Lecture Notes

Chem 51A
S. King

Chapter 14 Nuclear Magnetic Resonance

Spectroscopy
Nuclear Magnetic Resonance (NMR) spectroscopy uses energy in the radiowave
portion of the electromagnetic spectrum. The nuclei of atoms such as hydrogen and
carbon absorb radio-frequency radiation when placed in a magnetic field.

Principle: Nuclei of atoms with an odd mass number such as 13C and 1H (which
have a spin number of 1/2) have nuclear spin. Consider a proton, for
example:

N
+
S

spinning proton loop of current bar magnet

The movement of charge is like an electric current in a loop of wire. It generates a

magnetic field, and resembles a small bar magnet. When placed in a magnetic field,
the nuclei align themselves either with or against an applied magnetic field, Ho.

+
+ +
higher energy
+ +
!E Ho (applied magnetic field)
+ +

+ +
+

no external field lower energy

Ho increases

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Slightly more align themselves with (lower energy) than against the magnetic field.
Absorption of energy (radio frequency pulse, ν) causes more nuclei to align against
the magnetic field, a higher energy state.
☞ Once the radiofrequency pulse is discontinued, the nuclei relax back to the
ground state, releasing energy. The energy released is quantized, and is
dependent on the environment of the nuclei.
The environment of a proton is critical in determining how it will react to an
applied magnetic field. A typical proton is surrounded by electrons that partially
shield it from the external magnetic field. This shielding results from the electron's
ability to circulate and generate a small "induced" magnetic field that opposes the
externally applied field.

An example of a 1HNMR Spectrum:

H3C CH2 Br

4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 pp

Important points:
1) The signals are called chemical shifts and are reported in ppm (δ). The signals
are referenced to TMS (tetramethylsilane) which is set at 0 ppm.

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 distance downfield from TMS (Hz)
! = chemical shift (ppm) =
operating frequency of spectrometer (MHz)

2) The protons of TMS are more shielded than most organic compounds, because
they have a higher electron density around them.
Si CH3 compare with: C CH3

3) The terms upfield and downfield describe the relative locations of signals,
Upfield means to the right (towards TMS), and downfield means to the left
(away from TMS). Protons that are shielded are moved towards TMS (upfield),
and protons that are deshielded are moved away from TMS.

4) The area underneath each signal is displayed in the form of a line of integration
superimposed on the original spectrum. The vertical rise of the integration line
over each signal is proportional to the area under that signal, which, in turn, is
proportional to the number of H’s giving rise to that signal. Newer NMR
spectrometers automatically calculate and plot the value of each integral in
arbitrary units.

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Example: Give the number of protons corresponding to each signal in the
following 1HNMR of methyl tert-butyl ether (MBTE), a gasoline additive:

CH3
H3C C O CH3
CH3

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

5) Hydrogens in identical environments (aka: equivalent hydrogens) give the same

1
HNMR signal.
Examples:
CH3
H3C C CH2 CH3
H

H Cl
Cl H H
C C
H H
H H
H

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Q. How does the structure of a compound affect peak position (chemical shift)?

C C H
2.1!2.6

C H

2.3!2.9
H
O 4.5!6.0
C H
9!10
C H
1.6!2.8
H
O C H C H
6.5!8.0 3.2!4.2 0.7!1.7

C C H
2.5

"
(ppm)
11 10 9 8 7 6 5 4 3 2 1 0

Protons bonded to oxygen: I C H

O 2.2!4.2

C O H ! 10 ! 13 Br C H
2.7!4.2
R O H !1!4
! 4 ! 6 in DMSO Cl C H
3.3!4.2
Ph O H ! 4 ! 8
! 5 !12 (w/ intramolecular N C H
hydrogen bond)
2.3!3.0

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1. The electron density of substituents in a compound affects peak position.

a) Electronegative substituents shift things downfield. They are deshielding.

CH3I CH3Br CH3Cl CH3F

! 2.16 ! 2.68 ! 3.05 ! 4.26

b) There is a rapid falloff with distance (as the electronegative group gets
farther away, the deshielding affect rapidly decreases.)

