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F324
NMR Spectroscopy
NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
Origin of Spectra
Theory
All nuclei possess charge and mass. However, those with either an odd mass
number or an odd atomic number also possess spin and have angular momentum.
examples
but
1
1
12
C
6
2
1
13
C
6
14
7
17
O
8
19
F
9
31
P
15
possess spin
16
O
8
do not
A nucleus with spin can be detected by nuclear magnetic resonance (nmr)
spectroscopy.
A spinning nucleus such as
1
H behaves as a spinning
charge and generates a
magnetic field. It can be
likened to a bar magnet.
ENERGY
aligned against field
= h
When placed in an externally
applied field it can align with,
or against, the field.
aligned with field
The energy difference between the two states () depends on the applied field.
The sample is placed in the field of a large electromagnet and a radio-frequency
(RF) field is applied. The magnetic field is increased and the excitation or
flipping of nuclei from one orientation to another is detected as an induced
voltage resulting from the absorption of energy from the RF field.
The basic
arrangement of an
nmr spectrometer
Radiofrequency
oscillator
Ammeter
Ho
An nmr spectrum is the plot of the induced voltage against the sweep of the field.
The area under a peak is proportional to the number of nuclei flipping
Other
uses
NMR spectroscopy is the same technology as that used in MRI (magnetic
resonance imaging) to obtain diagnostic information about internal structures in
body scanners.
[Link]
F324
NMR Spectroscopy
INTERPRETATION OF PROTON NMR SPECTRA
Introduction Spectra provide information about the structure of organic molecules from the ...
Running
spectra
TMS
number of different signals in the spectrum
position of the signals (chemical shift)
splitting pattern of the signals
intensity of the signals
a liquid sample is placed in a long thin tube which spins in a magnetic field
solids are dissolved in solvents which wont affect the spectrum - CDCl3
tetramethylsilane, (CH3 )4 Si, is added to provide a reference signal
the spectrum can be integrated to find the relative peak heights
CH 3
it produces a single intense peak
signal is just outside the range shown by most protons
it is inert, non-toxic and has a low boiling point
it can be distilled off if required
CH 3 Si
CH 3
CH 3
TETRAMETHYLSILANE
Chemical
shift
each proton type is said to be chemically shifted relative to a standard
the chemical shift is the difference between the field strength at which it absorbs
and the field strength at which TMS protons absorb
the delta () scale is widely used as a means of reporting chemical shifts
Observed chemical shift (Hz) x 106
=
ppm
(parts per million)
Spectrometer frequency (Hz)
the chemical shift of a proton is constant under the same conditions
the TMS peak is assigned a value of ZERO ( = 0.00)
all peaks in the spectrum are related to it and reported in parts per million
Hs near to an electronegative species are shifted downfield to higher values
H
C X
Approximate
chemical shifts
R OH
C H
individual values depend
on the environment
COOH
13
12
11
10
TMS
PPM ( )
Downfield ("deshielding")
Upfield ("shielding")
[Link]
F324
NMR Spectroscopy
Multiplicity This occurs because the spin of one nucleus affects that of a chemically different
nucleus on an adjacent atom.
also known as coupling or spin-spin splitting
low resolution nmr gives 1 peak for each chemically different group of protons
high resolution nmr gives more complex signals - doublets, triplets, quartets...
the signal produced indicates the number of protons on adjacent carbon atoms
No. of peaks = number of Hs on adjacent chemically different atoms + 1
Ratio of peak sizes for 2 peaks
3 peaks
4 peaks
5 peaks
Theory
doublet
triplet
quartet
quintet
1:1
[Link]
[Link]
[Link]
Splitting patterns are worked out by considering the effect adjacent, chemically
different protons have on another signal in a given environment. The spin of the
proton producing the signal is affected by each of the two forms of the adjacent
proton.
One orientation augments/enhances its field and the other
opposes/reduces it. Splitting patterns can be worked out by calculating the
various possible combinations of alignment of adjacent protons.
1 adjacent H
can be aligned either with () or against () the field
only two equally probable possibilities
the signal is split into 2 peaks of equal intensity
Fig. 1
2 adjacent Hs
more possible combinations - signal is more complex
get 3 peaks in the ratio 1 : 2 : 1
Fig. 2
3 adjacent Hs
even more possible combinations
get 4 peaks in the ratio 1 : 3 : 3 : 1
Fig. 3
Fig. 1
Q.1
Fig. 2
Fig. 3
Explain the splitting pattern when there are four adjacent protons.
[Link]
F324
Chemically
different? Coupling only takes place with
It DOES NOT take place with
NMR Spectroscopy
chemically different protons
chemically similar protons
H atoms on OH groups
or
To see if a hydrogen is chemically different you need to look at the whole structure
of the molecule, not just the neighbouring atom(s).
