Kinetic Studies on Nucleophilic Addition Reactions of 4‐X‐substituted Anilines to N1‐methyl‐4‐nitro‐2,1,3 benzothiadiazolium terafluoroborate in Acetonitrile: Reaction Mechanism and Mayr's Approach

Salah, Saida Ben; Boubaker, Taoufik; Goumont, Régis

doi:10.1002/kin.20924

Cited by 14 publications

(28 citation statements)

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“…Under these experimental conditions, the general expression for the observed first‐order rate constants, k obsd , at a given concentration of amine 2 is defined as shown in Eq. .

\begin{matrix} true \\ right k_{obsd} [NuH] = k_{1} {[NuH]}^{2} + \frac{k_{- 1}}{K} [{NuH}_{2}^{+}] \end{matrix}

…”

Section: Resultsmentioning

confidence: 99%

“…N1‐Methyl‐4‐nitro‐2,1,3‐benzoselenadiazolium tetrafluoroborate 1 used in this work was prepared as described in . Analysis of the product gave the following results: 1 H NMR (300.13 MHz, CD 3 CN‐d3): δ H 8.59 (1H, dd, J 1 = 3.0, J 2 = 5.4), 8.19 (2H, m), 4.66 (3H, s); 13 C NMR (75.47 MHz, CD 3 CN‐d3): δ C 153.26, 149.71, 142.94, 137.23, 129.91, 122.96, 41.57.…”

Section: Methodsmentioning

confidence: 99%

“…Continuing the experimental studies on the reactivity of nitrobenzoselenadiazole and nitrobenzothiadiazole series , we here report our findings on the kinetic investigation of the reactions of N1‐methyl‐4‐nitro‐2,1,3‐benzoselenadiazolium tetrafluoroborate 1 with various amines 2a–f in acetonitrile solution at 20ºC (Eq. (2)).…”

Section: Introductionmentioning

confidence: 95%

“…In contrast, reactions of 4 with anilines possessing an electron‐donating group resulting in a large slope value (2.73) have been concluded to proceed through a single electron transfer mechanism .…”

Section: Introductionmentioning

confidence: 98%

“…In previous work, we have shown that it is possible to describe the second‐order rate constants k measured in acetonitrile solution pertaining to the nitrogen–nitrogen coupling step of the polar nucleophilic addition reactions of para‐substituted anilines possessing an electron‐withdrawing group with N1‐methyl‐4‐nitro‐2,1,3‐benzothiadiazolium tetrafluoroborate 4 by the linear free energy relationship (1) , in which N and s are nucleophile specific parameters and E is an electrophilicity parameter.

\begin{matrix} true \\ right prefixlog k ((), 20^{\circ} normalC) = italics (E + N) \end{matrix}

…”

Section: Introductionmentioning

confidence: 99%

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Reactions of N1-Methyl-4-nitro-2,1,3-benzoselenadiazolium Tetrafluoroborate with Aliphatic and Cyclic Amines in Acetonitrile: Kinetic and Structure-Reactivity Correlations

Salah

Boubaker

Goumont

2017

Int. J. Chem. Kinet.

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The nucleophilic addition reactions of N1‐methyl‐4‐nitro‐2,1,3‐benzoselenadiazolium tetrafluoroborate 1 with aliphatic amines 2a–c (diethylamine 2a, dipropylamine 2b, and allylamine 2c) have been kinetically studied by UV–vis spectroscopy in acetonitrile solution at 20°C. The kinetic data have been analyzed, using the Mayr equation, allowing the quantification of the electrophilicity parameter (E) value of benzoselenadiazolium cation 1 (E = −14.72). The reliability of parameter E has been reasonably verified by comparison of calculated and experimental second‐order rate constants for the reactions of cation 1 with other amines 2d–f (pyrrolidine 2d, piperidine 2e, and morpholine 2f) under the same conditions as those of the amines 2a–c. A linear Brönsted plot (R2 = 0.9945) with a βnuc value of 0.55 has been obtained for the reactions of 1 with the secondary amines employed in the present work. Interestingly, satisfactory correlation between the log values of measured and calculated rate constants with a slope very close to unity has been obtained and discussed.

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“…Under these experimental conditions, the general expression for the observed first‐order rate constants, k obsd , at a given concentration of amine 2 is defined as shown in Eq. .

\begin{matrix} true \\ right k_{obsd} [NuH] = k_{1} {[NuH]}^{2} + \frac{k_{- 1}}{K} [{NuH}_{2}^{+}] \end{matrix}

…”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 98%

\begin{matrix} true \\ right prefixlog k ((), 20^{\circ} normalC) = italics (E + N) \end{matrix}

…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Reactions of N1-Methyl-4-nitro-2,1,3-benzoselenadiazolium Tetrafluoroborate with Aliphatic and Cyclic Amines in Acetonitrile: Kinetic and Structure-Reactivity Correlations

Salah

Boubaker

Goumont

2017

Int. J. Chem. Kinet.

