INTRODUCTION:
Green chemistry is a developing field at a rapid
pace for designing the synthetic pathways in chemistry. Utilizing non-renewable
resources in preference to the maximum without generating waste or minimizing
it and thereby achieving more atom economy in the reaction is the one of the
important principles of Green Chemistry. This principle has caught the utmost
attention in recent years. To check pollution by virtue of overusing hazardous
reagents, emphasis should be laid upon the adoption of more eco-friendly
pathways for the synthesis of products1.
The most abundant and easily available resource on the
blue planet is water as a medium for the biochemical processes to take
place. Water has been recognized as a sustainable solvent in organic
chemistry for a long time. Water as a solvent is inexpensive, safe apart
from its environmental benefits. The study of organic reactions in
aqueous medium has been gaining momentum leading to surprising discoveries2.
A number of nucleophilic addition/substitution reactions with reasonable
increase in the reaction rate have so far been reported in water even when
water insoluble substrates were used as suspensions3.
Quinones are large class of naturally occurring
pigments that show outstanding photochemical properties4 and act as
a starting material in the biosynthesis of key antibiotics5. They
are characterized by a number of biological properties like anti-diabetic6,
anti-cancer7, cytotoxic8, enzyme inhibition9
and antioxidative10. They also find use as charge-transfer
complexes11 and chemical sensors12. The transformation
of hydroquinones to quinones, during the redox reactions that play an
important role in living organisms. They also work as electron–proton carriers
for carrying oxygen in biochemical reactions13.
Microwaves assisted synthesis has been an another
green, and well established initiative in chemistry that has emerged
as a option with widespread applications both in the laboratory and
industries. These days number of complexation reactions have been carried out
by using microwave Chemistry14. It is extensivelyused for the
synthesis of new drugs and other pharmaceuticals15. It is better
placed technique in terms of enhanced yield of product and rapid
reaction rates over conventional techniques16, because of the
shorter time span required for chemical transformations16. Quinone
and its derivatives are recognized as photo and electro chemically active
molecules. They find widespread applications in the areas like fabrication of
chemical transducers, molecular switch systems17. Fluorescent heterocyclic
compounds are used more often in devising emitters in electroluminescence
devices, probes in biochemical research, photo-conductive materials18,19,20.
In the present work, we report the comparison between green ulktrasound
assisted synthesis of 1,4- quinone derivatives against conventional heating
methods using water and ethanol as solvents and their lanthanide complexes.
The so synthesized complexes were purified, dried and subsquently
characterized by using different characterization tools like UV–Vis, FT-IR,
NMR spectroscopy. Melting point of the synthesized complex compound was
checked in open capillary tubes by using a melting point apparatus and was
found to be in tandem with the data quoted in the earlier literature21,22,23,24.
During the last three decades several papers concernmg
the synthesis, characterization, thermal stability, kinetic studies, and
biological functions of some metal chelates of hydroxyquinones have been
published. R.S.Bottei and P.L.Gerace synthesized metal chelate polymers of
naphthazarin (5,8-dihydroxy-1,4-naphthoquinone) with transition metal ions,
Cu(II), Zn(II), Ni(II), Co(II) and also Be(II)25 The composition,
thermal stabilities and infrared spectra of the chelates have been
investigated. Complexes of Co(II), Zn(Il) and Ni(II) ions showed coordination
number of six and are octahedral in configuration. Pierpont and coworkers
reported the synthesis and characterization of dimeric Ni(II) and Cu(II)
complexes bridged by the dianion of 2,5-dihydroxy-1,4-benzoquinones (DHPBQ) and
rhodizonate(II)dianion26. James T. Wrobleski et. al. reported
synthesis and characterization of polymeric Fe(II) and dimeric Fe(III)
complexes of the dianion of 2,5-dihydroxybenzoquinones27. Thermal
and spectral studies of metal chelates of 2,5-dihydroxy-1,4-benzoquinone,
lawsone (2-hydroxy-1,4-naphthoquinone), and
juglone(5-hydroxy-1,4-naphthoquinone), with Co(II), Ni(II), Zn(II) and Cu(II)
were done by Bottei R.S and coworkers and the properties were compared with
those of naphthazarin28,29 Chemical and spectral studies of metal
chelates of lawsone and its C-3 substituted derivatives with Fe(II) and Fe(III)
were done by Dufrene and coworkers30. Several papers were published
on the studies on transition metal complexes of hydroxyl anthraquinones.
Polymeric chelates of 1,4-dihydroxyanthraquinone with Cu(II) and Co(II) were
synthesized and their electrical resistance over a wide range of temperatures
were studied by Talati A M and Mistry V.N31. Naphthoquinone and its
derivatives have been used in industry, medicine, and qualitative and
quantitative estimation of metal ions32-36. The studies on the
effect of [H+] on juglone [5-hydroxy-1,4-naphthoquinone] had shown
that it could be successfully used as an indicator in acidimetry and
alkalimetry37. Many naphthoquinone derivatives have been used as
reagents for the determination of various metal ions38,39.
