Williams Aromatic rearrangements

For a monograph, see Shine Aromatic Rearrangements, Elsevier New York, 1967. For reviews, see Williams Bunccl lsot. Org. Chem. 1980, 5, 147-230 Williams, in Bamford Tipper, Ref. I, pp. 433-486,... 

We mention Williams work briefly here because it may also explain Blangey s observations strongly basic primary amines unequivocally form 7V-nitrosoanilinium ions in strongly acidic media. In contrast to the rate-limiting deprotonations of the less basic aromatic and heteroaromatic nitrosoamine cations discussed in this section, the TV-nitroso cation of a strongly basic amine deprotonates extremely slowly. Therefore, the nitroso rearrangement, the Fischer-Hepp reaction, competes effectively with the 7V-deprotonation. 

While at Leeds from 1924 to 1930, Ingold s laboratory focused on three main topics of research (1) the nature and mechanism of orienting effects of groups in aromatic substitution (mainly nitration) (2) the study of prototropic rearrangements (shifts of H+) and aniontropic rearrangements (shifts of anions) as the ionic mechanisms of tautomerism and (3) the effect of polar substituents on the velocity and orientation of addition reactions to unsaturated systems. One of Ingold s students at Leeds, John William Baker, wrote a widely read book on tautomerism. 16... 

The Smiles and Related Rearrangements of Aromatic Systems W. E. Truce. Eunice M. Kreider, and William W. Brand... 

Epoxides of aromatic rings (arene oxides) rearrange to phenols and are substrates for glutathione-S-epoxide transferase to give glutathione conjugates, the precursors of mercapturic acids (Boyland and Williams 1965). 

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