World Applied Sciences Journal 14 (8): 1154-1157, 2011

ISSN 1818-4952
© IDOSI Publications, 2011

Synthesis of -diketone and its Metal Complexes

Pooja N. Verma, Javed I. Sheikh and Harjit D. Juneja

Department of Chemistry, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur-440033, India

Abstract: 1-(2', 4' dihydroxyphenyl)-3-phenyl-propane-1, 3-dione and its transition metal complexes have
been synthesized. The -diketone is afforded by employing Baker-Venkataraman rearrangement on
4-hydroxy-2-benzoyloxyacetophenone. The synthesized compounds were characterized by analytical
techniques viz: IR, NMR, Mass and elemental analysis. The thermal stability and antibacterial activity of the
newly synthesized metal complexes have been studied.

Key words: -diketones Baker-Venkataraman rearrangement Metal complexes Thermo gravimetric

analysis Antibacterial activity

INTRODUCTION certain ultraviolet rays to protect skin [11]. -diketone in

its keto-enol form is also a important pharmacophores of
-diketones are used as ligands for almost 120 years. HIV-1 integrase inhibitors [12]. It is also used as chelating
These derivatives were synthesized for the first time in agents in some process based on supercritical CO 2 [13]. It
1887. The nature of bonding and chelation was elucidated is used as extractants for lanthanide ions [14].
by Werner and Morgan [1-2]. In present work, we have synthesized and studied
In the last decades, -diketones and their metal some properties of 1-(2', 4'-dihydroxyphenyl)-3-phenyl-
complexes have been used as model compounds in propane-1, 3-dione and its metal complexes. The title
physical chemistry studies. They have also been compound was synthesized from 4-hydroxy-2-
used as chelating ligands for lanthanides and transition benzoyloxyacetophenone by employing Baker-
metals [3]. They are bidentate ligands with the possibility Venkataraman rearrangement [15, 16] which was
of complexation with almost all the metal ions [4]. A wide previously synthesized by Resacetophenone. The
variety of -diketones with different substituents and synthesized compounds were characterized by analytical
their complexes have been synthesized and their techniques and screened for antibacterial study.
properties such as volatility, lewis acidity or aggregation
state, standard molar enthalpies of formation, standard MATERIALS AND METHOD
molar enthalpies of sublimation, vapour pressures and
enantioselective catalytic property have been studied [5] All the elemental analyses were done using the Perkin
-diketones have a wide range of uses in metal extraction Elmer 2400 CHN analyzer. FT-IR spectra were recorded
by chelation. 1, 3-Diketones are very important using (KBr) disc on Perkin-Elmer spectrum Rx-I
compounds in organic chemistry, because they exhibits spectrometer. 1H NMR were recorded on Brucker AC-300
some biological activities, such as antioxidants, antitumor F (300 MHz) NMR spectrometer by using DMSO-d6 and
and antibacterial activities and are also key intermediates CDCl 3 as solvent and tetramethylsilane as an internal
to various heterocyclic compounds [5-8]. -diketone like standard. Mass spectra were recorded on 70-S Mass
Anabaena -diketone hydrolase also possesses some spectrometer using m-nitro benzyl alcohol (NBA) matrix.
enzymatic activities [9], Europium (III) -diketonates have
excellent luminescent property [10]. Hydroxy-2-Benzoyloxyacetophenone 2: 3.8g (0.025mol)
-diketones like (4-tert-butyl-4’- of resacetophenone was taken in a flask along with 4.9g
methoxydibenzoylmethane) and 1-(4-t-butyl phenyl) (4ml, 0.035mol) benzoyl chloride and 5ml dry distilled
propane-1,3-dione and 1-p-cumenyl-3-phenyl-propane- pyridine. After 20min, the reaction mixture was poured
1,3-dione are used in UV sunscreen cosmetics that filters into 120ml of 1M hydrochloric acid containing 50g of

