Nuclear Magnetic Resonance

Spectroscopy
Part One: Basic Concept

1
 Introduction

IR  Types of functional groups

NMR  the number of each type of hydrogens

The structure of an unknown molecule

H3 C H NH
N
S
HN N N CH3
H

2
 Spin
 1H possesses spin property
• can be thought of as small B

• will cause nucleus to produce NMR signal

3
 Nuclear Spin States

Nucleus with odd mass or odd atomic number

A quantized spin angular momentum
A magnetic moment
Nuclear spin number, I
Allowed spin states (SS)

2I + 1

spin states, (+I ~ -I ): -I, (-I+1), ---- , (I -1), I

4
Magnetic Properties of Nuclei
 Nuclear spin: I
 Angular momentum of n: I ħ (ħ = h/2π)
 Magnetic moment of n: µ = γ I ħ
 γ: gyromagnetic ratio, const for ea n
γ∞Iħ

5
 Quantum Number

Table 1. The Spin Quantum Number of Some

Common Nuclei

Element 1H 2H 11B 12C 13C N 16O 17O 19F 31P 35Cl

14

SQ No. ½ 1 3/2 0 ½ 1 0 5/2 ½ ½ 3/2

No. of SS 2 3 4 0 2 3 0 6 2 2 4

e.g.:
2
H : 3 spin states: -1, 0, +1.
35
Cl: 4 spin states: -3/2, -1/2, +1/2, +3/2.
6
﹟protons ﹟neutrons Nuclear spin Examples
(Z) (N) (I)

even even 0 4
He,12O,16O,18O,
28
Si, 32S

odd even ½, 3/2, 5/2… 1H(1/2),11B(3/2),

15
N(1/2)
even odd ½, 3/2, 5/2… 13
C(1/2),17O(5/2)
odd odd 1, 2, 3…6
2
H(1),10B(3),36Cl(2)
7
 Nuclear Magnetic Moments

Nucleus has a magnetic moment (µ) generated

by its charge and spin.
µ

1
H:

µ
Spin +1/2 Spin -1/2 Applied magnetic
Aligned Opposed Field (Bo)
(lower energy) (higher energy) 8
 The NMR Phenomenon

1. A spinning charge generates 2. In the presence of an external magnetic field (B0),

a magnetic field two spin states exist, +1/2 and -1/2.

9
 Nuclear Spin States

3. The difference in energy between the two spin states is dependent on

the external magnetic field strength, and is always very small.

10
 Nuclear Spin States

The international unit for magnetic flux is the tesla (T). The earth's magnetic fiel
s not constant, but is approximately 10-4 T at ground level. Modern nmr
spectrometers use powerful magnets having fields of 1 to 20 T. Even with
these high fields, the energy difference between the two spin states is less than
0.1 cal/mole.

11
 Correlation of Frequency with Magnetic Moment

4. For spin 1/2 nuclei the energy difference between the two spin states at a given magnet
ield strength will be proportional to their magnetic moments. For the four common nuclei
noted above the magnetic moments are: 1H μ = 2.7927, 19F μ = 2.6273, 31P μ = 1.1305
& 13C μ = 0.7022. The following diagram gives the approximate frequencies that correspon
o the spin state energy separations for each of these nuclei in an external magnetic field o
2.34 T. The formula in the colored box shows the direct correlation of frequency
energy difference) with magnetic moment (h = Planck's constant).

12
 A Model for NMR Spectroscopy

magnetic moment
μ

A Spinning Gyroscope A Spinning Charge

in a Gravity Field in a Magnetic Field

13
The NMR Spectrometer

14
 Spin States of Proton

+1/2
-1/2 against
E
field ․
+1/2 with -1/2
field
Bo
No Applied alignments
field field

15
 Spin States of Chlorine

+3/2
-3/2 +1/2

E
-1/2
․
+1/2
-1/2
+3/2
Bo
-3/2
No Applied
field field alignments

16
 Absorption of Energy

-1/2

+ hν
+1/2
Bo

Figure: The NMR absorption process for a

proton

17
Quantized Process of Energy Absorption

Eabsorbed = (E -1/2 state - E +1/2 state ) = hν

-1/2

∆E= hν
E
+1/2

Bo
(increasing magnetic field)
18
 m = - 1/2
Zeeman eff + µ B0
Zeeman levels
- µ B0
m = + 1/2
B0
∆E = 2 µ B0
∆m = 1---- selection rule

