Relative solvolysis rates of allyl and dienyl 3,5-dinitrobenzoates

✍ Scribed by Nye A. Clinton; C.Peter Lillya

• Book ID: 104212412
• Publisher: Elsevier Science
• Year: 1968
• Tongue: French
• Weight: 178 KB
• Volume: 9
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)70754-4

✦ Synopsis

Of the many solvolysis rate studies involving ally1 compounds, only two have examined the effect of extending conjugation. Vernon' has estimated that replacement of a p-methyl group by a phenyl group (1. and 2) increases the rate by a factor of gg. 140. Friedrich and WinsteIn have studied some spirodienyl E-nitrobenzoates, and the 1.3 4 (OPNB = R-nitrobenzoate) in findings. CH3 d-CH2C1 WOPNB x lo7 fold rate difference between compounds 2 and 9046 aqueous acetone at 25O is typical of their C6H5 J-cH2c1 2 2 These authors noted the unusual reactivity of the spirodienyl compounds, but OPNB 4

Deno4 has suggested that the rate difference is consistent with estimated relative stabilities of ally1 and pentadienyl cations. We report here solvolysis rates for acyclic dienyl derivatives and their ally1 analogues5 which show that the spirodienyl compounds are indeed unusually reactive.