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Synthesis and DFT Quantum Chemical Calculations of Novel Pyrazolo[1,5-c]pyrimidin-7(1H)-one Derivatives.

Byline: Murat Saracoglu, Zulbiye Kokbudak, Zeynep Cimen and Fatma Kandemirli

Summary: In this study, a convenient procedure for the preparation of pyrazolo[1,5 -c]pyrimidin-7(1H)-one derivatives is described. The new pyrazolo[1,5-c]pyrimidin-7(1H)-one derivatives (2a, b) were synthesized from the cyclocondensation reaction of the compounds 1-amino-5-(4-methoxybenzoyl)-4-(4-methoxyphenyl)pyrimidin-2(1H)-one (1a) and 1-amino-5-(4-methylbenzoyl)-4-(4-methylphenyl)pyrimidin-2(1H)-one (1b) with [alpha]-chloroacetone. The structures of the compounds (2a, b) were characterized by elemental analysis, FT-IR, 1H-NMR and 13C-NMR spectroscopic techniques. In addition to experimental study in order to find molecular properties, quantum-chemical calculations of the new pyrazolo[1,5 -c]pyrimidin-7(1H)-one derivatives (2a, b) were carried out by using DFT/B3LYP method with the 6 -311G(d,p) and 6-311++G(2d,2p) basic sets.

Quantum chemical features such as HOMO, LUMO, HOMO -LUMO energy gap, chemical hardness, chemical softness, electronegativity, chemical potential, dipole moment etc. values for gas and solvent phase of neutral molecules were calculated and discussed.

Keywords: Aminopyrimidine; Pyrazolo[1,5-c]pyrimidin-7(1H)-one Derivatives; Synthesis; DFT; Quantum chemical calculations.

Introduction

In the recent years pyrimidines and pyrazoles have attracted much interest due to the biological and pharmacological properties. Pyrimidines have been used in synthesis for many years due to their importance about structural diversities and medicinal properties such as antibacterial [1], anticancer [2], antitumor [3] and anti-inflammatory [4] activities. Similarly, pyrazolopyrimidines exhibit important biological properties such as antitumor [5], anti-inflammatory [6], antiviral [7] and antifungal [8] activity. N-Amino-pyrimidine-2-one derivatives such as 1-amino-5-(4-methoxybenzoyl)-4-(4-methoxyphenyl)pyrimidin-2(1H)-one (1a) and 1-amino-5-(4-methylbenzoyl)-4-(4-methylphenyl)pyrimidin-2(1H)-one (1b) appeared to be an important starting compound in synthetic organic chemistry.

In recent years, the reactions of N-amino-pyrimidine-2-one derivatives (1a, b) with anhydrides [9], isothiocyanate [10], 1,3-dicarbonyl compounds [11] and acyl chlorides [12] have been reported in different solvents and at various temperatures. Moreover, transition metal complexes of N-amino-pyrimidine-2-one derivatives (1a, b) have been studied [13].

In this study, N-Aminopyrimidine-2-one derivatives (1a, b) were synthesized in two steps from furan-2,3-diones [14] (Scheme-1). The new pyrazolo[1,5-c]pyrimidin-7(1H)-one derivatives (2a, b) were prepared in 60-71% yields via the cyclocondensation reaction of N-aminopyrimidine-2-one derivatives (1a, b) with [alpha]-chloroacetone according to (Schemes-2 and 3). These compounds have been elucidated both experimentally and theoretically. In experimental studies, the molecules were characterized by FT-IR, 1H and 13C-NMR spectroscopies.

Optimization of synthesized molecules was performed using DFT/B3LYP method with 6-311G(d,p) and 6-311++G(2d,2p) basis sets of Gaussian program [15]. 6-311++G(2d,2p) basis set is known as one of the basis sets that gives more accurate results in terms of the determination of electronic and geometries properties for a wide range of organic compounds [16]. Quantum chemical parameters for synthesized molecules (2a, b) such as the energy of the highest occupied molecular orbital (EHOMO), the energy of the lowest unoccupied molecular orbital (ELUMO), HOMO-LUMO energy gap (IE), chemical hardness (), softness (I), electronegativity (X), chemical potential (u), dipole moment (DM), global electrophilicity (I), sum of the total negative charge (TNC) and sum of electronic and zero-point energies (SEZPE) for gas and solvent phase of neutral molecules were calculated and discussed.

