Leaving groups in nucleophilic aromatic

Fluonde Ion as Nucleophile and a Leaving Group in Aromatic Nucleophilic Substitution Reactions Vlasov V M J Fluorine Chem 6i. 193-216 77... 

One of the less common leaving groups in aromatic nucleophilic substitution reactions is the cyano group. However, a 4-cyano substituent in pyrido[2,3-t/]pyrimidine can be exchanged for methoxy or hydroxy functions by refluxing in methanolic sodium methoxide or aqueous sodium hydroxide solution.296... 

The basic concepts of nucleophilic substitution reactions appeared in the first semester of organic chemistry. These reactions follow or Sp 2 mechanisms. (In aromatic nucleophilic substitution mechanism, we use the designation Sp Ar.) In Sfjl and Sp 2 mechanisms, a nucleophile attacks the organic species and substitutes for a leaving group. In aromatic systems, the same concepts remain applicable, but with some differences that result from the inherent stability of aromatic systems. 

Aryl- and heteroaryl halides can undergo thermal or transition metal catalyzed substitution reactions with amines. These reactions proceed on insoluble supports under conditions similar to those used in solution. Not only halides, but also thiolates [76], nitro groups [76], sulfinates [77,78], and alcoholates [79] can serve as leaving groups for aromatic nucleophilic substitution. 

In the discussion of electrophilic aromatic substitution (Chapter 11) equal attention was paid to the effect of substrate structure on reactivity (activation or deactivation) and on orientation. The question of orientation was important because in a typical substitution there are four or five hydrogens that could serve as leaving groups. This type of question is much less important for aromatic nucleophilic substitution, since in most cases there is only one potential leaving group in a molecule. Therefore attention is largely focused on the reactivity of one molecule compared with another and not on the comparison of the reactivity of different positions within the same molecule. 

Groups that generally function well as leaving groups in nucleophilic aromatic photosubstitution are the methoxy(alkoxy)-group and the nitro-group. 

The SRN1 process has proven to be a versatile mechanism for replacing a suitable leaving group by a nucleophile at the ipso position. This reaction affords substitution in nonactivated aromatic (ArX) compounds, with an extensive variety of nucleophiles ( u ) derived from carbon, nitrogen, and oxygen to form new C—C bonds, and from tin, phosphorus, arsenic, antimony, sulfur, selenium, and tellurium to afford new C-heteroatom bonds. 

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