Cycloaddition reaction between [8]annulyne and isocyanate systems

ORGN 755

Steven J. Peters, sjpeter@ilstu.edu and Joseph Klen, jrklen@ilstu.edu. Department of Chemistry, Illinois State University, MS 4160, Normal, IL 61790
We have found that [8]annulyne (cyclooctatrienyne) can undergo cyclic addition reactions with various olefins. This suggests that [8]annulenoazetidinones (Structure 1) might be produced by the reaction of [8]annulyne with isocyanates. When a mixture of N-ethyl isocyanate and monobromo[8]annulene (C8H7Br) is exposed to a solution of potassium tert-butoxide in hexamethylphosphoramide (HMPA) the C8H7Br undergoes a dehydrohalogenation reaction that generates [8]annulyne. Subsequently, a cycloaddition reaction takes place between [8]annulyne and N-ethyl isocyanate. However, the cycloaddition reaction does not generate the N-ethyl [8]annulenoazetidinone as predicted, but instead generates [8]annuleno-2,3-diethyl-2,3-dihydropyrazine-1,4-dione. Exposure of this solution to potassium metal yields a strong well-resolved EPR spectrum of the anion radical of this product. This reaction, along with the electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopic results, will be discussed.