In general, I (2 I + 1) E levels (I, I - 1, …,- I)

Each sep’n: µ/I * B0
19
 Energy & Frequency
• Since E related to freq, can do some
insightful math…
∆E = h ν
ν = γ Bo/2π
∆E = γ h Bo/2π

20
Energy levels in a magnetic fields
 The potential energy E of a n in these two
orientations or quantum states:
(1) for lower energy state
E+1/2 = - γ (h I /2π) Bo (I = -1/2)
= - γ (h /4π) Bo
(2) for higher state:
E-1/2 = + γ (h /4π) Bo
 The different in energy ∆E btw these two
states ∆E = E-1/2 - E+1/2 = γ (h /2π) Bo
21
 Theoretical Concept

∆E = f (Bo) --- Energy difference between the spin state

∆E = f (γBo) = hν

(Each nucleus has a different ratio of its

magnetic moment to its angular momentum).

The ratio, magnetogyric ratio, γ, is a constant for

each nucleus

22
 Theoretical Concept

Angular momentum is quantized in units of h/2π

(Angular momentum = l ħ, ħ = h/2π)

∆E = hν = γ (h/2π)Bo

ν = (γ/2π)Bo

23
 Theoretical Concept

In order to obtain the resonance condition (Eq.1),

it is necessary to increase the Bo over that
for the isolated nucleus.

ν = (γ/2π)Bo (Eq. 1)

24
 Theoretical Concept

ν = (γ/2π)Bo

The value of γ value for the proton:

The unshielded proton absorb of frequency:

42.6 MHz in a field of the strength 10,000 Gauss or
60.0 MHz in a field of strength 14,100 Gauss.

25
 Spin Properties of Nuclei

Natural % Magnetic Magnetogyric

Isotope Spin (I)
Abundance Moment (μ) Ratio (γ) *

1
H 99.9844 1/2 2.7927 26.753
2
H 0.0156 1 0.8574 4,107
11
B 81.17 3/2 2.6880 --
13
C 1.108 1/2 0.7022 6,728
17
O 0.037 5/2 -1.8930 -3,628
19
F 100.0 1/2 2.6273 25,179
29
Si 4.700 1/2 -0.5555 -5,319
31
P 100.0 1/2 1.1305 10,840

*γ has units of 107rad T-1 sec-1

26
Impulse Frequencies and Field Strength

Isotope field strength frequency (ν)

1
H 10,000 Gauss 42.6 MHz
14,100 60.0
23,500 100.0
51,480 220.0
2
H 10,000 6.5
14,100 9.2
13
C 10,000 10.7
19
F 10,000 40.0
35
Cl 10,000 4.2 27
Mechanism of Absorption (Resonance)

Bo
A B
(A) Top precessing in gravitational field.
(B) The precessing of a spinning nucleus.
28
 Energy & Frequency
• To explain certain aspects of NMR, need to
refer to circular motion. Hz not best units to
do so
• Define precession or Larmor freq, ω

ω = 2πν ⇒ ωo = γ Bo (radians)

29
 The NMR Process
ω= 60 MHz Absorption
occurs
hν
hν = hω
+1/2
ν = 60 MHz
-1/2
Bo
14,100 G

Figure 8. The NMR process; absorption occurs

when ν = ω.
30
 The NMR Process
If rf energy having a frequency matching the Larmor frequency is
introduced at a right angle to the external field (e.g. along the x-axis),
the precessing nucleus will absorb energy and the magnetic moment
will flip to its I = - 1/2 state

frequencies in radians per second may be

converted to Hz (cps) by dividing by 2π.
31
 Macroscopic Magnetization

Net Macroscopic Magnetization of a Sample in

an External Magnetic Field Bo
32
Macroscopic Magnetization

Excitation by RF Energy and

Subsequent Relaxation
(Introduce RF energy)

33
 Theoretical Concept

Bnet = Bo - Bi

The electron density surrounding the nucleus

Produces a shift to low frequency. Thus, magnetic
field produced by the electron density is changed.

