ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
An LSER analysis based on the partitioning of 15 proton acceptor heterocycles has succeeded in extracting Σβ values, but only at the cost of demonstrating solvent dependence for some of them. As noted by Abraham, the division lies between protic and aprotic organic phases. His observation that pyridine and quinoline are less effective acceptors when surrounded by solvent than in 1 : 1 association was confirmed, and possible reasons for this are discussed. Two other such cases are N-methylimidazole and pyridazine, both of which give lower Σβ values in octanol than in PGDP. For both, Σβ in PGDP is what would be expected on the basis of log Kβ. The value for pyridazine in octanol suggests that, here, the ‘α-effect’ is no longer operative; it is possible that this result can be generalized to other such heterocycles. Elsewhere, the most remarkable finding is that, where there are two proton acceptor sites in one heterocyclic ring, Σβ is the simple unattenuated sum of the separate βf values. If this result is general, it leads to a very simple way of estimating Σβ for heterocycles by calculation where data are unavailable. Evidence was also found, in certain cases, for hydrogen bonding to the π-donor heteroatom or the aromatic ring. The QSAR implications of these results are discussed.
Additional Material:
5 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610071213
