MODERN

PHARMACEUTICAL
ANALYTICAL TECHNIQUE
SEMINAR-1

COUPLING CONSTANT AND ITS

APPLICATION
Submitted to, Presented by,
Dr.A.RAJASEKARAN ASHWIN RAM R
PRINCIPAL & PROFESSOR Master of pharmacy
DEPT OF PHARMACEUTICAL ANALYSIS
Pharmacology Department
KMCH COLLEGE OF PHARMACY
KMCH COLLEGE OF PHARMACY

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 CONTENT
 Spectroscopy

 NMR

 Spin -spin coupling

 Coupling constant

 Factors affecting coupling constant

 Applications
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 SPECTROSCOPY
DEFENITION:
• It is the study of sample with
respect to interaction of
Electromagnetic
Radiation(EMR).
• EMR: cosmic rays, gamma rays,
X-rays, UV rays, visible rays,
infrared radiation,
Micro waves, radio ways.

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 NUCLEAR MAGNETIC RESONANCE
SPECTROSCOPY(NMR)
DEFENITION:
NMR is the study of determining the content
and purity of the sample as well as its
molecular structure by recording the
interaction of Radio frequency (Rf) with the
nuclei of molecules placed in a strong external
applied magnetic field (Ho).

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 SPIN-SPIN COUPLING
DEFENITION:
The interaction between the spins of
neighbouring nuclei, non equivalent NMR
active nuclei(spin quantum number should be
more than zero) in a molecule may cause the
splitting of lines in the NMR spectrum. This is
known as spin-spin coupling.

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E.g. consider 1,1,2- tribromomethane(CHBr2-CH2Br)
which is having only two types of proton, therefore
its NMR spectrum may be have only 2 absorption
peaks but in actual practice the NMR spectrum
shows as many as 5 peaks in total.

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 • The number of signals in NMR spectrum is
equal to number of type of protons present in
the given molecules. There being one signal
each for every set of equivalent protons.

• In the above example the NMR spectra

shows the presence of many more peaks than
the number of types of proton present in the
molecule.

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 • This means that the individual signal which we
expect from a set of equivalent protons must
be appearing not as a single peak but as a
group of peak. This is called splitting of NMR
signal.

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 PASCALS TRIANGLE
• The pascals triangle is a graphical device used
to determine the ratio of heights of lines in a
split NMR peak.
• The number of peaks which N into which a
proton signal is split up is equal to 1 more
than the number of Vicinal protons(n)[proton
attached to the adjacent carbon atom].
• N=n+1

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 COUPLING CONSTANT
• The distance between the centre of two adjacent peaks in a
given multiplet is usually constant and is called as coupling
constant.

• The distance between two peaks for the resonance of one

nucleus split by another is a measure of how strongly the
nuclear spins influence each other.

• It is measured in Hertz (Hz) or in cycles per second (cps). It is

denoted by symbol “J”.

• The values of J generally lies upto 20 hertz.

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• For a pair of mutually coupled protons the
coupling constant due to splitting by one
proton has the same value as the coupling
constant due to splitting by second proton

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 • Unlike the chemical shifts, the values of J are
independent of externally applied magnetic
field and depends only upon the molecular
structure. This is because the strength of the
magnetic moment of the neighbouring
proton, which is the responsible for spin-spin
coupling.

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 FACTORS AFFECTING COUPLING CONSTANT

Various factor affecting:

1.Geminal coupling
2.vicinal coupling
3.Long range coupling
4. Aromatic group

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 GEMINAL COUPLING
• The values of J varies upto 20 Hz.

• In case of geminal proton, the proton are

attached to the same carbon atoms where the
protons are in different environment i.e they
are not chemically equivalent.

• Here the values of J depending upon the bond

angle and overall structure of the molecule.

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• i.e. the bond angle is directly proportional to
the coupling constant. If the bond angle
increases the coupling constant also increases.

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• e.g.: Methane (109o) = (-12Hz)
Ethylene (> 117o) = (-2.5Hz).

BOND ANGLE J VA L U E
105O -25Hz
109O -12Hz
125O 0
>125O p o s i ti v e v a l u e

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 VICINAL COUPLING
• The values J varies from 2-18Hz.

• The vicinal coupling, the protons are attached

to the adjacent carbon atoms, they are non
equivalent to each other.

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• Here the values of J are depending on the
dihedral angle (φ),valence angle(θ),bond
length of carbon and effect of electro
negative atom.

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• The dihedral angle is given by karplus
equation.

• KARPLUS EQUATION:
For 0-90o J = 8.5 Cos2 φ – 0.28
For 90-180o J = 9.5 Cos2 φ – 0.28
DIHEDRAL ANGLE J VALUE

0 or 180o positive value

90o 0 or negative value

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For e.g.
1. Freely rotating proton i.e. proton with anti-
conformation have J = 5-12 Hz, while proton
with gauche conformation have J = 2-14Hz.
Eg: propane = 6.5 (Hz) (anti)
propane = 7.2 Hz (gauche)

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2. In Restricted rotating protons, due to double
bond is involved the cis form have J = 6-14Hz ,
trans form J = 11-18Hz.

Eg: ethyl chloride (cis) J = 10 Hz

(trans)J = 15 Hz
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 LONG RANGE COUPLING

• Generally no coupling is observed the distance

between the two absorbing nuclei is more than
three covalent bond is called long range coupling.
• In some case appreciable coupling observed with
the help of high resolution spectrometer.
• In pi bond system appreciable coupling are
frequently observed even the protons are
separated by four or five bonds.
• Eg: 2,3 dimethyl butanoicacid = -1.2Hz
butene = -2.3Hz
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 AROMATIC COUPLING
• Coupling constant is depends on whether the
coupling proton are present in ortho, meta,
para position.
• The range of coupling constant varies for
ortho = 7-10Hz para = 0-1Hz
meta = 1-3Hz

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 OTHER FACTORS
• The substitution of deuterium for hydrogen
also affects the coupling constant.
• Substituent effect
1. The increase in electronegative atom or
group which withdraw sigma electrons
increase the value of coupling constant.
2. Similarly the coupling constant decreases
when the electronegative atom withdraw pi
electrons.
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HOW TO CALCULATE COUPLING CONSTANT

• In NMR spectrum where the peaks are in ppm(parts

per million).
• To calculate the coupling constant we need to convert
the ppm to Hz.
• Step 1: Determine the difference betweeen the two
adjacent peaks in ppm
• Step 2: multiply the value with the magnetic strength
we applied.
• By following these step coupling constant can be
calculated.
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• Eg: here the externely applied magnetic field
in 500Hz

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 APPLICATIONS
• coupling constant are very useful for
discussing the structure and nature of
chemical bonding through which it gives an
exact skeleton of compound.
• J value contains information of relative bond
length and angles.
• It helps in determine the cis and trans form of
the compound.

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• It also gives informtion regarding the presence
of proton in ortho ,meta and para position in
an aromatic compound.
• The J-coupling can be used as a sole criterion
for novel synthetic analogs to identify the
right stereochemistry.
• couplings are typically used in combination
with chemical shifts to trace the bond
connectivity in small molecules and proteins.

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• Coupling constant are very much useful in
conformational analysis of the compound.
(Conformational analysis is the study of
kinetic and thermodynamic properties of
molecules.)

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 REFERENCE

• Spectroscopy(Atomic and molecular) by

GERDEEP.R.CHATWALL.
• Organic spectroscopy by WILLIAM KEMP.
• JOURNAL OF MOLECULAR STRUCTURE.

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