FOOD CHEMISTRY

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6 MARCH 2003 1

Proton NMR
H-1 NMR is frequently referred to as proton
NMR.
Unlike C-13 NMR, the range of proton NMR
is relatively narrow: 0-12 ppm.
Like C-13 NMR, electronegativity affects the
chemical shift of the hydrogen atoms. This
is shown on the next page.

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Electronegativity and Chemical

Shift
The greater the electronegativity of a halogen, the further
downfield will be the chemical shift of the hydrogen.

F C H

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Cl

C H

Br

C H

C H

Electronegativity and Chemical

Shift

Tertiary hydrogens resonate further downfield

than primary hydrogens.
H

C C C

C C C

C C H

H C H

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An Overview of Chemical Shift

Regions

Protons on carbon next to saturated centers absorb

in the region of 0-1.5 ppm. Thus, the alkane
portions of most organic molecules show complex
absorption in this region.
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An Overview of Chemical Shift

Regions

Protons on carbon next to unsaturated centers

(allylic, benzylic, next to carbonyl), show
absorptions in this region, just downfield from
other alkane absorptions.
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An Overview of Chemical Shift

Regions

Protons on carbon next to electronegative atoms

(halogen, O, N) are deshielded because of the
electron-withdrawing ability of these atoms.
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An Overview of Chemical Shift

Regions

Protons on double-bond carbons (vinylic protons)

are strongly deshielded by the neighboring pi
electrons and thus absorb in this characteristic
range.
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An Overview of Chemical Shift

Regions

Protons on aromatic rings (aryl protons) are

strongly deshielded by the pi electrons of the ring
and absorb in this characteristic range.
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Proton NMR Spectroscopy Correlation

Chart

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Proton NMR Spectroscopy Correlation

Chart

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Proton NMR Spectroscopy Correlation

Chart

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Proton NMR Spectroscopy Correlation

Chart

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Anisotropy
Since the electronegativity of carbon follows the order:
sp

>

sp2

>

sp3

then protons on these carbons should have the following

order of chemical shifts.
C

H
C

C H

Instead, we see the following order:

H
C

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Anisotropy
Anisotropy is the dependence of the
properties of a substance on direction.
The protons in a compound, especially those
on double bonds, triple bonds, and aromatic
rings, can be magnetically shielded or
deshielded by the pi clouds.
This shielding or deshielding is dependent on
the position of the protons relative to the
electrons clouds.
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Anisotropy
Consider the influence of an induced magnetic field on the chemical
shift of the protons of ethene and ethyne

H
H C C H
H
H

Ho

C
C
H

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Anisotropy
In the case of ethene, the lines of force of the induced magnetic field,
caused by the circulating pi electrons, reinforce the applied field. The
protons are thus deshielded.

H
H C C H
H
H

Hi

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Ho

C
C
H

Hi

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Anisotropy
In the case of ethyne, the lines of force of the induced magnetic field,
caused by the circulating pi electrons, oppose the applied field. The
protons are thus shielded.

H
H C C H
H
H

Hi

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Ho

C
C
H

Hi

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Integration of Proton NMR

Absorptions
By running an NMR spectrum in integrating mode, it is possible to

determine the relative numbers of hydrogens that produce each type of

absorption. The height in each step of the integration is proportional
to the number of hydrogens.

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Spin-Spin Splitting in Proton NMR

Spectra
In C-13 NMR, a proton on a C-13 atom can
cause its resonance to be split into a
doublet. If two hydrogens are on a carbon
(CH2), it can be split into a triplet. Finally,
three hydrogen on a carbon (CH3) produce a
quartet.
In H-1 NMR, protons couple with protons
on adjacent carbon(s).
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Spin-Spin Splitting in Proton NMR

Spectra
Coupling can occur between the two
hydrogens of this type of system.
C-C
HH
While both carbons could couple with each
hydrogen, the percentage of C-13 in the
sample is very low, and coupling due to
carbon is not observed.
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Spin-Spin Splitting in Proton NMR

Spectra
The coupling of one proton with another results in
what is termed spin-spin splitting. Consider the
coupling in chloroethane.

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Spin-Spin Splitting in Proton NMR

Spectra

The splitting pattern of a resonance is determined by the possible spin

orientations of the adjacent hydrogens.

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Spin-Spin Splitting in Proton NMR

Spectra
The area under the peaks of a multiplet can
be determined from Pascals Triangle.

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Spin-Spin Splitting in Proton NMR

Spectra
Predict the patterns for some common proton groupings seen in
organic compounds.

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Coupling Constants
The distance between the peaks in a
multiplet is an indication of the
effectiveness of spin-spin coupling.
This distance is referred to as the coupling
constant, J, and is reported in units of Hz.
The coupling constant can be used to
provide additional information about the
structure of a compound.
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Coupling Constants
Here are some common coupling constants.

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Coupling Constants

Consider the spectrum of trans-cinnamaldehyde. The coupling constants indicate

that the geometry is trans and not cis. This is seen in more detail on the next page.

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Coupling Constants and Complex

Coupling
Notice that the
coupling of
protons 2 and
3 is about 15
Hz, indicating
a trans
geometry.

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Coupling Constants and Complex

Coupling
Proton 2
experiences a
complex
pattern due to
different
coupling
constant to
proton 3
compared to
proton 1.

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The Effect of Magnetic Field

Strength
Consider the spectrum of a compound with three resonances with very
similar chemical shifts.

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Spectral Interpretation 1
Determine the structural formula for the compound that gives the
following NMR spectrum.

C8H10O
5H

2H
3H

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Answer

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Spectral Interpretation 2
Determine the structural formula for the compound that gives the
following NMR spectrum.

C8H10
5H
2H

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Answer

3H

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Spectral Interpretation 3
Determine the structural formula for the compound that gives the
following NMR spectrum.

C8H9Br
5H

3H

1H

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Answer

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Spectral Interpretation 4
Determine the structural formula for the compound that gives the
following NMR spectrum.

C4H8O

3H
3H

2H

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Answer

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Spectral Interpretation 5
Determine the structural formula for the compound that gives the
following NMR spectrum.

C3H6Br2
4H
2H

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Answer

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Spectral Interpretation 6
Determine the structural formula for the compound that gives the
following NMR spectrum.

C5H10O

3H

3H
2H

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Answer

2H

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H-1 NMR Spectroscopy

The End

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Spectral Interpretation 1
Determine the structural formula for the compound that gives the
following NMR spectrum.

C8H10O
5H

CH2OCH3

2H
3H

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Next Problem

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Spectral Interpretation 2
Determine the structural formula for the compound that gives the
following NMR spectrum.

C8H10
5H

CH2CH3

2H

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Next Problem

3H

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Spectral Interpretation 3
Determine the structural formula for the compound that gives the
following NMR spectrum.

C8H9Br
Br

5H
1H

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CHCH3

Next Problem

3H

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Spectral Interpretation 4
Determine the structural formula for the compound that gives the
following NMR spectrum.

C4H8O

3H
3H

O
CH3CCH2CH3

2H

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Next Problem

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Spectral Interpretation 5
Determine the structural formula for the compound that gives the
following NMR spectrum.

C3H6Br2
4H
Br

2H

Br

CH2CH2CH2

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Next Problem

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Spectral Interpretation 6
Determine the structural formula for the compound that gives the
following NMR spectrum.

C5H10O

3H

3H

CH3CCH2CH2CH3

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2H

End

2H

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07/10/16

Thank You!

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