Recently, optimization of molecules with different basic sets and discussion of the results are widely used [17-36]. Arshad at al. have been synthesized and characterized by various spectroscopic techniques including FT-IR, UV-vis, 1H-NMR, 13C-NMR spectroscopy, the structure and density functional theory (DFT) study was unequivocally confirmed by single crystal X-ray diffraction studies of N-[3-anthracen-9-yl-1-(4-bromo-phenyl)-allylidene]-N-benzenesulfonohydrazine [37]. Nisa at al. are investigated acceleration of the electrocyclization of 1,3,5-hexatriene to 1,3-cyclohexadiene through early transition metal catalysis of through quantum mechanical methods [38].

Experimental

General materials and instruments

Chemicals and all solvents were commercially available and used without further purification. Melting points were determined on the digital melting point apparatus (Electrothermal 9100) and are uncorrected. The compounds were routinely checked for their homogeneity by TLC using DC Alufolien Kieselgel 60 F254 (Merck) and Camag TLC lamp (254/366 nm). Microanalyses were performed on a Leco CHNSO-932 Elemental Analyser and the results agreed favourably with the calculated values. The FT-IR spectra were recorded on a Shimadzu Model 8400 FT-IR spectrophotometer. The 1H and 13C-NMR spectra were recorded on a Bruker 400(100) MHz Ultra Shield instrument. The chemical shifts were reported in ppm from tetramethyl silane as an internal standard and are given in I' (ppm).

Synthesis of pyrazolo[1,5-c]pyrimidin-7(1H)-one derivatives (2a, b)

5-(4-Methoxyphenyl)-4-[(4-methoxyphenyl) carbonyl]-2-methylpyrazolo[1,5-c]pyrimidin-7(1H)-on (2a)

Compound 1a (0.35 g, 1 mmol) and [alpha]-chloroacetone (0.11 mL, 1.3 mmol) were refluxed in 30 mL xylene for 10 hours. The solvent was evaporated. The remaining oily residue was then treated with petroleum ether and stirred for 24 hours. The product 2a which precipitated was filtered off and washed with ethanol and allowed to dry on P2O5; 60% yield; m.p. 225-227 AdegC; FT-IR (cm-1): 3072 (aromatic C-H stretch.), 2921 (CH3O-), 1737-1647 (C=O carbonyl's), 1598-1550 (C=C and C=N), 740-660 (pyrimidine ring skeleton vib.); 1H-NMR (400 MHz, DMSO): I'= 9.01 (s, 1H, NH), 8.88-6.88 (m, 9H, Ar-H), 3.82-3.73 (s, 6H, 2CH3O-), 2.36 ppm (s, 3H, CH3); 13C-NMR (100 MHz, DMSO): I'= 191.97, 164.10 (C=O), 160.38-114.08 ppm (aromatic carbons), 56.09-55.65 (2CH3O-), 11.73 ppm (CH3-). Elemental analysis (%) for C22H19N3O4, Found (Calc.): C= 67.63 (67.86); H= 4.86 (4.92); N= 10.67 (10.79).

5-(4-Methylphenyl)-4-[(4-methylphenyl)carbonyl]-2-methylpyrazolo[1,5-c]pyrimidin-7(1H)-on (2b)

Compound 1b (0.32 g, 1 mmol) and [alpha]-chloroacetone (0.10 mL, 1.3 mmol) were refluxed in 30 mL xylene for 8 hours. The solvent was evaporated. The remaining oily residue was then treated with petroleum ether and stirred for 24 hours. The product 2b which precipitated was filtered off and washed with ethanol and allowed to dry on P2O5; 71% yield; m.p. 243-245 AdegC; FT-IR (cm-1): 3066 (aromatic C-H stretch.), 2920 (CH3-), 1737-1647 (C=O carbonyl's), 1581-1483 (C=C and C=N), 744-667 (pyrimidine ring skeleton vib.); 1H-NMR (400 MHz, DMSO): I'= 9.05 (s, 1H, NH), 8.90-7.12 (m, 9H, Ar-H), 2.26-2.37 ppm (s, 9H, 3CH3-); 13C-NMR (100 MHz, DMSO): I'= 192.92, 153.72 (C=O), 146.40-118.48 (aromatic carbons), 21.26 (2CH3-), 11.73 ppm (CH3-). Elemental analysis (%) for C22H19N3O2, Found (Calc.): C= 74.07 (73.93); H= 5.41 (5.36); N= 11.86 (11.76).