Example 1
CH3 CH 2 CH 2 CH3
1
two sets of signals
A triplet due to the CH3 groups - 2 adjacent Hs +1
A quartet due to the CH2 groups - 3 adjacent Hs +1
the signal due to the Hs on carbon 2 is not a hextet (5 + 1 = 6)
the 2 Hs on carbon 3 are CHEMICALLY IDENTICAL to those on carbon 2
chemically identical hydrogens do not affect the splitting pattern
CH 2
Example 2
CH 2
CH 2
CH 2
CH 2
one signal - a singlet
CH 2
all the hydrogen atoms are chemically equivalent
there are no chemically equivalent hydrogens on adjacent atoms
the signal will be a singlet - 0 + 1 = 1
Example 3
HO CH 2 CH 2 OH
two signals
- singlet due to the CH2 groups
- singlet due to the OH groups
signals due to Hs on OH groups are always singlets
the Hs on the CH2 give rise to a singlet because...
the H atoms on the adjacent CH2 are chemically equivalent so dont and
Hs on adjacent OH groups do not couple
Special note Signals for the H in an O-H bond
unaffected by Hs on adjacent atoms
are not split (see later)
A spectrum of a typical alcohol (ethanol) is shown on the next page. One would
expect a triplet signal (3 peaks) for the H in O-H but there is only one.
Q.2
Why are the signals due to the CH2 hydrogens in BrCH2 CH2 Br singlets not triplets ?
[Link]
F324
NMR Spectroscopy
Integration the area under a signal is proportional to the number of hydrogen atoms present
is achieved using an integration device which scans the peaks
lines on the spectrum show the relative abundance of each hydrogen type
By measuring the distances between the integration lines (dotted line on the
spectrum) one can work out a simple ratio between the various types of hydrogen.
The nmr spectrum of ethanol
(i) before integration
H
(ii) after integration
CH
OH
CH
OH
TMS
Q.3
4
3
PPM ( )
TMS
4
3
PPM ( )
Measure the ratio of the heights of the integration lines in the ethanol spectrum.
Does it correspond to the actual ratio of protons in the structure ?
D2 O shake The signal due any hydroxyl (OH) hydrogen is seen as a singlet; no splitting
This arises because proton on the OH,
rapidly exchanges with protons on other
molecules and is not attached to any
particular oxygen long enough to register
a splitting signal.
CH
CH
It is possible to exchange the H for
deuterium, 2 H or D. The usual source is
deuterium oxide, D2 O , a form of water.
Deuterium doesnt exhibit nuclear
magnetic resonance under the conditions
used for proton nmr so the signal is
removed to another part of the spectrum.
TMS
4
3 of ethanol
2
1
nmr5 spectrum
PPM ( )
after a D2 O shake
[Link]
F324
NMR Spectroscopy
SOME TYPICAL PROTON CHEMICAL SHIFTS
value and range
16
14
12
10
TMS ------------------------------------------------------------------------------------------------------------------------------------- CH2 - (cyclopropane) -----------------------------------------------------------------------------------------------------------CH3 ---------------------------------------------------------------------------------------------------------------------------------ROH (monomer)-------------------------------------------------------------------------------------------------------------------CH3 - C - ------------------------------------------------------------------------------------------------------------------------------R2NH ---------------------------------------------------------------------------------------------------------------------------------CH3 - C - C - X (X = F, Cl, Br, I, OH, OR ------------------------------------------------------------------------------------- CH2 - (saturated) ------------------------------------------------------------------------------------------------------------------ C - H (saturated)
----------------------------------------------------------------------------------------------------------------
CH3 - C - X (X = F, Cl, Br, I, OH, OR) ----------------------------------------------------------------------------------------CH3 - C=C-- -------------------------------------------------------------------------------------------------------------------------CH3 - C=O --------------------------------------------------------------------------------------------------------------------------CH3 - Ar -----------------------------------------------------------------------------------------------------------------------------CH3 - S
-----------------------------------------------------------------------------------------------------------------------------
CH3 - N
------------------------------------------------------------------------------------------------------------------------------
H - C = C -----------------------------------------------------------------------------------------------------------------------------ArSH
--------------------------------------------------------------------------------------------------------------------------------
CH3 - O - -----------------------------------------------------------------------------------------------------------------------------Ar-NH -
------------------------------------------------------------------------------------------------------------------------------
ROH (inert solvent)
-------------------------------------------------------------------------------------------------------------
CH2 = C - (non conjugated) -----------------------------------------------------------------------------------------------------ArOH
------------------------------------------------------------------------------------------------------------------------------
- CH = C - (conjugated) ----------------------------------------------------------------------------------------------------------H - N - CO -
----------------------------------------------------------------------------------------------------------------------
ArH (benzenoid) ------------------------------------------------------------------------------------------------------------------ArH (non benzenoid) ------------------------------------------------------------------------------------------------------------H - CO - N ---------------------------------------------------------------------------------------------------------------------------H - COO ---------------------------------------------------------------------------------------------------------------------------- C = N - OH
----------------------------------------------------------------------------------------------------------------------
RCHO (aliphatic) -------------------------------------------------------------------------------------------------------------------ArCHO
------------------------------------------------------------------------------------------------------------------------------
ArOH (intramolecularly bonded) ------------------------------------------------------------------------------------------------ SO3H
------------------------------------------------------------------------------------------------------------------------------
RCOOH (dimer, in non polar solvent) ----------------------------------------------------------------------------------------Enol ------------------------------------------------------------------------------------------------------------------------------------
[Link]
F324
NMR Spectroscopy
INTERPRETING THE NMR SPECTRUM OF 1-BROMOPROPANE
1-BROMOPROPANE
TMS
Analysis
Peaks
There are three different signals so there are three chemically different protons.
