3318
Substituent Effects. VI.’pz Fluorine Nuclear Magnetic Resonance Spectra of 3’- and 4’3ubstituted 4-Fluorobiphenyls and 3”-Substituted 4-Fluoroterphenyls Michael J. S. Dewar and Alan P. Marchand3 Contribution f r o m the Department of Chemistry, The University of Texas, Austin, Texas 78712. Received January 27,1966 Abstract: Derivatives of 4-fluorobiphenylwith a variety of substituents in the 3‘ and 4’ positions, and derivatives of 4-fluoroterphenylwith substituents in the 3” position, have been synthesized and their fluorine nmr spectra have
been measured. The chemical shifts for the biphenyls correlate well with u constants calculated by the F M m e t h ~ d , ~ while comparison with results for the corresponding terphenyls provides further support for the idea4 that the longrange interactions in such compounds are due to field effects rather than u-inductive effects. Comparison with the chemical shifts in metu-substitutedfluorobenzenes suggests that the latter are out of step with the effects of substituents on other side-chain properties, and suggests that some of the conclusions that have been drawn from nmr data for substituted benzenes may have been incorrect.
P
revious papers of this ~ e r i e s presented ~,~ evidence suggesting that the a-inductive effect of a substituent is unimportant at atoms separated by more than one bond from the atom to which the substituent is attached. Long-range interactions seem to be due solely to the field effect, or to the polarization of 7~ electrons in intervening conjugated systems (mesomeric effect), the a-inductive effect being rapidly attenuated with distance. On this basis a simple treatment ( F M method) was developed4 for calculating the effects of a variety of substituents on the pKA of a-naphthoic acid, and recent studies of substituented P-naphthoic acids have shown that the same is true of this system a1so.j The FM method is, however, admittedly a very crude approximation in that it assumes that the field effect of a dipolar substituent falls off inversely as the distance between it and the reaction center. While it is true4 that an inverse second-order dependence would not be expected since this law applies only to point dipoles in a medium of uniform dielectric constant, the assumption4 that the field due to one end of the dipole is damped out by the solvent is certainly much too extreme. Recent studies by Stock and his collaborators6 on the effects of substituents in the bicyclooctane system have indeed shown that the situation is best treated as one involving two separated point charges of equal and opposite sign at the ends of the dipole, a different effective dielectric constant being used in calculating the field at the reaction center due to each of the charges. The purpose of the present investigation was twofold. First, we wanted to get more evidence concerning the way the effect of an inductive substituent diminishes with distance; secondly, we wanted to see if the chemical shifts of the fluorine nmr spectra of organic fluorides could be used generally as a measure of substituent effects. Gutowsky and his collaborators7 showed (1) This work was supported by the Army Research Office (Durham) through Grant DA-AROD-31- 124-G713. (2) Part V : M. J. S. Dewar and A. P. Marchand, J . Am. Chem. SOC., in press. (3) NASA Predoctoral Fellow, 1962-1964; National Institutes of Health Predoctoral Fellow, 1964-1965. (4) M. J. S. Dewar and P. J. Grisdale, J . Am. Chem. SOC.,84, 3548 (1962). (5) W. Adcock and P. R. Wells, Australian J. Chem., 18, 1351 (1965). (6) H. D. Holtz and L. M. Stock, J . Am. Chem. Soc., 86, 5188 (1964); 87, 2404 (1965).
Journal of the American Chemical Society
/ 88:14 / July 20, 1966
some time ago that the effect of substituents on the nmr chemical shifts of fluorine in fluorobenzene followed roughly the Hammett p c relation, and recently Taft and his collaborators8 have studied the fluorobenzene system in great detail. However little work has been done on other ring systems, and the results for benzene are anomalous in certain respects; thus the effect of substituents in the meta position of fluorobenzene seems8 to follow aI rather than g m . For our purpose we needed data for the effects of a variety of substituents on the fluorine nmr chemical shifts of a series of fluoro compounds in which the geometrical distance between substituent and fluorine is clearly defined, Since we were interested primarily in the field effect rather than the mesomeric effect, it was also important that there should be no direct resonance interaction (mutual conjugation) between the substituent and fluorine. These considerations led us to compare the following series of compounds: 3-substituted fluorobenzenes (I), 3 ’-substituted 4-fluorobiphenyls (11), and 3 “-substituted 4-fluoroterphenyls (111). Rotation about the interannular bonds of I1 or 111 does not alter the distance from substituent to fluorine, and the meta orientation should inhibit mutual conjugation between them.
x
I
I1
I11
F
IV
Synthetic Procedures The meta-substituted fluorobenzenes (I) are all wellknown compounds and their fluorine nmr spectra have been exhaustively studied by Taft, et al.a (7) H. S. Gutowsky, D. W. McCall, B. R. McGravey, and L. H. Meyer, ibid., 74, 4809 (1952). (8) (a) R. W. Taft, E. Price, I. R. Fox, 1. C. Lewis, I
