Lecture 1, 2

Proton Nuclear Magnetic

Resonance (1H NMR)

Prof. Yassin Gabr and Prof. Magdy Ahmed

3/9/2023 1

Nuclear Spin States

❑ Any atomic nucleus that has an odd mass, an odd
atomic number, or both also has a spin and a
resulting nuclear magnetic moment.
❑ The allowed nuclear spin states are determined
by the spin quantum number, I, of the nucleus.
❑ A nucleus with spin quantum
number I has 2I + 1 spin states.
If I = 1/2, there are two allowed
spin states.

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 Nuclear Magnetic Resonance

▪ When nuclei with a spin quantum number of 1/2

are placed in an applied field, a small majority of
nuclear spin are aligned with the applied field in
the lower energy state.

▪ If a nucleus is irradiated with electromagnetic

(EM) radiation of the appropriate energy,
❑ the energy is absorbed, and
❑ the nuclear spin is flipped from spin state +1/2 (with
the applied field) to -1/2 (against the applied field).

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Proton Nuclear Magnetic Resonance

(1H NMR) spectroscopy
NMR Spectrometer
▪ The sample is dissolved in a solvent, most
commonly CDCl3 or D2O, and placed in a sample
tube which is then suspended in the magnetic
field and set spinning.

▪ Deuterated solvents are used to eliminate 1H

signals from the solvent. D2O, CD3COOD,
▪ CD3COCD3, CD3OD, CDCl3, CD3SOCD3

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 Information from 1H-NMR spectra
1. Number of signals: How many different types
of hydrogens in the molecule?
2. Position of signals (chemical shift): What types
of hydrogens?
3. Relative areas under signals (integration): How
many hydrogens of each type?
4. Splitting pattern: How many neighboring
hydrogens?

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1. Number of signals: How many different types of

hydrogens in the molecule.
➢ Magnetically equivalent hydrogens resonate at
the same applied field.
➢ Magnetically equivalent hydrogens are also
chemically equivalent.
What about the signals of CH4 and CH3CH3?
convention: let most upfield signal = a, next upfield = b,
and next upfield c etc…
magnetic field
downfield upfield
a b c d d c b a
CH3 CH2 CH2 CH2 X X CH2 CH2 CH2 CH3

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 Toluene

The ratio of integration 3 : 5

CH3
Relative intensity

b a
b
a
Two signals
The hydrogen atoms are differents
Two types of protons

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2-Methyl-2-butene

b d b
H3C H c
C C
c
H3C CH3 a
a

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 a

c b

c
b
H2
Cl C a splitting = n+ 1
CH3
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H H
p-Xylene
H3C CH3
H3C CH3
H H a a
b
a singlet 6H
Relative intensity

b b singlet 4H a

two signals
two different hydrogen atoms

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 NO2
NH2
(a) H H (a)
(a) H H (a)

(b) H H (b)
(b) H H (b)
H
(c) H
(c)

b b a
a
c c

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NH2
(a) H H (a)

(b) H H (b)
NO2

a
b

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 NH2
(a) H H (a)

(b) H H (b)
CH3

a
b

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NO2
(a) H NH2

(b) H H (d)
H
c d (c)

a b

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 Acetic acid
O
C
HO CH3
b a
Relative intensity

two signals
two different hydrogen atoms a

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1H Nuclei are shielded by the magnetic field

produced by the surrounding electrons. The higher
the electron density around the nucleus, the higher
the magnetic field required to cause resonance.

CH3Cl versus CH4

lower electron density higher electron density
resonate at lower resonate at higher
applied field applied field

What about the signal of CHCl3??

H2 Cl
Cl C Cl
Cl CH3 CH
Cl Cl
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 2. Position of signals (chemical shift): what types
of hydrogens.
reference compound = tetramethylsilane (CH3)4Si @ 0.0
ppm
remember: magnetic field →
 chemical shift
convention: let most upfield signal = a, next most
upfield = b, etc.
… c b a

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The Spectrum
magnetic field → TMS

downfield upfield

Deshielded region Shielded region

Lower d
Higherd

chemical shift (pmm)

Aromatic regiom Aliphatic regiom

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 1H NMR chemical shifts ranges

Correclation Tables

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 Chemical shifts

H3C CH3 CH3 a

C
a a a b
C
H3C CH3
CH3 a
a
CH3 a b a b c a b a
CH3 C CH3 CH3CH2-Br CH3CH2CH2-Br CH3CHCH3
a Br a
Cl
a
b d c a b a b CH3
CH3CHCH2CH3 Cl-CH2CH2CH2-Cl CH2Cl
b
Br
c

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1,1,2-Tribromoethane
Nonequivalent protons on adjacent carbons
Relative intensity

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 3. Relative areas under each signal (Integration ):
how many hydrogens of each type.