Computational details

The quantum chemical study of the title compound has been performed within the density functional theory with Becke's three parameter hybrid exchange functional with Lee-Yang-Parr correlation functional (B3LYP) employing 6-311G(d,p) and 6-311++G(2d,2p) basis sets. All quantum chemical calculations are performed using computer software Gaussian-03, Revision D.01 [15].

Molecular properties, related to the reactivity and selectivity of the compounds, were estimated following the Koopmans's theorem relating the energy of the HOMO and the LUMO. Electronegativity is estimated using the following the equation from EHOMO and ELUMO:

(Equation)

Chemical hardness (n) measures the resistance of an atom to a charge transfer [39], chemical hardness, chemical potential (u) and electronegativity (X) can be calculated with the help of the following equations from EHOMO and ELUMO [16]:

(Equation)

Electron polarizability, called chemical softness (I), describes the capacity of an atom or group of atoms to receive electrons [39] and it is estimated by using chemical hardness (n) or EHOMO and ELUMO:

(Equation)

The global electrophilicity () is a useful reactivity descriptor that can be used to compare the electron-donating abilities of molecules [40]. Global electrophilicity index is estimated by using the electronegativity and chemical hardness parameters through the equation:

(Equation)

A high value of electrophilicity describes a good electrophile while a small value of electrophilicity describes a good nucleophile [41].

Results and Discussion

Structural analysis

Main reasons of our interest in N-aminopyrimidine derivatives (1a, b) are related to their being important materials in the synthesis of heterocyclic compounds and their importance about structural diversities and medicinal properties. Hence, in our study, 5-(4-methoxyphenyl)-4-[(4-methoxyphenyl)carbonyl]-2-methylpyrazolo[1,5-c]pyrimidin-7(1H)-on (2a) and 5-(4-methylphenyl)-4-[(4-methylphenyl)carbonyl]-2-methylpyrazolo[1,5-c]pyrimidin-7(1H)-one (2b) were synthesized by the cyclization, involving the reaction of N-aminopyrimidine derivatives (1a, b) with [alpha]-chloroacetone in xylene under reflux for 8 h (Scheme-2) (for details see Experimental). The reactions of N-aminopyrimidine-2-one derivatives (1a, b) with [alpha]-chloroacetone yielded pyrazolo[1,5-c]pyrimidin-7(1H)-one derivatives (2a, b) in moderate yields (60-71%). The prepared compounds were characterized by means of 1H-NMR, 13C-NMR and FT-IR spectroscopic methods and elemental analysis.

The proposed mechanism for the formation of pyrazolo[1,5-c]pyrimidin-7(1H)-one derivatives (2a, b) are depicted in Scheme-3. On treatment of [alpha]-chloroacetone with N-aminopyrimidine-2-one derivatives (1a, b), the reaction should start by a nucleophilic attack of the nitrogen atom lone pair electrons of N-aminopyrimidine-2-one derivatives (1a, b) to the carbonyls' carbon of [alpha]-chloroacetone [42]. Then, schiff base occurs at first step by the condensation reactions of N-aminopyrimidine-2-one derivatives (1a, b) and [alpha]-chloroacetone. It is noteworthy that the reactivity of [alpha]-haloketones is due to the inductive effect of the carbonyl group which enhances the polarity of the carbon-halogen bond [43]. The cyclization reactions of (1a, b) to (2a, b), via elimination of a molecule of hydrogen chloride occur by refluxing in xylene. In the light of this, based on the proposed reaction pathway, we showed in detail the reaction pathway of 1 with [alpha]-chloroacetone as outlined in Scheme-3.

The product (2a) was obtained in 60 % yield by treating (1a) with [alpha]-chloroacetone and by refluxing them in 30 mL xylene for 10 hours. The FT-IR spectra are excellent evidences of compound (2a) structure. The C=O absorption bands were observed at 1737 and 1647 cm-1, respectively.

