1‐Phenyl‐1, 2, 4, 6‐cycloheptatetraene: the missing intermediate of the diphenylcarbene to fluorene rearrangement1. (9th October 2014)

• Record Type: Journal Article
• Authors: Costa, Paolo; Sander, Wolfram; Moss, R. A.; Gudmundsdottir, A.
• Is Part Of: Journal of physical organic chemistry. Volume 28:Number 2(2015:Feb.)
• Page Start: 71
• Page End: 74
• Publication Date: 2014-10-09
• Subjects: Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3355
• Languages: English
• ISSNs: 0894-3230

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>The photochemistry of diphenylcarbene <bold>5</bold>, matrix‐isolated in argon at 3–5 K was investigated by UV–Vis, IR, and EPR spectroscopy. Although carbene <bold>5</bold> proved to be stable toward broadband UV irradiation, it slowly rearranges to 1‐phenyl‐1, 2, 4, 6‐cycloheptatetraene <bold>8</bold> during irradiation with the intense light of a 445‐nm diode laser. Other intermediates were not observed. Allene <bold>8</bold> is the key <named-content content-type="reactionType" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">intermediate</named-content> that was missing in the proposed mechanism of the <named-content content-type="reactionType" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">rearrangement</named-content> of <bold>5</bold> to fluorene <bold>7</bold>. Copyright © 2014 John Wiley &amp; Sons, Ltd.</p> </abstract>