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(NMR) Spectroscopy
m
m = Magnetic Moment
Direction of External
Magnetic Field (B0)
m
Spin Aligned Spin Opposed
s = +1/2 s = -1/2
Thus, in a magnetic field, hydrogen nucleus splits into its two spin
states- either aligned or opposed to the external magnetic field.
N N
-3/2
-1/2 -1/2
E E
+1/2 +1/2
+3/2
1Hnucleus 35Cl
nucleus
I = 1/2, 2 states I = 3/2, 4 states
Spin aligned states are always lower in energy than spin opposed
states.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 5
Nuclear Spin State Energies
Stronger the applied magnetic field, greater will be the energy
difference (ΔE) between the spin states after splitting.
ΔE = γB0 … 1
ν = (γ/2π)B0 … 3
Opposed
DE = hn
Aligned
B0
w = 60 MHz
n = 60 MHz
hn
s = -1/2
s = +1/2
hn = hw
B0
The nuclei being charged, generates an oscillating electric field having
the same frequency ω.
Now if radiowaves of the same frequency are supplied to this
precessing nucleus, the two electric fields can couple and the energy
can be absorbed by the nucleus. This process is called resonance.
The FID signal decays exponentially with time as the nuclei relax.
However, the frequency of the FID is not the exact frequency of the
nucleus as it is an interference signal between the supplied
radiofrequency and the frequency emitted by the excited nucleus.
For any one type of proton, wavelength of the FID may be calculated
as:
FID for acetone in time domain FID signal in frequency domain after FT
Since noise is random, its intensity does not increase with multiple
iterations of the spectrum added together.
The whole process being computer generated takes very less time for
very complicated processes like Fourier Transform.
Internal Standard:
OMe
Downfield 1H Upfield 1H
1H Correlation Chart
Mono-substituted Rings:
CH3 NO2
NH2 OMe
H d 7.13 H H d 8.21
H H d 6.55 H H d 6.87 H
d- d- d+ d+
d- d- d- d-
H d 7.25 H H H d+ H d 7.55
H d- H d 7.08 H d-
H d 7.25 H
H H
d 7.70
d 6.70 d 6.93
OMe
CH3
NO2
2 d 1 0
H H
H H
B0
H H
H H
H H
Paramagnetic
deshielding
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 28
Factors Influencing Chemical Shifts
Magnetic Anisotropy:
The aldehyde proton directly falls under paramagnetic deshielding
zone due to anisotropy of C=O bond π electrons
Shielding Shielding
zone zone
Shielding Shielding
zone zone
H H H
Annular protons H H
resonate at d -1.8 ppm H H
H H H
H H
H H
Outer protons resonate at d 8.9 ppm
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 29
Factors Influencing Chemical Shifts
Magnetic Anisotropy:
Some other examples of magnetic anisotropy in different class of
compounds.
~ d -1.0 ppm ~ d -4.0 ppm
COOH (shielded) H2 Me (shielded)
~ d -0.5 ppm
H2 C (shielded)
H2 C C CH2
H
H H2 C CH2
Me ~ d 8.0 ppm
~ d 2.0 ppm H (deshielded)
~ d -1.4 ppm
(shielded) (deshielded)
d 0.85 d 3.75
d 0.83 d -0.17 d 1.27 d 3.53
CH3 HO H
H H H3 C H OH
CH3
Deshielding zone
Shielding zone
So, the alkynic protons experience much less magnetic field strength
than olefinic protons, as a result they appear in spectrum with a low
δ value.
H H H
Deshielding zone
H H
H
Spiro cyclopropane ring also can exert the same effect.
O O
H H H H
d 7.42 d 6.91
In this case induced magnetic field of cyclopropane ring shields
these protons.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 33
Factors Influencing Chemical Shifts
Magnetic Anisotropy:
Like double bonds and triple bonds, single bonds also can exert
anisotropic effect.
d 10-12 d 11-16
O H
H
O O
O
R1 R2
OR
Salicylates Enols
O H O
3 3
Eu(dpm)3 Eu(fod)3
Relative number of
protons in benzyl
acetate is:
5:2:3
HA HB HA HB
R CA CB R R CA CB R
B0
R R R R
Molecule X (HA and HB with same spin) Molecule Y (HA and HB with different spin)
HA HB HA HB
R CA CB R B0 R CA CB R
R R R R
Molecule X (HA and HB with same spin) Molecule Y (HA and HB with different spin)
R CA CB R R CA CB R
R R R R
B0
Molecule X Molecule Y
Doublet (d)
Triplet (t)
Quartet (q)
Quintet (quint)
Sextet (sex)
Septet (sep)
X
X HA HA, HB and HC all different types of protons.
HB
HB
We observe three doublets. Hence the name of
the pattern is triplet of doublets (td).
JB-C
JB-C This is observed if HB-HC coupling is stronger and
occurs first.
Each splitting would follow its own standard
intensity pattern.
