New Pyrazole-Hydrazone Derivatives: X-ray Analysis, Molecular Structure Investigation via Density Functional Theory (DFT) and Their High In-Situ Catecholase Activity
Abstract
:1. Introduction
2. Results
2.1. Synthesis
2.2. X-Ray Crystal Structures Description
2.3. Computational Studies
2.4. Catecholase Activity: Spectrophotometric Study
2.4.1. Effect of Ligand Concentration on the Catecholase Activity
2.4.2. Solvent Effect
2.4.3. Comparison with Alternative Catalysts
3. Experimental
3.1. General Methods
3.2. Synthesis
3.2.1. Synthesis of 3-phenyl-1H-pyrazole-4-carbohydrazides (2)
3.2.2. General Procedure for the Synthesis of Ligands (L1–L6)
3.2.3. N’-(4-hydroxy-3-methoxybenzylidene)-5-phenyl-1H-pyrazole-3-carbohydrazide (L1)
3.2.4. N’-(4-methylbenzylidene)-5-phenyl-1H-pyrazole-3-carbohydrazide (L2)
3.2.5. N’-(4-chlorobenzylidene)-5-phenyl-1H-pyrazole-3-carbohydrazide (L3)
3.2.6. N’-(4-fluorobenzylidene)-5-phenyl-1H-pyrazole-3-carbohydrazide (L4)
3.2.7. 5-phenyl-N’-(1-phenylethylidene)-1H-pyrazole-3-carbohydrazide (L5)
3.2.8. N’-(diphenylmethylene)-5-phenyl-1H-pyrazole-3-carbohydrazide (L6)
3.3. X-Ray Crystallographic Analysis
3.4. DFT Computational Method
3.5. Catecholase Activity Measurement
4. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Bond Length (Å) | Experimental Bond Lengths | Calculated Bond Lengths | Bond Angle (°) | Experimental Bond Angles | Calculated Bond Angles |
---|---|---|---|---|---|
O1–C10 | 1.22(3) | 1.24 | N2–C9–C8 | 106.0(2) | 109.2 |
O2–C14 | 1.36(3) | 1.39 | O1–C10–N3 | 122.8(2) | 125.0 |
O2–C18 | 1.41(4) | 1.45 | N3–C10–C9 | 116.0(2) | 112.7 |
O3–C15 | 1.36(3) | 1.38 | O1–C10–C9 | 121.3(2) | 122.2 |
N1–N2 | 1.33(3) | 1.37 | N4–C11–C12 | 122.9(2) | 121.3 |
N1–C7 | 1.33(3) | 1.38 | O2–C14–C13 | 125.7(2) | 126.0 |
N2–C9 | 1.34(3) | 1.36 | C14–O2–C18 | 118.3(2) | 118.5 |
N3–N4 | 1.38(3) | 1.37 | N2–N1–C7 | 105.3(2) | 113.2 |
N3–C10 | 1.34(3) | 1.38 | N1–N2–C9 | 112.6(2) | 105.0 |
N4–C11 | 1.27(3) | 1.29 | N4–N3–C10 | 119.5(2) | 121.0 |
Bond Length (Å) | Experimental Bond Lengths | Calculated Bond Lengths | Bond Angle (°) | Experimental Bond Angles | Calculated Bond Angles |
---|---|---|---|---|---|
O1–C10 | 1.22(2) | 1.21 | N2–N1–C7 | 113.4(15) | 113.6 |
N1–N2 | 1.34(2) | 1.34 | N1–N2–C9 | 103.9(15) | 105.4 |
N1–C7 | 1.34(3) | 1.37 | N4–N3–C10 | 119.2(17) | 117.2 |
N2–C9 | 1.33(2) | 1.34 | N3–N4–C11 | 115.6(18) | 114.2 |
N3–N4 | 1.38(2) | 1.41 | N1–C7–C6 | 122.7(17) | 122.39 |
N3–C10 | 1.33(3) | 1.36 | N1–C7–C8 | 105.3(18) | 103.59 |
N4–C11 | 1.26(3) | 1.27 | N2–C9–C8 | 111.4(16) | 109.21 |
C15–C18 | 1.512(4) | 1.50 | N2–C9–C10 | 119.4(17) | 119.83 |