Ultrasound assisted synthesis was carried out
using a sonicator with its probe suspended in the reaction mixture. The
fluorescence properties of compounds were studied too using acetone
as medium in a fluorescence spectrophotometer. The structure of
2,3-dihydroxy-1,4-napthaquinone is as shown in fig. 1.
Fig. 1 Structure of 2,3-dihydroxy-1,4-napthaquinone
MATERIALS AND METHODS:
Experimental
All the chemicals used are AR or equivalent grade
including Lanthanide chloride and solvents used are of high purity. Solvents
were purified by the standard methods in the literature. The method protocol
followed in both conventional and ultrasound assisted synthesis is as given
below :
Synthesis of 2,3-Dihydroxy-1,4-naphthoquinone (ligand)
Conventional heating method
A mixture of 2,3-dichloro-1,4-naphthaquinone (0.227
g, 0.01 mol.) and dapsone (0.248 g, 0.01 mol.) was added to ethanol (100 mL)
and the solution was refluxed for 5 h at 60 0C. The
resulting solution was cooled and the precipitate was filtered, dried
at room temperature and purified.
Ultrasound assisted method
The synthesis of the compound was achieved by a
green facile method using water as solvent. The reaction between the
2,3-dichloro1,4-naphthaquinone and dapsone (4-amino phenyl sulfone) in
the presence of ethanol yielded only 52% of product. However, when
water was used as the solvent, the yield of improved a lot 87%. The said
compound was previously synthesized and reported[6] wherein a mixture of
equimolar mixture of 2,3-dichloro-1,4-naphthaquinone and dapsone in the
presence of phenylene triethylamine as a catalyst with absolute ethanol as
solvent. The reaction mixture was refluxed for 18 h, black precipitate
was separated, and dried at room temperature, and recrystallized inethanol to
get refined product. In this work the same compound was synthesized in water
and assisted by ultrasound method which gave yield to the extent of 87%. Which
shows that it is greener way of synthesizing compound. The results indicate
that compound, quinone derivative synthesized, its yield was substantially
higher than conventional process. This testifies that our method of synthesis
is a facile and greener method.
A mixture of 2,3-dichloro-1,4-naphthaquinone
(0.227 g, 0.01 mol.) and dapsone (0.248 g, 0.01 mol.) was ground together and
subjected to ultrasonication in water and acetone separately for 15 minutes
each. After the given detention time with sonication, the product was
separated to cool in air and then subsequently ice cold water (100 mL) was
added. The solid product was filtered, dried at room temperature and
recrystallized using ethanol as a solvent.
Synthesis of lanthanide complex
The lanthanide complexes are synthesized by a general
procedure as given below. To a solution of 3 mM of
2,3-Dihydroxy-1,4-naphthoquinone (ligand) (0.54 g) in 25 ml of methanol, an
aqueous solution of 1 mM of metal (III) chloride hexa-hydrate was added with
constant stirring. The mixture was allowed to reflux for 3 h in oil bath. After
cooling the solution to room temperature, the product was formed on suitably
adjusting the pH of the solution between 7.5 and 8.0 by the addition 5% liquor
ammonia. The solid thus formed was filtered, washed with cold water and
methanol and finally dried in vacuum giving semi-crystalline product.
RESULTS AND DISCUSSION:
UV-Visible Spectroscopy
UV–Vis absorption spectrum was recorded for the
compound in acetone which shows absorption maximum at 466 nm (Fig.2). The
UV–Vis absorption spectra of complex was recorded in acetone as solvent, as
shown in Fig.2 which exhibited well defined band which may be attributed
to the typical intramolecular charge transfer. The photochemical properties
of the synthesized compounds were studied using UV–Vis and photoluminescence
spectroscopy.
Fig.2. UV–Vis spectrum of lanthanide complex
Fluorescence emission spectroscopy :
The compound also exhibited photoluminescence band at
about 410 nm in case of conventional heating method while it shows shift to
higher wavelength to 460 nm (red shift) which can be attributed to stronger
hydrogen bonding in the complex formation and a bit increase in the size and
morphology of the complex particles (Fig. 3).
Fig.3. The fluorescence spectrum [Left] for
conventional heating [Right] Ultrasound assisted
Fourier transform infrared spectroscopy (FTIR)
Fig.4. FTIR spectrum of lanthanide
complex with 2,3-Dihydroxy-1,4-naphthoquinone (ligand)
WhileFTIR shows characteristics vibrational
frequencies (cm-1) corresponding to 3240 (NH), 3363 (NH2aromatic), 1558, 1643 (C=O),
1141, 1296 (S=O), 833 (C–Cl), 1103, 1141 (C–N) (Fig. 5). FTIR absorption
spectral data indicate bonding through both hydroxyl oxygen with quinone
carbonyls acting as bridge between lanthanide ions and there exists an
extensive network of intermolecular hydrogen bonding involving coordinated
water and quinone carbonyl groups.
