Synthesis of fluorescent hydroxyl naphthalene-1,4-dione derivatives by a three-component reaction in water

Article abstract of DOI:10.1016/j.dyepig.2010.09.004

An efficient one-pot synthesis of fluorescent hydroxyl naphthalene-1,4- dione derivatives by a simple, atom-economical and three-component reaction of 2- hydroxynaphthalene-1,4-dione, aromatic aldehydes and heterocyclic or carbocyclic amines in the presence of a catalytic amount of InCl₃ in refluxing water is reported. The structures of the compounds were confirmed by IR, ¹H NMR, ¹³C NMR, and elemental analysis. UV- visible absorption coefficient, maximum wavelength and fluorescence emission wavelength were measured in methanol. The products were fluorescent in solution emitting at green light (546-560 nm). The advantages of this procedure are mild reaction conditions, high yields of products, operational simplicity and easy work-up procedures. The workup of these very clean reactions involves only a filtration and simple washing step with EtOH.

Full text of DOI:10.1016/j.dyepig.2010.09.004

Dyes and Pigments 89 (2011) 63e69
Contents lists available at ScienceDirect
Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
Synthesis of fluorescent hydroxyl naphthalene-1,4-dione derivatives
by a three-component reaction in water
*
*
Minoo Dabiri , Zeinab Noroozi Tisseh, Ayoob Bazgir
Department of Chemistry, Shahid Beheshti University, General Campus, Tehran 1983963113, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient one-pot synthesis of fluorescent hydroxyl naphthalene-1,4-dione derivatives by a simple,
atom-economical and three-component reaction of 2- hydroxynaphthalene-1,4-dione, aromatic alde-
hydes and heterocyclic or carbocyclic amines in the presence of a catalytic amount of InCl3 in refluxing
water is reported. The structures of the compounds were confirmed by IR, 1H NMR, 13C NMR, and
elemental analysis. UV- visible absorption coefficient, maximum wavelength and fluorescence emission
wavelength were measured in methanol. The products were fluorescent in solution emitting at green
light (546e560 nm). The advantages of this procedure are mild reaction conditions, high yields of
products, operational simplicity and easy work-up procedures. The workup of these very clean reactions
involves only a filtration and simple washing step with EtOH.
Received 15 June 2010
Received in revised form
5 September 2010
Accepted 16 September 2010
Available online 1 October 2010
Keywords:
Hydroxynaphthalene-1,4-dione
[1,4-naphthoquinone]
Indium chloride
Aldehyde
Ó 2010 Elsevier Ltd. All rights reserved.
Amine
Fluorescence
Aqueous media
1. Introduction
a hair dye, but also as a body paint and tattoo dye. Today, semi-
permanent hair dyes containing Henna as well as its pure dye
Multicomponent reactions (MCRs), in which multiple reactions
are combined into the synthetic operation have been used exten-
sively to form carbon-carbon bonds in synthetic chemistry [1]. Such
reactions offer a wide range of possibilities for the efficient
construction of highly complex molecules in a single procedural
step, thus avoiding complicated purification operations and
allowing savings of both solvents and reagents [2]. Designing of
multi-component reactions in water is another attractive area in
chemistry [3], because water is a cheap, safe and environmentally
benign solvent. In this context, fluorescent heterocyclic compounds
show interesting features that make them attractive for use in
MCRs.
Fluorescent heterocyclic compounds are of interest in many
disciplines such as emitters for electroluminescence devices [4],
molecular probes for biochemical research [5], in traditional textile
and polymer fields [6], fluorescent whitening agents [7] and photo
conducting materials [8].
ingredient HNQ are widely used and have become increasingly
popular due to their natural origin [9]. A series of related nahtho-
quinone pigments (streptocarpone,
a-dunnione, dunniol and dun-
nione) from Streptocapus dunnii have been isolated and
characterized [10]. Similarly, quinone derivatives were reported as
fluorescence compounds [11]. On the other hand, molecules with
the quinone structure constitute one of the most interesting classes
of compounds in organic chemistry, due to their biological prop-
erties, their industrial applications and their potential as interme-
diates in the synthesis of heterocycles [12]. In 1946 Wendel [13]
showed that certain 2-hydroxy-3-alkyl-naphthoquinones inhibited
the growth of P. Vivae upon the influence on the respiratory and
carbohydrate cycles in the parasite. Further studies proved that the
toxicity of naphthoquinones to Plasmodium sp. is due to interaction
with the mitochondrial respiratory chain [14]. The quinones are
also associated with antitumor, molluscicidal, leischmanicidal, anti
inflammatory, and antifungal activities [15]. Among the quinones
the following should be pointed out: atovaquone (I) [16], a coen-
zyme Q analogue which inhibits selectively P. Vivae by affecting the
mitochondrial electron transport; lapachol (II) [17], present in the
heartwood of the lapacho tree, Tabebuia avellanedae Lorentz ex.
