Naphthothiete und ihre Anwendung in der Heterocyclen-Synthese

✍ Scribed by Mayer, Axel ;Rumpf, Norbert ;Meier, Herbert

• Publisher: John Wiley and Sons
• Year: 1995
• Tongue: English
• Weight: 645 KB
• Volume: 1995
• Category: Article
• ISSN: 0947-3440
• DOI: 10.1002/jlac.1995199512308

✦ Synopsis

Naphtothietes and Their Application to the Synthesis of Heterocycles

The three isomeric naphthothietes 5, 11, and 16 were prepared according to the reaction sequences shown in Schemes 1–3. The final step was in each case a flash vacuum pyrolysis (FVP) of the corresponding mercaptonaphthalenemethanol 4, 9, and 15, respectively. The thiete rings in 5 and 11 can be opened by gentle heating; the ring opening of the isomer 16 possesses a much higher activation barrier. A MNDO calculation of the Δ__H__~f~ values of 5, 11, and 16 and the open isomers 5′, 11′, and 16′ provides an explanation for the different behavior. Photochemical ring opening represents a useful alternative. The reaction Schemes 4, 6, and 7 reveal the synthetic potential of the naphtho‐condensed thietes. Cycloaddition reactions with CC, CO, or CN double bonds lead into the series of differently condensed thiopyrans 17, 18, 24, 25, 26, 3,1‐oxathiine 19 and 1,3‐thiazines 20, 21.