Photochemical Smiles rearrangement

The thermal and photochemical Smiles rearrangement (Section III.A.4.a) is most often employed for the transformation of O-substituted phenol derivatives 226 into N-substituted anilines 227 that occurred with aryl migration from oxygen to nitrogen317 (equation 88). 

The photochemical Smiles rearrangement was also reported recently. An example involving a thiol is the conversion of 25 to 26 on irradiation in ethanoP . 

The 2-aminophenoxy triazine (50) readily undergoes the Smiles rearrangement in base (equation 23) (70JHC981), or photochemically (70TL1467). Budziarek reported a similar reaction with the naphthyl derivative (51 Scheme 37) (7lJCS(C)74>. 

Slater type orbitals 59 Smiles rearrangement 688-691 photochemical 691 Solvent effect, on oxidation rate of K-butanethiol 808, 810 Solvolysis, of 2-chlorocyclohexanethiols 440... 

Matsui et al. were interested in what kind of photochemical reactions would occur in molecules such as 1, and their work describes the photochemical reactions of such aromatic molecules. Figure 18.1 exemplifies such a reaction (3 4) using a mercury lamp as the radiation source [2]. Wadia and Patil have also utilized the Smiles rearrangement (e.g., 5 6) toward the synthesis of diclofenac analogues [3]. 

---