Proton Nuclear Magnetic Resonance (1H-NMR) Spectroscopy

Theory behind NMR:

In the late 1940s, physical chemists originally developed NMR spectroscopy to study
different properties of atomic nuclei, but later found it to be useful in determining the
molecular structure of organic compounds. The theory behind NMR comes from the
spin, I1 of a nucleus. Just as electrons have a +1/2, -1/2 spin, certain nuclei also
experience charged spins that create a magnetic field (called the magnetic moment),
which allows chemists to study them using NMR. Nuclei with even numbers of both
neutrons and protons experience NO spin and nuclei with odd numbers of both neutrons
and protons have integer spins. Nuclei that have the sum of protons and neutrons equal
to an odd number (like 1H and 13C) have half-integer spins. When there is no external or
applied magnetic field (B0), the nuclear spins orient randomly; however, when there is an
applied magnetic field, the nuclei orient themselves with or against the larger applied
field. The -spin state is parallel to the applied force and has lower energy than the _spin state that is antiparallel to the applied force. The energy difference (_ E) between
the - and _-spin states depends on the strength of the applied magnetic field. The
greater the strength of the applied magnetic field, the greater is the _ E between the and _-spin states2. The _ E between the - and _-spin state is ~0.02 cal mol-1, which lies
in the radio frequency region. The emitted energy in this region produces an NMR
signal.

Diagram 1
*Addition of energy results in a spin flip

Diagram 2
*nuclei shed excess energy in a
process called relaxation

1 http://www.chemistry.uoguelph.ca/driguana/NMR/SPIN.HTM (11/7/06)
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p. 527, P.Y. Bruice, Organic Chemistry (4th)
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 1Diagram 34
*As the applied magnetic field increases, so does the energy
difference between - and _-spin states3
http://www.chemistry.uoguelph.ca/driguana/NMR/ENERGIES.HTM

NMR Spectrum

Interpreting 1H NMR Spectra

Four types of Information from NMR:
1. Number of signals: Protons within a compound experience different
magnetic environments, which give a separate signal in the NMR spectrum
Equivalent: Protons that reside in the same magnetic environment are termed chemically
equivalent protons5. As a general rule of thumb, Hs in CH3 and CH2 groups are usually
equivalent. Symmetrical compounds, such as benzene, are also equivalent; however,
since many compounds are not symmetrical, it is important to know how to identify
nonequivalent protons.
Protons that are different in any way (even in their
stereochemistry) are not equivalent and will absorb at different frequencies (give a
separate signal on the NMR spectra).
Examples6: All of these compounds have 2 signals in their NMR spectrum

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(A)
4 Hs are on a plane of symmetry
with each other. CH3 are also on
a plane of symmetry so 2 signlas

(B)
The CH2 Hs are attached to a C
thats attached to a Cl. The CH3
Hs are attached to the same C
and have the same neighbors.

(C)
One CH3 is attached to an O,
while the other CH3 is attached
to a C.

2. Position of signals (chemical shift): The position on the horizontal

frequency scale at which the equivalent proton signals occur (_ E) is called a
chemical shift7 (measured in ppm). Protons generally sense 3 different
magnetic fields: magnetic field of the Earth, the NMR spectra, and different
protons in the molecule. Since the magnetic fields of the Earth and NMR
spectra are felt similarly by all the protons in the molecule, the chemical shift
depends only on the varying local magnetic fields from the neighboring
protons.
Reference compound: Tetramethylsilane (TMS)
In order to standardize the NMR spectra, the chemical shifts are
positioned in relation to a reference proton set at 0.00 ppm.
Tetramethylsilane, (CH3)4Si, is the standard for H1 NMR. TMS is
practical as a reference compound because of its inert quality that
prevents it from reacting with the sample and its highly volatile nature
that makes it easy to evaporate out of samples. Few compounds have a lower frequency
reading than TMS and it has 12 equivalent protons that read strongly on the NMR
spectra.
What influences a chemical shift?
Shielding effects: Under an applied magnetic field, circulating electrons in the electron
cloud produce a small opposing magnetic field, ultimately decreasing the effective
magnetic field felt by the proton, shifting the signal to the right (or upfield). This effect,
in which the electron cloud shields the proton from the applied magnetic field is called
local diamagnetic shielding8.
Electronegativity and deshielding1: Hs that are attached to more electronegative atoms
experience higher chemical shifts. Electronegative atoms also remove electrons from the
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electron cloud, which decreases their density and results in less shielding; hence
electronegative atoms are said to deshield the proton and cause it to have a higher
chemical shift, moving it to the left (or downfield). The magnitude of the deshielding
effect, however, rapidly decreases as the distance between the proton and electronegative
atom increases (refer to NMR spectrum diagram above).
Example9: Literature values of the methyl chemical shift as it moves away from bromine
CH3Br

