17.12
NMR-Spektroskopie aromatischer Verbindungen
Aromatische Verbindungen können mithilfe von Protonen-NMR und Kohlenstoff-13-NMR identifiziert oder analysiert werden. Typischerweise werden aromatisc…
Die 1-H- und 13-C-NMR-Spektroskopie ist sehr hilfreich bei der Identifizierung aromatischer Verbindungen.
Typischerweise werden aromatische Wasserstoffatome durch den aromatischen Ringstrom stark abgeschirmt.
Infolgedessen weisen sie charakteristische 1-H-NMR-Absorptionen im Bereich von 6,5–8 ppm auf.
Zum Beispiel absorbieren aromatische Wasserstoffatome von Benzol bei 7,3 ppm.
Aromatische Wasserstoffatome großer Ringe absorbieren jedoch weiter oben oder unten.
Betrachten wir [18]Anulen. Er hat 12 Wasserstoffatome außerhalb des Rings, die durch den aromatischen Ringstrom stark abgeschirmt sind. Die 6 Wasserstoffatome im Inneren des Rings sind stark abgeschirmt.
Folglich absorbieren die äußeren Wasserstoffatome mit hoher Frequenz das Abfeld. Die inneren Wasserstoffatome absorbieren das Upfield mit einer niedrigen Frequenz.
Aromatische Kohlen weisen eine NMR-Absorption von 13C im Bereich von 110–150 ppm auf.
Zum Beispiel absorbieren aromatische Kohlenbänze von Benzol bei 128 ppm.
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Q1: What chemical shift range do aromatic hydrogens typically appear in 1H NMR spectra?
Aromatic hydrogens are highly deshielded by the aromatic ring current and exhibit characteristic 1H NMR absorptions in the range of 6.5–8 ppm. For example, aromatic hydrogens of benzene absorb at 7.3 ppm. However, aromatic hydrogens of larger rings may absorb farther upfield or downfield than this typical range.
Q2: Why do aromatic hydrogens appear at different chemical shifts in [18]annulene?
In [18]annulene, the 12 outer hydrogens are highly deshielded by the aromatic ring current and absorb downfield at 9.3 ppm, while the 6 inner hydrogens are highly shielded and absorb upfield at −3.0 ppm. This dramatic difference occurs because the ring current affects hydrogens inside and outside the ring in opposite directions.
Q3: What chemical shift range characterizes aromatic carbons in 13C NMR?
Aromatic carbons exhibit 13C NMR absorptions in the range of 110–150 ppm. For instance, aromatic carbons of benzene absorb at 128 ppm. This distinct chemical shift range helps identify aromatic carbon environments in complex organic molecules and distinguishes them from aliphatic carbons.
Q4: How does the aromatic ring current affect hydrogen deshielding in NMR?
The aromatic ring current creates a magnetic field that deshields hydrogens bonded directly to aromatic rings, causing them to absorb at lower frequencies or higher ppm values. This deshielding effect is responsible for the characteristic downfield shifts observed in aromatic 1H NMR spectra, distinguishing aromatic hydrogens from aliphatic hydrogens.
Q5: How can NMR spectroscopy be used to identify aromatic compounds?
1H and 13C NMR spectroscopy are very helpful in identifying aromatic compounds because aromatic hydrogens and carbons exhibit characteristic chemical shift ranges. Aromatic hydrogens appear at 6.5–8 ppm in 1H NMR, while aromatic carbons appear at 110–150 ppm in 13C NMR, providing diagnostic signals for aromatic ring systems.
Q6: What is the relationship between ring size and aromatic hydrogen chemical shifts?
Aromatic hydrogens of larger rings absorb farther upfield or downfield than the typical 6.5–8 ppm range observed for benzene. The size and geometry of the aromatic ring system influence the magnitude of the ring current effect, causing variations in chemical shift positions for different conjugated systems.
Q7: How do inside and outside hydrogens differ in their NMR behavior?
Inside hydrogens of aromatic systems like [18]annulene are highly shielded by the aromatic ring current and absorb upfield at low frequencies, while outside hydrogens are highly deshielded and absorb downfield at high frequencies. This opposite shielding effect demonstrates how spatial position relative to the ring current dramatically influences NMR chemical shifts.