Activators strong

Reactions. The methylene group in the 2 position in 5,5-dimethyl-cyclohexan-i,3-dione (V) is strongly activated by the... 

This is also confirmed by the observation that in the reaction of 2.4- or 2,5-dihalogenothiazoles with anionic nucleophiles, the halogen in position 2 reacts first (8, 9, 35). This halogen is strongly activated by the aza substituent and by the other halogen substituent. Only when the halogen in position 2 is substituted more than 90% can the substitution proceed in position 4 or 5,... 

Table 12 2 summarizes orientation and rate effects m electrophilic aromatic sub stitution reactions for a variety of frequently encountered substituents It is arranged m order of decreasing activating power the most strongly activating substituents are at the top the most strongly deactivating substituents are at the bottom The mam features of the table can be summarized as follows... 

Very strongly activating —NH2 (ammo) Ortho para directing... 

Nitrosyl cation is a relatively weak electrophile and attacks only very strongly activated aromatic rings... 

A reaction of aryl diazonium salts that does not involve loss of nitrogen takes place when they react with phenols and arylamines Aryl diazonium ions are relatively weak elec trophiles but have sufficient reactivity to attack strongly activated aromatic rings The reaction is known as azo coupling two aryl groups are joined together by an azo (—N=N—) function... 

A nitro group is a strongly activating substituent in nucleophilic aromatic substitution where it stabilizes the key cyclohexadienyl anion intermediate... 

Reaction with arenediazonium salts Adding a phe nol to a solution of a diazonium salt formed from a primary aromatic amine leads to formation of an azo compound The reaction is carried out at a pH such that a significant portion of the phenol is pres ent as its phenoxide ion The diazonium ion acts as an electrophile toward the strongly activated ring of the phenoxide ion... 

Although a hydroxyl group strongly activates an aromatic ring toward electrophilic attack an oxyanion substituent is an even more powerful activator Electron delocaliza tion m phenoxide anion leads to increased electron density at the positions ortho and para to oxygen... 

The hydroxyl group of a phenol is a strongly activating substituent and electrophilic aromatic substitution occurs readily m phenol and its deriv atives Typical examples were presented m Table 24 4... 

Azo coupling (Section 22 18) Formation of a compound of the type ArN=NAr by reaction of an aryl diazonium salt with an arene The arene must be strongly activated toward... 

Examples of vibronic transitions involving non-totally symmetric vibrations are in the system of chlorobenzene, a C2 molecule. One 2 vibration V29, with a wavenumber of 615 cm in the X state and 523 cm in the A state, is active in 29q and 29j bands similar to the case shown in Figure 7.43. There are 10 2 vibrations in chlorobenzene but the others are much less strongly active. The reason is that (9J g/9029)eq is much greater than the corresponding terms for all the other 2 vibrations. 

Polymerization via Nucleophilic Substitution Reaction. Halo- and nitro- groups attached to phthahmide groups are strongly activated toward nucleophilic substitution reactions. Thus polyetherimides ate synthesized by the nucleophilic substitution reaction of bishaloimides (59,60) and bisnitroimides (61,62) with anhydrous bisphenol salts in dipolar aptotic solvents. 

In terms of general solvency, solvents may be described as active solvents, latent solvents, or diluents. This differentiation is particularly popular in coatings applications, but the designations are useful for almost any solvent appHcation. Active solvents are strong solvents for the particular solute in the apphcation, and are most commonly ketones or esters. Latent solvents function as active solvents in the presence of a strong active solvent. Alcohols exhibit this effect in nitrocellulose and acryUc resin solutions. Diluents, most often hydrocarbons, are nonsolvents for the solute in the apphcation. 

Potassium. Potassium 2-ethyIhexanoate [3164-85-0] functions best in conjunction with cobalt. Potassium strongly activates cobalt in aqueous coatings and in high soHds paints based on low molecular-weight vehicles. 

The effect of substituents on the reactivity of heterocyclic nuclei is broadly similar to that on benzene. Thus mem-directing groups such as methoxycarbonyl and nitro are deactivating. The effects of strongly activating groups such as amino and hydroxy are difficult to assess since simple amino compounds are unstable and hydroxy compounds exist in an alternative tautomeric form. Comparison of the rates of formylation and trifiuoroacetylation of the parent heterocycle and its 2-methyl derivative indicate the following order of sensitivity to substituent effects furan > tellurophene > selenophene = thiophene... 

Substituents in 1,3,4-thiadiazoles are quite strongly activated, as in the 2-position of pyridine. 

If the fV-aryl group is strongly activated, then it can be removed in nucleophilic substitution reactions in which the azole anion acts as leaving group. Thus l-t2,4-dinitrophenyl)pyrazole reacts with N2H4 or NaOMe. 

Very strongly activating —NHj (amino) Ortho, para-directing... 

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