Simulation of 1H NMR Spectra
In several cases of spectra
recorded at 60MHz, second order effects are observed.
Second order effects cause the N+1 rule to break down and
make it harder to directly determine chemical shifts and
J-couplings because the coupling patterns become more
complex. Second order effects arise when two nuclei in
magnetically different environments are J-coupled and the
magnitude of the J-coupling is close to the frequency
difference of the chemical shifts.
Second order effects can be
simulated in the NUTS data processing program. For
example, in the test sample provided with all system
equipped with the C-13 accessory, n-propylbenzoate
demonstrates departure from the first order behavior for the
b and c protons (CH2 and CH3, respectively). The
chemical shift for the CH2b is 1.6 and for the CH3c is 0.9,
the difference between the two chemical shifts is about
42Hz. The coupling constant for these two spectra is
on the order of 7Hz. The ratio of J/Ds
is important because it quantifies when second order
effects will begin to dominate the spectrum.
The figure below shows the upfield region (0.5-2.1ppm) of n-propylbenzoate. The two windows below establish the simulation parameters for the propyl group, CH2-CH2-CH3. The methyl group are assigned as H's 1-3, the internal CH2's are H's 4-5, and the O-CH2 are assigned as H's 6-7.

