1

F324

NMR Spectroscopy

NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY

Involves interaction of materials with the low-energy radiowave
region of the electromagnetic spectrum
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
H
1

12
C
6

2
H
1

13
C
6

14
N
7

17
O
8

19
F
9

16
O
8

31
P
15

possess spin

do not

A nucleus with spin can be detected

by nuclear magnetic resonance
(nmr) spectroscopy.

ENERGY

A spinning nucleus such as 1H

behaves as a spinning charge and
generates a magnetic field. It can
be likened to a bar magnet.

aligned against field

= h

aligned with field

When placed in an externally applied field it can align with, or against, the 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.

Radiofrequency
oscillator

Ammeter
Ho

The basic arrangement of an

nmr spectrometer

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.

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)4Si, is added to provide a reference signal
the spectrum can be integrated to find the relative peak heights

CH3

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

CH3 Si CH3
CH3
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")

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
1:2:1
1:3:3:1
1:4:6:4:1

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.

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 CH2 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

CH2
Example 2

CH 2

CH 2

CH 2

CH 2

one signal - a singlet

CH2
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 CH2 CH2 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 (see page 5)

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 BrCH2CH2Br singlets not triplets ?

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

NOTE

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 ?

Computers now analyse the area under each peak as the spectrum is run.
The relative values are printed on the spectrum rather than showing the
integration lines.

Q.4

How many different proton environments are there in the following molecules?
State the ratio of the number of protons in each environment.
no. of H environments
a) CH3CH2CH2CHBrCH3

b) CH3CH2CHBrCH2CH3

c) C6H6 (benzene)

ratio of Hs

F324

NMR Spectroscopy

Spectra of compounds containing OH groups

Introduction

Observation of spectra containing OH groups will reveal that OH protons ...

only produce a single peak (singlet)
are not counted as neighbouring protons when working out splitting patterns
the signal is split
into 4, not 5

CH

H C
CH

the signal is a singlet

not split into 3

C OH

ethanol

OH
TMS

4
3
PPM ( )

Explanation The proton (H) on any OH group can exchange rapidly with another H atom on
any trace water. Because of this the H isnt around long enough to register a
splitting signal for itself or any neighbouring protons.

D2O shake This is used to determine which signal is due to an OH proton

after a spectrum is run, the sample is shaken with a small amount of D2O
any signal due to an OH proton disappears.

CH

CH

CH

CH
2

OH
TMS

4
3
PPM ( )

TMS

nmr spectrum of ethanol

before a D2O shake
Explanation

4
3
PPM ( )

nmr spectrum of ethanol

after a D2O shake

It is possible to exchange the H for deuterium, 2H or D. The usual source

is deuterium oxide, D2O, a form of water.

ROH

D2O

ROD

HOD

Deuterium doesnt exhibit nuclear magnetic resonance under the conditions

used for proton nmr so the signal is removed to another part of the spectrum.

It also works with Hs on -NH- or -NH2

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 ------------------------------------------------------------------------------------------------------------------------------------

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

H
3

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 2:2:3

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.5

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

NMR Spectroscopy

F324

SAMPLE SPECTRA
C4H8O2

C4H8O

C3H6O

C3H6O

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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 C3H7Br

Br

3 peaks
all three carbons are different

C-13 nmr spectrum

of ethanol C2H5OH

CH

Br H
2

2 peaks
the two outer carbons are similar

CH3

This is where the

proton nmr spectrum
of ethanol would be
on the same scale.

OH

70

60

50

40
30
PPM ( )

20

10

11

F324

NMR Spectroscopy

The Carbon-13 spectrum of 2-methylbutane C5H12

There are four chemically
different carbon atoms in
the molecule so there are
four peaks in the 13C nmr
spectrum.

A
chemically
equivalent
carbon atoms

CH3

CH3 CH CH2 CH 3
B

NO SPLITTING WITH 13C

ONLY ONE PEAK FOR
EACH CARBON
220

200

180

160

140

120

100

80

60

40

20

ppm

Other isomers of C5H12

pentane CH3CH2CH2CH2CH3
2,3-dimethylpropane (CH3)4C

3 peaks
2 peaks

SUPPLEMENTARY QUESTIONS

Q.6

(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

CH3
CH3 CH2

CH3 CH CH CH CH CH 3

H2N CH2 C N CH2 C OH

H

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

12

F324

Q.7

NMR Spectroscopy

Identify the isomers of C4H8O

A
B
C
220

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100

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80

60

40

20

80

60

40

20

80

60

40

20

ppm

220

200

180

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100

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40

20

220

200

180

160

140

ppm

Q.8

120

100

ppm

Identify the isomers of C6H12

X
Y
Z
220

200

180

160

140

120

100

ppm

220

200

180

160

140

120

100

ppm

80

60

40

20

220

200

180

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140

120

100

ppm