Important structural information (2a) can be obtained from its 1H-NMR spectrum. The 1H-NMR spectrum of (2a), contains three singlet peaks at 3.82, 3.73, 2.36 ppm representing the methoxy and methyl groups respectively. Chemical shift value for the proton at -NH-in pyrazolo rings of the compound (2a) was observed at 9.01 ppm. The multiple peaks between 8.88-6.88 ppm are thought to represent the aromatic protons. The 13C-NMR signals were found to be at 191.97 (benzoyl, C=O), 164.10 (pyrimidine, C=O), 160.38-114.08 (aromatic C), 56.09-55.65 (2CH3O-), 11.73 ppm (CH3-). Finally, the elemental analysis data along with spectroscopic data confirm the structure of (2a).

In a similar way, the reaction of (1b) with [alpha]-chloroacetone led to the formation of the corresponding of 5-(4-methylphenyl)-4-[(4-methylphenyl) carbonyl]-2-methylpyrazolo[1,5-c]pyrimidin-7(1H)-on (2b) in moderate yields (71%) (Scheme-1). The information about spectra of (2b) was given in the experimental section and elemental analysis data confirmed the structure of (2b).

Molecular structure

EHOMO, ELUMO, IE, DM, MV, TNC, n, I, u, X, I, SEZPE were calculated for the pyrazolo[1,5-c]pyrimidin-7(1H)-one derivatives (2a, b) with the DFT/B3LYP method using 6-311G(d,p) and 6-311++G(2d,2p) basic sets for gas phase and solvent phase (ethanol) of neutral molecules, Fig. 1 and 2, and Table-1.

EHOMO is associated with electron donating ability of a molecule, and ELUMO is associated with electron accepting ability of a molecule. High EHOMO is essential for reaction with nucleophiles of molecule while low ELUMO is essential for reaction with electrophiles [44]. EHOMO values of 2a, b molecules were found by using 6-311++G(2d,2p) basic set for gas phase -5.87, -6.02 eV and for solvent phase -5.96, -6.16 eV, respectively (Fig. 1). According to these results, the electron donating trends for study molecules for gas and solvent phase can be written as: 2b>2a. The same trend can be written in 6-311G(d,p) basic set for gas and solvent phase (see Fig. 1). EHOMO values in 2a molecule is lower than other molecule 2b, for the gas phase and solvent phase for the two basic sets. This is due to the methoxy group attached to the phenyl ring of 2a molecule. As is known, the methoxy group is an electron attracting group.

ELUMO values of 2a, b molecules were found by using 6-311++G(2d,2p) basic set for gas phase -1.76, -1.88 eV and for solvent phase -1.97, -2.09 eV, respectively (Fig. 1). ELUMO values in 2a molecule is lower than another molecule 2b. The electron accepting trends for study molecules for gas and solvent phase can be written as: 2a>2b. The same trend can be written in 6-311G(d,p) basic set for gas and solvent phase (Fig. 1).

HOMO-LUMO energy gap (IE), chemical hardness and softness are closely related to chemical properties. IE value is smaller when the basis set of atomic orbitals are magnified due to the changing of HOMO, usually to a more negative energy and decreasing in energy of LUMO [45]. More stable molecules have large IE value and less stable molecules have small IE value. IE values of 2a, b molecules were found by using 6-311++G(2d,2p) basic set for gas phase 4.11, 4.14 eV and for solvent phase 3.99, 4.07 eV, respectively (Fig. 1). 2b molecule is found more stable than other molecule for gas and solvent phase due to the fact that a large IE value is observed (Fig. 1).

The hardness (n) and softness (I) are widely used in chemistry for explaining stability of compounds. According to Maximum Hardness Principle [46], chemical hardness is a measure of the stability of chemical species. The hardness is just half the energy gap between the EHOMO and ELUMO (see eq. 2). n values of 2a, b molecules were found by using 6-311++G(2d,2p) basic set for gas phase 2.05, 2.07 eV and for solvent phase 1.99, 2.03 eV, respectively (Fig. 2). This condition can also see in the SEZPE energies of the molecules (Table-1).

If a molecule has a large energy gap, it is called hard and other wise is called soft [47]. Softness is a measure of the polarizability and soft molecules give more easily electrons to an electron acceptor molecule or surface [16]. The calculated chemical hardness and softness values are given in Fig. 2. According to softness values, electron donating trend of studied chemical compounds may be written as: 2b>2a for gas and solvent phase.

