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NMR problems 2
nd
part
1.Below are the
1
H and
13
C NMR spectra of 2-hexanone (CH
3
COCH
2
CH
2
CH
2
CH
3
).
Explain carefully how, using homonuclear and heteronuclear decoupling experiments,
you could assign the each of the resonances in the
1
H and
13
C spectra to which nuclei
give rise to them.

1
H NMR spectra of 2-hexanone


13
C NMR spectra of 2-hexanone



Answer This is a commonly encountered problem. You obtain a
1
H and a
13
C NMR
spectrum and need to assign each of the resonances in both
1
H and
13
C spectra.
It is generally straight-forward to assign the
1
H spectrum using a combination of

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direct inspection (characteristic chemical shifts and multiplicities) in combination
with homonuclear decoupling experiments. For
1
H spectra, homonuclear decoupling
gives you connectivity (which protons are on adjacent carbon atoms) because
1
H is
100% abundant. Note that homonuclear decoupling cannot be used for
13
C spectra
because
13
C is isotopically dilute there essentially no possibility that there will be 2
13
C nuclei adjacent to each other in an organic molecule.
For 2-hexanone, the
1
H spectrum contains 5 resonances. You would expect to see one
singlet (integral 3H) for the CH
3
group attached to the ketone (ie at C1). The CH
2

group adjacent to the ketone (ie at C3) would appear as a triplet (with coupling to the
adjacent CH
2
. The CH
2
at C4 would appear as a multiplet (a triplet of triplets with
coupling to both the CH
2
at C3 and the CH
2
at C5). Likewise the CH
2
at C5 would
appear as a multiplet (a triplet of quartets with coupling to both the CH
2
at C4 and the
CH
3
at C6). The resonance of the CH
3
at C6 would be a triplet (integral 3H).
Intuitively, you would also expect the CH
3
and CH
2
groups adjacent to the carbonyl to
occur at low field (between 1.5 and 2.5 ppm) and the CH
3
at C6 to be at high field
(between 0.5 and 1 ppm). By inspection, you can assign the proton signals for C1
( 1.7), C3 ( 1.9) and C6 ( 0.8). The multiplet signals at 1.1 and 1.3 must
belong protons at C4 and C5 and to distinguish these you would use homonuclear
decoupling experiments. If the protons at C3 ( 1.9) are irradiated, the multiplet due
to protons at C4 would collapse from a triplet of triplets to a triplet and hence its shift
would be known. Similarly, if the protons at C6 ( 0.8) were irradiated, the multiplet
due to protons at C5 would collapse from a triplet of quartets to a triplet and hence its
shift would be known.
Having assigned the
1
H spectrum, the
13
C spectrum can be assigned using selective
heteronuclear decoupling experiments.
The
13
C spectrum contains 6 resonances, the resonance due to the carbonyl carbon is
obvious from its shift. For the remaining 5 carbons you would expect to have signals
from 2 x CH
3
and 3 x CH
2
groups and in the absence of any
1
H decoupling these
would appear as 2 quartets and 3 triplets. In the heteronuclear decoupling experiment
you would irradiate each of the resonances in the
1
H spectrum and observe the
13
C
spectrum. As each of the
1
H signals is irradiated, the resonance of the
13
C coupled to it
would collapse to a singlet - the multiplicity of the other signals would remain
essentially unchanged.
The correlation of
1
H and
13
C NMR spectra can also be achieved using
two-dimensional NMR using a heteronuclear shift correlation (HSC) experiment.

2.The simple molecules below contain the NMR-active nuclei
14
N (I=1),
31
P (I=1/2),
1
H (I=1/2) and
13
C (I=1/2). Considering only the coupling constants through one bond
(
1
J
ax
) as being significant, construct diagrams which schematically represent the
splitting pattern you would see in :
1 The
1
H NMR spectrum of the ammonium ion [NH
4
+
].
2 The
14
N NMR spectrum of the [NH
4
+
].
3 The
13
C NMR spectrum of trimethylamine [(CH
3
)
3
N]
4 The
31
P NMR spectrum of phosphine [PH
3
].

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5 The
1
H NMR spectrum of phosphine [PH
3
].
6 The
13
C NMR spectrum of H
2
P-CH
2
-PH
2
.
7 The
13
C NMR spectrum of [(PH
2
)
3
CH].