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Single‐Electron Transfer in σ‐Complexation Reactions of 2,6‐Dimethoxy‐3,5‐dinitropyridine with Para‐X‐phenoxide Anions in Aqueous Solution

Mahdhaoui

Dhahri

Boubaker

2016

Int J of Chemical Kinetics

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Second-order rate constants have been measured spectrophotometrically for reactions of 2,6-dimethoxy-3,5-dinitropyridine 1 with 4-X-substituted phenoxide anions (X = OMe, Me, H, Cl, and CN) 2a-e in aqueous solution at various temperatures. The effect of phenoxide substituents on the reaction rate was examined quantitatively on the basis of kinetic measurements, leading to nonlinear correlations of ࣔ H and ࣔ S with Hammett's substituent constants (σ ). Each Hammett plots exhibits two intersecting straight lines for the reactions of 1 with the phenoxide anions 2a-e, whereas the Yukawa-Tsuno plots for the same reactions are linear. The large negative ρ values (−4.03 to −3.80) obtained for the reactions of 1 with the phenoxide anions possessing an electron-donating group supports the proposal that the reactions proceed through a single-electron transfer mechanism. C 2016 Wiley Periodicals, Inc. Int J Chem Kinet 48: 523-530, 2016 Scheme 2 Reaction of 2,6-dimethoxy-3,5-dinitropyridine 1 with various phenoxide anions.

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Kinetic Studies on S_NAr Reactions of Substituted Benzofurazan Derivatives: Quantification of the Electrophilic Reactivities and Effect of Amine Nature on Reaction Mechanism

Raissi

Jamaoui

Goumont

et al. 2017

Int J of Chemical Kinetics

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Kinetics of the nucleophilic aromatic substitution reactions of 7-L-4nitrobenzofurazans 1 (1a: L = Cl and 1b: L = OCH 3 ) and secondary cyclic amines (morpholine, piperidine, and pyrolidine) 2a-c have been measured in acetonitrile solution at 20°C. The derived values of second-order rate constants (k 1 ) have been employed to determine the electrophilicity parameters E for both benzofurazans 1a and 1b according to the linear free enthalpy relationship: log k (20°C) = s N (E + N) (Eq. (1)). The second-order rate constants for reactions of benzofurazans 1 with a series of 4-X-substituted anilines 3a-d (X = OH, OCH 3 , CH 3 , and H) have also been measured in MeCN and found to agree within a factor of 0.14-50 with those calculated by Eq. (1) from the electrophilicity parameters E measured in this work and the known nucleophile-specific parameters N and s N of anilines 3. On the other hand, the reactions of these benzofurazans 1 with anilines 3 exhibit linear Brønsted-type plots with β nuc = 1.27 for 1a and 1.01 for 1b, which are considerably greater than those (0.57 for 1a and 0.62 for 1b) obtained with the secondary cyclic amines 2. These high values of β nuc have been interpreted

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Kinetic Studies on Nucleophilic Addition Reactions of 4‐X‐substituted Anilines to N1‐methyl‐4‐nitro‐2,1,3 benzothiadiazolium terafluoroborate in Acetonitrile: Reaction Mechanism and Mayr's Approach

Abstract: The kinetics of the coupling of N1-methyl-4-nitro-2,1,3 benzothiadiazolium tetrafluoroborate 1 with a series of 4-X-substituted anilines 2a-f (X = OH, OMe, Me, H, Cl, and CN) have been investigated in acetonitrile at 20°C. The second-order rate constants result in a

Cited by 14 publications

References 38 publications

Reactions of N1-Methyl-4-nitro-2,1,3-benzoselenadiazolium Tetrafluoroborate with Aliphatic and Cyclic Amines in Acetonitrile: Kinetic and Structure-Reactivity Correlations

Reactions of N1-Methyl-4-nitro-2,1,3-benzoselenadiazolium Tetrafluoroborate with Aliphatic and Cyclic Amines in Acetonitrile: Kinetic and Structure-Reactivity Correlations

Single‐Electron Transfer in σ‐Complexation Reactions of 2,6‐Dimethoxy‐3,5‐dinitropyridine with Para‐X‐phenoxide Anions in Aqueous Solution

Kinetic Studies on S_NAr Reactions of Substituted Benzofurazan Derivatives: Quantification of the Electrophilic Reactivities and Effect of Amine Nature on Reaction Mechanism

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Kinetic Studies on Nucleophilic Addition Reactions of 4‐X‐substituted Anilines to N1‐methyl‐4‐nitro‐2,1,3 benzothiadiazolium terafluoroborate in Acetonitrile: Reaction Mechanism and Mayr's Approach

Abstract: The kinetics of the coupling of N1-methyl-4-nitro-2,1,3 benzothiadiazolium tetrafluoroborate 1 with a series of 4-X-substituted anilines 2a-f (X = OH, OMe, Me, H, Cl, and CN) have been investigated in acetonitrile at 20°C. The second-order rate constants result in a

Cited by 14 publications

References 38 publications

Reactions of N1-Methyl-4-nitro-2,1,3-benzoselenadiazolium Tetrafluoroborate with Aliphatic and Cyclic Amines in Acetonitrile: Kinetic and Structure-Reactivity Correlations

Reactions of N1-Methyl-4-nitro-2,1,3-benzoselenadiazolium Tetrafluoroborate with Aliphatic and Cyclic Amines in Acetonitrile: Kinetic and Structure-Reactivity Correlations

Single‐Electron Transfer in σ‐Complexation Reactions of 2,6‐Dimethoxy‐3,5‐dinitropyridine with Para‐X‐phenoxide Anions in Aqueous Solution

Kinetic Studies on SNAr Reactions of Substituted Benzofurazan Derivatives: Quantification of the Electrophilic Reactivities and Effect of Amine Nature on Reaction Mechanism

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Kinetic Studies on S_NAr Reactions of Substituted Benzofurazan Derivatives: Quantification of the Electrophilic Reactivities and Effect of Amine Nature on Reaction Mechanism