Chapter 13. Review.

Structure Determination:
Nuclear Magnetic Resonance

Prepared for CHM 247S students

by Dr. Stanislaw Skonieczny
Toronto 2010
 Nuclear Magnetic Resonance (NMR)
Three types of information present in an NMR spectrum:

1. Chemical shift - provides information about the nucleus

studied: electron density, magnetic environment.

2. Multiplicity (number of peaks in each group) - provides

information about other atoms that are near the ones that
produce the peaks.
3. Integral (the area under a group of peaks).
 The 1H NMR spectrum of an organic compound
provides information concerning:

1. The number of different types of hydrogens

present in the molecule

2. The relative numbers of the different types

of hydrogens

3. The electronic environment of the different

types of hydrogens

4. The number of hydrogen "neighbours"

a hydrogen has
 Equivalent or nonequivalent hydrogen atoms
Homotopic protons are those that, when
substituted for by deuterium, lead to the same
structure. Homotopic protons are always
equivalent, and will give one signal in the NMR.
Ha D Ha
Cl Cl Cl
C C C
Cl Cl Cl
Hb Hb D

5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
 Equivalent or nonequivalent hydrogen atoms

Enantiotopic protons are those that, when

substituted for by deuterium, lead to a pair of
enantiomeric structures. Enantiotopic protons
appear to be equivalent (and will usually give one
signal in the NMR)

Ha D D
Cl Cl Cl
C C C
Br Br Br
Hb Hb Ha
 Equivalent or nonequivalent hydrogen atoms

Enantiotopic protons
Ha
Cl
C
Br
Hb

5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
 Equivalent or nonequivalent hydrogen atoms
Diastereotopic protons are those that, when
substituted for by deuterium, lead to a pair of
diastereomeric structures. Diastereotopic
protons are not equivalent and will usually give
different signals in the NMR.
COOH COOH COOH

Ha Hb D Hb Ha D

HO CH3 HO CH3 HO CH3

 Equivalent or nonequivalent hydrogen atoms
Diastereotopic protons
COOH

Ha Hb

HO CH3

Hb Ha

3.10 3.00 2.90

7.60 7.50 7.40 7.30 7.20

9 8 7 6 5 4 3 2 1 0
 Peak Splitting

3H Splitting ofHasignal Ha
Ha
X "doublet"(d) by 3 x Hb nuclei:
Hb
X
Hb Hb

1H Jab Jab Jab

"quartet"(q)
1 3 3 1
Ha Hb

Hb spins

δ (p.p.m)
 Coupling

Coupling to equivalent neighbouring nuclei (AXn spin system)

Multiplicity rules:

M = n +1
n is the number of equivalent neighbour nuclei

n=0 1
n=1 1 1
n=2 1 2 1
n=3 1 3 3 1
n=4 1 4 6 4 1
 The chemical shift and shielding
Bobs = Bo (1 − σ ) σ - shielding constant
σ = σ dia + σ para
σ dia - diamagnetic shielding term (for nuclei with a spherically symmetric
charge distribution, e.g. hydrogen atoms); shielding by s electrons
σ para - paramagnetic shielding term (for nonspherical molecules); deshielding

(i) the contribution from the magnetic anisotropy of neighbouring groups

(ii) the ring current effect in arenes (σR),

(iii) the electric field effect (σe),

(iv) effects of intermolecular interactions (σi), e.g. hydrogen bonding

and solvent effects.

σ =σ local
dia +σ local
para +σ N +σR +σe +σi
 Inductive effect

H O
C H
H
H

3.97, 3.417 ppm

Anisotropic effect

H CH2 R
C C
H H
 The chemical shift and shielding
σ = σ dia
local
+ σ local
para + σ N + σ R + σ e + σ i

(i) the contribution from the magnetic anisotropy of neighbouring groups (σN),
 The chemical shift and shielding
σ = σ dia
local
+ σ local
para + σ N + σ R + σ e + σ i

(ii) the ring current effect in arenes (σR),

 Cl Cl
O Cl

Br

7 6 5 4 3 2 1 0
 Cl Cl

2 4
1 3

2.30 2.20 2.10 2.00 1.90 1.80 1.70 1.60 1.50 1.40 1.30 1.20 1.10
 Br

2
1 3

4.30 4.20 1.70 1.60

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
 Br
2
1 3

3.50 3.40 2.00 1.90 1.00 0.90 0.80

4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0

 13C NMR Spectrometry
13C isotope constitutes 1.08 % of natural carbon.
1. Carbon-carbon splitting can be ignored.
2. Carbon-hydrogen coupling is observed. The splitting
of signals indicates how many protons are bonded
to each carbon atom (N + 1 rule).
3. The number of different absorptions implies how many
different types of carbons are present.
4. The chemical shifts of signals suggest what types of
functional groups contain those carbons.
5. The chemical shift scale is large: 0 - 220 ppm.

6. Reference: TMS.
 2
COOH
1
3
2
CH3O 4
3

OCH3

1
4
COOH
 6 OCH3
COOH
5
1
5
4 2 OCH3 3
3
2
4 6
1
COOH
 Proton Chemical Shift Ranges*

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

 Carbon Chemical Shift Ranges*

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