Unit-II Stereochemistry and Spectroscopy

Stereochemistry
Isomerism -It is the phenomenon in which more than one compounds have the same chemical
formula but different chemical structures. Chemical compounds that have identical chemical
formulae but differ in properties and the arrangement of atoms in the molecule are called
isomers.
Structural/constitutional isomerism- The functional groups and the atoms in the molecules of
these isomers are linked in different ways. Different structural isomers are assigned different
IUPAC names since they may or may not contain the same functional group.

Stereoisomerism
This type of isomerism arises in compounds having the same chemical formula with the same
order of bonding but different orientations of the atoms belonging to the molecule in three-
dimensional space (spatial arrangement). The compounds that exhibit stereoisomerism are often
referred to as stereoisomers. This phenomenon can be further categorized into two subtypes:
Geometrical and Optical Isomerism.
Please note:

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 Unit-II Stereochemistry and Spectroscopy

Geometric isomerism: The isomerism that arises when atoms or groups having different spatial
arrangements are restricted to rotate around a bond or bonds in a molecule is called geometric
isomerism.
Geometrical Isomerism in acyclic alkenes
The restricted rotation mainly occurs in a carbon-carbon double bond. The compounds which
have different spatial arrangements of atoms in three-dimensional space are known as
geometrical isomers. It is popularly known as cis-trans isomerism.
• When the two same atoms/groups are locked on opposite sides of the double bond,
the compound forms the trans isomer.
• When the two same atoms/groups are locked on the same side of the double bond,
the compound forms the cis isomer.
Eg. The geometric isomerism is shown in the But-2-ene molecule.

How to Recognize the Possibility of Geometrical Isomerism?

Organic compounds must satisfy the given conditions to form geometric isomers:
1. restricted rotation (often involving a carbon-carbon or carbon-nitrogen double bond);
2. Presence of two different groups on the left-hand end of the double bond and two
different groups on the right-hand end. For example 1-Chloroethene does not show
geometrical isomerism.

3. Terminals groups on the terminal carbons must be in the same plane and must not be in
perpendicular planes. Even cumulenes (having even number of double bonds) will not
show geometrical isomerism because of terminal groups in perpendicular plane. In even
cumulenes, groups on the terminal carbons exist in a perpendicular plane.

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 Unit-II Stereochemistry and Spectroscopy

Even cummulene Odd cummulene

Odd numbered cumulenes show geometrical isomerism. When there is three consecutive double
bonds, terminals lie in the same plane giving geometrical isomerism.
Geometrical Isomerism in Cyclic Compounds
The bond rotation is not only restricted in alkenes but also cyclic hydrocarbons. In a ring of
carbon atoms, there will also be no possibility of rotation about any of the carbon-carbon bonds.
In cyclic compounds, substituents attached to a ring system give rise to geometric isomers. The
substituents will either be on the same side of the ring or the opposite side of the alkane ring.
Thus, cyclic alkanes exhibit cis and trans geometrical isomerism.

cis-1,4-dimethylcyclohexane and trans-1,4-dimethylcyclohexane

Issue in cis-trans isomerism
• The presence of more than two different substituents on a double bond makes it difficult
for the geometric isomers to be named using cis- and trans- descriptors.
• If all groups attached to the two carbon atoms are different (C)(D) C=C(A)(B)

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 Unit-II Stereochemistry and Spectroscopy

E-Z nomenclature
The geometry of the isomers is determined by prioritizing the substituents on the two carbons of
the double bond. According to Cahn, Ingold and Prelog priority system:
v Higher the atomic number of the atom attached to the doubly bonded carbon atom- higher
priority.
v Same atomic number of the atom attached to the doubly bonded carbon atom- see second
atom: higher priority to the atom with high atomic number.
1. Isomer E (Enteggen) – The isomer is denoted by E if the higher priority group is present
on the opposite sides of the double bond.
2. Isomer Z (Zusammen)– The isomer is denoted by Z if the higher priority group is
present on the same side of the double bond.
E-Z nomenclature for alkenes

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 Unit-II Stereochemistry and Spectroscopy

Geometrical Isomerism in Oximes

When carbonyl compounds are treated with hydroxylamine, oximes are formed.

There are two types of oximes:

Aldoximes: Oximes derived from aldehydes are called aldoximes. In aldoximes, at least either R
or R’ is hydrogen.
Ketoximes: Oximes derived from ketones are ketoximes. In ketoximes, both R or R’ are alkyl or
aryl groups only.
The oximes exhibit geometrical isomerism due to the restricted rotation of C = N bond.
E-Z nomenclature for oximes
The Z oxime has hydroxyl group and the group with higher priority on the same side of C=N.
However in the E oxime, they are arranged on the opposite sides of the C=N.

Two geometrical forms are possible for the oximes- syn and anti

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 Unit-II Stereochemistry and Spectroscopy

Optical isomerism
Compounds that exhibit optical isomerism feature similar bonds but different spatial
arrangements of atoms forming non-superimposable mirror images. These optical isomers are
also known as enantiomers.
Enantiomers are defined as optically active isomers that are non-superimposable mirror images
of each other. Enantiomers differ only in reaction with other chiral molecules and the direction in
which polarized light is rotated and are difficult to separate. Dextro enantiomers rotate the plane
of polarized light to the right whereas laevo enantiomers rotate it to the left.
Diastereomers are defined as optically active isomers that are not mirror images of each other.
These are non-identical stereoisomers. Hence, they occur when two or more stereoisomers of a
compound have different configurations at one or more (but not all) of the equivalent (related)
stereo centers and are not mirror images of each other. Diastereomers have different physical
properties, so they can be easily separated.

A chemical compound with a chiral carbon (having four different atoms/functional groups) with
non-superimposable mirror images is expected to exhibit optical isomerism. Chiral molecules
don’t have a plane of symmetry or a centre of symmetry.

Center of symmetry: the center point from which the identical atoms exist on the opposite side
from this center at equal distance.

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 Unit-II Stereochemistry and Spectroscopy

An axis of symmetry is the line along which a molecule is considered to be half, and when
rotated from this axis, it is the same molecule from both the sides.
Chiral Plane: A plane of symmetry is an imaginary plane that bisects the molecule in such a
way that it gives identical mirror images.
Eg. Meso compounds: Symmetric, or achiral molecules that contain stereocenters. Meso
compounds and their mirror images are not stereoisomers, since they are identical.

Two chiral atoms but optically non-active

If any of these symmetry elements are present, the molecule will be optically inactive.