JA-B
12C
α
1H 1H
H H H H
C C C C
H D 19F 13C
H 19F H
C C C
H 19F 31P
H H
Bu
O
H H H
H H H H
Dihedral Angle = 0°
As a result, the best overlap occurs when the C-H bonds are at a
dihedral angle of 0°.
(End-on view)
Ha Hb Ha R
3J = 11-18 Hz 3J = 6-15 Hz
ab ab
Cyclohexane systems:
Ha Ha Y
Y Y Ha
X Hb Hb
Hb X X
Dihedral Angle = 180° Dihedral Angle = 60° Dihedral Angle = 60°
3J
ab = 2-5 Hz
3J
ab = 2-6 Hz
3J
ab = 10-14 Hz
R R X
Me
Ha X Ha
Me
Hb R Hb R
R
X Ha Hb
H H
R R R
R
H
The two bonds forming a W-type orientation gives rise to very small,
but highly characteristic and sometimes very significant coupling.
H H
H O
H H Bu
H H
H H
H
1 3
I
2
O
2 3 6
O 5 O
1 4 7
O O
HO
Cl O
Cl O
2 3 4 6
OMe
Coupling Behavior:
-CH-CH- 3J = 5-6 Hz
Coupling Behavior:
H-C=C-H 3J = 12-18 Hz
trans
3J
cis = 6-15 Hz
H
2J = 0-3 Hz
C C
H
4J = 0-3 Hz
C C C H
H
Coupling Behavior:
3J = 7-10 Hz
ortho
H 4J
meta = 2-3 Hz
H 5J
para = 0-1 Hz
OMe
Ha Ha'
Hb Hb'
Jab ¹ Jab'
Ja'b' ¹ Ja'b
d 10.15
OH
d 7.34 H H d 7.76
d 7.39 H NO2
H
d 7.82
High resolution
O 7 H
1
6 2
3
5 NO2
4
5 3 I
4
NO2
5 4
10
6 3
7 2
8 9 N
OH 1
3J 1.6-2.0 Hz
H b' Hb αβ
4J 0.3-0.8 Hz
αβ’
4J 1.3-1.8 Hz
Ha' Ha αα’
O 3J
ββ’ 3.2-3.8 Hz
3J 4.0-6.0 Hz
ab
Hc 4J 0.0-2.5 Hz
ac
Hd Hb 5J 0.0-2.5 Hz
ad
4J < 1.0 Hz
ae
He N Ha 3J 7.0-9.0 Hz
bc
4J 0.5-2.0 Hz
bd
Hb Hc
Ha O CH2OH
Hc
Ha Hb
Hd N CH3
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 100
Different Functional Groups
Alkynes
Chemical Shifts:
Due to anisotropic effect acetylenic
C C H ~ 1.9 ppm
protons appear in so upfield.
Coupling Behavior:
4J = 2-3 Hz
H C C C H
2
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 101
Different Functional Groups
Alkyl Halides
Chemical Shifts:
-CH-I 2.0-4.0 ppm Deshielding effect is due to
electronegativity of the halogen atoms.
-CH-Br 2.7-4.1 ppm
Coupling Behavior:
-CH-F 2J = 50 Hz
3J = 20 Hz
-CH-CF-
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 102
Different Functional Groups
Alcohols
Chemical Shifts: Position of hydroxyl group depends on
-C-OH 0.5-5.0 ppm concentration, solvent and
temperature. The may be broadened.
Coupling Behavior:
-CH-OH 3J = 5 Hz
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 103
Different Functional Groups
Ethers
Chemical Shifts:
These protons get deshielded due to
R-O-CH- 3.2-3.8 ppm
electronegativity of oxygen.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 104
Different Functional Groups
Amines
Chemical Shifts:
Variable chemical shift depending on
R-N-H 0.5-4.0 ppm
temperature.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 105
Different Functional Groups
Nitriles
Chemical Shifts:
These protons are shielded due to
-CH-CΞN 2.1-3.0 ppm
anisotropy of nitrile group.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 106
Different Functional Groups
Aldehydes
Chemical Shifts:
Aldehyde protons are so deshielded
R-CHO 9.0-10.0 ppm
because of anisotropic effect of
C=O.
R-CH-CHO 2.1-2.4 ppm α-protons appear in much upfield
range because they are much distant.
Coupling Behavior:
-CH-CHO 3J = 1-3 Hz
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 107
Different Functional Groups
Ketones
Chemical Shifts:
α-protons are deshielded because of
R-CH-CO-R 2.1-2.4 ppm
anisotropic effect of C=O.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 108
Different Functional Groups
Esters
Chemical Shifts:
α-protons are deshielded because of
-CH2-CO-OR 2.1-2.5 ppm
anisotropic effect of C=O.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 109
Different Functional Groups
Carboxylic Acids
Chemical Shifts:
Characteristic peak for carboxylic
R-COO-H 11.0-12.0 ppm
acids.