Corresponding Author: Pooja N. Verma, Department of Chemistry, Rashtrasant Tukadoji Maharaj Nagpur University,
Nagpur-440033, India. Tel: +919021727679.
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crushed ice with constant stirring. The product obtained The complex of synthesized compound 3 gives green
after sometimes was filtered and washed with 10ml of coloured Cu (II) -diketonate 4a in high yield. The
ice-cold methanol and then with 10ml of water. It was structure was then confirmed by the spectral analysis: IR
recrystallized from ethanol, filtered and dried. Yield: 81%; (KBr): 3336 (-OH), 3050 (=C-H), 1735 (-C=O), 1609 (C=C),
m.p. 99°C. 701 (Ar-H); 1H NMR (DMSO-d6): 12.56 (s, 2H), 4.99(s,
2H), 8.79(s, 2H), 8.78 (d, 4H), 7.67-8.21 (m,6H), 7.67 (d, 2H),
(2',4' Dihydroxyphenyl)-3-Phenyl-Propane-1, 3-Dione 3: 7.02 (d, 2H), 7.09 (s, 2H); MS (EI, 70eV): m/z (%) 612 (M+,
5.1g (0.02mol) of 4-hydroxy-2-benzoyloxyacetophenone 100); Anal. Calcd for C 30H28O10Cu: C, 58.82; H, 4.57; Cu,
2 was dissolved in 18ml of dry pyridine in a 50ml 10.38; Found: C, 58.43; H, 4.76; Cu, 10.89. The C=O band in
bolt-necked flask and heated to 50°C. With mechanical complex 4a shifted to lower frequency as compared to that
stirring 1.7g (0.03mol) of potassium hydroxide was added of free ligand which indicates the coordination of metal
which was powdered rapidly in a mortar preheated in an atom with the carbonyl group of diketone.
oven at 100°C and was stirred for 15min. The reaction Similarly, other transition metal complexes were
mixture was cooled to room temperature and acidified by prepared by the same method. The ligand and its metal
adding with stirring 25ml of 10% aqueous acetic acid. The complexes are quite stable. All the complexes are insoluble
pale yellow precipitate was collected by filtration and in water but soluble in acetone, Methanol and DMSO.
dried in an oven at 50°C and was recrystallized from The complexes are non-electrolytic in nature [17].
ethanol. Yield: 79%; m.p.164°C.
Thermogravimetric Analysis: All thermal analyses
were done on Perkin Elmer SII, Diamond TG/DTA
Bis( -diketonato) Cu(II) complex 4a: A mixture of Thermogravimetric analyzer at VNIT, Nagpur. The
2.56g (0.01 mol) of -diketone compound 3 and 0.9g Thermogravimetric curves of the synthesized complexes
(0.005 mol) anhydrous Cu (II) acetate and 5ml were recorded between 300C -10000C in air as medium.
anhydrous ethanol was stirred for 3h at room temperature. The TGA curves of all the complexes are almost similar
The pale green solid which precipitated was washed with and indicate a continuous weight loss till a stable metal
boiling ethanol and recrystallized from ethyl acetate oxide is formed. Weight loss of 5.73% - 6.01% between
to give pale green crystals of Cu (II) -diketonate 4a. 150°C - 180°C has been observed for cobalt, Nickel and
Yield: 92%. Manganese complex which indicate the presence of two
Similarly, the complexes of Cobalt, Nickel, Manganese molecules of water of coordination.
and Zinc were prepared by the same method. On further increasing the temperature, no weight loss
takes place probably due to the formation of stable metal
RESULTS AND DISCUSSION oxides
The antibacterial screening of ligand and its metal
4-hydroxy-2-benzoyloxyacetophenone 2 undergoes complexes shows that it possesses antibacterial activity
Baker-Venkataraman rearrangement to afford pale yellow with respect to pathogenic bacteria like Staphylococcus
needles of 1-(2', 4' dihydroxyphenyl)-3-phenyl-propane-1, aureus, Bacillus substilis (Gram +ve); Escherichia coli and
3-dione 3. The negative test for ester confirms that it is Proteus vulgaris (Gram –ve). From the antibacterial study
devoid of ester group. The structure was further it was observed that antimicrobial activity of ligand is
confirmed by the spectral analysis: IR (KBr): 3450 (-OH); higher than that of its metal complexes for most of the
3061 (=C-H); 1744 (-C=O); 1606 (C=C); 735 (Ar-H); 1H bacteria.
NMR (DMSO-d6) : 15.72 (s, 1H), 12.02 (s, 1H), 4.76(s, 1H),
8.89(s, 1H), 8.84 (d, 2H), 7.10-8.17 (m,3H), 7.26 (d, 1H), 6.92 Antibacterial Screening: Antibacterial activities of the
(d, 1H), 7.02 (s, 1H); MS (EI, 70eV): m/z (%) 256 ( M+, 100), prepared compounds were tested against bacteria
257 (M+1,16.5), 69 (50) Anal. Calcd. for C15H12O4: C, 70.31; Staphylococcus aureus, Bacillus substilis (Gram +ve);
H, 4.68. Found: C, 70.12; H, 4.81. In the 1H NMR Spectra it Escherichia coli and Proteus vulgaris (Gram –ve) using
gives characteristic peak at 15.72 which corresponds to filter paper disc diffusion method (Peach and Traey, 1950)
enolic proton and at 12.02 which is being due to using acetone as solvent. Antibiotic drugs such as
phenolic proton adjacent to carbonyl group. It confirms Streptomycin and Amoxicillin were used as reference
the formation of -diketones. The compound in enolic drugs. Selected pathogenic bacteria were maintained on
form is more stable than that of ketonic one. nutrient agar medium for 36 hrs. Old bacterial culture were