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 Unit-II Stereochemistry and Spectroscopy

Optical isomerism in absence of chiral carbon atom

However, a compound may not have chiral carbon yet exhibit optical activity. Eg. allenes, spiro
compounds, and biphenyls. This is because these compounds are non-planar and give rise to non-
superimposable mirror images.
Optical Isomerism in Biphenyls
Biphenyls are formed by 2 benzene rings attached via a single sigma bond. Also, to minimise
steric hindrances, both the rings lie perpendicular to each other.
When biphenyl rings are substituted over ortho position, the carbon atoms in benzene are sp2
hybridised, thus the rotation across the sigma bond is restricted causing the possibility of
atropisomerism. Atropisomers are stereoisomers resulting from hindered rotation about single
bonds where the steric strain barrier to rotation is high enough to allow for the isolation of
the conformers.

Optical activity in biphenyls is observed when ortho substitution is present over both the rings
and the groups are not identical. Otherwise, a plane of symmetry will exist and it will become
optically inactive.
Substitution over meta or para positions allows the rings to move across the single sigma bond,
causing it to become planar and create a plane of symmetry, rendering it optically inactive. Eg.
6,6’-dinitrobiphenyl-2,2’-dicarboxylic acid

Optical Isomerism in Allene

A consecutive diene or a cumulated diene is known as an allene. The 3 carbon atoms in allene
are doubly bonded, so the central carbon atom is sp hybridised while the 2 carbon atoms on
either side are sp2 hybridised. In 3-D, as the p-orbitals are at right angles, the overlapping of
perpendicular p-orbitals results in one double bond being vertical while the other is horizontal.

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 Unit-II Stereochemistry and Spectroscopy

Therefore, the carbon with a horizontal double bond is attached to 2 groups vertically, while the
vertically double bonded carbon is attached to 2 groups horizontally.

• For allenes to exhibit optical isomerism, the 2 groups attached to sp2 hybridised carbon
must not be the same. However, they may or may not be identical to the groups attached to the
other sp2 hybridised carbon as shown below.

• This way, no plane of symmetry or centre of symmetry will exist and will make them
optically active. One example of optical isomerism in an allene is shown below.

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 Unit-II Stereochemistry and Spectroscopy

Thus, asymmetrically substituted compounds having even number of cumulative double

bond exhibit optical isomerism where compounds having odd number of cumulative double
bonds exhibit geometrical isomerism.
Optical Isomerism in Spiro Compounds
Spiro compounds are made up of two rings attached to a single carbon atom (spiro carbon atom),
which is sp3 hybridised. This results in a tetrahedral geometry which makes the 2 rings
perpendicular to each other (non-planar in 3-D). Spiro compounds thus give non-superimposable
mirror images. The 3-D structure of the spiro compound can be equated with the structure of
allene. Thereafter, similar conditions for the compound to show its optical activity are applied.

1,7-dicarboxylspirocycloheptane

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 Unit-II Stereochemistry and Spectroscopy

Racemization is a conversion, by heat or by chemical reaction, of an optically active compound

into a racemic (optically inactive) form. This creates a 1:1 molar ratio of enantiomers and is
referred to as a racemic mixture (i.e. contain equal amount of (+) and (−) forms). Plus and minus
forms are called Dextrorotation and laevorotations. The D and L enantiomers are present in equal
quantities, the resulting sample is described as a racemic mixture or a racemate.
Racemization can proceed through a number of different mechanisms, and it has particular
significance in pharmacology as different enantiomers may have different pharmaceutical
effects. The net optical rotation of a racemate is zero.
Enantiomeric excess (ee)
It is a measurement of the degree of purity of any chiral sample. It reflects the degree to which a
sample contains one enantiomer in excess over the other. A racemic mixture has an ee of 0%
(both enantiomers are present in a 1:1 ratio), while a completely pure enantiomer has an ee of
100%. For example, if a sample contains 70% of the R isomer and 30% of S isomer, it will have
an enantiomeric excess of 40%. This can be rationalized as a mixture of 40% pure R with 60%
(30% R and 30% S) of a racemic mixture. The enantiomer ratio is extremely important because
while one enantiomer is beneficial to the body, the other enantiomer can be highly toxic to the
body.
Chiral drugs
All natural compounds have a single enantiomeric form. For eg. The l form of amino acids and
the d form of sugars (primarily glucose) are usually the biologically reactive form. Human
olfactory sensory organs are chiral, so the following pair of enantiomers smell very differently to
us. The R-isomer of carvone smells like spearmint leaves, while S-isomer of carvone smells like
caraway seeds. Chirality has become a major role for the synthesis and development of drugs.
Most of the drugs discovered are chiral. The pharmacological activity of drugs depends mainly
on its interaction with biological targets such as proteins, nucleic acids and bio membranes. One
enantiomer of a chiral drug may be a medicine for particular disease whereas; another
enantiomer of the molecule may be not only inactive but can also be toxic. Hence Chirality plays
an essential role in drugs. Synthesizing compound as single enantiomer is crucial in the design
and synthesis of drugs.
Examples of chiral drugs:

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 Unit-II Stereochemistry and Spectroscopy

1. Thalidomide: The R-enantiomer is an effective sedative, which has a soothing effect that
relieves anxiety and makes the patient drowsy; while, the S-enantiomer is known to cause
teratogenic birth defects.
2. Pain killer Ibuprofen: the S enantiomer has desired pharmacological activity while the
R enantiomer is completely inactive.
3. Ketamine: intravenous anesthetics: S-ketamine has greater analgesic and anesthetic
effects than R-ketamine
4. Dopa: 3,4-dihydroxyphenylalanine: The initial use of racemic dopa for the treatment of
Parkinson's disease resulted in a number of adverse effects viz. nausea, vomiting,
anorexia, involuntary movements, and granulocytopenia. The use of L-dopa [the (S)-
enantiomer] resulted in reducing the required dose, and adverse effects.
Although the enantiomers of chiral drugs have the same chemical connectivity of atoms; they
drug differ in their interactions with enzymes, proteins, receptors and other chiral molecules
including chiral catalysts. These differences in interactions, in turn, lead to differences in the
biological activities of the two enantiomers, such as their pharmacology, pharmacokinetics,
metabolism, toxicity, immune response etc. Biological systems can recognize the two
enantiomers as two very different substances. Therefore, when chiral drugs are synthesized, as
much effort goes towards the rigorous separation of the two enantiomers. This ensures that only
the biologically active enantiomer is present in the final drug preparation.
Interaction between the two enantiomers of a racemic drug with a receptor at the drug
binding sites
Recognition of chiral drugs by specific drug receptors is explained by a three-point interaction of
the drug with the receptor site, as proposed by Easson and Stedman. The difference between the
interaction of the two enantiomers of a chiral drug with its receptor is illustrated below.