Griseb. (Bignoniaceae), and other Tabebuia trees native to Central
and South America (Fig. 1). Therefore, the development of simple
2-Hydroxy-1,4-naphthoquinone (HNQ; Lawsone) is the prin-
cipal natural dye (1.0e1.4%) in the leaves of henna, Lawsonia iner-
mis. Henna has been used for more than 4000 years not only as
* Corresponding authors. Tel./fax: þ98 21 22431661.
E-mail addresses: m-dabiri@sbu.ac.ir (M. Dabiri), a_bazgir@sbu.ac.ir (A. Bazgir).
0143-7208/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dyepig.2010.09.004

64
M. Dabiri et al. / Dyes and Pigments 89 (2011) 63e69
O
R
O
Cl
H2O (Reflux)
OH
O
O
Ar
N
H
RCHO
ArNH2
+
+
O
O
InCl3 (20 mol%)
OH
O
O
OH
1
2
3
4
OH
Fig. 2. Synthesis of hydroxyl naphthalene-1,4-diones 4.
lapachol (II)
atovaquone (I)
2.2.2. 2-hydroxy-3-[(phenylamino)(p-tolyl)methyl]naphthalene-
Fig. 1. Examples of antimalarial naphthoquinones.
1,4-dione (4b)
Orange Powder (yield 80%); mp 145e148 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3390 (OH), 3312 (NH), 1662 (CO), 1633 (CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 2.21 (3H, s, CH3), 6.03 (1H, S, CH),
6.90e8.06, (13H, m, H-Ar), 9.09 (1H, s, OH). MS, m/z: 369 (Mþ).
Anal. Calcd for C24H19NO3: C, 78.03; H, 5.18; N, 3.79%. Found:
C, 78.16; H, 5.10; N, 3.71%.
synthetic methods for efficient preparation of the new quinone
derivatives will be a beneficial and interesting challenge. Recently,
the syntheses of quinones in water have been reported [18].
Considering the above reports, and as part of our program aimed
at synthesis of heterocycles and new dyes containing nahthoqui-
none moiety [19], we are currently investigating the synthesis of
hydroxyl naphthalene-1,4-dione derivatives via a facile, atom-
economical, and three-component condensation reaction of 2-
2.2.3. 2-Hydroxy-3-[(4-hydroxyphenyl)(phenylamino)methyl]
naphthalene-1,4-dione (4c)
Yellow Powder (yield 86%); mp 185e190 ꢀC. IR (KBr) (nmax
/
hydroxynaphthalene-1,4-dione 1, aromatic aldehydes
2 and
cmꢁ1): 3423 (OH), 3221 (NH), 1630 (CO),1610 (CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 5.90, (1H, s, CH), 7.05-8.03, (13H, m,
H-Ar), 9.26 (1H, s, OH), 13C NMR (75 MHz, DMSO-d6): dC (ppm) 37.8,
102.0, 124.1, 125.7, 126.4, 126.5, 128.0, 128.4, 130.2, 130.4, 130.8,
133.0, 133.1, 133.4, 135.3, 135.8, 146.8, 182.0, 182.8. MS, m/z: 371
(Mþ). Anal. Calcd for C23H17NO4: C, 74.38; H, 4.61; N, 3.77%. Found:
C, 74.29; H, 4.66; N, 3.68%.
heterocyclic or carbocyclic amines 3 in the presence of a catalytic
amount of InCl3 in refluxing water (Fig. 2).
2. Experimental
2.1. General
Melting points were measured on an Elecrtothermal 9100
apparatus and are uncorrected. Mass spectra were recorded on
a FINNIGAN-MAT 8430 mass spectrometer operating at an ioniza-
tion potential of 70 eV. 1H NMR spectra were recorded on a BRUKER
DRX-300 AVANCE spectrometer at 300.13 MHz. IR spectra were
2.2.4. 2-Hydroxy-3-[(4-nitrophenyl)(phenylamino)methyl]
naphthalene-1,4-dione (4d)
Orange Powder (yield 82%); mp 145e148 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3394 (OH), 3316 (NH), 1661 (CO), 1631 (CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 5.99 (1H, s, CH), 7.25-8.06, (13H, m,
H-Ar), 9.25 (1H, s, OH), 13C NMR (75 MHz, DMSO-d6): dC (ppm) 37.8,
120.5, 122.7, 126.0, 126.1, 127.8, 128.3, 130.1, 130.3, 131.3, 132.6, 133,
135.1, 144.4, 156.9, 181.6, 183.8. MS, m/z: 400 (Mþ). Anal. Calcd for
C23H16N2O5: C, 69.00; H, 4.03; N, 7.00%. Found: C, 68.86; H, 4.09;
N, 6.92%.
recorded on
a Bomem MB-Series FT-IR spectrophotometer.