The average values of the HOMO and LUMO energies have been defined as the chemical potential (u). The chemical potential was defined as the first derivative of the total energy with respect to the number of electrons. The negative of the chemical potential was known as the electronegativity (X) (see eq. 3). Chemical potential, electronegativity and hardness are descriptors for the predictions about chemical properties of molecules [12]. Electronegativity that represents the power to attract the electrons of chemical species is a useful quantity in the prediction of inhibitive performance of molecules [16]. The electronegativity values were found 3.82, 3.95 for gas phase and 3.97, 4.12 eV for solvent phase of 2a, b molecules with 6-311++G(2d,2p) basic set, respectively. The electronegativity value of 2b is more than other molecule for gas and solvent phase (Fig. 2).

The results of other calculations: dipole moment (DM), global electrophilicity (I), sum of the total negative charge (TNC) and sum of electronic and zero-point energies (SEZPE) can be seen in Table-1.

Table-1: The calculated quantum chemical parameters for gas and solvent phase of the non-protonated compounds using B3LYP method 6-311G(d,p) and 6-311++G(2d,2p) basic sets.

###Molecule###Method (B3LYP)###DM, Debye###MV, cm3/mol###TNC,e###I, eV###SEZPE, eV

###2a###6-311G(d,p)###3.564###270.585###-2.905###3.244###-35779.206

###2a###6-311++G(2d,2p)###4.036###313.314###-3.062###3.548###-35781.056

###2a*###6-311G(d,p)###5.453###288.814###-3.031###3.666###-35780.174

###2a*###6-311++G(2d,2p)###6.884###289.558###-3.432###3.944###-35782.760

###2b###6-311G(d,p)###3.647###248.704###-2.285###3.491###-31685.432

###2b###6-311++G(2d,2p)###3.952###255.671###-3.192###3.774###-31686.993

###2b*###6-311G(d,p)###5.361###192.973###-2.426###3.854###-31686.252

###2b*###6-311++G(2d,2p)###6.131###281.660###-3.289###4.177###-31687.854

A typical electron density distribution of total electronic charge (TNC) values calculated with the 6-311G(d,p) and 6-311++G(2d,2p) basis sets. TNC values are lower in gas phase than in solvent phase. SEZPE for 2a molecule containing one methoxy group is higher than 2b molecule containing one methyl group (Table-1).

The optimized molecular structures HOMOs, LUMOs and total electron density are also given in Fig. 3. This figure shows that there is much more electron density in the vicinity of oxygen atoms for all studied molecules.

The HOMO and LUMO orbitals contribution of the atoms for 2a, b molecules are shown in Table-2. The HOMO and LUMO orbitals were calculated with AOmix program [48, 49] after optimization with DFT/B3LYP method 6-311G(d,p) basic set for gas and solvent phase. HOMO orbitals for 6-311G(d,p) basic set at gas phase consist of + 10.6% 3PZ(C1) + 8.2% 4PZ(C1) + 4.8% 2PZ(C1) - 2.3% 3PZ(C9) + 2.3% 3PZ(N7) - 2.2% 4PZ(C9), + 12.7% 3PZ(C1) + 9.2% 4PZ(C1) + 5.7% 2PZ(C1) + 3.7% 3PZ(O12) + 3.1% 4PZ(O12) - 3.0% 3PZ(N3) for 2a, b respectively.

Their LUMO consist of + 4.8% 3PZ(C2) - 3.8% 3PZ(C10) - 3.0% 3PY(C10) + 3.0% 4PY(C16) + 2.8% 4PZ(C2) + 2.7% 3PZ(O11), + 4.7% 3PZ(C2) - 4.0% 3PZ(C10) + 3.0% 3PZ(O11) + 2.8% 3PY(C10) + 2.7% 4PZ(C2) - 2.6% 4PZ(C10), respectively. HOMO and LUMO orbitals result for non-protonated gas and solvent phase of molecules can be seen from Table-2. As seen from Table-2, HOMO orbitals of 2a, b molecules for gas phase consist of mainly C1 carbon atom, and their LUMO orbitals of all molecules for gas and solvent phase can be seen mainly at C2 and C10 carbon atoms.

