2D NMR

Two dimensional FT yields the 2D spectrum with two

frequency axes. If the spectrum is homonuclear (signals of
the same isotope (usually 1H) are detected during the two
evolution periods) it has a characteristic topology:
 2D NMR: COSY
Ethyl benzene is plotted on each of the two
axes. Note that the diagonal within the box is
also the spectrum for ethyl benzene as seen
from "above.“
Off-diagonal peaks denote splitting between
protons on adjacent carbons.
Note the coupling of the methyl protons at 1.1
ppm to the methylene protons at 2.8 ppm. The
aromatic multiplet at 7.2 ppm is coupled with
itself. Also note that neither the methyl or
methylene protons are coupled to the aromatic
protons at 7.2 ppm.
Spectrum of Ethyl Benzene
 2D-NMR Spectra
In two dimensional experiments, both
the x and the y axes have chemical shift
scales and the 2D spectra are plotted as
a grid like a map.
Information is obtained from the spectra
by looking at the peaks in the grid and
matching them to the x and y axes.
COSY - Correlation Spectroscopy
both axes correspond to the proton nmr spectra.
the COSY spectra indicates which H atoms are
coupling with each other.

HETCOR- Heteronuclear Correlation Spectroscopy

proton nmr spectra on one axis and the 13C nmr
spectra on the other.
the HETCOR spectra matches the H to the
appropriate C.
 COSY spectra
The information on the H that are coupling
with each other is obtained by looking at the
peaks inside the grid. These peaks are
usually shown in a contour type format, like
height intervals on a map.
In order to see where this information comes
from, let's consider an example shown below,
the COSY of ethyl 2-butenoate
First look at the peak marked A in the top left
corner. This peak indicates a coupling
interaction between the H at 6.9 ppm and the
H at 1.8 ppm. This corresponds to the
coupling of the CH3 group and the adjacent H
on the alkene.
 COSY spectra

Similarly, the peak marked B indicates a

coupling interaction between the H at 4.15
ppm and the H at 1.25 ppm. This
corresponds to the coupling of the CH2 and
the CH3 in the ethyl group.
Notice that there are a second set of
equivalent peaks, also marked A and Bon
the other side of the diagonal.
COSY spectra
 HETCOR spectra
• The information on how the H are C are matched is
obtained by looking at the peaks inside the
grid. Again, these peaks are usually shown in a
contour type format, like height intervals on a map.
• In order to see where this information comes from,
let's consider an example shown below, the
HETCOR of ethyl 2-butenoate.
• First look at the peak marked A near the middle of
the grid. This peak indicates that the H at 4.1 ppm is
attached to the C at 60 ppm. This corresponds to the
-OCH2- group.
 HETCOR spectra

• Similarly, the peak marked B towards the top

right in the grid indicates that the H at 1.85 ppm
is attached to the C at17 ppm. Since the H is a
singlet, we know that this corresponds to the
CH3- group attached to the carbonyl in the acid
part of the ester and not the CH3- group attached
to the -CH2- in the alcohol part of the ester.
• Notice that the carbonyl group from the ester
has no "match" since it has no H attached in this
example.
HETCOR spectra
2D COSY spectrum of ethylbenzene
 3
1C DEPT
This DEPT experiment (Distortionless
Enhancement by Polarization Transfer) is
an example of a carbon-editing pulse
sequence.

Systematic changes in the internal delays

in the complex pulse program make
different carbons respond in different
fashions, based upon the number of
protons attached.
 HMC13CDEPT45
of Ethyl Benzene
The DEPT 45 experiment yields a
positive peak for every carbon with
attached protons: Ca at 16 ppm, Cb at
29 ppm, and Cd, Ce, and Cf at 128.5,
128.9, and 129 ppm, respectively.
Note in the spectrum below that
carbon in the CDCl3 solvent does
not give a signal, since it has no
attached protons
HMC13CDEPT45
HMC13CDEPT90

In this variant of the DEPT

experiment, only CH yields
peaks; CH0, CH2, and CH3 are
invisible.
In our example we see only
three lines due to Cd, Ce, and
Cf in the aromatic range from
126 to 129 ppm.
HMC13CDEPT90
HMC13CDEPT135

• In this variant of the DEPT

experiment, CH2 yields
negative peaks, whereas CH
and CH3 are positive
• Thus, we see Ca, Cd, Ce, and
Cf as positive peaks, while Cb
is negative
Thank you