Absorption spectra were recorded on an Shimadzu UV-2100 spec-
trophotometer. Fluorescence spectra were recorded using Perki-
nElmer LS45 spectrofluorophotometer. The chemical used in this
work were purchased from Fluka (Buchs, Switzerland) chemical
company. Elemental analyses were performed using a Heracus
CHN-O-Rapid analyzer.
2.2.5. 2-Hydroxy-3-[phenyl(p-tolylamino)methyl]naphthalene-
1,4-dione (4e)
Red Powder (yield 86%); mp 147e150 ꢀC. IR (KBr) (nmax/cmꢁ1):
3389 (OH), 3322 (NH), 1663 (CO), 1631 (CO).1H NMR (300 MHz,
DMSO-d6): dH (ppm) 2.31 (3H, s, CH3), 6.03 (1H, s, CH), 7.10e8.06,
(13H, m, H-Ar), 9.19 (1H, s, OH). MS, m/z: 369 (Mþ). Anal. Calcd for
C24H19NO3: C, 78.03; H, 5.18; N, 3.79%. Found: C, 77.91; H, 5.08;
N, 3.64%.
2.2. Typical procedure for the preparation of 2-hydroxy-
naphthalene-1,4-diones 4 and 5
A mixture of 2-hydroxynaphthalene-1,4-dione (1 mmol), amine
(1 mmol), aldehyde (1 mmol), InCl3 (20 mol%) was refluxed in
water (5 mL) for appropriate time (Table 2 and 3). After completion
of the reaction confirmed by TLC (eluent: EtOAc/n-hexane, 1:1), the
reaction mixture was filtered and the precipitate washed with
water (5 mL) and EtOH (5 mL) to afford the pure product 4 and 5.
Due to very low solubility of the products 4a, 4b, 4e, 4j, 4k and
4n we cannot report the 13C NMR data for these products.
2.2.6. 2-Hydroxy-3-[(4-methoxyphenyl)(p-tolylamino)methyl]
naphthalene-1,4-dione (4f)
Dark orange Powder (yield 85%); mp 144e147 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3452 (OH), 3324 (NH), 1665 (CO), 1631(CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 2.31 (3H, s, CH3), 3.69 (3H, s, OCH3),
6.03 (1H, s, CH), 7.22-8.06, (12H, m, H-Ar), 9.19 (1H, s, OH), 13C NMR
(75 MHz, DMSO-d6): dC (ppm) 21.2, 37.3, 55.3, 113.4, 123.9,
125.9,125.9, 126.4, 128.5, 129.6, 130.3, 132.6, 133.1, 135.0, 138.1, 146,
156.8, 157.6, 181.8, 184.0. MS, m/z: 399 (Mþ). Anal. Calcd for
C25H21NO4: C, 75.17; H, 5.30; N, 3.51%. Found: C, 75.08; H, 5.20;
N, 3.57%.
2.2.1. 2-hydroxy-3-[phenyl(phenylamino)methyl]naphthalene-
1,4-dione (4a)
Orange powder (yield 90%); mp 143e146 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3434 (OH), 3321 (NH), 1660 (CO), 1636(CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 5.98 (1H, s, CH), 7.25e8.07, (14H, m,
H-Ar), 9.26 (1H, s, OH), 13C NMR (75 MHz, DMSO-d6): dC (ppm) 37.3,
113.4, 123.9, 125.9, 125.9, 126.4, 128.5, 129.6, 130.3, 132.6, 133.1,
133.5, 135.0, 138.1, 146.0, 156.8, 157.6, 181.8, 184. MS, m/z: 355 (Mþ).
Anal. Calcd for C23H17NO3: C, 77.73; H, 4.82; N, 3.94%. Found:
C, 77.61; H, 4.73; N, 3.83%.
2.2.7. 2-Hydroxy-3-[p-tolyl(p-tolylamino)methyl]naphthalene-
1,4-dione (4g)
Dark red Powder (yield 91%); mp 146e149 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3446 (OH), 3326 (NH), 1669 (CO), 1638 (CO). 1H NMR

M. Dabiri et al. / Dyes and Pigments 89 (2011) 63e69
65
(300 MHz, DMSO-d6): dH (ppm) 2.22 (3H, s, CH3), 2.31 (3H,CH3),
6.03 (1H, s, CH), 5.99-8.06, (12H, m, H-Ar), 9.19 (1H, s, OH), 13C NMR
(75 MHz, DMSO-d6): dC (ppm) 19.3, 19.9, 101.9, 116.0, 121.7, 125.2,
125.7, 126.5, 130.5, 130.6, 130.8, 130.9, 132.9, 133.1, 134.0, 135.3,
137.7, 146.8, 182.0, 188.8. MS, m/z: 83 (Mþ). Anal. Calcd for
C25H21NO3: C, 78.31; H, 5.52; N, 3.65%. Found: C, 78.18; H, 5.43;
N, 3.74%.
