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Electrophilic Aromatic Substitution: Nitration of Benzene01:20

Electrophilic Aromatic Substitution: Nitration of Benzene

6.3K
The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.
6.3K
Nucleophilic Aromatic Substitution: Elimination–Addition01:11

Nucleophilic Aromatic Substitution: Elimination–Addition

4.1K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
4.1K
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)01:30

Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)

3.9K
Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
3.9K
Rate-Determining Steps03:08

Rate-Determining Steps

33.2K
Relating Reaction Mechanisms
In a multistep reaction mechanism, one of the elementary steps progresses significantly slower than the others. This slowest step is called the rate-limiting step (or rate-determining step). A reaction cannot proceed faster than its slowest step, and hence, the rate-determining step limits the overall reaction rate.
The concept of rate-determining step can be understood from the analogy of a 4-lane freeway with a short-stretch of traffic-bottleneck caused due to...
33.2K
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN101:14

Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1

2.2K
Treating arylamines with nitrous acid gives aryldiazonium salts that are effective substrates in nucleophilic aromatic substitution reactions. The diazonio group in these salts can be easily displaced by different nucleophiles, yielding a wide variety of substituted benzenes. The leaving group departs as nitrogen gas, and this easy elimination is the driving force for the substitution reaction.
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
2.2K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH301:11

ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3

6.2K
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
6.2K

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Is a thin mechanism appropriate for aromatic nitration?

Francesco Ambrosio1,2, Amedeo Capobianco2, Alessandro Landi2

  • 1Dipartimento di Scienze, Università degli Studi della Basilicata, Viale dell'Ateneo Lucano, 10 - 85100 Potenza (PZ), Italy. francesco.ambrosio@unibas.it.

Physical Chemistry Chemical Physics : PCCP
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Advanced simulations reveal toluene nitration via NO2BF4 involves a crucial electron transfer step before sigma-complex formation. This suggests spin-density drives regioselectivity in aromatic nitration reactions.

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Area of Science:

  • Computational Chemistry
  • Reaction Mechanisms
  • Physical Organic Chemistry

Background:

  • Aromatic nitration is a fundamental organic reaction.
  • Understanding the precise mechanism, including solvent and counterion effects, remains crucial.
  • Nitration using nitronium tetrafluoroborate (NO2BF4) is a common synthetic method.

Purpose of the Study:

  • To elucidate the detailed mechanism of toluene nitration by NO2BF4 in dichloromethane.
  • To investigate the influence of solvent and counterion on the reaction pathway.
  • To determine the factors governing the regioselectivity of the nitration process.

Main Methods:

  • Advanced *ab initio* molecular dynamics (MD) simulations were employed.
  • Reaction trajectories were simulated at a full quantum mechanical level.
  • The effects of solvent (dichloromethane) and counterion (BF4-) were explicitly included.

Main Results:

  • A single electron transfer step was consistently observed after reactant solvation.
  • This electron transfer precedes the formation of the sigma-complex.
  • The regioselectivity of toluene nitration is strongly suggested to be spin-density driven.

Conclusions:

  • The findings support a mechanism involving electron transfer prior to sigma-complex formation.
  • Spin-density plays a pivotal role in determining the regioselectivity of aromatic nitration.
  • A simplified mechanism focusing on intermediates and transition states is adequate for describing aromatic nitration.