Table-2: HOMO and LUMO population for gas and solvent phase of neutral molecules by using AOmix method after from B3LYP/6-311G(d,p) basic set.

###Molecule###HOMO

###2a###+ 10.6% 3PZ(C1) + 8.2% 4PZ(C1) + 4.8% 2PZ(C1) - 2.3% 3PZ(C9) + 2.3% 3PZ(N7) - 2.2% 4PZ(C9)

###2a*###+ 7.6% 3PZ(C1) + 5.7% 4PZ(C1) + 3.5% 2PZ(C1) + 2.9% 4PY(C1) + 2.7% 3PY(C1) - 2.6% 3PY(C15)

###2b###+ 12.7% 3PZ(C1) + 9.2% 4PZ(C1) + 5.7% 2PZ(C1) + 3.7% 3PZ(O12) + 3.1% 4PZ(O12) - 3.0% 3PZ(N3)

###2b*###+ 11.6% 3PZ(C1) + 8.5% 4PZ(C1) + 5.2% 2PZ(C1) - 3.8% 3PZ(C9) - 3.6% 4PZ(C9) + 3.2% 3PZ(N7)

###LUMO

###2a###+ 4.8% 3PZ(C2) - 3.8% 3PZ(C10) - 3.0% 3PY(C10) + 3.0% 4PY(C16) + 2.8% 4PZ(C2) + 2.7% 3PZ(O11)

###2a*###+ 5.3% 3PY(C10) + 4.2% 4PY(C10) - 3.7% 3PZ(C2) - 3.5% 3PY(O11) + 2.7% 3PX(C10) - 2.6% 4PY(C16)

###2b###+ 4.7% 3PZ(C2) - 4.0% 3PZ(C10) + 3.0% 3PZ(O11) + 2.8% 3PY(C10) + 2.7% 4PZ(C2) - 2.6% 4PZ(C10)

###2b*###+ 4.3% 3PZ(C2) + 3.8% 3PY(C10) - 3.7% 3PZ(C10) + 3.2% 4PY(C10) - 2.9% 4PY(C16) - 2.6% 3PY(O11)

Conclusions

In this study, the new pyrazolo[1,5-c]pyrimidin-7(1H)-one derivatives 2a, b were synthesized from the cyclocondensation reaction of N-Amino-pyrimidine-2-one derivatives 1a, b with [alpha]-chloroacetone. Mechanistic proposal for the formation of 2a, b was given in Scheme-3. The structures of these newly synthesized compounds (2a, b) were determined from the FT-IR, 1H and 13C-NMR spectroscopic data and elemental analysis.

In addition to experimental study in order to find molecular properties. Quantum-chemical calculations of the new pyrazolo[1,5-c]pyrimidin-7(1H)-one derivatives (2a, b) were carried out by using DFT/B3LYP method with basis sets of the 6-311G(d,p) and 6-311++G(2d,2p). Quantum chemical features such as HOMO, LUMO, HOMO-LUMO energy gap, chemical hardness, chemical softness, electronegativity, chemical potential, dipole moment etc. values for gas and solvent phase of neutral molecules were calculated and discussed. According to quantum chemical calculation results, the electron donating trends for 2a, b molecules for gas and solvent phase can be written as: 2b>2a. According to energy gap (IE) results, 2b molecule is found more stable than 2a molecule for gas and solvent phase. The HOMO populations of 2a, b molecules for gas and solvent phase consist of mainly C1 carbon atom, and LUMO populations can be seen mainly at C2 and C10 carbon atoms.

Acknowledgements

Computers allocated by the Erciyes University data center were used for quantum chemical calculations.

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30. A. Tazouti, M. Galai, R. Touir, M. Ebn Touhami, A. Zarrouk, Y. Ramli, M. Saracoglu, S. Kaya, F. Kandemirli and C. Kaya, Experimental and theoretical studies for mild steel corrosion inhibition in 1 M HCl by three new quinoxalinone derivatives, J. Mol. Liquids, 221, 815 (2016).

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Title Annotation:density functional theory
Author:Saracoglu, Murat; Kokbudak, Zulbiye; Cimen, Zeynep; Kandemirli, Fatma
Publication:Journal of the Chemical Society of Pakistan
Article Type:Technical report
Date:Jun 30, 2019
Words:5662
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