(ppm) 21.0, 37.7, 101, 124.1, 125.7, 125.9, 126.4, 126.5, 129.5, 130.2,
130.3, 130.8, 132.7, 133.0, 135.1, 135.5, 135.8, 146.8, 182.0, 182.8. MS,
m/z: 403 (Mþ). Anal. Calcd for C24H18ClNO3: C, 71.38; H, 4.49;
N, 3.47%. Found: C, 71.27; H, 4.56; N, 3.40%.
2.2.14. 2-hydroxy-3-[(3-nitrophenyl)(p-tolylamino)methyl]
naphthalene-1,4-dione (4n)
Red Powder (yield 90%); mp 144e147 ꢀC. IR (KBr) (nmax/cmꢁ1):
3388 (OH), 3289, (NH),1668 (CO), 1643(CO).1H NMR (300 MHz,
DMSO-d6): dH (ppm) 2.30 (3H, s, CH3), 5.97 (1H, s, CH), 6.58e7.93,
(12H, m, H-Ar), 9.14 (1H, s, OH). MS, m/z: 414 (Mþ).Anal. Calcd for
C24H18N2O5: C, 69.56; H, 4.38; N, 6.76%. Found: C, 69.43; H, 4.29;
N, 6.66%.
2.2.8. 2-Hydroxy-3-[(4-hydroxyphenyl)(p-tolylamino)methyl]
naphthalene-1,4-dione (4h)
Dark red Powder (yield 85%); mp 149e152 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3440 (OH), 3315 (NH), 1660 (CO), 1633 (CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 2.31 (3H, s, CH3), 6.03 (1H, s, CH),
7.25e8.05, (12H, m, H-Ar), 9.19 (1H, s, OH), 13C NMR (75 MHz,
DMSO-d6): dC (ppm) 21.0, 37.2, 102, 124, 125.7, 126.4, 126.5, 128.0,
128.4, 130.2, 130.8, 133, 133.1, 133.4, 135.1, 135.3, 135.8, 146.8, 182,
182.8. MS, m/z: 385 (Mþ). Anal Calcd for C24H19NO4: C, 74.79;
H, 4.97; N, 3.63%. Found: C, 74.71; H, 4.91; N, 3.54%.
2.2.15. 2-[(4-Fluorophenylamino)(phenyl)methyl]-
3-hydroxynaphthalene-1,4-dione (4o)
Dark red Powder (yield 85%); mp 150e153 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3431 (OH), 3328 (NH), 1669 (CO), 1646 (CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 5.98 (1H, s, CH), 7.25-8.06, (13H, m,
H-Ar), 9.25 (1H, s, OH), 13C NMR (75 MHz, DMSO-d6): dC (ppm) 37.3,
102, 124.1, 125.7, 126.4,126.5, 128.0, 128.4, 130.2, 130.4, 130.8, 133,
133.1, 133.4, 135.1, 135.3, 135.8, 146.8, 182.0, 182.8. MS, m/z: 373
(Mþ). Anal. Calcd for C23H16FNO3: C, 73.99; H, 4.32; N, 3.75%. Found:
C, 73.90; H, 4.26; N, 3.68%.
2.2.9. 2-Hydroxy-3-[(2-hydroxy-4-nitrophenyl)(p-tolylamino)
methyl]naphthalene-1,4- dione (4i)
Orange Powder (yield 78%); mp 141e144 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3434 (OH), 3320 (NH), 1682 (CO), 1673 (CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 2.31 (3H, s, CH3), 5.93(1H, s, CH),
7.23e8.00, (11H, m, H-Ar), 9.10 (1H, s, OH), 13C NMR (75 MHz,
DMSO- d6): dC (ppm) 21.0, 37.7, 101.6, 112.8, 119, 121.7, 125, 126.1
127.5, 129, 130.1, 130.3, 130.7, 131.6, 133.0, 134.3, 135.1, 135.8, 146.2,
182.6, 182.8. MS, m/z: 414 (Mþ). Anal. Calcd for C24H18N2O6:
C, 66.97; H, 4.22; N, 6.51%. Found: Found: C, 66.90; H, 4.27; N, 6.45%.
