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Reactivity of the 5‐Hydroacenaphthylene Anion towards Electrophiles
Author(s) -
Van Loo Marcia E.,
Lugtenburg Johan,
Cornelisse Jan
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199809)1998:9<1907::aid-ejoc1907>3.0.co;2-s
Subject(s) - chemistry , electrophile , bromide , medicinal chemistry , reactivity (psychology) , sn2 reaction , iodide , protonation , propargyl bromide , benzyl bromide , cyclopropane , propargyl , organic chemistry , ion , ring (chemistry) , catalysis , medicine , alternative medicine , pathology
The dianion of acenaphthylene can be converted into the 5‐hydroanion by protonation with one equivalent of methanol. Subsequent reaction with electrophiles such as allyl bromide and propargyl bromide occurs selectively at position 1, resulting in the formation of the novel 1‐allylacenaphthene and 1‐propargylacenaphthene. In addition to what was observed in the case of methyl iodide, the hitherto unknown 1,1‐dialkylated acenaphthene derivatives are formed as minor products; probably the lower reactivity of the unsaturated bromides is responsible for this side reaction. From the products of the reactions with 3,3‐dimethylallyl bromide and (bromomethyl)cyclopropane the mechanism was found to be S N 2. Reaction of the hydroanion with benzyl bromide takes place at position 1 as well as at position 2a. The reactivity of carbon 2a towards the soft electrophile benzyl bromide is attributed to the high HOMO coefficient at this position.