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NMR is the most powerful tool available


for organic structure determination.
It is used to study a wide variety of nuclei:
1H
13C

15N

19F

31P

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Nuclei having nuclear spin(I) are NMR
active.
NUCLEAR ATOMIC ATOMIC
SPIN(I) MASS NUMBER

Half odd Odd or NMR active


integer even
Integer even Odd NMR active
zero Even Even NMR inactive

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A nucleus with an odd atomic number or
an odd mass number has a nuclear spin.
The spinning charged nucleus generates a
magnetic field.

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When placed in an external field,
spinning protons act like bar magnets.

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The magnetic fields
of the spinning
nuclei will align
either with the
external field, or
against the field.
A photon with the
right amount of
energy can be
absorbed and
cause the spinning
proton to flip.
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Energy difference is proportional to
the magnetic field strength.
E = h = h B0
2
Gyromagnetic ratio, , is a constant for
each nucleus (26,753 s-1gauss-1 for H).
In a 14,092 gauss field, a 60 MHz
photon is required to flip a proton.
Low energy, radio frequency.
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If all protons absorbed the same amount
of energy in a given magnetic field, not
much information could be obtained.
But protons are surrounded by electrons
that shield them from the external field.
Circulating electrons create an induced
magnetic field that opposes the external
magnetic field.

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Magnetic field strength must be
increased for a shielded proton to flip
at the same frequency.

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When electronic magnetic field is in
opposite direction of external
magnetic field then, such a proton is
called shielded proton.
When electronic magnetic field is in
same direction of external magnetic
field then, such proton is called
deshielded proton.

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Depending on their chemical
environment, protons in a molecule
are shielded by different amounts.

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The number of signals shows how many
different kinds of protons are present.
The location of the signals shows how
shielded or deshielded the proton is.
The intensity of the signal shows the
number of protons of that type.
Signal splitting shows the number of
protons on adjacent atoms. =>

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NMR = Nuclear Magnetic Resonance
Physical Principles:
Some (but not all) nuclei, such as 1H, 13C, 19F, 31P have nuclear spin.
A spinning charge creates a magnetic moment, so these nuclei can be thought of as
tiny magnets.
If we place these nuclei in a magnetic field, they can line up with or against the
field by spinning clockwise or counter clockwise.
N N

N - spin state, S - spin state,


favorable, unfavorable,
lower energy higher energy
S N
S S

A spinning nucleus with it's magnetic field A spinning nucleus with it's magnetic field
aligned with the magnetic field of a magnet aligned against the magnetic field of a magnet
Alignment with the magnetic field (called ) is lower energy than against the
magnetic field (called ). How much lower it is depends on the strength of the
magnetic field
Note that for nuclei that dont have spin, such as 12C, there is no difference in
energy between alignments in a magnetic field since they are not magnets. As such,
we cant do NMR spectroscopy on 12C.
NMR: Basic Experimental Principles
Imagine placing a molecule, for example, CH4, in a magnetic field.
We can probe the energy difference of the - and - state of the protons by
irradiating them with EM radiation of just the right energy.
In a magnet of 7.05 Tesla, it takes EM radiation of about 300 MHz (radio waves).
So, if we bombard the molecule with 300 MHz radio waves, the protons will absorb
that energy and we can measure that absorbance. at no magnetic field,
In a magnet of 11.75 Tesla, it takes EM radiation of about 500 MHz (stronger
there is no difference betee
- and - states.
magnet means greater energy difference
Graphical between
relationship the - and - state of the protons)
between
magnetic field (B o) and frequency ( E E = h x 300 MHz

for 1 H NMR absorptions

0T 7.05 T
Bo

But theres a problem. If two researchers want to compare their data using magnets
of different strengths, they have to adjust for that difference. Thats a pain, so, data
is instead reported using the chemical shift scale as described on the next slide.
The Chemical Shift (Also Called ) Scale
Heres how it works. We decide on a sample well use to standardize our
instruments. We take an NMR of that standard and measure its absorbance
frequency. We then measure the frequency of our sample and subtract its frequency
from that of the standard. We then then divide by the frequency of the standard.
This gives a number called the chemical shift, also called , which does not
depend on the magnetic field strength. Why not? Lets look at two examples.