2.2.16. 2-[(4-Fluorophenylamino)(p-tolyl)methyl]-
3-hydroxynaphthalene-1,4-dione (4p)
Orange Powder (yield 78%); mp 149e152 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3426 (OH), 3315 (NH), 1680 (CO), 1643 (CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 2.20 (3H, s, CH3), 6.06 (1H, s, CH),
6.09e8.06, (12H, m, H-Ar), 9.25 (1H, s, OH), 13C NMR (75 MHz,
DMSO-d6): dC (ppm) 21.0, 38.0,110.8,114.9,121.1,123.4, 126.0, 126.4,
128.9, 130.3, 132.6, 133.5, 135.1, 142.8, 156.7, 159.3, 181.6, 183.9. MS,
m/z: 387 (Mþ). Anal. Calcd for C24H18FNO3: C, 74.41; H, 4.68;
N, 3.62%. Found: C, 74.33; H, 4.58; N, 3.51%.
2.2.10. 2-[(4-Fluorophenyl)(p-tolylamino)methyl]-
3-hydroxynaphthalene-1,4-dione (4j)
Orange Powder (yield 80%); mp 143e146 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3384 (OH), 3310 (NH), 1674 (CO), 1653 (CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 2.31 (3H, s, CH3), 6.03 (1H, s, CH),
7.25e8.06, (12H, m, H-Ar), 9.20 (1H, s, OH). MS, m/z: 387 (Mþ). Anal.
Calcd for C24H18FNO3: C, 74.41; H, 4.68; N, 3.62%. Found: C, 74.50;
H, 4.59; N, 3.69%.
2.2.17. 2-[(4-Fluorophenylamino)(4-nitrophenyl)methyl]-
3-hydroxynaphthalene-1,4- dione (4q)
Orange Powder (yield 81%); mp 149e152 ꢀC. IR (KBr) (nmax
/
2.2.11. 2-[(4-Bromophenyl)(p-tolylamino)methyl]-
cmꢁ1): 3446 (OH), 3315 (NH), 1680 (CO), 1643 (CO). 1H NMR
3-hydroxynaphthalene-1,4-dione (4k)
(300 MHz, DMSO-d6): dH (ppm) 5.90 (1H, s, CH), 7.20e8.06, (12H,
Orange Powder (yield 79%); mp 147e150 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3421 (OH), 3335 (NH), 1678 (CO), 1662 (CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 2.31 (3H, s, CH3), 6.00 (1H, s, CH),
7.23e8.07, (12H, m, H-Ar), 9.14 (1H, s, OH). MS, m/z: 449 (Mþ), 447
(Mþ). Anal. Calcd for C24H18BrNO3: C, 64.30; H,4.05; N, 3.12%.
Found: C, 64.41; H, 4.13; N, 3.04%.
Table 1
Model reaction, conditions, and yield.a
2.2.12. 2-[(2,4-Dichlorophenyl)(p-tolylamino)methyl]-
3-hydroxynaphthalene-1,4-dione (4l)
Red Powder (yield 89%); mp 144e147 ꢀC. IR (KBr) (nmax/cmꢁ1):
3380 (OH), 3314 (NH), 1658 (CO), 1650 (CO).1H NMR (300 MHz,
DMSO-d6): dH (ppm) 2.31 (3H, s, CH3), 6.03 (1H, s, CH), 7.02e8.06,
(11H, m, H-Ar), 9.10 (1H, s, OH), 13C NMR (75 MHz, DMSO-d6): dC
(ppm) 21.1, 37.3, 124.1, 125.7, 126.1, 126.5, 130.1, 130.3, 130.8, 132.3,
133.6, , 135.1, 135.1, 135.3, 135.8, , 146.7, 181.9, 182.9, 182. MS, m/z:
437 (Mþ). Anal. Calcd for C24H17Cl2NO3: C, 65.77; H, 3.91; N, 3.20%.
Found: C, 65.62; H, 3.84; N, 3.13%.
Entry
Conditions
Catalyst
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
H2O (reflux)
H2O (reflux)
H2O (reflux)
H2O/r.t
H2O (reflux)
H2O (reflux)
H2O (reflux)
H2O (reflux)
H2O (reflux)
EtOH (reflux)
MeCN (reflux)
PhCH3 (reflux)
InCl3 (10mol %)
InCl3 (20 mol %)
InCl3 (25 mol %)
InCl3 (20 mol %)
None
LiCl (20 mol %)
LiClO4 (20 mol %)
ZnCl2 (20 mol %)
p-TSA (20 mol %)
InCl3 (20 mol %)
InCl3 (20 mol %)
InCl3 (20 mol %)
6
6
6
6
10
6
6
6
6
67
90
91
45
Trace
53
61
43
73
78
2.2.13. 2-[(2-Chlorophenyl)(p-tolylamino)methyl]-
3-hydroxynaphthalene-1,4-dione (4m)
9
10
11
12
10
10
10
Red Powder (yield 89%); mp 149e152 ꢀC. IR (KBr) (nmax/cmꢁ1):
3383 (OH), 3324, (NH),1665 (CO), 1644 (CO). 1H NMR (300 MHz,
DMSO-d6): dH (ppm) 2.30 (3H, s, CH3), 6.01 (1H, s, CH), 7.26e8.16,
(12H, m, H-Ar), 9.20 (1H, s, OH), 13C NMR (75 MHz, DMSO-d6): dC
<40
<40
a
2-hydroxynaphthalene-1,4-dione (1 mmol), benzaldehyde (1 mmol) and aniline
(1 mmol).