Bnet = Bo (1-σ)

σ : the shielding constant

34
The extent of diamagnetic shift is determined by Bi

Bi depends on 3 factors:
4.The amount of electron density.
5.The ease the electron density can circulate about
6.The magnitude of Bo.

35
 Shielding & Deshielding

Shielding: an upfield, higher field, or

diamagnetic shift.

Deshielding: a downfield, lower field, or

paramagnetic shift.

36
 Chemical Shift and Shielding

․The proton generate counter magnetic field (Bi)

which opposes the applied magnetic field (Bo)
(Lenz’s law)
․ The nuclear shielding is proportional to the
applied field.
․ The net field (Bnet) which the nucleus experience
is less than the applied field.

Bnet = Bo - Bi

37
 Chemical Shift (Also Called δ) Scale

Here’s how it works.  We decide on a sample we’ll use to standardize our instruments.  We 
take an NMR of that standard and measure its absorbance  frequency.  We then measure the 
frequency of our sample and subtract its frequency from that of the standard.  We then then 
divide by the frequency of the standard. This gives a number called the “chemical shift,” also 
called δ, which does not depend on the magnetic field strength.  Why not?  Let’s look at two 
examples.

Imagine that we have a magnet where our standard absorbs at 300,000,000 Hz (300 
megahertz), and our sample absorbs at 300,000,300 Hz.  The difference is 300 Hz, so we 
take 300/300,000,000 = 1/1,000,000 and call that 1 part per million (or 1 PPM).  Now lets 
examine the same sample in a stronger magnetic field where the reference comes at 
500,000,000 Hz, or 500 megahertz.  The frequency of our sample will increase 
proportionally, and will come at 500,000,500 Hz.  The difference is now 500 Hz, but we 
divide by 500,000,000 (500/500,000,000 = 1/1,000,000, = 1 PPM). 
It’s brilliant.  

Of course, we don’t do any of this, it’s all done automatically by the NMR machine.  
Even more brilliant.
38
 The Chemical Shift of Different Protons
NMR would not be very valuable if all protons absorbed at the same frequency.  You’d see a 
signal that indicates the presence of hydrogens in your sample, but any fool knows there’s 
hydrogen in organic molecules.  What makes it useful is that different protons usually appear 
at different chemical shifts (δ).  So, we can distinguish one kind of proton from another.  
Why do different protons appear at different δ?  There are several reasons, one of which is 
shielding.  The electrons in a bond shield the nuclei from the magnetic field.  So, if there is 
more electron density around a proton, it sees a slightly lower magnetic field, less electron 
density means it sees a higher magnetic field:

This represents the electron density of a C­H bond.  How much electron 
Z density is on the proton depends on what else is attached to the carbon.  If Z 
C H is an elelctronegative atom, the carbon becomes electron deficient and pulls 
some of the electron density away from the H.  if Z is an electron donating 
group, more electron density ends up on the H.

How do the electrons shield the magnetic field?  By moving.  A moving charge creates a 
magnetic field, and the field created by the moving electrons opposes the magnetic field of 
our NMR machine.  It’s not a huge effect, but it’s enough to enable us to distinguish between 
different protons in our sample. 39
 Shielding Constant, δ

• δd, The diamagnetic shielding contribution

 from unhindered circulation, producing a Bi
opposed to Bo.
 it is positive  Bnet < Bo

2. δp, The paramagnetic shielding contribution

 Bi is reduced from hindered circulation
(reinforce Bo)
 it is always negative  Bnet > Bo
40
 Chemical Shift (δ)

Definition:
The nuclear shielding divided by the applied field

δ = (Breference – Bsample)/Bo x 106 ppm

(νsample – νreference)
δ= X 106
oscillator frequency (Hz)

41
 Chemical Shift (δ)

Conditions affect Chemical Shift, δ, in ppm

•solvent
•concentration
•temperature
# not on spectrometer frequency
e.g.
1
H spectrum
at 60 MHz: 1 ppm apart = 60 Hz
at 100 MHz : 1 ppm apart = 100 Hz
42
 Proton
(1H)
․Diamagnetic shift with s-electrons.