CH3CH2Br

CH3CH2CH2Br

CH3CH2CH2CH2Br

2.69 ppm

1.66 ppm

1.06 ppm

0.93 ppm

Magnetic Anisotropy (_-system ring currents) 9 : In molecules

containing _ orbitals, anisotropy (having a different effect along
different axes) is responsible for different shielding effects on a proton
relative to the applied magnetic field since _-orbitals arent spherically
symmetrical.
Characteristic Chemical Shifts10: tables of typical chemical shifts
can be made since similar functional groups experience similar
chemical shifts; however, due to the variability between molecules,
one cannot assume a certain frequency corresponds to one type of proton. An exception
occurs with a range of 6.5-8.0 ppm, which usually indicates benzene ring protons.
3. Relative Intensity of Signals (Integration): The area under the signals
(integration11) corresponds to the number of protons responsible for that
signal. Therefore, the relative intensities of the signal are proportional to the
relative number of proton equivalents. It is important to remember that
integration only provides ratios of protons, not the absolute number. For
convenience in calculating the relative signal strengths, the smallest
integration is set to 1 and the other values are converted accordingly.

p530, P.Y. Bruice, Organic Chemistry (4th)

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p530, P.Y. Bruice, Organic Chemistry (4th)
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Diagram 412
*Integrals appear as lines on the spectra above the signals, in which
their heights correspond to the integration ratios. In this spectra,
the OH H is correctly determined to be in a 3:1 ratio with the 3
CH3 Hs

4. Splitting of signals (spin-spin coupling): NMR signals are not usually

single triangles, but a complex pattern of split triangles labeled as doublets (2
peaks), triplets (3 peaks), quartets (4 peaks), etc. The distance between the
split peaks are called coupling constants, denoted by J 13. The interaction
between nearby protons produce different spin flip energies (_ E) as they can
orient themselves in a pattern of parallel or antiparallel to the applied
magnetic force. This phenomenon, where the spin of the nucleus of one
proton is close enough to affect the spin of another, is called spin-spin
coupling. Splitting is always reciprocated between the protonsif Ha splits
Hb, then Hb must split Haand provides information on the neighbors of a
proton within the molecule.
N+1 Rule: For a proton with n neighbors, its signal will be split into
n+1 lines
Intensity ratios

Diagram 513
*Pascals triangle gives the intensity ratios
between the split signals
10

Diagram 614
*1 neighbor doublet; 2 neighbors triplet; 3 neighbors quartet
Splitting patterns that are too difficult to analyze are called multiplet

p58, Prof. Steven Hardinger, Chem 14C Thinkbook (version 4)

p538, P.Y. Bruice, Organic Chemistry (4th)
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Splitting results from the different energies from spin patterns

3 Rules/Restrictions for Proton coupling15

1.) Nuclei with the same chemical shift (isochronous) do not couple with each
other: the protons must be nonequivalent in order to couple.
2.) Vicinal protons (protons separated by 3 bonds) can
couple with each other. Protons that are more than 3
bonds away cannot because the signal they feel from
their neighbor is too small to affect their spin. There is
also geminal couplingcoupling through 2 bonds) and
allylic coupling16coupling through1 4 bonds, if one is
a pi bond. Pi bonds do not follow the 3 bond rule because the electron density
around a pi bond is higher then in a single bond; hence, pi bonds can be
counted as a free spacer. All hydrogens on the benzene ring couple with each
other and the ring itself can be counted as a free spacer; however, Hs on the
benzene ring only couple with each other and not with Hs attached to other
atoms even if they are within the 3 bond max limit (coupling club)17.
3.) Hydrogens bonded to a Nitrogen or Oxygen usually do not couple with other
protons and appear as singlets on the NMR spectra.
Non-first order splitting: the N+1 rule cannot predict the exact splitting patterns
of non-first order splitting. First order splitting produces normal splitting
patterns that have equal J values. Non-first order splitting occurs when a nucleus
spin-couples with 2 or more sets of nearby nuclei that have different J values.
Example of First Order Splitting and Non-First Order

2nd Order Coupling Effects18

First order theory is sufficient when describing
NMR signals of coupled nuclei that are far
enough apart from each other; however, when the
13

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p61, Prof. Steven Hardinger, Chem 14C Thinkbook (version 4)
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P.302, J.R. Mohrig, Techniques in Organic Chemistry (2nd)
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p62, Prof. Steven Hardinger, Chem 14C Thinkbook (version 4)
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chemical shifts come closer, other effects (second order coupling effects) begin to
take over. Two things occur as a result of these weaker interactions: spin state
energies shift and the intensities of the peak change and no longer adhere to the
pascal triangle pattern.
1

Hydrogen a and b are

both
doublet of
doublets due to 2nd order
coupling effects
QUICK SUMMARY

Major Pieces of Info from NMR19

Number of signals = number of sets of nonequivalent protons
Integration = relative number of nonequivalent protons
Chemical shift = info about proton environment and presence of
benzene rings
Splitting = info about neighboring protons
Technique for solving NMR Problems
Calculate DBE first: NMR data is interpreted after the molecular formula and functional
groups are found from mass and IR spectrometry, so this information is already known.
When the molecular formula is provided, it can be used to determine the DBE or double
bond equivalents. DBE provides the degree of unsaturation (double bonds) and reveals
the presence of rings in the molecule.
20

