Solvent-induced rearrangements

Table 4 Solvent induced rearrangement of diblock brushes ...

Heating the acyl azide (719) in an inert solvent induced rearrangement to the isocyanate with loss of nitrogen followed by ring closure to (720) (76CHE924). 

Lubineau A, Aug6 J (1999) Water as Solvent in Organic Synthesis. 206 1-39 Lundt I, Madsen R (2001) Synthetically Useful Base Induced Rearrangements of Aldonolac-tones. 215 177-191... 

Treatment of compound 185 with the pyrazole 186, and subsequent cyclization with acetic acid, afforded a mixture of products 187 and 188 in a ratio of 3 2 (Scheme 15). Trituration of the mixture in acetonitrile induced dissolution of one of the two products, and the remaining product was found to be 187 a pure sample of 188 was not isolated upon evaporation of the solvent as rearrangement to 187 had occurred. Thus, 188 is believed to be the kinetic product and 187 the thermodynamic product. 

J. Kiss and W. Arnold, A new base-induced rearrangement of hexopyranuronic acid derivatives with solvent participation, Helv. Chim. Acta, 64 (1981) 1566-1569. 

The acylsilane moiety in poly(l-trimethylsilyl-2- propen-l-one) readily undergoes UV-radiation- and thermally induced rearrangement. The solid polymer is stable when stored at low temperature in the dark. PVTMSK exhibited an unusually high solubility in a wide range of solvents, a property that turned out to be a major obstacle in the practical utilization of this... 

---