․ No p-electrons, no paramagnetic term from

its own valence electrons.
(so, small range of chemical shifts, ca. 10 ppm)

․ Can be affected by the neighboring p-electrons.

43
 Carbon-13 (13C)

•2 1s electrons, 2 2s electrons, 2 2p electrons

•lack fully spherical symmetry of electron densit
surrounding the carbon
 diminished circulation of electron density
a lower Bi, relative to the spherical circulation

44
Chemical Shift (δ)

45
 Chemical Shift (δ)

Proton Chemical Shifts of Methyl Derivatives

Compound (CH3)4C (CH3)3N (CH3)2O CH3F

δ 0.9 2.1 3.2 4.1

Compound (CH3)4Si (CH3)3P (CH3)2S CH3Cl

δ 0.0 0.9 2.1 3.0

46
 Chemical Shift (δ)

Cpd. / X X
X=Cl X=Br X=I
Sub. =OR =SR
CH3X 3.0 2.7 2.1 3.1 2.1
CH2X2 5.3 5.0 3.9 4.4 3.7

CHX3 7.3 6.8 4.9 5.0

47
 Chemical Shift (δ)

Low High Field

Field Region
Region

  * For samples in CDCl3 solution. The δ scale is relative to TMS at δ = 0.

48
Chemical Shift (δ)

49
Chemical Shift (δ)

50
 Reference Compounds

ecause proton in a molecule show only slightly

fferent chemical environment (e.g. shielding),
hich results in a slightly different resonance
equency (e.g. only more than one part in a million
is difficult to measure exact frequency and hence
reference compound is placed in the solution
d measured.

e resonance frequency of each proton is measured

lative to that of reference compound.
51
 Reference Compounds

TMS (tetramethylsilane), (CH3)4Si.

The reason was chosen:

The protons of Me group are more shielded
than those of most other known compounds.

Sample is measured relative to how far (in Hz)

from those of TMS.
52
 δ / τ Scales

Direction of scan 
TMS
12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
δ scale
τscale
-2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12

Low Gauss τ = (10-δ) High Gauss

(fast rate of (slow rate of
H-precessing) H-precessing)

53
 Signal Strength

Area under peak (AUP)

 relative number of each type of hydrogen 54
 The NMR Spectrometer

RF (60 MHz) RF
Detector
Recorder
Oscillator

~ 14,100 Gauss
N S ±a few ppm

igure 6. The Basic Elements of the NMR Spectrometer

55
 Typical NMR Spectrometer

•Uses a constant frequency RF signal.

•Varies the magnetic field strength.
•Changes the field (ca. several ppm) to bring
the various protons in a sample into resonance.
•field strength increasing ∝ a pen traveling from
left to right on a recording chart.

56
 Resonance Frequency and Field Strength

TMS
12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
δ scale
τscale
-2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12

downfield Upfield
(less shielded protons) (highly shielded protons)
(higher RF) (lower RF)

Highly shielded protons precess at a slower

rate that need to increase the field to
induce them to precess at 60 MHz.
(use a constant RF !!)
57
Chemical Equivalence

H
HH
H H H H
H H
H H HH HH
H
One peak - all protons
Chemically equivalent

58
 NMR Spectrum

•Distinguishes different types of protons.

•Reveals each different type of protons.

H H O
H C CH3
H2
H H
Three chemically distinct
types of protons

59
 Chemical Shift (δ)

(shift in Hz)
δ=
(spectrometer frequency in MHz)

δ expresses the amount by which a proton resonanc

s shifted from TMS in parts per million (ppm).

60
 Chemical Shift (δ)

δ Values are irrespective of field strength.

e.g.
CH3Br, at 60 MHz is 162 Hz, at 100 MHz is
270 Hz from TMS.
Both are the same value of δ= 2.70.
162 Hz 270 Hz
δ= = = 2.70 ppm
60 MHz 100 MHz

61
 Resonance Frequency and Field Strength

100 MHz / 60 MHz = 23,500 G / 14,100 G

=5/3
The shift (in Hz) for a proton in 100 MHz
is 5/3 larger than that in 60 MHz.