66
M. Dabiri et al. / Dyes and Pigments 89 (2011) 63e69
Table 2
Table 3
2-Hydroxy (aryl(arylamino) methyl)naphthalene-1,4-diones 4.
Heterocyclic 2-hydroxy naphthalene-1,4-diones 5.
X
O
O
O
CHO
Heterocycle
Heterocycle
H2N
H2O (Reflux)
N
OH
+
H
InCl3 (20 mol%)
+
OH
O
X
1
2
3e-g
5a-f
Product 4
X
Y
Time (h)
Yield (%)
Product 5
X
Compound 3
Time (h)
Yield (%)
a
b
c
d
e
f
g
h
i
j
k
l
m
n
o
p
q
r
H
H
H
H
H
6
6.5
6
5
7
5.5
6.5
7
6
7
90
80
86
82
86
85
91
85
78
80
79
89
89
90
85
78
81
80
79
78
a
b
c
d
e
f
H
4-NO2
H
4-NO2
H
4-OH
3e
3e
3f
3f
3g
3g
5
4
5
6
5.5
6
81
80
83
80
82
78
4-Me
4-OH
4-NO2
H
4-OMe
4-Me
4-OH
4-NO2
4-F
4-Br
2,4-diCl
2-Cl
3-NO2
H
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
4-F
4-F
4-F
2-Cl, 4-NO2
2-Cl, 4-NO2
2-Cl, 4-NO2
C24H17ClN2O5: C, 64.22; H, 3.82; N, 6.24%. Found: C, 64.33; H, 3.77;
N, 6.31%.
7
7.5
5.5
5
7
6.5
5
6.5
6
7
2.2.20. 2-[(2-chloro-4-nitrophenylamino)(4-nitrophenyl)methyl]-
3-hydroxynaphthalene-1,4-dione (4t)
Orange Powder (yield 78%); mp 143e146 ꢀC. IR (KBr) (nmax
/
4-Me
4-NO2
H
Me
4-NO2
cmꢁ1): 3389 (OH), 3320 (NH), 1680 (CO), 1647 (CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 6.04 (1H, s, CH), 7.24e8.09, (11H,
m, H-Ar), 9.19 (1H, s, OH), 13C NMR (75 MHz, DMSO-d6): dC (ppm)
38.0, 112.8, 113.1, 122.1, 124.4, 125.1, 126.7, 128.4, 132.3, 133.6, 134.1,
135.1, 141.8, 156.4,159.8, 181.3, 183.6. MS, m/z: 479 (Mþ). Anal. Calcd
for C23H14ClN3O7: C, 57.57; H, 2.94; N, 8.76%. Found: C, 57.43;
H, 2.85; N, 8.65%.
s
t
m, H-Ar), 9.20 (1H, s, OH), 13C NMR (75 MHz, DMSO-d6): dC (ppm)
37.3, 101.9, 116.0, 121.7, 125.2, 125,7, 126.5, 130.5, 130.6, 130.8, 130.9,
132.9, 133.1, 134.0, 135.3, 136.0, 137.7, 146.8, 182.0, 182.8. MS, m/z:
418 (Mþ).Anal. Calcd for C23H15FN2O5: C, 66.03; H, 3.61; N, 6.70%.
Found: C, 66.17; H, 3.67; N, 6.62%.
2.2.21. 2-Hydroxy-3-[phenyl(pyridin-2-ylamino)methyl]
naphthalene-1,4-dione (5a)
Orange Powder (yield 81%); mp 145e148 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3435 (OH), 3328 (NH), 1676 (CO), 1653(CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 6.55 (1H, s, CH), 6.57e7.97, (14H, m,
H-Ar, NH), 9.78 (1H, s, OH). MS, m/z: 356 (Mþ). Anal. Calcd for
C22H16N2O3: C22H16N2O3: C, 74.15; H, 4.53; N, 7.86%. Found:
C, 74.03; H, 4.46; N, 7.78%.
