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3.5
COSY
4.0
4.5
5.5
HETCOR 6.0
6.5
7.0
7.5
1
COrrelation SpectroscopY (COSY)
COSY allows us to easily determine which peaks in the 1H
NMR are coupled to which other peaks, i.e. what is splitting
what.
(old method: peak-by-peak decoupling)
2
COSY
Recall that in NMR experiment, we can saturate a
particular nucleus by irradiating it with an intense rf pulse.
This has the effect of averaging the nuclear spins to zero, or
erasing the peak from the spectrum.
3
COSY
The COSY spectrum is really a 3-D plot with the x- and y-axes
both chemical shift, and the z-axis is the signal.
4
Contour Maps
5
COSY
The two axes now both correspond to the 1H NMR spectrum.
6
COSY: 2-Nitropropane
CH3
H3C C NO 2
doublet
septet
7
CH3
-CH -CH3
H3C C NO2
-CH3
Points on diagonal:
Hs correlated with
themselves! Not
important.
-CH
8
COSY
(3-methyl)butyl ethanoate
3
1
O O CH2 2 CH3
C CH2 CH
4
6 1
CH3 CH3
1
3
4 6
t s d
9
6 1
4 2 3
3
O O CH2 CH31
C CH2
2
CH
6 4
CH3 CH3 1
10
COSY
11
COSY Example
The following molecule has a complex 1H NMR. It is nearly
impossible to determine what peaks are splitting one another
in this spectrum. c
d b
e a
OH
f f
g g
h h
i j i
12
COSY Example
The following molecule has a complex 1H NMR. It is nearly
impossible to determine what peaks are splitting one another
in this spectrum. c
d b
Ha
e a
OH
f f
g g
Hj
h h
i j i
13
COSY Spectrum
avcg271.001.001.2rr.esp
1D 1H NMR Spectrum
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.8
7.9
8.0
Correlations 8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.5 8.0 7.5
F2 Chemical Shift (ppm)
14
Diagonal Peaks
avcg271.001.001.2rr.esp
7.3
7.5
7.6
7.9
8.0
Notice that some 8.1
magnitude of J. 8.6
8.7
8.5 8.0 7.5
F2 Chemical Shift (ppm)
15
Off-Diagonal Peaks
avcg271.001.001.2rr.esp
7.3
protons. The weak 7.4
c Strong 7.8
d b 7.9
8.0
e a
OH 8.1
f f 8.2
g g
8.3
h h 8.4
i j i 8.5
8.6
8.7
8.5 8.0 7.5
F2 Chemical Shift (ppm)
16
COSY
avcg271.001.001.2rr.esp
7.3
7.4
7.5
7.6
c 7.8
d b 7.9
8.0
e a
OH 8.1
f f 8.2
g g
8.3
h h 8.4
i j i 8.5
8.6
8.7
8.5 8.0 7.5
F2 Chemical Shift (ppm)
17
COSY
avcg271.001.001.2rr.esp
We make correlations
by drawing vertical
and horizontal lines 7.0
7.3
coupled. 7.4
7.5
7.6
c 7.8
d b 7.9
8.0
e a
OH 8.1
f f 8.2
g g
8.3
h h 8.4
i j i 8.5
8.6
8.7
8.5 8.0 7.5
F2 Chemical Shift (ppm)
18
COSY
avcg271.001.001.2rr.esp
In this image, we
see that it is a
triplet coupled to
a doublet. 7.25
7.30
7.35
7.40
This guy is meta
the x-axis
7.50
19
COSY
avcg271.001.001.2rr.esp
Zoom
**
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.5 8.0 7.5
F2 Chemical Shift (ppm)
20
COSY
avcg271.001.001.2rr.esp
* *
There is a strong 6.90
7.05
7.15
7.20
7.30
suspicion. 7.35
7.40
7.45
7.50
7.55
7.60
7.65
7.70
7.75
7.65 7.60 7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00
F2 Chemical Shift (ppm)
21
Back to 1H NMR
The COSY tells us that the following peaks are ortho to another.
As expected, the triplets are coupled to 2H and the doublets to 1H.
c
d b
Ha e a
OH
f f
g g
h h
Hj i j i
22
Back to 1H NMR
We see 2 sets of d-t-t-d combinations, one worth 4H and the other
8H.
c
d b
Ha e a
OH
f f
g g
h h
Hj i j i
23
Back to 1H NMR
We see 2 sets of d-t-t-d combinations, one worth 4H and the other
8H.
c
We can assign the d b
4H group to the e a
Ha OH
phenol ring. f f
g g
h h
Hj Hc i j i
Hb
He Hd
24
Back to 1H NMR
We do not have enough information to assign the 8H set. If we
knew one, we could figure out the rest.
c
Hf or Hi ?? d b
e a
Ha OH
f f
g g
h h
Hj Hc i j i
Hb
He Hd
25
NOESY
COSY: 1H-1H correlations via spin coupling interactions, nuclei
must be closely connected by bonds.
NOESY is a type of 2D NMR that is also a 1H-1H correlation. It
correlates nuclei that are physically near each other in space, but not
necessarily coupled to one another.
It takes advantage of the Nuclear Overhauser Effect, recall from our
discussion of 13C NMR. When a proton is in close proximity to
another proton, they can influence the relaxation rates of one
another even if they are not coupled. This effect is removed when
one proton is saturated.
So in NOESY, we see correlation peaks due to nuclei that are
spatially near to each other, but not coupled. A THROUGH-SPACE
EFFECT.
Sometimes we see coupled peaks too, but we can rule these out with
the COSY spectrum.
26
NOESY
avcg272.001.001.2rr.esp
As with COSY,
the diagonal 7.0
NOESY 7.1
meaningless. 7.3
7.4
7.5
7.8
NOESY 8.0
8.3
blue/red. 8.5
8.6
27
NOESY
avcg272.001.001.2rr.esp
OH
a
With NOESY we now
see peaks correlated 7.0
to the OH 7.1
7.2
7.3
c 7.4
d b 7.5
e a 7.6
OH
g g 7.8
8.2
8.3
8.4
8.5
8.6
28
NOESY
avcg272.001.001.2rr.esp
c He 7.20
d b
7.25
e a
OH
f f
7.30
g g
h h
7.40
i j i Hc
7.45
7.50
29
Back to 1H NMR
We can now assign all protons
Hi and Hj are close to c
each other as well, but d b
Hi Hf h h
Hj Hc i j i
Hh
Hg Hb
He Hd
30
NOESY
avcg272.001.001.2rr.esp
Hj Hf
There is indeed a
NOESY peak here. 7.0
7.1
He 7.2
7.3
c 7.4
d b 7.5
e a 7.6
OH
7.9
h h
8.0
i j i
Hi 8.1
8.2
8.3
8.6
31
1H 13C Correlations
There are a number of heteronuclear 2D NMR methods that allow
correlations between carbon and hydrogen nuclei.
32
HETCOR
3
O O CH2 CH31
C CH2
2
CH
6 4
CH3 CH3 1
1
3
2
6
No diagonal line!
33
HETCOR of Menthol
In HETCOR, there
are no cross peaks
to worry about.
Unambiguous
assignments of C,H
connectivities
Intensity of spot
related to
magnitude of
coupling constant J
34