62
 Chemical Shift (δ)
-OH, -NH

12 11 10 9 8 7 6 5 4 3 2 1 0

-2 -1 0 1 2 3 4 5 6 7 8 9 10

CH2F CH2Ar C-CH-C

RCOOH RCHO Ar-H =C-H CH2Cl CH2NR2 C-CH2-C
CHCl3
CH2Br CH2S, C-CH3
CH2I =C-CH2
CH2O C≡C-H 63

CH NO CH2C=O
 Shielding & Deshielding

Shielding: an upfield, higher field, or

diamagnetic shift.

Deshielding: a downfield, lower field, or

paramagnetic shift.

64
 Diamagnetic Shielding
A. Electronegativity Effects
Table 7. The dependence of the chemical shift
of CH3X on the Element X

CH3X CH3F CH3OH CH3Cl CH3Br CH3I CH4 Me4Si

Elng. 4.0 3.5 3.1 2.8 2.5 2.1 1.8

of X

Che. Sft. 4.26 3.40 3.05 2.68 2.16 0.23 0.00

65
 Diamagnetic Shielding

Table 9.2 Substitution Effects

CHCl3 CH2Cl2 CH3Cl -CH2Br -CH2-CH2Br –CH2-CH2-

CH2Br

δ 7.27 5.30 3.05 3.30 1.69 1.25

66
 Diamagnetic Deshielding

The e.w. effects of electronegative substituents reduce the

electron density around the protons and they reduce
the local diamagnetic shielding around those protons.

The greater the electronegativity of the substituent,

the more it deshields protons and hence, the greater
is the chemical shift.

67
 Local Diamagnetic Shielding

Bo applied H reduced
Figure 9.3 Local diamagnetic shielding of a proton
owing to its valence electrons
68
 Hybridization Effects

“sp3” Hydrogens

H - C (sp3): 0 ~ 2 ppm
H – C (highly strained): 0 ~ 1 ppm
C – CH2 – C : 1.2 ~ 1.4 ppm
C – C H – C : 2.0 ~ 2.3 ppm

(s orbitals hold closer to the nucleus than do the

carbon p orbitals)
69
 Hybridization Effects
“sp2” Hydrogens
Vinyl C- Hs : 4.5 ~ 7.0 ppm
(has more s character than at sp3 carbon)

The sp2 carbon holds its electrons more tightly,

resulting in less shielding for the H nucleus than in
an sp3 carbons.

70
 Hybridization Effects

Aromatic hydrogens: even downfield 7 ~ 8 ppm

Aldehyde protons (also sp2 carbon): 9 ~ 10 ppm

(anisotropic effects)

O
R H

71
 Hybridization Effects

“sp” Hydrogens
Acetylenic hydrogens (C-H, sp – 1s):
at 2 ~ 3 ppm (due to anisotropy 異向性 )

This is the opposite of what is actually observed.

72
 Proton Exchange

C. Acidic and Exchangeable Protons:

Hydrogen Bonding

-COOH: 10 ~ 12 ppm (the least shelded proton)

O O
R R +
O H O H

73
Hydrogen Bonding/Exchangeable Hydrogen

-OH, -NH: variable absorption positions over

a wide range.
Table 10. Typical Ranges for Protons with
Variable Chemical Shift
Acids RCOOH 10.5 ~ 12.0 ppm
Phenols ArOH 4.0 ~ 7.0
Alcohols ROH 0.5 ~ 5.0
Amines RNH2 0.5 ~ 5.0
Amides RCONH2 5.0 ~ 8.0
Enols CH=CH-OH ≧ 15