N1–H | 0.86(2) | 1.00 | N3–C10–C9 | 114.9(16) | 111.05 |
Molecular Energy (a.u.) (eV) | L1 | L2 |
---|---|---|
TE | −31008.6 | −26911.4 |
EHOMO | −5.8186 | −6.4850 |
ELUMO | −1.0152 | −0.7349 |
Gap ΔE | 4.8034 | 5.7500 |
Chemical potential µ (D) | 5.8871 | 6.3122 |
Ionization potential (IP) | 5.8186 | 6.4850 |
Electron affinity (EA) | 1.0152 | 0.7349 |
Electron negatiity (χ) | 3.4169 | 3.6100 |
Global hardness (η) | 2.4017 | 2.875 |
Global electrophilicity (ω) | 2.4306 | 2.2664 |
Ligand/Metallic Salt | Cu(NO3)2 | CuCl2 | Cu(CH3COO)2 | CuSO4 |
---|---|---|---|---|
L1 | 10.57 | 10.28 | 9.80 | 9.27 |
L2 | 15.52 | 0.05 | 22.92 | 16.06 |
L3 | 37.89 | 9.19 | 24.58 | 21.01 |
L4 | 17.71 | 11.43 | 15.02 | 6.57 |
L5 | 3.10 | 8.07 | 19.62 | 10.61 |
L6 | 27.77 | 40.27 | 60.50 | 72.92 |
Cu(II)-Ligands | Cu(II) Salt Used | Oxidation Rate (µmol·L−1·min−1) | Ref. |
---|---|---|---|
ligand L6 | CuSO4 | 72.920 | - |
ligand L6 | Cu(CH3COO)2 | 60.500 | - |
ligand L6 | CuCl2 | 40.270 | - |
C,N-bipyrazole | Cu(CH3COO)2 | 4.440 | [29] |
bipyrazolic tripode-prop-2-ylacetate | Cu(CH3COO)2 | 11.825 | [30] |
bipyrazolic tripode-4-hydroxyphenyl | CuCl2 | 1.458 | [31] |
bipyrazolic tripode-3-hydroxypropyl | CuSO4 | 28.990 | [32] |
bipyrazolic tripode-3-hydroxypropyl | CuCl2 | 4.378 | [33] |
indole-3-chalcone | Cu(CH3COO)2 | 31.780 | [34] |
[(3,5-dimethyl-pyrazol-1-ylmethyl)-amino]-propionitrile | CuSO4 | 8.710 | [35] |
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Karrouchi, K.; Yousfi, E.B.; Sebbar, N.K.; Ramli, Y.; Taoufik, J.; Ouzidan, Y.; Ansar, M.; Mabkhot, Y.N.; Ghabbour, H.A.; Radi, S. New Pyrazole-Hydrazone Derivatives: X-ray Analysis, Molecular Structure Investigation via Density Functional Theory (DFT) and Their High In-Situ Catecholase Activity. Int. J. Mol. Sci. 2017, 18, 2215. https://doi.org/10.3390/ijms18112215
Karrouchi K, Yousfi EB, Sebbar NK, Ramli Y, Taoufik J, Ouzidan Y, Ansar M, Mabkhot YN, Ghabbour HA, Radi S. New Pyrazole-Hydrazone Derivatives: X-ray Analysis, Molecular Structure Investigation via Density Functional Theory (DFT) and Their High In-Situ Catecholase Activity. International Journal of Molecular Sciences. 2017; 18(11):2215. https://doi.org/10.3390/ijms18112215
Chicago/Turabian StyleKarrouchi, Khalid, El Bekkaye Yousfi, Nada Kheira Sebbar, Youssef Ramli, Jamal Taoufik, Younes Ouzidan, M’hammed Ansar, Yahia N. Mabkhot, Hazem A. Ghabbour, and Smaail Radi. 2017. "New Pyrazole-Hydrazone Derivatives: X-ray Analysis, Molecular Structure Investigation via Density Functional Theory (DFT) and Their High In-Situ Catecholase Activity" International Journal of Molecular Sciences 18, no. 11: 2215. https://doi.org/10.3390/ijms18112215