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15 N‐NMR. Studies of Aminopyridines, Aminopyrimidines and of Some Diazine N‐Oxides
Author(s) -
Städeli Werner,
Philipsborn Wolfgang Von,
Wick Alexander,
Kompiš Ivan
Publication year - 1980
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19800630223
Subject(s) - aminopyridines , chemistry , pyridazine , substituent , protonation , pyrazine , ring (chemistry) , chemical shift , diazine , medicinal chemistry , stereochemistry , organic chemistry , ion
15 N‐NMR. spectra of mono‐ and diaminopyridines, and mono‐, di‐ and triaminopyrimidines including trimethoprim and other dihydrofolate reductase inhibitors have been studied in neutral and acidic media. Complete chemical shift assignments are given. Ring‐nitrogen shifts are discussed in terms of β‐, χ‐ and δ‐substituent effects of amino and alkyl groups. Protonation states in TFA‐ and FSO 3 H‐solution and protonation increments for the 15 N‐shifts of ring and amino N‐atoms are determined. A linear correlation is observed between amino substituent effects (Δδ( 15 N)) on the ring N‐atom in aminopyridines and corresponding Δδ ( 13 C) values in aminobenzenes and, similarly, between Δδ( 15 N) values in aminopyrimidines and Δδ( 13 C) values in aminopyridines. Assignment of the 15 N‐NMR. spectra of pyrimidine N ‐oxides, pyrazine N ‐oxides and pyridazine N ‐oxides is achieved by comparison with 14 N‐NMR. data and with the aid of Yb(fod) 3 ‐induced shifts. One‐bond 15 N, 1 H‐coupling constants are reported for aminopyridines and aminopyrimidines and discussed in terms of conjugative interaction between NH 2 ‐group and ring system.