74
 Hydrogen Bonding

Cool the sample

Under routine conditions, rapid intermolecular exchange of the OH protons

of alcohols often prevents their coupling with adjacent hydrogens from
being observed. 75
 Hydrogen Bonding

r many alcohols in dilute chloroform-d solution, the hydroxyl resonance signal

often broad and obscured by other signals in the δ 1.5 to 3.0 region. The simple
chnique of using DMSO-d6 as a solvent, not only shifts this signal to a lower field
t permits 1°-, 2 °- & 3 °-alcohols to be distinguished. Thus, the hydroxyl proton
2-propanol generates a doublet at δ 4.35 ppm, and the corresponding signal
om 2-methyl-2-propanol is a singlet at δ 4.2 ppm. The more acidic OH protons
phenols are similarly shifted – from δ 4 to 7 in chloroform-d to δ 8.5 to 9.5
DMSO-d6. 76
 Solvent Influence

1
H Chemical Shifts of Methanol in Selected Solvents

Solvent CDCl3 CD3COCD3 CD3SOCD3 CD3C≡N

CH3–O–H
CH3 3.40 3.31 3.16 3.28
OH 1.10 3.12 4.01 2.16

77
The more H-bonding, the more deshielded
a proton becomes.
H-bonding ∝ concentration, temperature.

R H H
R O
δ+O Oδ+ O δ+
H
H R R
Free H-bonded
(dilute sol’n) (conc. sol’n)
0.5 ~ 1.0 ppm 4.0 ~ 5.0 ppm
78
Hydrogen exchanging with the solvent medium
or one another tend to be variable in δ values.

R-O-Ha + R’-O-Hb ⇔ R-O-Hb + R’-O-Ha

R-O-H + H:Solv ⇔ R-OH2 + :Solv-

R-O-H + :Solv ⇔ H:Solv+ + R-O-

79
 Magnetic Anisotropy

Circulating electron

H H

2nd magnetic field

Generated by circulating π
Electrons deshields aromatic
Bo protons
Figure 10. Diamagnetic Anisotropy in Benzene 80
 π-Electron Functions

egions in which the induced field supports or adds to the external field are said to be
eshielded, because a slightly weaker external field will bring about resonance for nuclei
such areas. However, regions in which the induced field opposes the external field are
rmed shielded because an increase in the applied field is needed for resonance.
hielded regions are designated by a plus sign, and deshielded regions by a negative sign
81
 Molecular Orbitals

Figure. Molecular orbitals of ethylene and acetylene

82
 Anisotropic Effects

․ Ar-Hs are deshielded by

the diamagnetic anisotropy
․ An anisotropy field is “not isotropic” or
“non-uniform”.
․3 magnetic fields affect benzene protons.
one applied field.
two weak fields:
a) valence electron around protons
b) the anisotropy generated by the ring electrons.
83
 Anisotropic Effects

C1

C2

Bo H

Figure 10. Diamagnetic Anisotropy in Acetylene

84
 Anisotropic Effects

+ + +
O
(-) (-)
(-) (-) (-) (-)
+
+ +

(-)
+ + (+): shielded
H C1(-) C2 H (-): unshielded

Figure 12. Anisotropy by π electrons in some

multiple bond system 85
Signal Splitting

86
 Spin-Spin Splitting (n+1) Rule

Ha Hb Ha Hb
Cl Cl Cl Cl
Cl Hc Cl Hc

Two neighbors One neighbor

give a triplet gives a doublet
(n+1 = 3) (n+1 = 2)

87
 Signal Splitting

What causes this signal splitting,

and what useful information can be obtained from it ?

The symbol J to designate the number of bonds linking the coupled

nuclei (colored orange below). Using this terminology, a vicinal coupling
constant is 3J and a geminal constant is 2J.

