n Nuclear Magnetic Resonance

NMR

CHY 416 Organic Chemistry

Prof. Dr. Ali Hashem Essa
Lecture 5

What is NMR?
How does NMR work?
How is a three dimensional structure elucidated?
 1H NMR Integration
• Modern NMR spectrometers automatically calculate and plot the value of each
integral in arbitrary units.
• The ratio of integrals to one another gives the ratio of absorbing protons in a
spectrum.
• Note that this gives a ratio, and not the absolute number, of absorbing protons.

Prof. Dr. Ali Hashem Essa Department of Chemistry

Prof. Dr. Ali Hashem Essa Department of Chemistry
 1H NMR of Neopentyl Bromide

Prof. Dr. Ali Hashem Essa Department of Chemistry

 1H NMR of Neopentyl Bromide

Prof. Dr. Ali Hashem Essa Department of Chemistry

 integration

H3C CH3
C
a C a
H3C CH3

a 12 H a 12 H

CH3 a

a b

CH3
a 6H a
a 6H
b 4H
Prof. Dr. Ali Hashem Essa Department of Chemistry
 a a b
CH3
H3C C CH3 CH3CH2-Br
a Br a
a 3H
a 9H b 2H

a b c a b a
CH3CH2CH2-Br CH3CHCH3
Cl
a 3H
b 2H a 6H
c 2H b 1H

Prof. Dr. Ali Hashem Essa Department of Chemistry

 b d c a b a b
CH3CHCH2CH3 Cl-CH2CH2CH2-Cl
Br
a 3H a 2H
b 3H b 4H
c 2H a
d 1H CH3
CH2Cl
b
a 3H
c b 2H
c 4H

Prof. Dr. Ali Hashem Essa Department of Chemistry

 4.Splitting pattern: how many neighboring hydrogens.

Often a group of hydrogens will appear as a multiplet

rather than as a single peak.

Multiplets are named as follows:

Singlet (s) Quintet (quin)

Doublet (d) Sixtet (six)
Triplet (t) Septet (sept)
Quartet (q) Multiplet (m)
This happens because of interaction with neighboring
hydrogens and is called
SPIN-SPIN SPLITTING
Spin-spin coupling
Prof. Dr. Ali Hashem Essa Department of Chemistry
 Rules for Spin-Spin Splitting
n Equivalent protons do not split each other

n Protons that are farther than two carbon atoms apart do not
split each other

Prof. Dr. Ali Hashem Essa Department of Chemistry

 1H NMR—Spin-Spin Splitting
If Ha and Hb are not equivalent, splitting is observed when:

Splitting is not generally observed between protons separated by more

than three sbonds.

Prof. Dr. Ali Hashem Essa Department of Chemistry

 The Origin of 1H NMR—Spin-Spin Splitting
• Spin-spin splitting occurs only between nonequivalent protons
on the same carbon or adjacent carbons.
Let us consider how the doublet due to the CH2 group on
BrCH2CHBr2 occurs:
• When placed in an applied field, (B0), the adjacent proton
(CHBr2) can be aligned with (↑) or against (↓) B0. The likelihood
of either case is about 50% (i.e., 1,000,006 ↑ vs 1,000,000 ↓).
• Thus, the absorbing CH2 protons feel two slightly different
magnetic fields—one slightly larger than B0, and one slightly
smaller than B0.
• Since the absorbing protons feel two different magnetic fields,
they absorb at two different frequencies in the NMR spectrum,
thus splitting a single absorption into a doublet, where the two
peaks of the doublet have equal intensity.
Prof. Dr. Ali Hashem Essa Department of Chemistry
 The Origin of 1H NMR—Spin-Spin Splitting
The frequency difference, measured in Hz, between two peaks of the
doublet is called the coupling constant, J.

Prof. Dr. Ali Hashem Essa Department of Chemistry

 The Origin of 1H NMR—Spin-Spin Splitting
Let us now consider how a triplet arises:

• When placed in an applied magnetic field (B0), the adjacent

protons Ha and Hb can each be aligned with (↑) or against (↓) B0.
• Thus, the absorbing proton feels three slightly different
magnetic fields—one slightly larger than B0(↑ a ↑ b). one slightly
smaller than B0(↓ a ↓ b) and one the same strength as B0 (↓ a ↑ b).

Prof. Dr. Ali Hashem Essa Department of Chemistry

 The Origin of 1H NMR—Spin-Spin Splitting
• Because the absorbing proton feels three different magnetic
fields, it absorbs at three different frequencies in the NMR
spectrum, thus splitting a single absorption into a triplet.
• Because there are two different ways to align one proton with B0,
and one proton against B0—that is, ↑ a ↓ b and ↓ a ↑ b—the middle
peak of the triplet is twice as intense as the two outer peaks,
making the ratio of the areas under the three peaks 1:2:1.
• Two adjacent protons split an NMR signal into a triplet.
• When two protons split each other, they are said to be coupled.
• The spacing between peaks in a split NMR signal, measured by the
J value, is equal for coupled protons.

Prof. Dr. Ali Hashem Essa Department of Chemistry

 For 2 protons:
• Each proton has its own spin
• The spin can be +½ or –½
• We can draw all the combinations:

High; Low;
opposed aligned

Relative spin population 1 2 1

Prof. Dr. Ali Hashem Essa Department of Chemistry
 For 3 protons:
• Each proton has its own spin
• The spin can be +½ or –½
• We can draw all the combinations:

High; Low;
opposed aligned

Relative spin
population 1 3 3 1
Prof. Dr. Ali Hashem Essa Department of Chemistry
The principle of multiplicity: the n + 1 rule and peak splitting

n is the number of adjacent

(neighboring) protons that
Multiplicity, m = n + 1
are in a different
chemical environment
Pattern follows Pascal’s triangle

Prof. Dr. Ali Hashem Essa Department of Chemistry