The Substituent Effect. XIII. Solvolysis of 1-(7-Substituted 2-Fluorenyl)ethyl Chlorides and Alkaline Hydrolysis of Ethyl 7-Substituted 2-Fluorenecarboxylates
- 1 February 1978
- journal article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 51 (2) , 601-607
- https://doi.org/10.1246/bcsj.51.601
Abstract
Two sets of rate constants for (i) solvolysis of 1-(7-substituted 2-fluorenyl)ethyl chlorides in both 90 and 80% aqueous acetone and (ii) alkaline hydrolysis of ethyl 7-substituted 2-fluorenecarboxylates in 85% aq EtOH have been determined. Both substituent effects could be correlated excellently with the LArSR relationship; the resulting r+ values (0.82 and 0.47, respectively) were comparable with the r+’s in the corresponding biphenylyl system under the same conditions. The comparison of ρπ+ values clearly indicates a more efficient transmission of the pi-electronic effect in the fluorenyl than in the biphenylyl ststem (1:0.75). This can be attributed to a factor of twisting in the latter pi-system. The attenuation of the transmission of the Pi effect was found to be characteristic of the intervening pi-systems independent of reactions: 1.00(4-X-1-phenyl), 0.55(6-X-2-naphthyl), 0.35(7-X-2-fluorenyl), and 0.25(4′-X-4-biphenylyl).Keywords
This publication has 32 references indexed in Scilit:
- The Substituent Effect. XII. Solvolysis of 3′- and 4′-Substituted 1-(4-Biphenylyl)ethyl ChloridesBulletin of the Chemical Society of Japan, 1978
- The Substituent Effect. XI. Solvolysis of 5-, 6-, and 7-Substituted 1-(1-Naphthylethyl) ChloridesBulletin of the Chemical Society of Japan, 1975
- Fundamental frequencies and molecular configuration of biphenyl—II Normal coordinatesSpectrochimica Acta Part A: Molecular Spectroscopy, 1968
- Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. III. o,o′-Bridged BiphenylsBulletin of the Chemical Society of Japan, 1959
- Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. II. o-Alkyl-and o,o′-DialkylbiphenylsBulletin of the Chemical Society of Japan, 1959
- Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. I. BiphenylBulletin of the Chemical Society of Japan, 1959
- Ultraviolet Absorption Spectra of ortho- and para-Linked Polyphenyls.Acta Chemica Scandinavica, 1957
- Conjugation in the Biphenyl SystemJournal of the American Chemical Society, 1954
- The Spatial Configurations and the Ultraviolet Absorption Spectra of Biphenyl and Some Related CompoundsBulletin of the Chemical Society of Japan, 1954
- Molecular Structure of FluoreneNature, 1954