2.2.18. 2-[(2-Chloro-4-nitrophenylamino)(phenyl)methyl]-3-
hydroxynaphthalene-1,4-dione (4r)
Orange Powder (yield 80%); mp 153e156 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3428 (OH), 3315 (NH), 1683 (CO), 1636 (CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 6.09 (1H, s, CH), 7.20e8.08, (12H,
m, H-Ar), 9.22 (1H, s, OH), 13C NMR (75 MHz, DMSO-d6): dC (ppm)
38.1, 111.8, 114.1, 121.1, 123.4, 126.1, 126.4, 128.1, 130.3, 132.6, 133.1,
135.1, 142.8, 156.1, 159.1, 181.6, 183.9. MS, m/z: 434 (Mþ).Anal. Calcd
for C23H15ClN2O5: C, 63.53; H, 3.48; N, 6.44%. Found: C, 63.45;
H, 3.57; N, 6.51%.
Due to very low solubility of the products 5a, 5b, 5e and 5f, we
cannot report the 13C NMR data for these products.
2.2.22. 2-Hydroxy-3-[(4-nitrophenyl)(pyridin-2-ylamino)methyl]
naphthalene-1,4-dione (5b)
Orange Powder(yield 80%); mp 148e151 ꢀC. IR (KBr) (nmax/cmꢁ1):
3387 (OH), 3325 (NH), 1678 (CO), 1665 (CO). 1H NMR (300 MHz,
DMSO-d6): dH (ppm) 6.50 (1H, s, CH), 6.64e8.09, (13H, m, H-Ar, NH),
9.81 (1H, s, OH). MS, m/z: 401 (Mþ). Anal. Calcd for C22H15N3O5:
C, 65.83; H, 3.77; N, 10.47%. Found: C, 65.74; H, 3.85; N, 10.34%.
2.2.19. 2-[(2-Chloro-4-nitrophenylamino)(p-tolyl)methyl]-3-
hydroxynaphthalene-1,4- dione (4s)
Orange Powder (yield 79%); mp 145e148 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3435 (OH), 3321 (NH), 1685 (CO), 1645 (CO). 1H NMR
(300 MHz, DMSO-d6): dH (ppm) 2.19 (3H, s, CH3), 6.04(1H, s, CH),
7.19e8.01, (11H, m, H-Ar), 9.15 (1H, s, OH), 13C NMR (75 MHz,
DMSO- d6): dC (ppm) 20.2, 38.7, 101.0, 104.9, 114.1, 123.7, 125.8,
126.4, 126.5, 129.8, 130.2, 130.3, 131.0, 132.3, 133.0, 133.1, 135.5,
135.8, 149.8, 182.0, 182.8. MS, m/z: 448 (Mþ). Anal. Calcd for
2.2.23. 2-[(1H-benzo[d]imidazol-2-ylamino)(phenyl)methyl]-
3-hydroxynaphthalene-1,4- dione (5c)
Orange Powder (yield 83%); mp 151e155 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3438 (OH), 3335 (NH), 3329 (NH), 1680 (CO), 1665 (CO). 1H
O
NH2
N
O
O
Ar
NH-R
OH
N
N
N
NH2
HO
N
NH2
Ar
R
InCl3
N
H
O
+ R-NH2
ArCHO
N
3
2
3e
4
InCl3
3g
3f
Fig. 3. Diversity heterocyclic amines 3eeg.
Fig. 4. Possible mechanism for the formation of products 4.

M. Dabiri et al. / Dyes and Pigments 89 (2011) 63e69
67
Table 4
DMSO-d6): dH (ppm) 5.26 (1H, s, CH), 6.55e8.02, (11H, m, H-Ar, NH),
9.15 (1H, s, OH). MS, m/z: 346 (Mþ). Anal. Calcd for C19H14N4O3: C,
65.89; H, 4.07; N, 16.18%. Found: C, 65.75; H, 4.16; N, 16.09%.
Photophysical data for absorption (abs) and fluorescence (flu) of selected products in
methanol.
Product
log
e
labs,max/nm
lflu,max/nm
Stock’s shift
4a
4b
4c
4d
4e
4g
4i
3.44
3.40
3.39
3.58
3.45
3.50
3.58
3.55
3.47
3.42
4.45
3.55
3.46
3.46
3.49
3.76
3.41
462
514
471
476
477
473
444
469
477
476
473
469
476
478
440
418
449
560
559
558
558
557
556
550
549
548
548
547
547
547
546
548
558
555
98
45
87
82
80
83
106
80
71
72
74
78
71
68
108
140
106
2.2.26. 2-[(4H-1,2,4-triazol-4-ylamino)(4-hydroxyphenyl)methyl]-
3-hydroxynaphthalene-1,4-dione (5f)
Orange Powder(yield78%); mp161e163 ꢀC. IR (KBr) (nmax/cmꢁ1):
3342 (OH), 3323 (NH), 1683 (CO), 1671 (CO). 1H NMR (300 MHz,
DMSO-d6): dH (ppm) 5.99 (1H, S, CH), 7.25e8.06 (11H, m, H-Ar, NH),
9.90 (1H, s, OH), MS, m/z: 362 (Mþ). Anal. Calcd for C19H14N4O4: C,
62.98; H, 3.89; N, 15.46%. Found: C, 62.90; H, 3.82; N, 15.74%.