Scanning electron microscopy (SEM)
Fig.6 shows the SEM image of the sample is shown
showing an ice square-like shape although there is change in the morphology
among different particles as observed in the complex with the variation in the
particle size averaging out to 30±3 nm which is comparatively smaller than that
obtained using conventional process. The SEM image shows the reasonably good
binding between the metal and ligand. The results are in harmony with those
obtained using other analytical tools.
Fig. 5. SEM image of Lanthanide complex of
2,3-dihydroxy-1,4-napthoquinone
CONCLUSION:
The compound, 2,3-dihydroxy-1,4-napthoquinone
napthoquinone was synthesized by ultrasound assisted method using an alternative
green solvent and by conventional heating method and the former method was
found to be superior, facile, greener, and rapid with better yield and purity
of the product. This method can further be used for synthesizing other
derivatives of quinone as ligands as well. As the developed method is
eco-benign it is preferable too for the complexation reactions efficiently and
effectively using quinone and its derivatives as ligands with lanthanides or
transition metals40,41,42.
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solvent-free one-pot multicomponent synthesis of 3-substituted quinazolin-4(3H)
ones and thienopyrimidin-4(3H) ones, Tetrahedron Lett., 2012, 53, 4062–4064.
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S. Witayakran, A. J. Ragauskas,
One-pot synthesis of 1, 4-naphthoquinones and related structures with Laccase,
Green Chem, 2007, 9, 475–480.
27.
V. K. Tandon, H. K. Maurya, ‘On
water’: unprecedented nucleophilic substitution and addition reactions with 1,
4-quinones in aqueous suspension, Tetrahedron Lett., 2009, 50, 5896–5902.
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30. F. I. Carroll, E. Snethh, E.
Dudley, H. Waynemiller, Aration of some sulfonamide and diaminodiphenylsulfone
analogs of 1,4- naphthoquinone, J. Org. Chem., 1969, 12, 187– 189.
31.
B. Zhang, G. Salituro, D.
Szalkowski, Z. Li, Y. Zhang, I.Royo, D. Vilella, M. T. Diez, F. Pelaez, C.
Ruby, R. L. Kendall, X. Mao, P. Griffin, J. Calaycay, J. R. Zierath, J. V.
Heck, R. G. Smith, D. E. Moller, Discovery of a small molecule insulin mimetic
with antidiabetic activity in mice,Science, 1999, 284, 974–977.
32.
M. Kinugawa, Y. Masuda, H. Arai, H.
Nishikawa, T.Ogasa, S. Tomioka, M. Kasai, Large scale synthesis of the high
quality indoloquinone antitumor agent EO 9 via [bis(trifluoroacet-
oxy)iodo]benzene oxidation of 4-aminoindole,Synthesis, 1996, 5, 633– 636.
33.
L. T. Jonathan, C. T. Che, J. M.
Pezzuto, H. H. S. Fong, F. N. R. Farnsworth, 7-Omethylhorminone and other
cytotoxic diterpenequinone from Lepechinia bullata, J. Nat. Prod.,1989,
52, 571–575.
34.
C. Puder, K. Wagner, R. Vettermann,
R. Hauptmann, O. J. Potterat, Terphenylquinone inhibitors of the Src protein
tyrosine kinase from Stilbella, sp. J. Nat. Prod., 2005, 68, 323–326.
35.
I. K. Lee, B. S. Yun, S. M. Cho, W.
C. Kim, J. P. Kim, I. J.Ryoo, H. Koshino, I. D. J. Yoo,Betulinans A and B, two
benzoquinone compounds from Lenzitesbetulina,J. Nat. Prod.,59,
1090–1092.
36.
T. Murata, Y. Morita, K. Fukui, K.
Sato, D.Shiomi, T. Takui, M. Maesato, H. Yamochi, G. Saito, K. A. Nakasuji, A
purely organic molecular metal based on a hydrogenbonded charge-transfer
complex: crystal structure and electronic properties of
ttfimidazole–p-chloranil, Chem. Int. Ed., 2004, 43, 6343–6346.
37.
K. C. Nam, S. O. Kang, H. S. Jeong,
S. Jeon, Urea derivative of calix[4]diquinone: HSO4 ion selective receptor,
Tetrahedron Lett., 1999, 40, 7343–7346.
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F. A. Khan, S. Choudhury, Synthesis
and electrochemical properties of substituted parabenzoquinone derivatives,
TetrahedronLett., 2010, 51, 2541–2544.
39.
A. Solhy, W. Amer, M. Karkouri, R.
Tahir, A. E. Bouari, A. Fihri, M. Bousmina, M. Zahouily, Bi-functional
modified-phosphate catalyzed the synthesis of (EE)-
bis(benzylidene)-cycloalkanones: microwave versus conventional-heating,J. Mol.
Catal., 2011, 336, 8–15.
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