Answer This is simply an exercise in predicting the multiplicity observed using the
formula: multiplicity = 2nI + 1.
1 The
1
H NMR spectrum of CH
4
will be a singlet (no multiplicity) since the
molecule is tetrahedral in shape and all of the protons are equivalent. There is no
coupling from carbon since almost all C is
12
C and this is NMR silent.
2 The
13
C NMR spectrum of CH
4
is a quintet. The C is coupled to 4 equivalent
protons and the spin of
1
H is .

(2nI + 1) = (2 x 4 x ) + 1 = 5
3 The
1
H NMR spectrum of NH
4
+
will have 3 lines. The molecule is tetrahedral in
shape and all of the protons are equivalent and these will be coupled to
14
N (which
has a spin I = 1).

(2nI + 1) = (2 x 1 x 1) + 1 = 3
4 The
14
N NMR spectrum of NH
4
+
is a quintet. The
14
N is coupled to 4 equivalent
protons and the spin of
1
H is .

(2nI + 1) = (2 x 4 x ) + 1 = 5
5 The
1
H NMR spectrum of PH
3
is a doublet. The molecule (like ammonia) is
pyramidal and all 3 protons are equivalent. The protons (with spin I = ) are
coupled to one
31
P nucleus.

(2nI + 1) = (2 x 1 x ) + 1 = 2
6 The
31
P NMR spectrum of PH
3
will have 4 lines (quartet). The molecule is
pyramidal in shape and all of the protons are equivalent (with a spin I = ). and
these will be coupled to
31
P.

(2nI + 1) = (2 x 3 x ) + 1 = 4
7 The
13
C NMR spectrum of H
2
PCH
2
PH
2
will be a triplet of triplets. The
13
C will be
coupled to 2 x
31
P (giving a triplet splitting) and the
13
C will be coupled to 2 x
1
H
(giving a triplet splitting).
8 The
13
C NMR spectrum of (H
2
P)
3
CH will be a doublet of quartets. The
13
C will be
coupled to 3 x
31
P (giving a quartet splitting) and the
13
C will be coupled to 1 x
1
H
(giving a doublet splitting).

3 The
1
H NMR spectrum of (E)-2-pentenal (given below) has 5 distinct resonances:
9.5 (1H, doublet), 6.9 (1h, doublet of triplets), 6.0 (1H, doublet of doublets), 2.2
(2H, multiplet) and 1.0 (3H, triplet). Sketch and clearly describe the
1
H spectra you
would obtain while applying strong Rf. irradiation at :

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1 9.5
2 6.9
3 6.0
4 2.2
5 2.2
6 1.0


Answer The signals in the spectrum can be readily assigned by inspection:
9.5 is due to the aldehydic proton - it appears as a doublet due to coupling
with the vinylic proton on the adjacent carbon.
6.0 is due to the vinyl proton at C2. It appears as a doublet of doublets with
one doublet splitting due to the aldehyde proton and the other doublet splitting
due to the vinylic proton at C3.
6.9 is due to the vinyl proton at C3. It appears as a doublet of triplets with
the doublet splitting due to the vinylic proton at C2 and the triplet splitting due
to coupling to the CH
2
group at C4.
2.2 is due to the CH
2
group at C4. It appears as a multiplet but must be a

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doublet of quartets with the doublet splitting due to coupling to the vinylic
proton at C3 and the quartet splitting due to the CH
3
group at C5.
1.0 is due to the CH
3
group at C5. It appears as a triplet due to coupling to
the CH
2
group at C4 ( 2.2).

The effect of irradiation at each of these frequencies is to decouple the nuclei
which have signals at these frequencies. Decoupling effectively removes the
nucleus from the spin system.
1 With irradiation at 9.5, the multiplicity of the vinylic CH resonance at 6.0
is simplified from a doublet of doublets to a doublet. The remaining
resonances in the spectrum are unchanged.
2 With irradiation at 6.9, the multiplicity of the vinylic CH resonance at 6.0
is simplified from a doublet of doublets to a doublet and the CH
2
resonance
at C4 ( 2.2) is simplified from a doublet of quartet to a simple quartet. The
remaining resonances are unchanged.
3 With irradiation at 6.0, the multiplicity of the vinylic CH resonance at 6.9
is simplified from a doublet of triplets to a simple triplet and the resonance
of the aldehyde proton is simplified from a doublet to a singlet.
4 With irradiation at 2.2, the multiplicity of the vinylic CH resonance 6.9 is
simplified from a doublet of triplets to a simple doublet and the multiplicity of
the CH
3
resonance ( 1.0) is simplified from a triplet to a singlet.
5 With irradiation at 1.0, the multiplicity of the CH
2
group at C4 ( 2.2) is
simplified from a doublet of quartets to a simple doublet. The remaining
resonances in the spectrum are unchanged.