4j
4l
4n
4o
4q
4r
4t
5a
5c
5f
3. Results and discussion
The choice of an appropriate reaction media is of crucial
importance for successful synthesis. Initially, the three-component
reaction of 2-hydroxynaphthalene-1,4-dione 1, benzaldehyde 2a
and aniline 3a as a simple model substrate was investigated to
establish the feasibility of the strategy and optimize the reaction
conditions (Table 1). Different solvents and catalysts were screened
in the model reaction. As could be seen in Table 1, the best result
was obtained with a 20 mol% of InCl3 as the catalyst in refluxing
water and the desired product, 2-hydroxy-(phenyl(phenylamino)
methyl)naphthalene-1,4- dione 4a, is obtained in good yield (Entry
2). Using lower amount of catalyst resulted in lower yields, while
higher amount of catalyst did not affected reaction times and yields
(Table 1). When this reaction was carried out without any catalyst,
TLC and 1H NMR spectra of the reaction mixture showed a combi-
nation of starting materials and numerous products, the yield of the
expected product was very poor (Table 1, entry 5).
NMR (300 MHz, DMSO-d)6: dH (ppm) 5.91 (1H, s, CH), 6.56e8.06,
(14H, m, H-Ar, NH), 9.09 (1H, s, OH), 13C NMR (75 MHz, DMSO-d6):
dC (ppm) 35.5, 101.2, 111,4, 113.5, 123.8, 126.4, 127.3, 127.9, 128.2,
128.6, 129.0, 130.0, 130.3, 135.7, 136.9, 138.5, 140.3, 141.7, 178.9,
181.0. MS, m/z: 395 (Mþ). Anal. Calcd for C24H17N3O3: C, 72.90;
H, 4.33; N, 10.63%. Found: C, 72.79; H, 4.40; N, 10.72%.
2.2.24. 2-[(1H-benzo[d]imidazol-2-ylamino)(4-nitrophenyl)
methyl]-3-hydroxynaphthalene-1,4-dione (5d)
Orange Powder (yield 80%); mp 150e153 ꢀC. IR (KBr) (nmax
/
cmꢁ1): 3440 (OH), 3337 (NH), 3331 (NH), 1685 (CO), 1673 (CO). 1H
NMR (300 MHz, DMSO-d6): dH (ppm) 5.21 (1H, s, CH), 6.26e8.71,
(13H, m, H-Ar, NH), 9.05 (1H, s, OH). 13C NMR (75 MHz, DMSO-d6):
dC (ppm) 34.7, 110.4, 123.8, 126.5, 127.4, 128.0, 128.2, 128.6, 130.0,
130.4, 131.4, 132.2, 132.6, 133.8, 135.6, 138.5, 139.5, 142.2, 149.7,
178.9, 181.0. MS, m/z: 440 (Mþ). Anal. Calcd for C24H16N4O5:
C, 65.45; H, 3.66; N, 12.72%. Found: C, 65.32; H, 3.57; N, 12.64%.
After optimizing the reaction conditions, a variety of aromatic
aldehydes and amines were employed under similar circumstances
to evaluate the substrate scope of this reaction. The results are
shown in Table 2. As anticipated from our original results, these
reactions proceeded very cleanly at refluxing water and no unde-
sirable side reactions were observed.
The aromatic aldehydes carrying both electron-withdrawing
and electron-releasing substituents were also converted to their
corresponding 2-hydroxy naphthalene-1,4- diones derivatives in
good yields. It is noteworthy that the reactions of halosubstitueted
benzaldehydes proceeded with the expected mechanism and
exhibit good yields (Table 2).
2.2.25. 2-[(4H-1,2,4-triazol-4-ylamino)(phenyl)methy]-
3-hydroxynaphthalene-1,4-dione (5e)
Orange Powder (yield82%); mp 145e148 ꢀC. IR (KBr) (nmax/cmꢁ1):
3338 (OH), 3333 (NH), 1681 (CO), 1675 (CO). 1H NMR (300 MHz,
Fig. 5. The emission spectra of selected compounds 4 (5 ꢂ10ꢁ5 M in CH3OH).

68
M. Dabiri et al. / Dyes and Pigments 89 (2011) 63e69
Appendix. Supplementary data
Supplementary data associated with this article can be found in
the online version, at doi:10.1016/j.dyepig.2010.09.004.
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We gratefully acknowledge the financial support from the
Research Council of Shahid Beheshti University.

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