RO CH3 RO CH2CH3
! 3.3 ! 1.58

c) Each additional electronegative group increases the chemical shift by a

predictable increment:

CH3Cl CH2Cl2 CHCl3

! 3.1 ! 5.3 ! 7.3

d) In a similar environment, the signal for methyl protons (−CH3) occurs at a

lower frequency than the signal for methylene protons (−CH2−), which in
turn occurs at a lower frequency than the signal for a methine proton (−CH−):

CH3
H3 C C CH2 CH3
H

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2. Special effects are seen in protons on π bonds due to magnetic anisotrophy.

ring
current

Ho

R
Ho O C

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 R H

Ho C C
R H

ring
current
H

C
Ho

3. Protons attached to heteroatoms are highly variable and sometimes absent.

RO H

PhO H

RCO2 H

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4. The chemical shifts of protons attached to sp2-hybridized carbons are
affected by substituents bonded to the π-system.
 The protons ortho and para to electron donating and electron-withdrawing
groups on a benzene ring show distinct upfield and downfield shifts:

NH2

7 6
OCH3

7
CH3

7
NO2

8 7 6
8.0 7.5 7.0 6.5

 Electron donating and electron withdrawing groups also affect peak

position of protons bonded to alkenes:
4.18 6.55 5.03
H H O H

O N CH3 1.71
4.04 H CH3 3.50 5.87 H O 4.97 H

H H H
6.47 7.12 5.70

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Q. Why are peaks in HNMR split?
A. This is due to spin-spin coupling. We must consider the small local magnetic
field caused by hydrogen nuclei on adjacent carbons.
Example 1:

O
Cl
Ha
Cl
Hb

9 8 7 6 5 4 3 2 1 0
PPM

Looking at Ha:
• Ha is affected by Hb because it is on an adjacent carbon. But Hb exists in two
spin states:
Ha sees:

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The magnitude of the nuclei splitting is called the coupling constant J and is
usually reported in Hz.

Example 2:

H3C CH2 Br

3.45 ppm 1.70 ppm

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

Consider Hb in detail:

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If a hydrogen is adjacent to two different hydrogens, you can get complex splitting
patterns:
Example 3:
H
H

5.80 5.30

6.8 6.7 6.6

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
9.5 9.0 8.5

6.8 6.7 6.6 5.80

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Special features of spin-spin coupling:

a) Chemical shift equivalent protons don't couple to each other.

b) N+1 Rule: Protons with N equivalent H’s on adjacent carbons are split into
N+1 peaks, with the area ratios given by the appropriate line of Pascal's
Triangle.

Approximate Relative Peak Intensities of Symmetrical Multiplets

# EQUIVALENT # of peaks (multiplicity) Area ratios
adjacent protons (N) (N+1) (Pascal’s Triangle)
0 1 (singlet) 1
1 2 (doublet) 1 1
2 3 (triplet) 1 2 1
3 4 (quartet) 1 3 3 1
4 5 (quintet) 1 4 6 4 1
5 6 (sextet) 1 5 10 10 5 1
6 7 (septet) 1 6 15 20 15 6 1

• Splitting can be difficult to resolve if greater than 3 adjacent protons are

present.

c) Two groups of protons coupled to each other must have the same J value
(coupling constant).
5.681
5.668
5.655

4.103
4.090

Br2CH CH2Br

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

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 • Unlike chemical shifts, which are measure in ppm (parts per million),
coupling constants (J values) are measured in Hz. To get J values in Hz, take
the chemical shift difference and multiply it by the operating frequency of the
spectrometer.

• The signals for each are often point towards each other, distorting the
idealized relative peak intensities.

d) When hydrogen atoms of similar chemical shift interact, complex patterns arise,
and the signal appears as a multiplet.

e) The magnitude of the coupling constant is somewhat diagnostic of the relative

spatial orientation of the coupling nuclei.
Ha Ha
Ha Hb
H
C C Hb Hb a
Hb
6 ! 8 Hz 8 ! 14 Hz 0 ! 5 Hz 0 ! 5 Hz

Ha Ha Hb Ha Ha
C C C C C C
Hb Hb Hb
11 !18 Hz 5 ! 10 Hz 0 ! 5 Hz 8 ! 11 Hz

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 f) Under usual conditions, an OH proton does not split the NMR signal of adjacent
protons, and the signal due to an OH proton is not split by adjacent protons:

CH3CH2 OH

6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

Why? Protons on electronegative elements rapidly exchange between molecules

in the presence of trace amounts of acid or base. It is as if the CH2 group in
ethanol never “feels” the presence of the OH proton because the OH proton is
moving so rapidly from one molecule to the other.
How?

(If care is taken to remove all traces of acid and base, splitting will occur)

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g) Resolution: Many compounds give spectra whose protons absorb so close to
each other that their multiplets overlap. In addition, when two or more protons
split each other by a coupling constant that is nearly as large as their chemical
shift separation, second-order effects can alter the shapes of the multiplets,
making them difficult to interpret. Some of these issues can be resolved by
going to higher spectrometer frequencies and magnetic fields.

Compare the following two HNMRs:

H3C CH2 CH2 CH2 Br

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

H3C CH2 CH2 CH2 Br

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

Q. Both spectra are plotted on a δ 0 −10 scale, so the peaks come at the same
positions, but the splitting appears to be smaller in the 300MHz instrument. But
chemical shift and coupling constants are constant! How can this be?

