Reactivities of stable rotamers. XIX Basicities of rotameric 9-[2-(dialkylaminomethyl)-6-methylphenyl]fluorenes and solvent effects on them.
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The p<I>K</I><SUB>a</SUB>′ values of the trifluoroacetate salts of the title compounds were determined in THF–water (3:2) solution at 25 °C by potentiometric titration: in every compound examined, basicity of the <I>ap</I> rotamer was higher than that of the <I>sp</I> rotamer. Differences in p<I>K</I><SUB>a</SUB>′ values (Δp<I>K</I><SUB>a</SUB>) between the rotamers are in the range of 0.55 to 1.14 p<I>K</I><SUB>a</SUB> units, depending upon the substituents on the nitrogen atom. The Δp<I>K</I><SUB>a</SUB> values in chloroform-<I>d</I> solution at 80.1 °C determined by taking advantage of the equilibrium constants of the salts and the free amines were larger than those obtained in aqueous THF solutions and were nearly independent of the substituents. The results were explained in terms of the intramolecular NH-π interactions in the <I>ap</I> salts, which are not possible in the <I>sp</I>. <SUP>1</SUP>H and <SUP>13</SUP>C NMR spectral data were in conformity with the presence of the interactions. Examination of the population ratios in various solvents revealed that <I>sp</I> conformers of the free amines are generally favored over the <I>ap</I> in polar, proton-accepting solvents, but the reverse is true for the trifluoroacetate salts. As the results, Δp<I>K</I><SUB>a</SUB> values are large in toluene and chloroform but are rather small in tetrahydrofuran, acetonitrile, and nitromethane. Possible causes for the differences including solvation and hydrogen bond formation are discussed.
- 公益社団法人 日本化学会の論文
著者
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Oki Michinori
Department Of Chemistry Faculty Of Science Okawama University Of Science
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Nakamura Mikio
Department Of Anatomy Jikei-kai School Of Medicine
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