88
 Common Splitting Patterns

X C C Y H 3C CH
H H
(X=Y)

CH2 CH H3 C C
H2
H3 C H
X C C Y C
H2 H 2
H3 C
(X=Y)

89
 General Rules for Spin 1/2 Nuclei

1) Nuclei having the same chemical shift (called isochronous) do not

exhibit spin-splitting. They may actually be spin-coupled, but the splitting
cannot be observed directly.
2) Nuclei separated by three or fewer bonds (e.g. vicinal and geminal
nuclei ) will usually be spin-coupled and will show mutual spin-splitting of
the resonance signals (same J's), provided they have different chemical
shifts. Longer-range coupling may be observed in molecules having rigid
configurations of atoms.
3) The magnitude of the observed spin-splitting depends on many factors
and is given by the coupling constant J (units of Hz). J is the same for
both partners in a spin-splitting interaction and is independent of the
external magnetic field strength.
4) The splitting pattern of a given nucleus (or set of equivalent nuclei)
can be predicted by the n+1 rule, where n is the number of neighboring
spin-coupled nuclei with the same (or very similar) Js. If there are 2
neighboring, spin-coupled, nuclei the observed signal is a triplet ( 2+1=3 );
if there are three spin-coupled neighbors the signal is a quartet ( 3+1=4 ).
In all cases the central line(s) of the splitting pattern are stronger than
those on the periphery.
90
Spin-Spin Splitting

91
Spin-Spin Couplings

92
Typical Coupling Constants

93
Example of Spectrum

94
Example of Spectrum

95
Example of Spectrum

96
Example of Spectrum

97
Example of Spectrum

98
Example of Spectrum

99
 Example of Spectrum

All above hand-outs for undergraduate

100
 Spin-Spin Splitting

Ha Hb (+1/2) Ha Hb (-1/2)

Ha Hb Ha Hb
X C1 C2 Y X C1 C2 Y

R R R R

X Type Molecule Y Type Molecule

(Ha deshielded) (Ha shielded)

(see next pattern)

101
 Spin-Spin Splitting

Ha in X Type Ha in Y Type
Molecule Molecule
(deshielded – (deshielded –
Proton B has spin Proton B has spin
aligned with Bo) opposed with Bo)

Chemical shift of Ha
If Hb were absent)

Figure 13. The Origin of Spin-Spin Splitting in

Ha’s NMR Spectrum
102
 Spin-Spin Splitting

The Final Spectrum of X-CHaR-CHbR-Y:

Ha Hb

e.g. Cl2CH-CH(OMe)2

103
 Spin-Spin Splitting

13. The Ethyl Group (CH3CH2-)

e.g. CH3CH2I

3.20 1.83

104
 Spin-Spin Splitting
# 理論上有 8 (= 23) 種方向 , 但有些相等 , 故只有四根峰線

= spin +1/2

= spin -1/2

Possible spin arrangements

of the methyl protons

+3/2 +1/2 -1/2 -3/2

Figure 14. The Splitting Pattern of CH2 protons of Ethyl Iodide

105
 Spin-Spin Splitting

Possible spin arrangements

of the methylene protons

+1 0 -1
Figure 14. The Splitting Pattern of CH3 protons of Ethyl Iodide

106
 Pascal’s Triangle

The n+1 rule for the intensity ratios of multiplets

follows Pascal’s Triangle
Singlet 1
Doublet 1 1
Triplet 1 2 1
Quartet 1 3 3 1
Quintet 1 4 6 4 1
Sextet 1 5 10 10 5 1
Septet 1 6 15 20 15 6 1
Figure 15. Pascal’s Triangle 107
 Coupling Constant (J )

The distance between the splitted peaks in a

Simple multiplet is called the coupling constant
e.g. CH3CH2I

3J 2J
Chemical shift
is center of group δA δB

108
 Coupling Constant (J )

Table 10. Some representative J and Their Approx. Values (Con’d

H H H
H
H H O
H H
a,a 8 ~ 14 cis 6 ~ 12 cis 2 ~ 5 5 ~ 7
a,e 0 ~ 7 trans 4 ~ 8 trans 1 ~ 3
e,e 0 ~ 5

109
Table 10. Some representative J and Their Approx. Values
H H
H
6~8 C1 C2 H 6 ~ 10
H
11 ~ 18
H H

H H 1~4
6 ~ 15 H

H
0~5 H
H 0~2
H
H H
4 ~ 10 8 ~ 11
CH H

0~3 H
CH 110
 Problems

1. What are the allowed nuclear spin states

for the following atoms?
(a) 14N (b) 13C (c) 17O (d) 19F

2. Calculate the ppm for a proton resonancing

at 128 Hz downfield from TMS on 60 MHz
spectrometer.