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 Unit-II Stereochemistry and Spectroscopy

• The three substituents A, B, C of the active enantiomer (left) can interact with three
binding sites a, b, c of a receptor by forming three contacts Aa, Bb and Cc, whereas the inactive
enantiomer (right) cannot because the contact is insufficient. In this case, one enantiomer is
biologically active while the other enantiomer is not.
• The substituents of the active enantiomer drug labeled A, B, and C must interact with the
corresponding regions of the binding site labeled a, b, and c of the receptor to have a proper
alignment Aa, Bb, and Cc. In this case, this fitting interaction produces an active biological
effect.
• In contrast, the inactive enantiomer cannot bind in the same way with its receptor; thus,
there is no active response.
• The attachment of an enantiomer to the chiral receptor is analogous to a hand fitting into
a glove. Indeed, a right hand can only fit into a right-hand glove. Similarly, only a particular
enantiomer that has a complementary shape to the receptor site can fit into a receptor site. The
other enantiomer will not fit, like a right hand will never fit into a left glove.

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 Unit-II Stereochemistry and Spectroscopy

Electromagnetic Radiation
Radiation is absorbed and emitted in photons. The defining characteristic of a photon is that its
energy cannot be split into smaller pieces. Each photon’s energy is defined by its frequency (u)
or wave length (l) or wave number
Ephoton = hν = hc/λ
h = plank’s constant, 6.63 x 10-34 J s and c = speed of light, 3.00 x 108 ms-1
Wave number = 1/ λ

Beer-Lambert Law
When monochromatic radiation is passed through a homogeneous solution, then the rate of
decrease in the intensity of the transmitted radiation with the increase in the thickness of the
medium varies directly with the concentration of the solution and intensity of incident radiation.
!"
&"
"! " " " % where I is the light intensity after it passes through
&'
!"
&"
" = "$%#&' "
the sample and Io is the initial light intensity. c is
"
"
&"
# the concentration of solution and b is the thickness
!" # " = "$% # &'
"
"! ! of the medium or path length, and c is the analyte
"
!"() " = "$#%
"! concentration.
" $#%
" = "!*

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 Unit-II Stereochemistry and Spectroscopy

" " "

!"#A " = "%&'
"! # = ! !"# = ! !"# $ %&'(A =
"! "!
" %&'
" #$% =
" ! &'()( where A is the measured absorbance, is a
"
" #$% = ! &'
"! wavelength-dependent absorptivity coefficient,
( = ! &'
and T is the transmittance.
Here, ε (= a/2.303) is extinction coefficient or absorptivity
Absorptivity, ε = dm3g-1cm-1, when concentration is expressed in terms of g dm-3 and b in cm.
Molar absorptivity, ε = dm3mol-1cm-1 , or Lmol-1cm-1, when concentration is expressed in terms
of mol dm-3 or mol/L or M and b in cm.
Molar extinction coefficient: It measures the probability of electronic transitions. The higher
the molar extinction coefficient, the higher the likelihood of electronic transitions.
Experimental measurements are usually made in terms of T.
Question: A solution of thickness 8 cm transmits 80% incident light. Calculate
concentration of solution if molar absorptivity is 4000 dm3mol-1 cm-1.
"
#= = $%&$
"!
"
A = " '() = ! %&
"!
" '() ( $%&$ ) = *$$$ '(! (!) ""&( "" # & &( # &
$%$+#+
&=
!,$$$
= !%$!- # -"$"# (!) -'( "!
Questions for practice:
• The percentage transmittance of an aqueous solution of unknown compound is 40% at
25º C and 700 nm for a 1.5 x 10-5 M solution in a 5 cm cell. Calculate the absorbance and the
molar extinction coefficient.
• The percentage transmittance of an aqueous solution of unknown compound is 55% at
25º C and 650 nm for a 2.6 x 10-5 mol dm-3 solution in a 10 cm cell. Calculate the absorbance
and the molar extinction coefficient.
Energy levels
When a molecule absorbs U.V. radiation, the electron in that molecule undergoes transition from
a lower to a higher energy level. The difference in energy in given by

15
 Unit-II Stereochemistry and Spectroscopy

E = hv
The actual amount of energy required depends on the difference in energy between the ground
state (E0) and the excited state (E1) of the electrons.
E1 – E0 = hv
The total energy of a molecule is the sum of electronic energy (Eelec), vibrational energy (Evib)
and rotational energy (Erot)
Eelec > Evib > Erot
The superposition of rotational and vibrational transitions on the electronic transitions gives a
combination of overlapping lines. This appears as a continuous absorption band.

UV spectroscopy
The absorption of UV or visible radiation corresponds to the excitation of outer electrons. It
involves the promotion of electrons from HOMO (Highest Occupied Molecular Orbital) to
LUMO (Lowest Unoccupied Molecular Orbital). There are three types of electronic transition
which can be considered;
1. Transitions involving σ, Π and n electrons
2. Transitions involving charge-transfer electrons
3. Transitions involving d and f electrons

Type of transitions in UV-spectrum

• σ - σ* Transitions: An electron in a bonding σ orbital is excited to the corresponding
antibonding orbital. The energy required is large. For example, methane (which has only C-H
bonds, and can only undergo σ -σ* transitions) shows an absorbance maximum at 125 nm.
Absorption maxima due to σ -σ* transitions are not seen in typical UV-Vis. spectra (200 - 700
nm).

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 Unit-II Stereochemistry and Spectroscopy

• π- π * transition: These type of transitions are related to the promotion of an electron

from a bonding π orbital to an antibonding π * orbital. For example, ethene shows absorption
maximum around 171-174 nm. This corresponds to the π→π* electronic transition, where an
electron in the π molecular orbital of the carbon-carbon double bond is excited to the π*
antibonding orbital.

