Monatshefte für Chemie / Chemical Monthly

, Volume 123, Issue 8–9, pp 769–777 | Cite as

13C-NMR-Untersuchungen von Substituenteneffekten in mehrfach substituierten Benzen-und Naphthalenverbindungen: Inkrementberechnungen der13C-chemischen Verschiebungen

  • Dieter Ströhl
  • Steffen Thomas
  • Erich Kleinpeter
  • Reiner Radeglia
  • Joachim Brunn
Organische Chemie Und Biochemie

Substituent effects in the13C-NMR chemical shifts of polysubstituted benzene and naphthalene compounds: An incremental calculation

Summary

The aryl13C chemical shifts of Cl-substituted 4-amino-, 4-diazonium-N,N-dimethylanilines, N,N-dimethylanilines and differently substituted naphthalenes were assigned by means of different NMR methods. The assignments were compared with chemical shifts obtained by using empirical additivity relationship for mono substituted aromatic substances. As a means of substitutent interactions, the chemical shift difference between calculated and experimental values (Δδ c i ) has been used. In the presence of remarkable steric and electronic substituent interactions, large deviations from additivity (Δδ c i values up to 15.4 ppm) were found. Which originate primarily from steric interactions between the substitutents. In order to account therefore, correction increments have been developed by employing the Δδ c i values obtained from 1,2-disubstituted benzenes or naphthalenes. The13C chemical shifts of more than seventy substituted benzenes and naphthalenes have been predicted. The results corroborate that reasonable calculation of chemical shifts in sterically hindered benzenes is possible by using the extended additivity rule. The Δδ c i values are much lower and allow reasonable structural assignments.

For external users of this incremental system, a computer program for IBM compatible PC/AT was developed. By means of this program, the13C chemical shifts for different benzenes and naphthalenes with or without 1,2-disubstituted correction increments will be calculated and the corresponding spectrum displayed. The program can assist the successful assignment of experimental13C chemical shifts.

Keywords

13C Incremental system Substituted benzenes and naphthalenes INEPT 

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Copyright information

© Springer-Verlag 1992

Authors and Affiliations

  • Dieter Ströhl
    • 1
  • Steffen Thomas
    • 1
  • Erich Kleinpeter
    • 1
  • Reiner Radeglia
    • 2
  • Joachim Brunn
    • 3
  1. 1.Institut für Analytische ChemieMartin-Luther-Universität Halle-WittenbergHalle/SaaleBundesrepublik Deutschland
  2. 2.Analytisches ZenturmBerlinBundesrepublik Deutschland
  3. 3.Institut für AnalytikTH MerseburgMerseburgBundesrepublik Deutschland

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