Imagine that we have a magnet where our standard absorbs at 300,000,000 Hz (300
megahertz), and our sample absorbs at 300,000,300 Hz. The difference is 300 Hz,
so we take 300/300,000,000 = 1/1,000,000 and call that 1 part per million (or 1
PPM). Now lets examine the same sample in a stronger magnetic field where the
reference comes at 500,000,000 Hz, or 500 megahertz. The frequency of our
sample will increase proportionally, and will come at 500,000,500 Hz. The
difference is now 500 Hz, but we divide by 500,000,000 (500/500,000,000 =
1/1,000,000, = 1 PPM).
Its brilliant.
TMS is added to the sample as solvent.
Since silicon is less electronegative
than carbon, TMS protons are highly
shielded. Signal defined as zero.
Organic protons absorb downfield (to
the left) of the TMS signal.
In TMS there are 12 equivalent protons
so the intensity of the signal is high and
a distinguished peak observed.
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The difference in the absorption position of
a particular proton from the absorption
position of reference proton is called
chemical shift.
Measured in parts per million.
Ratio of shift downfield from TMS (Hz) to
total spectrometer frequency (Hz).
Same value for 60, 100, or 300 MHz
machine.
Called the delta scale.
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sample reference Hz 10 6

ppm

operating frequency
MHz

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More electronegative
atoms deshield more
and give larger shift
values.
Effect decreases with
distance.
Additional
electronegative atoms
cause increase in
chemical shift.

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Equivalent hydrogens have the same
chemical shift.

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The area under each peak is
proportional to the number of protons.
Shown by integral trace.

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When the molecular formula is known,
each integral rise can be assigned to
a particular number of hydrogens.

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Nonequivalent protons on adjacent
carbons have magnetic fields that may
align with or oppose the external field.
This magnetic coupling causes the proton
to absorb slightly downfield when the
external field is reinforced and slightly
upfield when the external field is opposed.
All possibilities exist, so signal is split. =>

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1H
- 1H Coupling
Youll notice in the spectra that weve seen that the signals dont appear as single
lines, sometimes they appear as multiple lines. This is due to 1H - 1H coupling (also
called spin-spin splitting or J-coupling). Heres how it works: Imagine we have a
molecule which contains a proton (lets call it HA) attached to a carbon, and that this
carbon is attached to another carbon which also contains a proton (lets call it HB). It
turns out that HA feels the presence of HB. Recall that these protons are tiny little
magnets, that can be oriented either with or against the magnetic field of the NMR
machine. When the field created by HB reinforces the magnetic field of the NMR
machine (B0 ) HA feels a slightly stronger field, but when the field created by HB
opposes B0, HA feels a slightly weaker field. So, we see two signals for HA
depending on the alignment of HB. The same is true for HB, it can feel either a
slightly stronger or weaker field due to HAs presence. So, rather than see a single
line for each of these protons, we see two lines for each.

For this line, H B is lined up For this line, H B is lined up


with the magnetic field against the magnetic field
(adds to the overall (subtracts from the overall
magnetic field, so the line magnetic field, so the line
comes at higher frequency) comes at lower frequency) HA HB

C C
HA HB
HA is split into two lines because HB is split into two lines because
it feels the magnetic field of H B. it feels the magnetic field of H A.
More 1H - 1H Coupling
What happens when there is more than one proton splitting a neighboring proton?
We get more lines. Consider the molecule below where we have two protons on one
carbon and one proton on another.

Note that the signal produced


by HA + HA' is twice the size
of that produced by H B

HA HB

HA' C C
HA + HA' HB
HA and H A' appear at the same HB is split into three lines
chemical shift because they are because it feels the magnetic
in identical environments field of H A and HA'
They are also split into two lines
(called a doublet) because they
feel the magnetic field of H B.
Why are There Three Lines for HB?

HB feels the splitting of both HA and HA. So, lets imagine starting with HB as a
single line, then lets turn on the coupling from HA and HA one at a time:

HB If uncoupled, H B would appear as a


singlet where the dashed line indicates
the chemical shift of the singlet.

