Benzoxetes and benzothietes--heterocyclic analogues of benzocyclobutene.
Benzo-condensed four-ring heterocycles, such as benzoxetes 1 and benzothietes 3 represent multi-purpose starting compounds for the preparation of various higher heterocyclic ring systems. The thermal or photochemical valence isomerizations between the benzenoid forms 1,3 and the higher reactive o-quinoid structures 2,4 provide the basis for the synthetic applications. On the other hand, this valence isomerization impedes in particular the generation and storage of 1 because the thermal equilibrium 1<=> 2 is completely on the side of 2. Thus, the number of erroneous or questionable benzoxete structures published to date is surprisingly high. On the contrary, the thermal equilibrium 3<=> 4 is on the side of the benzothietes 3, which makes them easily accessible, especially by different flash vacuum pyrolysis techniques. The present article gives a survey of the preparations of 1 and 2, and tries to stimulate their use in synthetic projects. Naphtho-condensed and higher condensed compounds and compounds with an exocyclic C=O or S=O double bond (lactones, thiolactones, sulfoxides and sulfones) are not covered in this article.
Institute of Organic Chemistry, University of Mainz, Duesbergweg 10-14, Mainz, Germany. hmeier@mail.uni-mainz.de
Herbert
H
Meier
D006571:Heterocyclic Compounds / Q000737:chemistry*; D011083:Polycyclic Compounds / Q000737:chemistry*
D006571:Heterocyclic Compounds; D011083:Polycyclic Compounds; C079040:benzocyclobutene