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A. The coupling constants in the 300MHz spectrum are exactly the same as in the in
the 60 MHz instrument, but the sweep width of the 300 MHz spectrum is five
times as large, making the coupling constants appear smaller.

To produce separate signals with clean splitting patterns, the difference in

chemical shifts (Δν in Hz) of two adjacent coupled protons must be at least 10
times the value of the coupling constant (J).

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h) Sometimes a signal is split by two or more different kinds of protons with similar
coupling constants. In propyl iodide, for example, the protons on the middle
carbon (Hb) are split by two different types of protons (Ha, and Hc). The
coupling constants for these two protons are similar (Jab = 7.3 Hz and Jac = 6.8
Hz.) The spectrum shows the Hb signal as a sextet, almost as though Hb was
coupled to 5 equivalent protons. The second trace, enlarged and offset, shows
that the pattern is not a perfect sextet. It is actually a quartet of triplets:

H3C CH2 CH2 I

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

Taking this HNMR on a higher field instrument gives even better resolution:

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

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How do you interpret an 1HNMR spectrum?
1) Evaluate the units of unsaturation (as for IR) from the molecular formula.
2) If you have an IR of the compound, analyze the IR spectrum to determine
functional groups.
3) Look for major features in the NMR first before worrying about details.
Consider the following:

a) Broad singlets are usually due to hydrogens bound to O or N. If a broad

singlet appears above 10 ppm, you probably have a carboxylic acid.
O

O H N H C O H

b) Absorptions around 3 or 4 ppm are typical for hydrogens on carbons bonded

to electronegative groups such as halogens or oxygen.

Cl C H Br C H I C H O C H

c) Absorptions from about 2.1-2.5 ppm usually mean you have protons adjacent
to a carbonyl.
O O O

R C CH3 R C CH2CH3 R C CH(CH3)2

d) A sharp singlet at 2.5 ppm is consistent with a proton on a terminal alkyne.

R C C H

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e) Absorptions from about 9-10 ppm are consistent with an aldehyde proton.
An aldehyde proton has a very small coupling constant with protons on the
carbon adjacent to the aldehyde carbonyl, so the peak can often appear as a
singlet, especially if the NMR is taken on a lower field instrument.
O

RCH2 C H

f) Absorptions around 7-8 ppm are typical for hydrogens bonded to aromatic
rings.
EWG EDG
H H H

g) Absorptions between 5-6 ppm are consistent with vinyl protons. Coupling
constants can be measured and used to determine whether you have a cis,
trans, or germinal substitution pattern. If you don’t have any units of
unsaturation to account for a alkene, you may have a hydrogen on a carbon
bonded to more than one electronegative group.

H H H H
or CH2Cl2 CH3OCH2OH
H H

h) Vinylic protons can be moved significantly downfield when electron-

withdrawing groups are bonded to the π-system.

H O H O
N
OCH3 O
H H

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 i) Look for common splitting patterns:

CH2CH3 CH(CH3)2

3 2 1 4 3 0 2 1
PPM PPM

C C CH2 CH2

H H

6 5 4 4 3 3
PPM PPM

4) Now for the details: Look at the relative integrations to determine how many
kinds of hydrogens there are.
5) Correlate H's with diagnostic hydrogens listed in the table given.
6) Propose structures. Correlate the splitting patterns with the structures.

II. 13C Nuclear Magnetic Resonance

Any nucleus with a spin number of 1/2 can be studied by NMR spectroscopy. The
nucleus of 13C has a spin number of 1/2 just like hydrogen. The natural abundance
of 13C, however, is only 1% so there is a huge sensitivity problem. A 13CNMR is
expected to be about 1% as intense as a 1HNMR spectrum.

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 • must use more concentrated samples and/or scan longer to get a
comparable spectrum.
The 13C principles are basically the same as 1HNMR, but some aspects are unique
to 13CNMR:
1) Coupling between carbons is generally not observed. Why?

CH3
H3C C CH2CH3
CH3

2) The range of chemical shifts is very large compared to 1HNMR:

aromatic C C C C Cl, C Br

C O C C C O alkanes

200 150 100 50 0

TMS

3) Coupling between carbon and hydrogens (13C −1H) does occur. This presents
its own problems:

• Typical coupling constants are large (20 to 120 Hz for directly attached
protons, but longer range coupling is also observed.) Protons on
carbons one and two and three carbons away can also cause splitting!

CH3
H3C C CH2CH3
CH3

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 • Typically, the spectra are run proton-decoupled to simplify the
analysis

13
4) CNMR spectra are not integrated.

5) We will rely on two features of 13CNMR spectra to solve structures in this class:

Sample problem: How many lines are observed in the 13CNMR spectra of the
following compound? Which carbon signal would be the
furthest downfield?

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Compare the 1HNMR and 13CNMR for cholesterol:

H3C CH3

CH3
CH3 H

H H
HO

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

194