111
3. A proton has resonance 90 Hz downfield from TMS whe
the field strength is 15,100 Gauss and the oscillator
frequency is 60 MHz.

e) What will its shift in Hz be if the field strength is

increased to 28,200 Gauss and the oscillator frequency
to 120 MHz.
b) What will be its chemical shift in ppm (δ)?

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 1
H ­ 1H Coupling
You’ll notice in the spectra that we’ve seen that the signals don’t appear as single lines, 
sometimes they appear as multiple lines.  This is due to 1H ­ 1H coupling (also called spin­spin 
splitting or J­coupling).  Here’s how  it works:  Imagine we have a molecule which contains a 
proton (let’s call it HA) attached to a carbon, and that this carbon is attached to another carbon 
which also contains a proton (let’s call it HB).  It turns out that HA feels the presence of HB.  
Recall that these protons are tiny little magnets, that can be oriented either with or against the 
magnetic field of the NMR machine.  When the field created by HB reinforces the magnetic 
field of the NMR machine (B0 ) HA feels a slightly stronger field, but when the field created 
by HB opposes B0, HA feels a slightly weaker field.  So, we see two signals for HA depending 
on the alignment of HB.  The same is true for HB, it can feel either a slightly stronger or 
weaker field due to HA’s presence. So, rather than see a single line for each of these protons, 
we see two lines for each. 

For this line, H B is lined up  For this line, H B is lined up 

with the magnetic field against the magnetic field
(adds to the overall  (subtracts from the overall 
magnetic field, so the line  magnetic field, so the line 
comes at higher frequency) comes at lower frequency) HA HB

C C
HA HB
HA is split into two lines because  HB is split into two lines because  113
it feels the magnetic field of HB. it feels the magnetic field of HA.
 More 1H ­ 1H Coupling
What happens when there is more than one proton splitting a neighboring proton?  We get 
more lines.  Consider the molecule below where we have two protons on one carbon and one 
proton on another.  

Note that the signal produced 
by HA + HA'  is twice the size 
of that produced by HB

HA HB

HA' C C
HA + HA' HB
HA and HA'  appear at the same  HB is split into three lines 
chemical shift because they are  because it feels the magnetic 
in identical environments  field of HA and HA'
They are also split into two lines 
(called a doublet) because they  
feel the magnetic field of HB.

114
 Why are There Three Lines for HB?

HB feels the splitting  of both HA and HA’.  So, let’s imagine starting with HB as a single 
line, then let’s “turn on” the coupling from HA and HA’ one at a time:

HB If uncoupled, H B would appear as a 
singlet where the dashed line indicates 
the chemical shift of the singlet.

Now, let's "turn on"  HB ­ H A coupling.  This splits 

the single line into two lines
HA HB
Now, let's "turn on"  H B ­ H A' coupling.  This 
HA' C C
splits each of the two new lines into two lines, 
but notice how the two lines in the middle 
overlap.  Overall, we then have three lines.

Because the two lines in the middle overlap, that line is twice as big as the lines on the 
outside.  More neighboring protons leads to more lines as shown on the next slide.

115
 Splitting Patterns with Multiple Neighboring Protons
If a proton has n neighboring protons that are equivalent, that proton will be split into n+1 
lines.  So, if we have four equivalent neighbors, we will have five lines, six equivalent 
neighbors… well, you can do the math.  The lines will not be of equal intensity, rather their 
intensity will be given by Pascal’s triangle as shown below.
no. of neighbors relative intensities pattern example
0                 1 singlet (s)

H H
1             1     1 doublet (d)
C C
H H
2          1     2     1 triplet (t) C C H
H H

3        1    3    3    1 quartet (q) C C H
H H H H

4      1   4    6    4    1 pentet  C C C H

H H H H

5   1   5   10  10    5  1 sextet H C C C H
H H H H

6 1  6  15   20  15   6  1 septet H C C C H
H H

We keep emphasizing that this pattern only holds for when the neighboring protons 
are equivalent.  Why is that?  The answer is two slides away.
116