUSCRIPT
Characterization of the new compounds (4d, 4o and 4t)
FT-IR spectrum of 4d

Supplementary data
ACCEPTED MANUSCRIPT
1H NMR spectrum of 4d

Supplementary data
Expanded 1H NMR spectrum of 4d
ACCEPTED MANUSCRIPT

Supplementary data
Expanded 1H NMR spectrum of 4d
ACCEPTED MANUSCRIPT

Supplementary data
ACCEPTED MANUSCRIPT
FT-IR spectrum of 4o

Supplementary data
ACCEPTED MANUSCRIPT
1H NMR spectrum of 4o

Supplementary data
Expanded 1H NMR spectrum of 4o
ACCEPTED MANUSCRIPT