• n- σ * transition:Saturated compounds with lone pair (non-bonding) electrons undergo n

→ σ * transitions apart from σ − σ* transitions. The energy required for n → σ* transition is
generally less than that required for σ → σ* transition and their corresponding absorption bands
appear at longer wavelengths in the near ultraviolet region (180 to 200 nm).
• n-π* transition: These transitions are shown by unsaturated molecules which contain
atoms with lone pair like N, O and S linked by multiple bonds with C or other atom. These
transitions show a weak band in their absorption spectrum.
In aldehydes and ketones (having no C = C bonds), the band due to n → π* transition generally
occurs in the range 270-300 nm. On the other hand, carbonyl compounds having double bonds
separated by 2 or more single bonds exhibit the bands in the range 300 to 350 nm due to n → π*
transitions.
Question: Tell whether a molecule can undergo more than one electronic shift.
Ans. Depending upon the wavelength of light used, a molecule can undergo all the possible
electronic transitions. For example, acetaldehyde (CH3CHO) can undergo all the four types of
transitions.
Some definitions
Chromophore: A covalently bonded unsaturated group that shows characteristic absorption in
UV or visible region. The functional groups containing multiple bonds are capable of absorbing
radiations above 200 nm due to n→ π* & π → π* transitions. e.g. N=O, C=O, C=N, C≡N, C=C,
C=S, etc. Eg. Benzene λmax=255 nm

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 Unit-II Stereochemistry and Spectroscopy

Auxochrome: A chemical group which does not give rise to an absorption band by itself, but
upon being attached to a chromophore alters both the position and intensity of the absorption
peak. These are functional groups with non-bonding electrons e.g., -OH, -NH2, halogens etc.
Phenol λmax=270 nm, Aniline λmax=280 nm

Shifts in UV-Spectra
Bathochromic shift: It is a shift of the λmax to a higher wavelength due to the effect of a
substituent group or solvent, it is also known as red shift.
Eg. Benzene λmax=255 nm, Phenol λmax=270 nm, Aniline λmax=280 nm. Substitution of benzene
results in Bathochromic shift due to increased extent of conjugation with resonance and
delocalization of electrons.
Hypsochromic shift: It is a shift of λmax to lower wavelength. It is also known as blue shift. Eg.
Aniline absorbs at 280 nm (εmax 8600) but in acidic solution, the main absorption band is seen at
203 nm (εmax 7500) which is comparable to benzene. In the acidic medium, aniline is converted
to anilinium ion. Thus, due to removal of conjugation of lone pair of electrons on nitrogen atom
of aniline with π-bond system of benzene,
the hypsochromic shift takes place.

Hyper chromic shift: An increase in

absorptivity of the molecule. It is usually

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 Unit-II Stereochemistry and Spectroscopy

effected by the introduction of an auxochrome. Eg. Benzene shows band at 256 nm and Ɛmax 200,
whereas aniline shows B-band at 280 nm and Ɛmax at 1430. The increase in the value of Ɛmax is
due to the hyperchromic effect of auxochrome NH2.

Hypochromic shift: Decrease in absorptivity of the molecule. Hypochromic shift is caused by

the groups which distorts the geometry of the molecule. e.g. Biphenyl shows λmax at 250 nm and
Ɛmax at 19,000, whereas 2-methyl biphenyl absorbs at λmax 237 nm, Ɛmax 10250. The decrease in
the value of absorbance is due to hypochromic effect of methyl group which distorts the
chromophore by forcing the rings out of coplanarity resulting in the loss of conjugation.

Effect of conjugation
Greater the number of conjugated double bonds, greater is the bathochromic shift. With
continuous increase in conjugation, the absorption may even shift to the visible region. For
example, ethylene (one double bond) absorbs at 170 mμ while butadiene (two double bonds in
conjugation) absorbs at 217 mμ. In compound ‘A’, double bonds are in conjugation therefore ‘A’
possessing higher wavelength (𝜆max) as compare to compound ‘B’ (non-conjugated derivative).

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 Unit-II Stereochemistry and Spectroscopy

Question: Arrange the following compounds in the increasing order of their UV absorption
maxima: (i) Ethylene (ii) Naphthalene (iii) Anthracene (iv) 1, 3 Butadiene (v) Benzene.
Hint: Peak wavelengths tend to be shifted toward the long wavelength region as the conjugated
system gets larger
Substance Absorption Peak
Ethylene 180nm
1,3-butadiene 217nm
Benzene 255nm
Naphthalene 286nm
Anthracene 375 nm
(i) Ethylene: Ethylene has a simple double bond and limited conjugation.
(iv) 1,3-Butadiene: 1,3-Butadiene is a conjugated diene with two double bonds separated by a
single bond. Hence, it will have the more UV absorption maximum than ethylene.
(v) Benzene: One aromatic ring.
(ii) Naphthalene: Naphthalene is a polycyclic aromatic hydrocarbon with a fused benzene ring
system. It exhibits more extensive conjugation compared to benzene.
(iii) Anthracene: Anthracene consists of three fused benzene rings, providing a larger conjugated
system compared to naphthalene. As a result, anthracene will have a higher UV absorption
maximum than naphthalene.

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 Unit-II Stereochemistry and Spectroscopy

Solvent effect
(i) σ→σ* Transition:
1. Molecules are non-polar.
2. σ MOs are non-polar.
3. Solvent polarity change: No effect on transition.
4. Result: Absorption spectrum remains unchanged.
"σ→σ* transitions are unaffected by solvent polarity due to non-polar
nature of σ MOs."
(ii) 𝛑⟶𝛑* Transition:
1. Ground state: Molecule is non-polar.
2. Excited state: Molecule becomes polar.
3. Polar solvent: Stabilizes excited state, lowers transition energy.
4. Result: Absorption shifts to longer wavelengths."
"Polar solvents stabilize polar excited states in π→π* transitions, shifting absorption to
longer wavelengths."

For example, In alkenes or arenes λmax value shifts to longer wavelength (red-shift) when solvent
polarity is raised. The compound para-N,Ndiethylaminonitrobenzene absorbs at 364 nm in
cyclohexane but at 431 nm in water. Likewise value of absorption maximum in ethanol will be
greater than that observed in hexane.
(ii) n⟶π* Transition:
1. Both ground (n) and excited (π*) states are polar.
2. Polar solvent interacts more strongly with ground state (n) than excited state (π*).

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 Unit-II Stereochemistry and Spectroscopy

3. Ground state energy decreases more than excited state energy.

4. Result: Transition energy increases, λmax shifts to shorter wavelength (blue-shift).
"Polar solvents blue-shift n→π* transitions by stabilizing the ground state more than

the excited state."

