2691
are appreciably more deshielded than the third proton, in agreement with the introduction of the nitro group 0 to the norbornyl ring fusion (111-OAc). The mixtureg of the two isomeric acetates was hydrolyzed to the exo alcohols (111-OH, 111-OBs mp 116-117”), oxidized to the ketones, and reduced with tetrahydrofuran-borane to the endo alcohols (VI-OH, VI-OBs mp 140-146‘)).
Ill
Because of the great reactivity of 11-OH, the rate of solvolysis of 11421 in 80% aqueous acetone was determined and compared with that of the parent chloride. The rate data are summarized in Table I. First, a methoxy group in the 7 position (“homomet~7’’~~) has little effect on the rate of solvolysis. In the 6 position (“homo-para”) the methoxy substituent increases the rate by a factor of 210. It is noteworthy that this is the largest rate acceleration yet observed for a neighboring “p-anisyl” group. lo The point of major interest for the present objective is the exo:endo rate ratio for the nitro derivative. A value of 94 was observed. (This value may be low, since the acetolysis of 2-dl-endo-benzonorbornadienyl brosylate revealed that 28% of the reaction involved an inversion at the 2 position, without scrambling of the tag. If this is the result of an S N com~ ponent, the exo:endo ratio rises to 130.) A nitro substituent has an enormous deactivating effect on the aromatic ring. l 1 For example, 3-p-nitrophenyl2-butyl tosylate fails to exhibit any evidence of the unique properties of the parent structure. l 2 Similarly, a nitro substituent causes the anti:syn rate ratio to decrease from 1200 for the parent benzonorbornan-9-yl brosylates to 4.4 for the 6-nitro derivative^.^^ If the nitro substituent in 111-OBs effectively cancels out a participation from the aromatic ring, then the 15,000 exo:endo ratio involves a factor of 160 for a participation and a factor of 94 for steric and torsional (9) Since the cr+ values of m-NO, and p-NOn are not greatly different, f0.674 and +0.790, it did not appear important for the purposes of this study to separate the isomers. (10) For example, rate accelerations in the range from 26 to 78 are observed for the acetolysis and formolysis of P-anisylethyl and 3-anisyl-2butyl derivatives. See Table V of H. C. Brown, R. Bernheimer, C. J. Kim, and S. E. Scheppele, J . A m . Chem. Soc., 89, 370 (1967). (11) I t is of interest that the effect of the nitro substituent (0.044) on the rate of the endo isomer, VI-OBs, is almost identical with its effect on the rate of the syn isomervb (0.037). (12) D. J. Cram and J. A . Thompson, J . A m . Chem. Soc., 89, 6766 (1967).
contributions. (Corrected for the possible S N com~ ponent, the factor would be 115 for a participation and 130 for steric and torsional contributions.) Unfortunately, the possibility that there may not be some residual ir participation, even in the presence of this highly deactivating group, cannot now be excluded. Only by making a systematic study of a series of compounds with deactivating substituents will it be possible to state whether one approaches a plateau value for the exo:endo rate ratio or whether the value diminishes to unity. These results indicate that a participation makes an important contribution to the exo :endo rate ratio of the secondary benzonorbornen-2-yl derivatives. But what can we say about the behavior of the tertiary derivatives? It has recently been reported that a p-anisyl group in the 7 position of dehydronorbornyl causes the loss of nearly all of the 10” of ir participation in the parent secondary compound.13 Consequently, the close similarity in the exo:endo rate ratio for the tertiary 2-methyl and 2-phenyl derivatives is not consistent with a large contribution of ir participation to the observed high exo:endo ratio in these tertiary derivatives. This indicates that the high exo: endo rate ratios in these tertiary derivatives must arise primarily from steric and torsional contributions. We hope to make tertiary benzonorbornen-2-yl derivatives containing deactivating substituents in the aromatic ring to test this indication. (13) P. G. Gassman, J. Zeller, and J. T. Lumb, Chem. Commun., 69 (1968). (14) Purdue Research Foundation Fellow, 1964-1966.
Herbert C. Brown, Gary L. Tritlel4 Richard B. Wetherill Laborutory Purdue University, Lafayette, Indiana 47907 Receiued March 14, 1968
High exo :endo Rate Ratio and Predominant exo Substitution in the Solvolysis of 2-p-Anisylnorbornyl Derivatives. The Characteristics of a Highly Stabilized, Classical Norbornyl Cation
Sir : The rate of ethanolysis of 2-p-anisyl-exo-norbornyl chloride is greater than that of exo-norbornyl chloride by the enormous factor of 500,000,000,0001 (Figure 1). Clearly the p-anisyl group must provide major stabilization of the incipient cation in the transition state. It has been generally accepted that the more stable the carbonium ion center, the less demand that center will make upon neighboring groups for additional stabilization through participation. The remarkable ability of the p-anisyl group to cause such participation to vanish is elegantly indicated by the recent study of Gassman and his coworker^.^ They observed that the 10” acceleration arising from participation of the double bond in the solvolysis of anti-7-dehydronorbornyl derivatives4 essentially vanishes in the corresponding 7-p-anisyl derivatives3(1). (1) H. C. Brown and K. Takeuchi, J . A m . Chem. Soc., 88,5336 (1966). (2) S . Winstein, B. K. Morse, E. Grunwald, I
