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The stereochemistry of SRN1 reactions in Nitroacenaphthenes
Journal article   Peer reviewed

The stereochemistry of SRN1 reactions in Nitroacenaphthenes

F.I. McLure and R.K. Norris
Australian Journal of Chemistry, Vol.40(3)
1987
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Abstract

The reaction of the 2-chloro-1,l-dialkyl-6-nitroacenaphthenes (1)-(3) with azide and p- toluenethiolate ions takes place by the SRN1 mechanism, to give the substitution products (27)-(32), despite the fact that the nitro group and the chlorine-bearing benzylic carbon are attached to different aromatic rings. The reaction of the stereoisomers (2) and (3) of 2-chloro-1-ethyl-1-methyl-6-nitroacenaphthene takes place through an effectively planar benzylic radical (35), which is preferentially attacked from the face remote from the a-ethyl group. The presence of geminal alkyl groups α to the reaction site in the rigid acenaphthene system restricts the scope of the substitution processes to sterically unhindered nucleophiles, and the reaction fails with reagents such as sodium p- toluenesulfinate (23) and the salts, (24) and (25), derived from 2-ethylmalononitrile and 2-nitropropane.

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Citation topics
2 Chemistry
2.1 Synthesis
2.1.824 Solvolysis
Web Of Science research areas
Chemistry, Multidisciplinary
ESI research areas
Chemistry
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