|
|
NMR Analysis and Consulting (217) 423 2517 |
|
DEPT DEPT is a very useful 13C technique. The procedure is used to determine the
hydrogen substitutions on the carbon atoms responsible for the 13C
signals. The method uses a sequence of
1H and 13C rf pulses and delays to generate 1H-13C
double quantum coherence and then transfer the information back to the 13C
resonances. The final results
(display) of the 13C spectrum are determined by the last 1H
pulse. If the last 1H pulse
is set to 450 , the
resonances of all H bearing
carbons will be positive in phase.
It is important to stress that quaternary carbon atoms do not give
DEPT signals. If that last pulse
is set to 900 only methine carbons will show and they will be
positive in phase. The most useful 1H
pulse is 1350. All methyl
and methine resonances will be positive in phase and methylene resonances
will be negative in phase. Here is the structure of trans-
fenretidine with our best guess of 13C assignments. (Don’t use this as a reference; the
assignments may be in error.)
We have many resonances in the spectrum as we can see in the nOe
enhanced 13C spectrum.
The three lines at 77.00 ppm are from the deuterochloroform used
as the solvent. To help assign all these
resonances, it will be very helpful to know which signals correspond to
methyl, methylene, methine, quaternary carbon atoms. The first step would be to run DEPT-135.
Notice the three negatively phased signals at 18.9 ppm, 32.8,
39.3. These are the three
methylenes. There are four positively
phased signals at low frequency, 12.6ppm, 13.3, 21.5, 28.7. By also considering the chemical shifts,
these have to be from the methyl groups.
In the high frequency end of the spectrum we have seven move positive
signals. Two are from the aromatic
ring, 115.2ppm, 121.4, which we can determine by chemical shifts and also
their intensities give a clue. This
leaves five more methine signals that we can assign to the alkene
carbons. Notice that some of the
signals that are observable in the nOe enhanced spectrum are not seen in the
DEPT-135. These are from the quaternary carbon atoms, viz,
33.9ppm, 137.4, 129.5, 138.3, 153.3, 165.0, 130.6, 148.6. At this point we have gleaned all the information possible from
the DEPT technique. In some cases
though it may be useful to differentiate methyl signals from methine
signals. Here is the DEPT-90 spectrum,
where only the methine signals are observed.
DEPT-45 isn’t useful so it is very seldom done. |
|