Now, let's "turn on" HB - HA coupling. This splits


the single line into two lines
HA HB
Now, let's "turn on" HB - HA' coupling. This
splits each of the two new lines into two lines,
HA' C C
but notice how the two lines in the middle
overlap. Overall, we then have three lines.

Because the two lines in the middle overlap, that line is twice as big as the lines on
the outside. More neighboring protons leads to more lines as shown on the next
slide.
Splitting Patterns with Multiple Neighboring Protons
If a proton has n neighboring protons that are equivalent, that proton will be split
into n+1 lines. So, if we have four equivalent neighbors, we will have five lines, six
equivalent neighbors well, you can do the math. The lines will not be of equal
intensity, rather their intensity will be given by Pascals triangle as shown below.
no. of neighbors relative intensities pattern example
0 1 singlet (s)

H H
1 1 1 doublet (d)
C C
H H
2 1 2 1 triplet (t) C C H
H H
3 1 3 3 1 quartet (q) C C H
H H H H

4 1 4 6 4 1 pentet C C C H

H H H H

5 1 5 10 10 5 1 sextet H C C C H
H H H H

6 1 6 15 20 15 6 1 septet H C C C H
H H

We keep emphasizing that this pattern only holds for when the neighboring protons
are equivalent. Why is that? The answer is two slides away.
If a signal is split by N equivalent
protons,
it is split into N + 1 peaks.

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Equivalent protons do not split each other.
Protons bonded to the same carbon will
split each other only if they are not
equivalent.
Protons on adjacent carbons normally will
couple.
Protons separated by four or more bonds
will not couple.
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Distance between the peaks of multiplet
Measured in Hz
Not dependent on strength of the
external field
Multiplets with the same coupling
constants may come from adjacent
groups of protons that split each other.
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a c
H H
C C
Hb

Signals may be split by adjacent


protons, different from each other,
with different coupling constants.
Example: Ha of styrene which is split by
an adjacent H trans to it (J = 17 Hz)
and an adjacent H cis to it (J = 11 Hz).
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a c
H H
C C
Hb

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Usually, two protons on the same C are
equivalent and do not split each other.
If the replacement of each of the protons
of a -CH2 group with an imaginary Z
gives stereoisomers, then the protons are
non-equivalent and will split each other.
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a c c
H H H OHa
C C
dH Hb
Hb

CH3
H Cl
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aH Hb
Cl

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12C has no magnetic spin.
13C has a magnetic spin, but is only 1%
of the carbon in a sample.
The gyromagnetic ratio of 13C is one-
fourth of that of 1H.
Signals are weak, getting lost in noise.
Hundreds of spectra are taken,
averaged.
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Nuclei in a magnetic field are given a
radio-frequency pulse close to their
resonance frequency.
The nuclei absorb energy and precess
(spin) like little tops.
A complex signal is produced, then
decays as the nuclei lose energy.
Free induction decay is converted to
spectrum. =>

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Resonance frequency is ~ one-fourth,
15.1 MHz instead of 60 MHz.
Peak areas are not proportional to
number of carbons.
Carbon atoms with more hydrogens
absorb more strongly.
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It is unlikely that a 13C would be adjacent
to another 13C, so splitting by carbon is
negligible.
13C will magnetically couple with
attached protons and adjacent protons.
These complex splitting patterns are
difficult to interpret.
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To simplify the spectrum, protons are
continuously irradiated with noise, so
they are rapidly flipping.
The carbon nuclei see an average of all
the possible proton spin states.
Thus, each different kind of carbon gives
a single, unsplit peak.
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13C nuclei are split only by the protons
attached directly to them.
The N + 1 rule applies: a carbon with N
number of protons gives a signal with
N + 1 peaks.
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The number of different signals indicates
the number of different kinds of carbon.
The location (chemical shift) indicates
the type of functional group.
The peak area indicates the numbers of
carbons (if integrated).
The splitting pattern of off-resonance
decoupled spectrum indicates the
number of protons attached to the
carbon. =>

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