Reaction of 2,4-Dinitrochlorobenzene with Aromatic Amines in Toluene: Effect of Nucleophile Structure

Alvaro, Cecilia E. Silvana; Savini, Mónica C.; Nicotra, Viviana E.; Yankelevich, Jeannette; Nudelman, Norma Sbarbati

doi:10.3390/50300401

Cited by 5 publications

(5 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the third example, the formation of Tobias acid is an important reaction because it permits the use of a noncarcinogenic "form" of beta-naphthylamine in azo dye synthesis, with the sulfonic acid group removed in a later step (8). The Figure 9 examples of aromatic amine formation illustrate the ability of nitro groups to activate replacement of chloro groups (9). The first example shows that this can be a selective replacement when only one of the chloro groups is adjacent to a nitro group (cf.…”

Section: Formationmentioning

confidence: 99%

Aromatic amines: use in azo dye chemistry

Freeman¹

2013

Front Biosci

View full text Add to dashboard Cite

show abstract

Section: Formationmentioning

confidence: 99%

Aromatic amines: use in azo dye chemistry

Freeman¹

2013

Front Biosci

View full text Add to dashboard Cite

show abstract

“…Although several pathways and competing side‐reactions are possible, a substantial number of these reactions proceed through an addition‐elimination mechanism. Experimental evidence generally points to a two‐step process, which is dependent upon nucleophile, leaving group, and the presence of electron‐withdrawing substituents . In contrast, ab initio and semiempirical theoretical treatments reveal both two‐step and single‐step mechanisms …”

Section: Introductionmentioning

confidence: 99%

Nucleophilic aromatic substitution in chlorinated aromatic systems with a glutathione thiolate model

Boerth

Arvanites

2016

J. Phys. Org. Chem.

View full text Add to dashboard Cite

The conjugation of glutathione with chlorobenzene and di‐, tri‐, tetra‐, and hexa‐chlorinated benzenes via nucleophilic aromatic substitution was modeled for isolated reacting species by ab initio molecular orbital theory to provide an understanding of the intrinsic reactivity of unactivated chloroaromatic systems. Computations at the HF/6‐31+G(d,p) level were augmented with electron correlation corrections using MP2 theory and density functional theory at the B3LYP level. Features of the reaction hypersurface were elaborated using thiolate (thiomethoxide) as the model for an enzyme‐activated glutathione molecule. Unlike the similar reaction with 1‐chloro‐2, 4‐dinitrobenzene a known substrate with glutathione, no σ‐complex or Meisenheimer complex was isolated as a true intermediate on the hypersurface. Instead, the σ‐complex appears as a transition state, preceded and followed by two ion‐molecule complexes in which the approaching and departing anions reside in the plane of the aromatic ring. Solvent calculations show a very similar hypersurface landscape with only one transition state and no intermediate. Activation energies are somewhat greater than for 1‐chloro‐2, 4‐dinitrobenzene owing to the lack of nitro substituents, which provide stabilization in these systems. Nevertheless, activation energies calculated at correlated levels indicate that these reactions are still feasible and consistent with experiment. Transition states and activation energies for dichlorobenzenes and polychlorobenzenes are lower in energy than for chlorobenzene implying greater stability conferred to the transition state by ortho and para substituents.

show abstract

“…The dependence of the reaction on two amine molecules for the reactions of 1 with An and CHA in Tol can proceed by a dimer mechanism [28,29], specific base-general acid (SB-GA) [27], or specific base catalysis (SB) [22][23][24][25][26] (Scheme 3). The dimer mechanism is rejected on the ground that the plots of k 2 against [amine] for the reactions of 1 with An and CHA do not exhibit a curvilinear response and the plots of quotient k 2 [amine] against [amine] did not gave straight lines [28,29].…”

Section: Methodsmentioning

confidence: 99%

“…Kinetic studies involving primary and secondary amines as nucleophiles, in solvents of different polarities, play a central role not only in firmly establishing the two or multi-step nature of the mechanism, but also in answering questions regarding the relative rates of intermediate complex formation and decomposition [16][17][18][19][20][21][22][23][24]. Possible pathway mechanism for this type of reactions are specific base (SB) [22][23][24][25][26], specific basegeneral acid (SB-GA) [27], or dimer-mechanism [28,29].…”

Section: Introductionmentioning

confidence: 99%

Aminolysis of 1-(1-Hydroxybenzotriazolyl)-2,4-dinitrobenzene and 2-(1-Hydroxybenzotriazolyl)-5-nitropyridine

Khattab¹,

Kharaba²,

El-Hawary³

et al. 2012

OJPC

View full text Add to dashboard Cite

The reaction 1-(1-hydroxybenzotriazolyl)-2,4-dinitrobenzene 1 and 2-(1-hydroxybenzotriazolyl)-5-nitro-pyridine 2 with amines undergoes amination followed by elimination of the 1-hydroxyl benzotriazolyl anion. The kinetic data for the reaction of 1 and 2 with Mo, CHA and An in MeOH and AN proceeded by uncatalysed mechanism in which the rate limiting step is the leaving group departure, whereas the reaction with Mo in toluene proceeded by uncatalysed mechanism in which the formation of the zwitterionic intermediate is the rate determining step. While the reactions of 1 with CHA and An and the reaction of 2 with CHA in toluene proceeded by SB mechanism in which the rate determining step is the proton transfer process. The reactions of 1 and 2 with Mo in the three solvents and with CHA and An in MeOH and AN is greatly depended on the stability of the zwitterionic intermediate. The effect of ring activation is due to the ground state stabilization and the more efficient delocalization of the negative charge with a nitro group than with a ring-nitrogen in the transition state. The low activation enthalpies ΔH # and the highly negative activation entropies ΔS # are due to the intramolecular hydrogen bonding with the ammonio hydrogen present in the transition state.

show abstract

Reaction of 2,4-Dinitrochlorobenzene with Aromatic Amines in Toluene: Effect of Nucleophile Structure

Cited by 5 publications

References 2 publications

Aromatic amines: use in azo dye chemistry

Aromatic amines: use in azo dye chemistry

Nucleophilic aromatic substitution in chlorinated aromatic systems with a glutathione thiolate model

Aminolysis of 1-(1-Hydroxybenzotriazolyl)-2,4-dinitrobenzene and 2-(1-Hydroxybenzotriazolyl)-5-nitropyridine

Contact Info

Product

Resources

About