α-protons are deshielded because of
-CH2-COOH 2.1-2.5 ppm
anisotropic effect of C=O.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 110
Different Functional Groups
Amides
Chemical Shifts:
Variable chemical shift value, depends on
R-CO-NH- 5.0-9.0 ppm
temperature, concentration, solvent.
α-protons are deshielded because of
-CH-CONH- 5.0-9.0 ppm
anisotropic effect of C=O.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 111
Different Functional Groups
Nitroalkanes
Chemical Shifts:
-CH-NO2 4.1-4.4 ppm Deshielded by nitro group.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 112
Chemical Equivalence
If any element of symmetry renders two or more nuclei equivalent by
symmetry, then they are said to be chemically equivalent.
O Cl
O
H H H
H H
H3C H H
H H
H H
Cl
H CH3
Plane as well as Plane as well as
axis of symmetry axis of symmetry
Axis of symmetry
All protons in each of the individual groups are chemically equivalent due to symmetry
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 113
Magnetic Equivalence
A group of nuclei are magnetically equivalent when their magnetic
environments, including their coupling interactions are identical.
Magnetically equivalent nuclei must have the same chemical shift.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 114
Magnetic Inequivalence
X
HA HA
HB HB
Y
Even though the two HB nuclei are chemically equivalent, they do not
have the same coupling constants with the same HA nuclei.
Thus even though the two HA nuclei (and the two HB nuclei) are
chemically equivalent, they are magnetically nonequivalent.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 115
Magnetic Inequivalence
Jtrans
HA HB (HA, HB) & (FA, FB) are both chemically
Jcis
equivalent, but magnetically nonequivalent
FA FB pairs.
CH3
Janti
HA & HB are both chemically equivalent, but
Jsyn
HA HA magnetically nonequivalent.
HB HB
Cl
If conformation is locked
Geminal groups (protons and methyl groups mainly) are the subjects of
interest in terms of their stereochemical relationship.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 116
Topicity
Homotopic groups:
HB
X
C2, s Homotopic methyls
X
HA
H3 C CH3
HA and HB interchangeable
both by a C2 axis as well
as by a mirror plane. OH OH
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 117
Topicity
Enantiotopic groups:
HB H3C CH3
X
s HB
Enantiotopic protons
Y HA
HA
HA and HB interchangeable OH OH
only by a mirror plane.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 118
Topicity
Diastereotopic groups:
HB Diastereotopic methyls
X
Y*
HA H 3C CH3
HB
H3C Diastereotopic protons
Y* contains chiral group(s) HA
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 119
Order of an NMR Spectrum
An NMR spectrum is said to be of first order if:
(Δν/J) ≥ 7 ; where:
• Δν is the difference in chemical
shift between two groups (in Hertz)
• J is the coupling constant between
the two groups (in Hertz)
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 120
Second Order Spectrum
An NMR spectrum is said to be of second order (or non-first order)
if (Δν/J) value is less than 7.
Such situations arise due to the presence of magnetically
nonequivalent nuclei.
Second order spectra are much more difficult to analyze: splitting
patterns do not correspond to the (n+1) rule, coupling constants are
not uniform.
Normally, the presence of diastereotopic groups lead to second order
spectra.
With spectrometers of higher frequency, chemical shifts become
more resolved (Δν increases), but J values remain the same. (Δν/J)
increases overall.
Hence with spectrometers of higher frequency, second order effects
begin to disappear.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 121
Spin System Notation
Pople Notation:
A2X2 O A2B2
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 122
AX Systems
Relatively simple to analyze.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 123
AB Systems
C C
H H
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 124
AB Quartets
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 125
AB Quartets
SMe O
H
HB HA
The AB quartet is for the two protons HA and HB and they further
couple with the two adjacent protons to split into another dd.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 126
A2B2 Systems
60 MHz
500
MHz
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 127
A2B2 Systems
60 MHz
500
MHz
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 128
AMX Systems
When 3 protons of widely varying chemical shifts are present, it is
denoted by three widely spaced letters in the alphabet series:
A,M,X.
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 129
AMX Systems
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 130
Home Work
Assign aromatic protons of methyl salicylate using chemical shift
values and splitting pattern of given spectrum:
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 131
Home Work
1H spectrum was obtained from dimethyl cyclopropanedicarboxy-
late. Is it a cis or trans isomer? [CDCl3, 400 MHz, 298 K]
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 132
Home Work
Derive the structure of a compound using following NMR spectrum.
Molecular formula C5H8O2. [CDCl3, 90 MHz, 298 K]
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 133
Home Work
Predict the structure using following NMR spectrum. Molecular
formula C5H6O. [CDCl3, 90 MHz, 298 K]
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 134
Home Work
Predict the structure using following NMR spectrum. Molecular
formula C7H7NO. [CDCl3, 90 MHz, 298 K]
CH-521 Course on Interpretative Molecular Spectroscopy; Course Instructor: Krishna P. Kaliappan 135