For eg. In hexane, acetone absorbs at 279 nm, whereas the same absorption moves to 264.5 nm
in water. The ground state of a carbonyl compound is highly stabilized by water because of
hydrogen bonding involving the carbonyl oxygen lone pair. In the excited state, an electron is
removed from the lone pair and promoted to a π* orbital. As a result, this state can no longer
form an efficient hydrogen bond with water. Hence, polar solvent will solvate the ground state
that lowers its energy due to solvation. Hence, absorption shifts to shorter wavelength.
(iii)n⟶σ* Transition:
1. Ground state (n) is polar.
2. Excited state (σ*) is non-polar (neutral).
3. Polar solvent: Solvates and stabilizes ground state (n).
4. Ground state energy decreases.
5. Result: Transition energy increases, absorption shifts to shorter wavelength (blue-shift).
"Polar solvents blue-shift n→σ* transitions by stabilizing the polar ground state."
For eg. Alcohols as well as amines form hydrogen bonding with the solvent molecules. Hence,
there absorption shifts to shorter wavelength in water as compared to hexane.

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 Unit-II Stereochemistry and Spectroscopy

Applications of UV spectroscopy
1. Detection of Impurities: UV absorption spectroscopy is one of the best methods for
determination of impurities in organic molecules.
Additional peaks can be observed due to
impurities in the sample and it can be compared
with that of standard raw material. By also
measuring the absorbance at specific wavelength,
the impurities can be detected. Benzene appears
as a common impurity in cyclohexane. Its
presence can be easily detected by its absorption at 255 nm.
2. Structure elucidation of organic compounds: UV spectroscopy is useful in the
structure elucidation of organic molecules, the presence or absence of unsaturation, the presence
of hetero atoms. From the location of peaks and combination of peaks, it can be concluded that
whether the compound is saturated or unsaturated, hetero atoms are present or not etc.
3. Quantitative analysis:
UV absorption spectroscopy can be used for the quantitative determination of compounds that
absorb UV radiation. This determination is based on Beer’s law.
4. Qualitative analysis:
UV absorption spectroscopy can characterize those types of compounds which absorbs UV
radiation. Identification is done by comparing the absorption spectrum with the spectra of known
compounds. UV absorption spectroscopy is generally used for characterizing aromatic
compounds and aromatic olefins.
5. Dissociation constants of acids and bases.
pH = pKa + log [A-] / [HA]
From the above equation the pKa value can be calculated if the ratio of [A-] / [HA] is known at a
particular pH. The ratio of [A-] / [HA] can be determined spectrophotometrically from the graph
plotted between absorbance and wavelength at different pH values.
6. Chemical kinetics:
Kinetics of reaction can also be studied using UV spectroscopy. The UV radiation is passed
through the reaction cell and the absorbance changes can be observed.
7. Quantitative analysis of pharmaceutical substances:

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 Unit-II Stereochemistry and Spectroscopy

Many drugs are either in the form of raw material or in the form of formulation. They can be
assayed by making a suitable solution of the drug in a solvent and measuring the absorbance at
specific wavelength. Diazepam tablet can be analyzed by 0.5% H2SO4 in methanol at the
wavelength 284 nm.
8. Molecular weight determination:
Molecular weights of compounds can be measured spectrophotometrically by preparing the
suitable derivatives of these compounds. For example, if we want to determine the molecular
weight of amine then it is converted in to amine picrate. Then known concentration of amine
picrate is dissolved in a litre of solution and its optical density is measured at λmax 380 nm. After
this the concentration of the solution in gm moles per litre can be calculated by using the
following formula
8. Cis-trans isomerism differentiation
cis-isomer absorbs at lower wavelength, because the bulky groups on the same side cause
repulsive interactions resulting in the reduction in conjugation.

Question: Identify the two geometric isomers of stilbene, C6H5CH=CHC6H5 from their λmax
values, 294 nm and 278 nm.

trans-stilbene: 294 nm cis-stilbene: 278 nm

Question: How will you distinguish between cis and trans-1, 3, 5-Hexatriene.

Ans.
cis-isomer absorbs at lower wavelength, because the bulky groups on the same side cause
repulsive interactions resulting in the reduction in conjugation.

24
 Unit-II Stereochemistry and Spectroscopy

IR Spectroscopy
Principle of IR spectroscopy
When IR radiation interact with sample molecule, the sample molecule will absorb the specific
applied quantized IR light which is matched with the internal vibrational frequency of the
molecule and other residual frequencies are transmitted via the sample. Due to absorption of IR
radiation, the net change of dipole moment in molecule is occurred and causes vibration of bonds
in the molecule like Stretching and bending vibration. The transmitted light is detected by the
detector and IR spectrum interpreted on the computer screen by analysis of the transmitted light.
ü IR active species: The molecules that undergo a net change in dipole moment during
vibrations are said to be infrared active. Eg. H2O
ü Molecules may not have a permanent dipole moment but some of its vibrational
mode must be accompanied by change in dipole moment. Eg. CO2
ü IR inactive species: If there is no permanent dipole moment or no change in the dipole
moment of the molecule during vibrations, these molecules are said to be infrared inactive. Eg.
Homodiatomic molecules like O2, H2, N2 etc.
Question: Which of the following molecules will show IR spectrum and why H2, HCl, CO2,
H2O?
Ans: HCl, CO2, H2O
Fundamental vibrations (How many vibrations are possible )
A molecule has as many degrees of freedom as the total degree of freedom of its individual
atoms. Each atom has three degrees of freedom (corresponding to the Cartesian coordinates),
thus in an N-atom molecule there will be 3N degree of freedom. In molecules, movements of the
atoms are constrained by interactions through chemical bonds.
Translational - the movement of the entire molecule while the positions of the atoms relative to
each other remain fixed: 3 degrees of translational freedom.
Rotational transitions – interatomic distances remain constant but the entire molecule rotates
with respect to three mutually perpendicular axes:
Nonlinear: 3 rotational freedom (because it can rotate around any of three perpendicular axes)
Linear: 2 rotational freedom.
Vibrations – relative positions of the atoms change while the average position and orientation of
the molecule remain fixed.

25
 Unit-II Stereochemistry and Spectroscopy

The fundamental vibrations correspond (in quantum treatment) to the first vibrational transition
from the zeroth vibrational level i.e v0 to v1. The term overtone is used for any multiple of the
given fundamental frequency. Thus, the transition from v0 to v2 and v0 to v3 are the first and the
second overtones of the fundamental.

