Reactivity of the 5-Hydroacenaphthylene Anion towards Electrophiles

✍ Scribed by Marcia E. Van Loo; Johan Lugtenburg; Jan Cornelisse

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 382 KB
• Volume: 1998
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/(sici)1099-0690(199809)1998:9<1907::aid-ejoc1907>3.0.co;2-s

✦ Synopsis

The dianion of acenaphthylene can be converted into the 5-unsaturated bromides is responsible for this side reaction.

From the products of the reactions with 3,3-dimethylallyl hydroanion by protonation with one equivalent of methanol. Subsequent reaction with electrophiles such as allyl bromide bromide and (bromomethyl)cyclopropane the mechanism was found to be S N 2. Reaction of the hydroanion with benzyl and propargyl bromide occurs selectively at position 1, resulting in the formation of the novel 1-allylacenaphthene bromide takes place at position 1 as well as at position 2a.

The reactivity of carbon 2a towards the soft electrophile and 1-propargylacenaphthene. In addition to what was observed in the case of methyl iodide, the hitherto unknown benzyl bromide is attributed to the high HOMO coefficient at this position. 1,1-dialkylated acenaphthene derivatives are formed as minor products; probably the lower reactivity of the