4.The
1
H NMR spectrum of 1,4-dioxan-d7 at room temperature consists of a singlet
(with broadband decoupling of
2
H). At -150
o
C the spectrum appears as two singlets of
equal intensity. Using your knowledge about the conformation (and conformational
mobility) of 6-membered rings, give a rationalisation as to why the room temperature
and low temperature spectra appear as they do.

Answer 1,4-dioxan is a 6-membered ring and adopts a chair conformation (like
other 6-membered rings such as cyclohexane). In the chair conformation, there are
two proton environments and protons can be either axial or equatorial. At room
temperature, rapid ring flipping causes protons to exchange between axial and
equatorial sites so the proton spectrum is a singlet.

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In 1,4-dioxan-d7, seven out of the 8 protons have been substituted deuterium, leaving
only 1 proton. Again this proton would be expected to be in either the axial or
equatorial position and at low temperature (slow exchange) the protons in axial
positions will have a different chemical shift to protons in the equatorial sites.

At low temperature where the ring flip is slow, there will be molecules with the single
proton axial some with the proton equatorial. There would be two signals one
corresponding to axial protons and one corresponding to equatorial protons. The fact
that these signals are of approximately equal in intensity indicates that there is no
significant thermodynamic preference to have the proton to be equatorial or axial.

At high temperature, the ring flip is rapid and the proton is rapidly exchanged
between axial and equatorial sites and the shift is averaged to a single resonance at a
shift half way between the signals between the signals in the slow exchange spectrum.

5.The
1
H free induction decay (FID) was acquired following a single 90
o
pulse to a
sample of chloroform (CHCl
3
). The spectrum following Fourier transformation (FT)
is given on the right.

Describe what would happen to the FID and to the spectrum obtained following FT
when :
1 The pulse angle was increased to 150
o
.
2 A small amount of an Fe(III) salt was dissolved in the solution before acquisition
of the FID.
3 16 FIDs were accumulated and added together before FT.
4 A second FID was acquired using a 270
o
pulse instead of a 90
o
pulse and added to
the first before FT.
5 The sample was dissolved in a viscous solvent before acquisition of the FID.
6 The FID was accumulated for twice the acquisition time before FT.
7 The proton spectrum was saturated for several seconds immediately before (but
not during) the acquisition of the FID.
What would happen to the spectrum if 16 FIDs were accumulated, each was

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transformed and the resulting spectra were added together to give the final spectrum ?

Answer The
1
H FID and spectrum are derived from a sample of CHCl
3
.
1 The response of the sample is a sinusoidal function of the pulse angle. Sin(90) = 1
and Sin(150) = Sin(30) = so the intensity of the signal in the FID and in the
spectrum will be decreased by a factor of 2.
2 Addition of a small amount of a paramagnetic salt will increase the efficiency of
relaxation. Nuclei would be expected to relax more quickly and this would be
reflected in a change in the appearance of the FID and the spectrum. The signal in
the FID would decay to zero more rapidly (i.e. in less time); signals in the
spectrum would be broader.
3 The signal-to-noise ratio (S/N) of the spectrum increases as the square root of the
number of acquisitions that are added together. If 16 acquisitions are added the
S/N increases by a factor of 16 = 4.
4 If an FID was accumulated with a 270
o
pulse, it would be a mirror image (about
the zero level in the FID) of the FID accumulated with a 90
o
pulse. This means
that at every point where the 90
o
FID was above zero, the 270
o
FID would be
below zero and addition of the 90
o
and 270
o
FID's would mean that the signals
would exactly cancel - only noise would remain. The spectrum would contain
only noise.
5 A viscous solvent will slow the rate of molecular tumbling and this in turn
increases the efficiency of relaxation. Nuclei would be expected to relax more
quickly and this would be reflected in a change in the appearance of the FID and
the spectrum. The signal in the FID would decay to zero more rapidly (ie in less
time); signals in the spectrum would be broader.
6 The FID as presented has clearly decayed to zero well before the accumulation of
the FID has stopped. By the end of the acquisition time, there is no signal only
noise being accumulated. Increasing the acquisition time by a factor of two will
double the time for which the FID signal is accumulated however the real signal in
the FID will still decay at the same rate so the real signal will be proportionally
less of the FID and there would be proportionally more noise. In the spectrum, the
S/N would be decreased.
7 Saturation of the
1
H spectrum would mean that the
1
H spectrum would not be
observable, providing there was no significant delay between the saturation and
recording the FID. Nuclei take several T
1
's to recover following saturation.
8 If 16 FIDs were accumulated then each transformed and the spectra added, there
would be no difference to the situation where 16 FID's were added and the
summed FID was transformed. In practice since the FT actually takes some time it
is more time-economical to minimise the number of tiems that the FT has to be
performed.