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Table 1: Thermal data of the complexes

Coordination water (%) Decomposition % Weight loss
Sr. No. Complex Obs (calc) Temperature (°C) Obs (calc) Residue comp
1. C30H22O8Mn.2H2O 6.45 (5.98) 431.66 88.402 (88.21) MnO
2. C30H22O8Co.2H2O 6.294 (5.94) 396.31 71.98 (72.61) Co2O3
3. C30H22O8Ni.2H2O 5.702 (5.94) 475.99 87.014 (87.66) NiO
4. C30H22O8Cu ---- 360 85.246 (86.15) CuO
5. C30H22O8Zn ---- 421.51 85.249 (85.87) ZnO

Table 2: Screening of antimicrobial activity of compounds

Inhibition in mm
----------------------------------------------------------------------------------------------------------------------
Source S. aureus B. subtilis E. coli P. vulgaris
1. Ligand 3 20.0 6.8 17.0 13.6
2. Cu Complex 11.6 10.3 10.0 8.4
3. Mn Complex -- 9.2 12.4 --
4. Co complex -- -- 16.9 --
5. Zn Complex 7.6 -- -- 8.7
6. Ni Complex -- -- 11.4 --

O
O

CH3
CH3 Ph.COCl
Pyridine
HO O C
HO OH
O
1 2

KOH
HO OH

O O

O O M(OAc)2
Ethanol
H2O M O2H
HO OH
O O
3

HO OH

M = Co(II), Ni(II) and Mn(II), however in case of Cu(II) and Zn(II) water of coordination is absent

Scheme: Synthesis of ligand and its metal complexes.

inoculated into nutrient broth and incubated at (Streptomycin and Amoxicillin) were used as positive
37±2°c on a rotary shaker at 100 rpm. After 36 hrs controls.
incubation, the bacterial suspensions were used for The results of tested compounds against these
further tests. bacteria are shown in Table 2 given below. The ligand
Antibacterial activity was then carried out using shows high antibacterial activity against S.aureus, E.Coli
synthesized compounds. Filter paper disc soaked in and P.vulgaris bacterium as compared to its complexes
solvent was used as negative controls while the discs while in the case of B.subtilis ligand shows activity less
soaked in standard broad-spectrum antibiotic solution than some of its complexes.

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ACKNOWLEDGMENT 9. Bennett, I, J. Broom, R. Cassels, J. Elder, N. Masson

and J. Hanlon, 1999. Synthesis and antibacterial
My sincere thanks are due to the Head, Department properties of -diketone acrylate bioisosteres of
of Chemistry, Rashtrasant Tukadoji Maharaj Nagpur pseudomonic acid, Bioorganic and Medicinal
University, Nagpur for providing all the necessary chemistry Lett., 9: 1847-1852.
laboratory facilities, the Director, SAIF, Punjab University, 10. Bunzli, J., 2006. Lanthanide-containing luminescent
Chandigarh for providing spectral analysis and Head, molecular edifices, J. Alloys Compds, 408: 934-944.
Department of Botany, S.F.S. College, Nagpur for 11. Andrae, I., A. Bringhen, F. Bohm, H. Gonzenbach,
screening the compounds for antibacterial activity. T. Hill, L. Mulroy and T. Truscott, 1997. A UVA filter
(4-tert-butyl-4’-methoxydibenzoylmethane):
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