Simple diatomic molecules:

N=2, 3N-5 =1, only one vibrational band.
Symmetrical diatomic molecule, e.g. N2, the band is not observed in the IR spectrum, but only
in the Raman spectrum. Asymmetrical diatomic molecules, e.g. CO, absorb in the IR spectrum.
More complex molecules: vibrational spectra are correspondingly more complex, i.e. big
molecules have many peaks in their IR spectra.
Non-linear:
The atoms in a CH2X2 group, can vibrate in different ways. N=5, 3N-6 =9
H2O, N=3, 3 × 3 – 6 = 3 degrees of vibrational freedom, or modes.
Linear:
CO2, N=3, 3 × 3 – 5 = 4 degrees of vibrational freedom, or modes.
Question: Calculate the fundamental vibrations for the following compounds: CO2, H2O,
SO2, CH4, & C2H2.
ü For linear molecules (such as CO2 and C2H2), the formula 3N-5 is used. This is because
linear molecules have one fewer rotational degree of freedom compared to non-linear molecules.
ü For non-linear molecules (such as H2O, SO2, and CH4), the formula 3N-6 is used. This is
because non-linear molecules have both rotational and vibrational degrees of freedom.
ü CO2 (Carbon dioxide): N = 3 (two oxygen atoms and one carbon atom) Number of
vibrations = 3N-5 = 3(3) - 5 = 9 - 5 = 4 vibrations

26
 Unit-II Stereochemistry and Spectroscopy

ü H2O (Water): N = 3 (two hydrogen atoms and one oxygen atom) Number of vibrations =
3N-6 = 3(3) - 6 = 9 - 6 = 3 vibrations
ü SO2 (Sulfur dioxide): N = 3 (two oxygen atoms and one sulfur atom) Number of
vibrations = 3N-6 = 3(3) - 6 = 9 - 6 = 3 vibrations
ü CH4 (Methane): N = 5 (four hydrogen atoms and one carbon atom) Number of vibrations
= 3N-6 = 3(5) - 6 = 15 - 6 = 9 vibrations
ü C2H2 (Acetylene): N = 5 (two carbon atoms and two hydrogen atoms) Number of
vibrations = 3N-5 = 3(5) - 5 = 15 - 5 = 10 vibrations.
Why not 3N-6/3N-5 bands in IR spectrum?
The theoretical number of fundamental vibrations (absorption frequencies) will seldom be
observed. There may be
ü overtones (multiples of a given frequency), combination (sum of two other vibrations) or
difference (the difference of two other vibrations) tones increase the number of bands
ü frequencies which fall outside the measured spectral region (400-4000 cm –1 )
ü bands which are too weak, too close and coalesce
ü occurrence of a degenerate band from several absorptions of the same frequency
ü lack of change in molecular dipole
Types of vibrations
Different covalent bonds have different strengths due to the masses of different atoms at either
end of the bond. As a result, the bonds vibrate at different frequencies. The frequency of
vibration can be found by detecting when the molecules absorb electro-magnetic radiation.
Various types of vibration are possible as STRETCHING and BENDING
1. Stretching vibrations: Bond angle remains same but involves a continuous change in bond
length along the axis of bond between 2 atoms. These are of two types:
A. Symmetric Stretching, the bond length increase & decrease symmetrically by alternate
stretching and compression of bonds in a symmetric manner.
B. Asymmetric Stretching, length of one bond increase & the other one decrease at the same time
without changing bond angle. One bond is stretched and other is compressed and vice-versa.
2. Bending vibrations: involves the change of bond angle between two atoms but bond length
remains the same. These are of two types: In plane and out of plane bending.
In plane bending is further of two types:

27
 Unit-II Stereochemistry and Spectroscopy

A. Scissoring is the movement of two atoms toward and away from each other. So bond
angle decrease and increase with time.
B. Rocking in which the bond angle is maintained but bonds moves within the same plane.
Changing angle b/w a group of atoms.
Out of plane bending is further of two types:
A. Wagging in which both atoms move to one side of the plane. Changing angle b/w the
plane a group of atoms
B. Twisting in which one atom is above the plane and the other is below the plane.
Changing angle b/w the plane 2 groups of atoms.

28
 Unit-II Stereochemistry and Spectroscopy

Types of vibrations for water molecule

Types of vibrations for CO2 molecule

The symmetric stretch of carbon dioxide is not IR active because there is no change in the net
molecular dipole.
Vibrational frequency
! !
! ="
# "

k: force constant (measure of bond stiffness), Single bonds: k ~ 3x105 to 8 x105 dyne/cm (Avg ~
5x105) while for double and triple bonds ~ 2x and 3x k for single bond.
!!!"
µ: reduced mass " = #
!! + !"
Question: Calculate the wave number of stretching vibration of a carbon-carbon double
bond. Given force constant (k = 10 × 105 dynes cm–1)

29
 Unit-II Stereochemistry and Spectroscopy

Factors affecting vibrational frequency

The value of absorption frequency depends upon
• the force constant of a bond
• Reduced mass of atoms
• State of substance
• Electronic structure
• Hydrogen bonding
A. Force constant, k
ü The triple bonds are stronger than the double bonds followed by single bonds between the
same two atoms and hence vibrational frequency is in the order of triple>double>single.

B. Effect of reduced mass, µ

ü As the atom attached to carbon a particular atom say carbon increases in mass, the
reduced mass increases and hence the frequency of vibration decreases.

F-H > O-H > C-C

O—H stretching absorbs at higher frequency compared to C—C bond. Due to smaller value of
reduced mass for O—H compared with C—C bond. O—H should absorb at higher frequency as
compared to F—H. But this is not true. Actually, F—H absorbs at the higher frequency. This can
be explained due to the higher electronegativity of fluorine compared to that of oxygen.
C. State of substance
ü Frequency shifts also take place on working with the same substance in different states
(solids, liquids & vapour).
------A substance usually absorbs at higher frequency in a vapour state as compared to liquid and
solid states.

30
 Unit-II Stereochemistry and Spectroscopy

D. Electronic effect
ü The introduction of alkyl group causes + I effect which results in the lengthening or the
weakening of the bond and hence the force constant is lowered and wave number of absorption
decreases.
Formaldehyde (HCHO) 1750 cm–1 , Acetaldehyde (CH3CHO) 1745 cm–1 and Acetone
(CH3COCH3) 1715 cm–1
ü The introduction of an electronegative atom or group causes–I effect which results in the
bond order to increase. Thus, the force constant increases and hence the wave number of
absorption rises.
Acetone (CH3COCH3) 1715 cm–1 , Chloroacetone (CH3COCH2Cl) 1725 cm–1 and
Dichloroacetone (CH3COCHCl2) 1740 cm–1

E. Mesomeric effect
It causes weakening of a bond leading to decrease of force constant and lesser absorption
frequency.
ü –I effect is dominated by mesomeric effect and thus, the absorption frequency decreases.