6.The
13
C NMR spectrum of 2-methyl-4,5-dihydrofuran (A) is given below. The
spectrum was the result of 32 scans with 1 sec. delay between acquisitions and no
proton decoupling.

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1 What would happen to the spectrum if 128 scans were accumulated and added
together ?
2 What would happen to the spectrum if the spectrum was acquired with a long
delay (say 300 seconds) between acquisitions?
3 What would happen to the spectrum if a small amount of soluble paramagnetic
salt was added to the sample prior to acquisition ?
4 What would happen to the spectrum if the 1H spectrum was irradiated with
broad-band Rf radiation before (but not during) each acquisition ?
5 Could the
1
H NMR spectrum of this molecule be analysed by first order splitting
rules? Why?

Answer The
13
C spectrum of the compound (A) contains 5 signals and from the
multiplicity these can be assigned to the two CH
2
carbons, one CH carbon, one CH
3

signal and one quaternary carbon.
1 The signal-to-noise ratio (S/N) of the spectrum increases as the square root of the
number of acquisitions that are added together. If 128 acquisitions are added, this
4 times the number of scans as the 32 used to accumulate the basic spectrum. The
S/N increases by a factor of 4 = 2.
2 With only a 1 sec delay between acquisitions, it very likely that all of the carbons
in the sample are not fully relaxed between scans and hence the relative intensities
of the signals are not correct. A long delay between acquisitions would ensure that
all the nuclei are fully relaxed and therefore all 5 signals should all be of the same
intensity.
3 A paramagnetic species added to the sample will cause more efficient relaxation
of all nuclei. Any differences in intensity resulting from differences in relaxation
times would be reduced. All of the lines in the spectrum would be broadened.
4 Irradiation of the proton spectrum before (but not during) the acquisition would
provide an NOE enhancement to the carbon spectrum (without decoupling carbon
from protons). So the intensity of the signals from protonated carbons in the
sample would be increased. The spectrum would not be proton decoupled so the
multiplicities of signals would remain the same.
5 There are 8 protons in this molecule and the spin system can be assigned as an
AA'GG'RX
3
spin system. Because the spin system contains nuclei which are

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chemically equivalent but magnetically non equivalent it cannot be analysed by
first order rules.

7.The
1
H free induction decay (FID) below was acquired following a single 45
o
pulse
to a sample of containing two species. The spectrum obtained following Fourier
transformation (FT) is given on the right.

Describe what would happen to the FID and to the spectrum obtained following FT
when:
1 The pulse angle was doubled.
2 The pulse angle was increased by a factor of 4.
3 The pulse angle was increased by a factor of 3.
4 64 FIDs were accumulated and added together before FT.

Answer The FID and the spectrum are derived from a sample containing 2 species.
The spectrum clearly contains one sharp resonance and one broad resonance and you
would predict that the broad signal arises from a species with a short relaxation time
and the narrow resonance arises from a species with a long relaxation time.
1 The pulse angle is 45
o
so increasing this by a factor of 2 will mean that a 90
o
pulse
is delivered to the sample. The response of the sample is a sinusoidal function of
the pulse angle. Sin(45) = 1/ 2 and Sin(90) = 1 so the intensity of the signal in the
FID and in the spectrum will be increased by a factor of 2 (1.414).
2 The pulse angle is 45
o
so increasing this by a factor of 4 will mean that a 180
o

pulse is delivered to the sample. The response of the sample is a sinusoidal
function of the pulse angle. Sin(180) = 0 so the intensity of the signal in the FID
and in the spectrum will be zero. Both the FID and the spectrum would contain
only noise.
3 The pulse angle is 45
o
so increasing this by a factor of 3 will mean that a 135
o

pulse is delivered to the sample. The response of the sample is a sinusoidal
function of the pulse angle. Sin(135) = Sin(45) = 1/ 2 so the intensity of the signal
in the FID and in the spectrum will be unchanged.
4 The signal-to-noise ratio (S/N) of the spectrum increases as the square root of the
number of acquisitions that are added together. If 64 acquisitions are added the
S/N increases by a factor of 64 = 8.