Position
The further the signals are shifted from TMS signal, the nearer they are to the Br.
Splitting
The signals include a
triplet
sextet
triplet
( = 1.0)
( = 1.8)
( = 3.4)
H
H
H
2
Br
The signals due to the protons attached to carbon ...
C1
C2
C3
triplet ( = 1.0)
sextet ( = 1.8)
triplet ( = 3.4)
coupled to the two protons on carbon C2
coupled to five protons on carbons C1 and C3
coupled to the two protons on carbon C2
Integration
The integration lines show that the ratio of protons is [Link]
Summary
An nmr spectrum provides several types of information :
number of signal groups
chemical shift
multiplicity
peak area
( 2+1 = 3 )
( 5+1 = 6 )
( 2+1 = 3 )
the number of different proton environments
the general environment of the protons
how many protons are on adjacent atoms
the number of protons in each environment
In many cases this information is sufficient to deduce the structure of a molecule.
Q.4
What would you expect the spectrum of 2-bromopropane to be like ?
Explain your answer in terms of
a) the chemical shift
b) the splitting pattern
c) integration
[Link]
F324
SAMPLE SPECTRA
C4H8O2
C4H8O
C3H6O
C3H6O
[Link]
NMR Spectroscopy
F324
NMR Spectroscopy
CARBON-13 SPECTRA
Theory
After hydrogen, the most useful atom providing information to organic chemists is
carbon-13. Natural carbon contains about 1% of this isotope so the instruments
for its detection need to be sensitive and spectra will take longer to record.
Only the chemical shift is important as each spectrum gives only single lines
for each chemically equivalent carbon. Carbon-13 nmr has wide applications in
the study of natural products, biological molecules and polymers.
Chemical shift, ppm
Type of carbon
C - C (alkanes)
10 - 35
C - C=O
10 - 35
C - Cl or C - Br
30 - 70
C - N (amines)
35 - 65
C - OH
50 - 65
C = C (alkenes)
115 - 140
aromatic Cs (benzene rings)
125 - 150
C=O (esters, acids, amides)
160 - 185
C=O (aldehydes, ketones)
190 - 220
Interpretation
for C3 H7 Br
H
2
Br
3 peaks
all three carbons are different
C-13 nmr spectrum
of ethanol C2 H5 OH
CH
Br
H
1
2 peaks
the two outer carbons are similar
CH
This is where the
proton nmr spectrum
of ethanol would be
on the same scale.
OH
70
60
50
40
30
PPM ( )
20
10
[Link]
10
F324
NMR Spectroscopy
The Carbon-13 spectrum of 2-methylbutane C5 H12
There are four chemically
different carbon atoms in
the molecule so there are
four peaks in the 13 C nmr
spectrum.
A
chemically
equivalent
carbon atoms
CH3
CH 3 CH CH 2 CH 3
B
NO SPLITTING WITH 13 C
ONLY ONE PEAK FOR
EACH CARBON
220
200
180
160
140
120
100
80
60
40
20
ppm
Other isomers of C5 H12
pentane CH3 CH2 CH2 CH2 CH3
2,3-dimethylpropane (CH3 )4 C
3 peaks
2 peaks
SUPPLEMENTARY QUESTIONS
Q.5
(i) State how many peaks would you expect to see in the carbon-13 spectrum of...
butane
2-methylpropane
butanal
butanone
pentanal
pentan-2-one
pentan-3-one
ethanol
CH 3
CH 3 CH 2
CH 3 CH
CH CH CH CH 3
H2N
CH 2 C
O
N
H
CH 2 C
OH
OH
HO
O
(ii) State a similarity and a difference between the spectra of...
a) butane and 2-methyl propane
b) butanal and butanone
[Link]
OH
Q.6
11
F324
NMR Spectroscopy
Identify the isomers of C4 H8 O
A
A
B
C
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40
20
80
60
40
20
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60
40
20
80
60
40
20
ppm
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100
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60
40
20
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200
180
160
140
ppm
Q.7
120
100
ppm
Identify the isomers of C6 H12
X
Y
Z
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200
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120
100
ppm
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120
100
ppm
80
60
40
20
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200
180
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120
100
ppm
[Link]
