Activated aromatic rings

Review Problem 6 Some chemists who were investigating the possibility of reversible Friedel-Crafts reactions, wanted an activated aromatic ring cormected to a branched alkyl chain and chose to make TM 82. How would you do it ... 

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... 

The way in which various substituents affect the polarization of a carbonyl group is similar to the way they affect the reactivity of an aromatic ring toward electrophilic substitution (Section 16.5). A chlorine substituent, for example, inductively withdraws electrons from an acyl group in the same way that it withdraws elections from and thus deactivates an aromatic ring. Similarly, amino, methoxvl, and methylthio substituents donate electrons to acyl groups by resonance in the same way that they donate electrons to and thus activate aromatic rings. 

Arenediazonium salts undergo a coupling reaction with activated aromatic rings such as phenols and arylamines to yield brightly colored azo compounds, Ar—N=N—Ar. ... 

The selective oxidation of the activated aromatic ring, substituted with electron-donating hydroxy or methoxy groups, can be perfomed at relatively low electrode potential (Ep = 0.3-1.2 V vs SCE) and ring closure is the result of the intramolecular nucleophilic attack of an amino group on the oxidized aromatic ring. 

Nitration (at C-2 and C-4) and diazocoupling (C-4) of I-hydroxythianthrene occur in the activated aromatic ring, in the former case with 5-oxidation (57JA991). 

When paraformaldehyde is added to a solution of II in concentrated sulfuric acid at room temperature, a rapid reaction takes place, yielding colorless to orange polymeric compositions depending upon the ratio of reactants and the reaction condition employed (17). It is reasonable to assume that the polymerization of II with formaldehyde proceeds in a fashion similar to that of an activated aromatic ring with formaldehyde to yield as final products the diarylmethane and dimethylene oxy-derivatives, IV and V (Equation 9). 

Karl Anker Jorgensen of Aarhus University, Denmark has found (J. Am. Chem. Soc. 2005, /27, 3670) that face-selective addition can also be carried out on an activated aromatic ring. In this work, the chirality is delivered by a quinine-derived organocatalyst. 

There is direct evidence, from ir and nmr spectra, that the f-butyl cation is quantitatively formed when f-butyl chloride reacts with A1CI3 in anhydrous liquid HCI.246 In the case of olefins, Markovnikov s rule (p. 750) is followed. Carbocation formation is particularly easy from some reagents, because of the stability of the cations. Triphenylmethyl chloride247 and 1-chloroadamantane248 alkylate activated aromatic rings (e.g., phenols, amines) with no catalyst or solvent. Ions as stable as this are less reactive than other carbocations and often attack only active substrates. The tropylium ion, for example, alkylates anisole but not benzene.249 It was noted on p. 337 that relatively stable vinylic cations can be generated from certain vinylic compounds. These have been used to introduce vinylic groups into aryl substrates.250... 

Notes Used for allylic and benzylic brominations (Wohl-Zieeler Reaction). With moist DMSO the reagent is useful for bromohydrin formation, providing trans addition of bromine and water. Can brominate alpha to carbonyl in carbonyl (carboxyl)-containing compounds. With DMF useful for aromatic bromination of activated aromatic rings, such as phenols, aromatic ethers, aniline derivatives and activated heterocyclic compounds. For similar chemistry, see also NBA, N-Bromoacetamide. 

The preference for bromination of C=C vs activated aromatic ring has been elucidated with the aid of model compounds 83 and 84. Bromination of 83 has been found to occur first at the double bond with excess of Br2, subsequent bromination of the aromatic ring has been observed. By contrast, 84 is first brominated in the aromatic nucleus before the... 

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