| Publication Type |
Journal Article |
| Title |
HYPERBOLIC MODEL FOR THE META PARA INTERRELATIONSHIP IN BENZENE-DERIVATIVES |
| Authors |
JC Reis MAP Segurado JDG DEOLIVEIRA |
| Groups |
MTFT |
| Journal |
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY |
| Year |
1995 |
| Month |
January |
| Volume |
8 |
| Number |
1 |
| Pages |
5-14 |
| Abstract |
A new approach to the long-standing problem of interrelating meta and para substituent constants is presented. An analysis of the unified sigma0-scale shows that the interrelation between sigma4(0) and sigma4(0)/sigma3(0) can be modelled by a pair of conjugate rectangular hyperbolae, one for normal (n) and the other for special (s) substituents. The latter are characterized by a lone electron pair in the first atom. The equations sigma4n0(sigma4n0 - gamma0)/(sigma4n0 - 2gamma0) = lambda0sigma3n0 and sigma4s0 = gamma0 + lambda0sigma3s0 are derived and discussed in terms of Taft s separation of mesomeric and non-mesomeric effects. Asymptotic values lambda0 = 0.960 and gamma0 = -0.225 were obtained by non-linear least rectangles fitting. A non-negligible mesomeric contribution to sigma0 constants for normal substituents is predicted by the hyperbolic model. The present results are at variance with Exner s analysis of the meta-para interrelationship in benzene compounds with normal substituents. This divergence is ascribed to opposite views concerning the role of the pi-inductive effect. |
| DOI |
http://dx.doi.org/10.1002/poc.610080104 |
| ISBN |
|
| Publisher |
|
| Book Title |
|
| ISSN |
0894-3230 |
| EISSN |
|
| Conference Name |
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| Bibtex ID |
ISI:A1995QH94200002 |
| Observations |
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