ü N atom is less electronegative than O atom, the electron pair on N atom in amide is easy
to move in conjugation. Greater conjugation, lesser force constant and lesser absorption
frequency.

31
 Unit-II Stereochemistry and Spectroscopy

The intensity of absorption frequency depends upon

ü Not all covalent bonds display bands in the IR spectrum. Only polar bonds do so.
These are referred to as IR active. The intensity of the bands depends on the magnitude of the
dipole moment associated with the bond in question:
ü More polarity of bond, more the intensity of peak. Strongly polar bonds such as
carbonyl groups (C=O) produce strong bands. Medium polarity bonds and asymmetric bonds
produce medium bands. Weakly polar bond and symmetric bonds produce weak or non
observable bands.

C-O is more polar than C-N bond that is more polar than C-C bond. Propylene is slightly polar
and but-2-yne is non-polar.
O-H > N-H > C-H
O-H bond is more polar that N-H bond that is more polar than C-H bond.
ü More bonds, more intense peaks. the IR spectra of methane to that of octane, the octane
molecule will have a much more intense C-H peak because it has many more C-H bonds than
methane.
ü More concentration, more intense peaks. The concentration of the sample used to
obtain an IR spectrum also affects the intensity of the absorption bands. Concentrated samples
have greater numbers of absorbing molecules and, therefore, more intense absorption bands.
ü Coupled vibrations: When two bond oscillators share a common atom, they seldom
behave as individual oscillators (unless the individual oscillation frequencies are widely
different). The frequency of the asymmetric stretching vibration in CO2 is at a shorter

32
 Unit-II Stereochemistry and Spectroscopy

wavelength (higher frequency) than for a carbonyl group in aliphatic ketones (around 1715 cm–1
) due to strong mechanical coupling or interaction.
ü Fermi resonance arises when there is a strong coupling between two vibrational modes,
typically involving a lower energy fundamental vibration and a higher energy combination or
overtone vibration. The interaction between these modes can result in the splitting or merging of
the vibrational bands in the infrared (IR) spectrum, as well as changes in the intensities and
relative positions of the absorption peaks. It can be observed in different types of molecules and
is particularly common in molecules with conjugated systems or multiple vibrational modes that
are close in frequency.
ü Hydrogen bonding: This results in the lengthening of the original X—H group. It is
easier to stretch an X-H bond if it is hydrogen bonded Thus, small energy will be required to
stretch such a bond (O—H) and hence absorption occurs at a lower wave number. In general,
The X-H stretching bands move to lower frequency usually with increased intensity and band
widening while X-H bending vibration usually shifts to higher frequencies.
ü Intermolecular hydrogen bonds give rise to broad bands whereas bands arising from
intramolecular hydrogen bonds are sharp and well defined.
ü Intermolecular hydrogen bonds are concentration dependent. The more concentrated the
solution, the more likely it is for the OH-containing molecules to form intermolecular hydrogen
bonds.
For example,
1. amines show N—H stretching at 3500 cm–1 in dilute solutions while in condensed phase
spectra, absorption occurs at 3300 cm–1.
2. In aliphatic alcohols, the O-H stretching of a concentrated (hydrogen bonded) solution of
an alcohol occurs at about 3550 cm-1, whereas the O-H stretching band of a dilute solution (with
little or no hydrogen bonding) appears at 3650 cm-1.
3. o—Nitro phenol exhibits intramolecular hydrogen bonding whereas p-Nitro phenol
exhibits intermolecular hydrogen bonding. Intramolecular hydrogen bonded compound does not
show any shift in absorption on dilution whereas intermolecular H-bonded does.

33
 Unit-II Stereochemistry and Spectroscopy

Functional group and Fingerprint region

In infrared (IR) spectroscopy, the spectrum is typically divided into two main regions: the
functional group region and the fingerprint region.
Functional Group Region: This region of the IR spectrum typically spans from about 4000 to
1400 cm-1. It contains the characteristic peaks associated with the stretching and bending
vibrations of functional groups present in the molecule. Different functional groups absorb
infrared radiation at characteristic frequencies due to the vibrational modes of the bonds within
those functional groups.
Examples of common functional groups and their characteristic peaks in this region include:
C=O in aldehyde and ketones-sharp, strong absorption between 1700 and 1760 cm-1
ü -OH in alcohols,broad absorption between 3200 and 3600 cm-1
ü -COOH in carboxylic- broad absorption between 3200 and 3300 cm-1 (O-H bond) and
1725 - 1700 cm-1 (C=O bond)
-COOR in esters-strong absorption between 1750 cm-1 and 1730 cm-1 (C=O bond)
Fingerprint Region: This region of the IR spectrum typically spans from about 1400 to 400 cm-
1
. It contains a complex pattern of peaks that are unique to each molecule. The fingerprint region
arises from more complex molecular motions and interactions, such as out-of-plane bending and
torsional vibrations. It provides a unique "fingerprint" for each molecule, allowing for
identification and differentiation of compounds. Peaks in this region are often less predictable
and more difficult to assign to specific functional groups, but they provide valuable information
for compound identification and structural elucidation. Finger print region can be subdivided into
three regions as: 1) 1400-1350 cm-1 2) 1350-1000 cm-1 3) Below 1000 cm-1
Characteristic peaks
Bond Class of compound Range / cm-1 Intensity
Alkane 3000-2850 strong
C-H
Alkene/aromatic 3100-3000 strong
C-C Alkane 1200 - 700 weak
C=C Alkene 1680 - 1620 variable
CºC Alkyne 2260–2100 weak
N-H Amine, Amide 3500-3300 medium