 The area under each peak is proportional

to the number of protons
 Shown by integration line
 Height the area under a peak a H’s in set.
 Measure height with ruler or look at graph paper.
 Ratio of height = ratio of hydrogens.

a b c a b a
CH3CH2CH2Br a 3H CH3CHCH3
b 2H a 6H
c 2H Br b 1H
a:b:c=3:2:2 a:b=6:1

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Integration (number of equivalent protons of each type)

a
CH3
H3 C CH3
C
a b
a C a
H3 C CH3
CH3
a

a 12 H a 12 H a 6H a 6H
b 4H

a
CH3 a b a b c a b a
H3C C CH3 CH3CH2-Br CH3CH2CH2-Br CH3CHCH3
a Br a Cl
a 3H a 3H a 6H
a 9H b 2H b 2H b 1H
c 2H

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 a
b d c a b a b CH3
CH2Cl
CH3CHCH2CH3 Cl-CH2CH2CH2-Cl
b
Br
c

a 3H a 3H
b 3H a 2H b 2H
c 2H b 4H c 4H
d 1H

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Relative intensity Ethyl bromide

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c b

c
b
H2 intergration
Cl C a
4: 2: 3
CH3
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 Relative intensity 2-Methoxy-2-methylpropane

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4. Splitting pattern: how many neighboring hydrogens.

 n-equivalent neighboring hydrogens will split a 1H

signal into an (n + 1) Pascal pattern.
 n = neighboring (“neighboring” – no more than three
bonds away).

Area ratios
n n +1
(Pascal’s triangle)
n = Number of
0 1 (singlet) 1
equivalent protons
1 2 (doublet) 1 1
causing splitting.
2 3 (triplet) 1 2 1
3 4 (quartet) 1 3 3 1 n + 1 = Number of
4 5 (quintet) 1 4 6 4 1 peaks (multiplicity)
5 6 (sextet) 1 5 10 10 5 1
1 6 15 20 15 6
6 7 (septet)
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 Range of Magnetic Coupling
 Equivalent protons do not split each other.
 Protons bonded to adjacent carbon will split each
other only if they are not equivalent.
 Protons on adjacent carbons normally will couple, If
the neighbors are not equivalent, then you will see a
complex pattern (complex multiplet).
 Protons separated by four or more bonds will not
couple.
 The alcohol hydrogen –OH usually does not split
neighboring hydrogen signals nor is it split. Normally
a singlet of integration 1 between 1 – 5.5 ppm
(variable).
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Splitting pattern?
a
CH3
H3C CH3
C
a b
a C a
H3C CH3
CH3
a
a 12 H singlet a 12 H singlet a 6 H singlet a 6 H singlet
b 4 H singlet
a
CH3 a b a b c a b a
H3C C CH3 CH3CH2-Br CH3CH2CH2-Br CH3CHCH3
a Br a Cl
a 3 H triplet a 3 H triplet a 6 H doublet
a 9 H singlet b 2 H quartet b 2 H sixtet b 1 H septet
c 2 H triplet

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 a
b d c a b a b CH3 a b c
CH2Cl
CH3CHCH2CH3 Cl-CH2CH2CH2-Cl CH3CH2-OH
b
Br
c

a 3 H triplet a 3 H singlet a 3 H triplet

b 3 H doublet a 2 H quintet b 2 H singlet b 2 H quartet
c 2 H quintet b 4 H triplet c 4 H ~singlet c 1 H singlet
d 1 H sextet

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b d
H H c a
H C CH3
H2
H Br

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 1,1,2-Tribromoethane
Relative intensity

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Doublet: 1 Adjacent Proton

1,1,2-Tribromoethane

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 Triplet: 2 Adjacent Protons

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Ethyl chloride

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 Ethyl bromide

a
b TMS
a
Relative intensity

b
a b
CH3CH2-Br

a 3H, triplet
b 2H, quartet

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a b
CH3CH2 I
a 3H triplet
b 2H quartet
Relative intensity

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Relative intensity 1,1-Dichloroethane

H Cl
H H
H Cl

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H H2
H3C C C
1,2-Dichloropropane
Cl Cl
Relative intensity

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 Cl
H2
1,2,2-Trichloropropane H3C C C
Cl Cl
Relative intensity

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1-Bromopropane

a b c
Relative intensity

a
c
CH3CH2CH2-Br

a 3H, triplet
b 2H, sextet (m) b
c 2H, triplet

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 Br
H3C C CH
1,1-Dibromopropane H2
Br

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H2 H2
1,3-Dibromopropane C C C
Br H2
Br
Relative intensity

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 Isopropyl chloride

a b a
CH3CHCH3
Cl
Relative intensity

a 6H, doublet
b 1H, septet (m) a

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2-Bromobutane

b d c a
CH3CHCH2CH3
Br
b&c
Relative intensity

a triplet, 3H
b doublet, 3H
c complex (multiplet), 2H
d complex (multiplet), 1H a
b & c overlap

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 1-Bromo-2,2-dimethylpropane

H3C
H2
H3C C C
Br
Relative intensity

CH3

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2-Bromo-2-methylbutane

b
CH3
Relative intensity

CH3 C CH2CH3
b Br c a

a triplet, 3H
b singlet, 6H
c quartet, 2H b&c
b & c overlap a

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 Ethyl benzene
Relative intensity

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o-Methyl benzylchloride

a
CH3
CH2Cl
b
Relative intensity

c a
c
a singlet, 3H b
b singlet, 2H
c ~singlet, 4H

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 p-Diethylbenzene

c
a b b a
CH3CH2 CH2CH3

a triplet, 6H
Relative intensity

b quartet, 4H
c ~singlet, 4H a
c
b

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H2
H H2 m-Diethylbenzene
C C
H3C CH3
b a
CH2CH3
H H
c
H
c CH2CH3
Relative intensity

b a
a triplet, 6H a
b quartet, 4H
c complex, 4H
c
b

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 H2 H2 o-Diethylbenzene
H3C CH3
C C

b a
H H CH2CH3
CH2CH3
Relative intensity

H H b a
c

a triplet, 6H
c a
b quartet, 4H
c ~singlet, 4H

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Ethyl acetate
Relative intensity

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