Relationships between experimental and theoretical scales of electrophilicity of 7-L-4-nitrobenzofurazans

Raissi, Hanen; Ayachi, Hajer; Mahdhaoui, Faouzi; Ayachi, S.; Boubaker, Taoufik

doi:10.1016/j.molstruc.2020.128843

Cited by 18 publications

(9 citation statements)

References 36 publications

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“…Samples of 7-methoxy-4-nitrobenzofurazan (NBD-OCH 3 ) and 7phenoxy-4-nitrobenzofurazan (NBD-OC 6 H 5 ) were prepared according to the standard methods described in the literature. [27][28][29] The secondary cyclic amines (morpholine, piperidine and pyrrolidine) were commercial products (Aldrich, Darmstadt-Germany) and were redistilled before use whenever necessary.…”

Section: Experimental Details 21 Materialsmentioning

confidence: 99%

“…In a recent study, we showed that the second-order rate constants for the reactions of 7-X-4-nitrobenzofurazans 1 (1a, X = Cl, 1b,X=OC 6 H 5 and 1c: X = OCH 3 ) with secondary cyclic amines 2 (2a, morpholine, 2b, piperidine and 2c, pyrrolidine) in acetonitrile at 20°C [27,29] can be described by the linear free energy relationship log k = s N (N+ E), [45][46][47][48] and we determined the E parameters of these electrophiles 1a-c which are collected in Figure 12. We have now used these parameters E in order to elucidate the relationship between Mayr's electrophilicities E [45] and Parr's global electrophilicity index w values [49,50].…”

Section: Correlation Analysismentioning

confidence: 99%

“…[24][25][26] Recently, we reported a kinetic study for S N Ar reactions of NBD with secondary amines. [27][28][29][30] The present chapter is focused on the elucidation of the combined experimental-theoretical investigation relationships between the optical (UV-Vis, PL and time resolved photoluminescence (TR-PL), electrochemical (CV) properties and the chemical structures of 4.7-di-substituted benzofurazans (NBDs), based on the kinetic reactivity process of compounds. Parr's approach was employed to develop a relationship which rationalizes the kinetic data previously reported for the reactions of 4-X-7-nitrobenzofurazans with various nucleophiles.…”

Section: Introductionmentioning

confidence: 99%

“…Parr's approach was employed to develop a relationship which rationalizes the kinetic data previously reported for the reactions of 4-X-7-nitrobenzofurazans with various nucleophiles. [27][28][29].…”

Section: Introductionmentioning

confidence: 99%

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Structure-Property Relationships in Benzofurazan Derivatives: A Combined Experimental and DFT/TD-DFT Investigation

Raissi¹,

Chérif²,

Ayachi³

et al. 2022

Density Functional Theory - Recent Advances, New Perspectives and Applications

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In this work we seek to understand and to quantify the reactivity of benzofurazan derivatives toward secondary cyclic amines, like pyrrolidine, piperidine and morpholine, acting as nucleophile groups in SNAr reactions. For this aim, physico-chemical and structural descriptors were determined experimentally and theoretically using the DFT/B3LYP/6-31+ g (d,p) methodology. Thus, different 4-X-7-nitrobenzofurazans (X = OCH3, OC6H5 and Cl) and products corresponding to the electrophilic aromatic substitution by pyrrolidine, piperidine and morpholine, were investigated. Particularly, the HOMO and LUMO energy levels of the studied compounds, determined by Cyclic Voltammetry (CV) and DFT calculations, were used to evaluate the electrophilicity index (ω). The latter was exploited, according to Parr’s approach, to develop a relationship which rationalizes the kinetic data previously reported for the reactions of the 4-X-7-nitrobenzofurazans with nucleophiles cited above. Moreover, the Parr’s electrophilicity index (ω) of these benzofurazans determined in this work were combined with their electrophilicity parameters (E), reported in preceding papers, was found to predict the unknown electrophilicity parameters E of 4-piperidino, 4-morpholino and 4-pyrrolidino-7-nitrobenzofurazan. In addition, the relationship between the Parr’s electrophilicity index (ω) and Hammett constants σ, has been used as a good model to predict the electronic effect of the nucleophile groups. Finally, we will subsequently compare the electrophilicity index (ω) and the electrophilicity parameters (E) of these series of 7-X-4-nitrobenzofurazans with the calculated dipole moment (μ) in order to elucidate general relationships between E, ω and μ.

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Section: Experimental Details 21 Materialsmentioning

confidence: 99%

Section: Correlation Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Structure-Property Relationships in Benzofurazan Derivatives: A Combined Experimental and DFT/TD-DFT Investigation

Raissi¹,

Chérif²,

Ayachi³

et al. 2022

Density Functional Theory - Recent Advances, New Perspectives and Applications

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“…We have previously reported that the 4-nitrobenzochalcogenadiazoles 4, [1][2][3] the 7-L-4-nitrobenzofurazans 5, [4][5][6] and the 2methoxy-3-X-5-nitrothiophene 6 [7][8][9] (Scheme 1) represent a class of neutral electron-deficient substrates which can be described by the experimental model based on the following three-parameter equation (1):…”

Section: Introductionmentioning

confidence: 99%

Quantification of the Electrophilic Reactivities of Benzotriazoles and Structure‐Reactivity Relationships

et al. 2021

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The kinetics of the coupling of 2-N-(4'-X-pheny1)-4,6-dinitrobenzotriazole 1-oxides 1 a-d (X = OMe, H, Br and CN) with nitroalkyl anions 2 a-c have been investigated in aqueous solution at 20°C. Using the derived second-order rate constants and this series of nucleophiles 2 a-c as reference, the electrophilicity parameters E of the four electrophiles 1 a-d have been determined according to the linear free enthalpy relationship log k (20°C) = s N (E + N). With the electrophilicity parameters E range from À 9.72 to À 11.78, the substituent effects on the electrophilic reactivity was examined quantitatively, leading to linear correlation of E with Hammett substituent constants (σ). Based on this correlation, the unknown electrophilicity parameters E of other 2-N-(4'-X-pheny1)-4,6-dinitrobenzotriazole 1oxides (X = CF 3 , Me and OH) were evaluated. Excellent linear correlation (r 2 = 0.9962) between the electrophilicity parameters E of benzotriazoles 1 a-d and their pK a values for σ-complexation has also been observed and discussed.

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Structure–property relationships in para-substituted nitrobenzofurazans: electrochemical, optical, and theoretical analysis

et al. 2022

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Relationships between experimental and theoretical scales of electrophilicity of 7-L-4-nitrobenzofurazans

Cited by 18 publications

References 36 publications

Structure-Property Relationships in Benzofurazan Derivatives: A Combined Experimental and DFT/TD-DFT Investigation

Structure-Property Relationships in Benzofurazan Derivatives: A Combined Experimental and DFT/TD-DFT Investigation

Quantification of the Electrophilic Reactivities of Benzotriazoles and Structure‐Reactivity Relationships

Structure–property relationships in para-substituted nitrobenzofurazans: electrochemical, optical, and theoretical analysis

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