DBE = C H, h + N +1
2
2

C = number of carbons
H = number of Hydrogens
h = number of halogens
N = number of Nitrogens

Organize Spectral Information21: Looking at all of the NMR Spec data at once can get
too overwhelming so it is a good idea to organize all of the information into a table and
work with the pieces individually. A table with the following headings is recommended:

Chemical Shift (ppm)

Splitting
Integration
# Hydrogens
Possible Fragment Structure

Once the information is organized, add up the number of hydrogens, carbons, and DBEs
to make sure that everything has been used up. Perform an atom check and a DBE check.
Checking the individual atoms before forming them into pieces will prevent mistakes in
later stages that may become frustrating. After the pieces are gathered, all you have to do
is put them together like pieces of a puzzle.
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19

CASE STUDY
This example is to illustrate NMR solving techniques for a molecule that also
contains atoms other than just hydrogen and carbon.

Interpret the NMR spectra and find the final structure.

Molecular formula: C4H9BrO
1
H-NMR: 4.49 ppm (sextet, integral=1); 3.73 ppm (triplet, integral = 2); 3.20 ppm
(singlet, integral =1); 1.95 ppm (quartet, integral=2) and 1.70 ppm (doublet, integral =
3)22
Step 1: The molecular formula is given to be C4H9BrO, so calculate the DBE
DBE = 4C 9H + 1h + 0 +1 = 0 DBE
2
*0 DBE indicate that there are no pi bonds or rings. The molecule is made up entirely of
alkanes1
Step 2: Fill in all of the given information into the table.

4.49

sextet

3.73

triplet

3.20

singlet

1.95

quartet

1.70

doublet

All of the information above was given in the problem. Before going on, you should see
what any of this can tell you even before filling in the possible fragments. Analyzing on
paper or in your head at every step will help you remember all of the details as you go
through the problem, rather than trying to fill in the gaps at the very end.
Analysis:
As seen above, the NMR spectrum indicates that there are 5 signals, which means
that there are 5 nonequivalent protons. There is no symmetry in this molecule.
Also, there are 5 proton signals, but only 4 carbons. Remember that you have an
oxygen and a bromine in the molecule. One proton must be attached to another

20

p46, Prof. Steven Hardinger, Chem 14C Thinkbook (version 4)

p.312, J.R. Mohrig, Techniques in Organic Chemistry (2nd)
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p67, Prof. Steven Hardinger, Chem 14C Thinkbook (version 4)
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atom, which can only be oxygen because oxygen can have 2 attachments, whereas
a halogen like bromine only has 1 center of attachment.
Now fill in the possible structures, keeping in mind the conclusions drawn above.

4.49

sextet

CH in CH2CHCH3

3.73

triplet

3.20

singlet

CH2 in CH2CH2
CHCH2CH
OH

1.95

quartet

1.71

doublet

CH2 in CH2CH3
CHCH2CH2
CH3 in CHCH3

Analysis:
The 3.20 ppm singlet must be an OH as we already determined in the above
analysis. Hydrogen-bonded molecules like NH and OH are usually singlets, so
we can write it down as a fragment with confidence.
Overall, the fragment suggested first will most likely be the correct one because
molecules favor simplicity and fewer atoms/bonds; however, you should always
be careful, especially when there are individual attachments like halogens because
you have to remember to leave enough openings to attach them. Also, you know
for a fact that there is a CH, so the possible fragments that contain a CH should be
equally considered.

Choose your pieces and check

Atom check: C4H9BrO - C4H9O = Br

DBE check: There were no DBEs to account for so no need to check
Analysis:
Everything has been used up except Br, which can be attached to the end
of a carbon later on. Now all you have to do is add Br to the total number
of molecular pieces you have and attach them together.

The CH2s werent boxed in because they could be either the first
possibility or the second.

Write out the pieces to see if you can integrate smaller pieces into a larger fragment.

Analysis: The triplet CH2 is most likely next to another CH2 (which would be the quartet
CH2) rather than 2 CHs because theres only 1 CH we know of in this molecule. Now all
we need to do is figure out the quartet CH2. In this case, the second possibility is most
likely correct because it contains 1 CH, which we know is in the molecule. This quartet
probably wouldnt be next to another methyl because that wouldnt leave enough room
for both OH and Br attachments.
The methylenes now match up with each other

Last three pieces:

H3CCHCH2CH2
OH
Br
Final Structure:

In some cases when the chemical shift may still be too hard to interpret, 2 final structures
may be accepted. For instance, this molecule may also be drawn with the Br and OH
switched because both structures still follow all of the splitting patterns in the NMR data.