Abstract
IT has been claimed by Pullman1 that the extent of conjugation of a given substituent with an aromatic ring system is determined by the electron density (index of free valence) at the position of substitution. Using the customary resonance terminology, this conclusion may be illustrated by the fact that for 1-substituted naphthalenes there are seven possible structures in which the substituent is linked to the ring by a double bond, but that for 2-substituted naphthalenes there are only six such structures. If X is a substituent, the C—X bond in 1-substituted naphthalenes should therefore have greater double-bond character than the corresponding bond in 2-substituted naphthalenes, and examination of the dipole moments of the halogenated naphthalenes confirms that this is the case2. Furthermore, examination of the ultra-violet absorption spectra of suitable substituted compounds shows that there is a correlation between the magnitude of the bathochromic shift, the extent of conjugation, and the index of free valency at the position of substitution3. The experimental evidence supporting Pullman's generalization is not, however, extensive, and the present work was undertaken to provide further information of interest.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Pullman, B., C.R. Acad. Sci., Paris, 222, 1396 (1946). See also Daudel, R., and Martin, M., Bull. Soc. chim., 15, 559 (1948).
Ketelaar, J. A. A., and van Oosterhout, G. W., Rec. trav. chim., 65, 448 (1946).
Pullman, A., C.R. Acad. Sci., Paris, 224, 1354 (1947).
Badger, G. M., J. Chem. Soc., 456 (1948) and unpublished work.
Badger, G. M., J. Chem. Soc., 535 (1941). Everett, J. L., and Kon, G. A. R., J. Chem. Soc., 1601 (1948).
Fulton, J. D., and Robinson, R., J. Chem. Soc., 200 (1939).
Böeseken, J., and Stuurman, J., Rec. trav. chim., 56, 1034 (1937). Paal, C., and Schiedewitz, H., Ber., 63, 766 (1930). Birks, A. M., and Wright, G. F., J. Amer. Chem. Soc., 62, 2412 (1940).
Ferguson, L. N., Chem. Rev., 43, 419 (1948).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
BADGER, G. Addition of Osmium Tetroxide to Dinaphthylethylenes. Nature 165, 647–649 (1950). https://doi.org/10.1038/165647b0
Issue Date:
DOI: https://doi.org/10.1038/165647b0
This article is cited by
-
Rates of Oxidation of Azonaphthalenes
Nature (1951)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.