Substituent Effect in Solvolysis of Spiro-1'-yl p-Nitrobenzoate

Article abstract of DOI:10.1021/jo00188a001

The preparation of a series of substituted spiro-1'-yl p-nitrobenzoates (4a-g) is described.The solvolysis rate constant is k = 8.53 * 10^-5 s^-1 at 25 deg C in 80percent aqueous acetone for the unsaturated derivative (4e) and is relatively high in comparison with the related secondary systems.The Hammett treatment (ρ?⁺) gives a straight line and the ρ value (-3.33) is more negative than that (-2.11) of 3,4-benzotricyclo<4.3.1.0^1,6>-dec-3-en-2-anti-yl p-nitrobenzoate (1).On the basis of the results, it can be considered that the mesomeric transmission of substituent effect is very weak in 1 relative to 4.