34
 Unit-II Stereochemistry and Spectroscopy

Alcohol (monomer) 3650 - 3590 variable, sharp

O-H Alcohol (H-bonded) 3420 - 3200 strong, broad
Carboxylic acid (H-bonded) 3300 - 3250 variable, broad
Ketone 1725 - 1705 strong
Aldehyde 1740 - 1720 strong
C=O Carboxylic acid 1725 - 1700 strong
Ester 1750 - 1730 strong
Amide 1700 - 1630 strong
C-O Alcohol, ester, acid, ether 1300 - 1000 strong
CºN Nitrile 2260 - 2240 medium
Applications of IR spectroscopy
1. Identification of functional group and structure elucidation: Entire IR region is
divided into group frequency region and fingerprint region. In group frequency region, the peaks
corresponding to different functional groups can be observed. According to corresponding peaks,
functional group can be determined. Each atom of the molecule is connected by bond and each
bond requires a different IR region so characteristic peaks are observed. This region of IR
spectrum is called as finger print region of the molecule. It can be determined by characteristic
peaks.
2. Identification of substances: IR spectroscopy is used to establish whether a given
sample of an organic substance is identical with another or not. This is because large number of
absorption bands is observed in the IR spectra of organic molecules and the probability that any
two compounds will produce identical spectra is almost zero. If two compounds have identical
IR spectra then both of them must be samples of the same substances.
q IR spectra of two enantiomeric compounds are identical. So IR spectroscopy fails to
distinguish between enantiomers.
3. Studying the progress of the reaction: Progress of chemical reaction can be determined by
examining the small portion of the reaction mixture withdrawn from time to time. The rate of
disappearance of a characteristic absorption band of the reactant group and/or the rate of
appearance of the characteristic absorption band of the product group due to the formation of
product is observed.

35
 Unit-II Stereochemistry and Spectroscopy

4. Detection of impurities: IR spectrum of the test sample to be determined is compared with

the standard compound. If any additional peaks are observed in the IR spectrum, then it is due to
impurities present in the compound.
5. Quantitative analysis: The quantity of the substance can be determined either in pure form or
as a mixure of two or more compounds. In this, characteristic peak corresponding to the drug
substance is chosen and log I0/It of peaks for standard and test sample is compared. This is called
base line technique to determine the quantity of the substance.

Begin by looking in the region from 4000-1300. Look at the C–H stretching bands around 3000:

Position Indicates:

alkyl groups (present in most organic

Are any or all to the right of 3000?
molecules)

Are any or all to the left of 3000? a C=C bond or aromatic group in the molecule

Look for a carbonyl in the region 1760-1690. If there is such a band:

Position Indicates:

Is an O–H band also present? a carboxylic acid group

Is a C–O band also present? an ester

Is an aldehydic C–H band also present? an aldehyde

Is an N–H band also present? an amide

Are none of the above present? a ketone

Look for a broad O–H band in the region 3500-3200 cm-1.

If there is such a single broad band:

Position Indicates:

Is an O–H band present? an alcohol or phenol

36
 Unit-II Stereochemistry and Spectroscopy

If there is such a weak band along with CO peak:

Position Indicates:

Is an O–H band present along with CO peak? A carboxylic acid

Look for a single or double sharp N–H band in the region 3400-3250 cm-1. If there is such a
band:

Position Indicates:

Are there two bands? a primary amine

Is there only one band? a secondary amine

Question: An organic compound having molecular formula C7H6O shows absorption

peaks at 3010, 2700, 1600, 1580, 1480, and 1270 cm-1in its IR spectrum. Suggest its
structure.
Answer:
• 3010 cm-1: presence of an aromatic C-H stretching vibration.
• 2700 cm-1: presence of a C-H stretching vibration.
• 1600 cm-1 and 1580 cm-1: presence of aromatic C=C stretching.

37
 Unit-II Stereochemistry and Spectroscopy

• 1480 cm-1 : presence of an aromatic ring (aromatic C-H bending).

• 1270 cm-1 suggests the presence of C-O stretching vibration of aromatic ketones.
• Possible structure for C7H6O could be benzaldehyde (C6H5CHO), which has an
aldehyde group (C=O) and an aromatic ring.
Possible structure for C7H6O could be benzaldehyde (C6H5CHO), which has an aldehyde group

(C=O) and an aromatic ring.

Question: Distinguish between the following pairs of compounds on the basis of Infrared
spectroscopy: (i) CH3COOH and CH3COO C2H5 (ii) C2H5OH and C2H5OC2H5 (iii) 3-
hydroxypropanal and propanoic acid
Answer:
(i) CH3COOH and CH3COO C2H5
CH3COOH: (-COOH).
• 2500-3500 cm-1- stretching vibration of the O-H bond in the carboxylic acid group.
• 1710 cm-1, C=O stretching vibration in the carboxylic acid group.
CH3COOC2H5: ester functional group (-COO-).
• Absence of 2500-3500 cm-1- stretching vibration of the O-H bond in the carboxylic acid
group.
• 1735 cm-1, C=O stretching vibration in the ester group.
• 1230-1300 cm-1, C-O stretching vibration in the ester group.
(ii) C2H5OH and C2H5OC2H5
• C2H5OH: (-OH).
• 3200-3600 cm-1, stretching vibration of the O-H bond in the alcohol group.
• 1050-1100 cm-1, C-O stretching vibration in the alcohol group.
C2H5OC2H5: ether functional group (-O-).
• 1050-1100 cm-1-C-O stretching vibration in the ether group.
• no peak at 3200-3600 cm-1, indicating the absence of the hydroxyl group.
(iii) 3-hydroxypropanal and propanoic acid

38
 Unit-II Stereochemistry and Spectroscopy

3-hydroxypropanal -
• C=O stretch (aldehyde) --- 1740~1720 (saturated) and 1715~1680 cm −1
(conjugated);
medium; sharp
• O−H stretch (alcohol) --- 3650~3550 and 3550~3200 cm −1; medium to strong; broad
Propanoic acid -
• C=O stretch (carboxylic acid) --- 1725~1700 (saturated) and 1715~1680 cm −1

(conjugated); strong; sharp

• C−O stretch (carboxylic acid) --- 1300~1000 cm −1; strong; sharp
• O−H stretch (carboxylic acid) --- 3200~2500 cm −1; medium to weak; broad
Question: cis-1, 2-dichloroethene is Infra-red active while trans-1, 2-dichloroethene is IR
inactive. Explain.
Answer: When the compound under examination is exposed to IR radiations, cis-1, 2-
dichloroethene undergoes a net change in dipolemoment and hence absorbs in IR. Thus, it is IR
active. On the other hand, trans-1, 2-dichloroethene is symmetrical and does not show any
change in dipole-moment. Hence, it is IR inactive.
• Question: How will you note the progress of the oxidation of 2-Propanol to
Propanone in Infra-red spectroscopy ?
Ans. 2-Propanol shows a strong band at 3400-3200 cm–1 due to O—H str. On the other hand,
propanone shows a strong band at 1715 cm–1 due to C = O str. As oxidation of 2-propanol takes
place, the intensity of O—H band decreases while that of C = Ostr increases. On complete
oxidation, the band at 3400 cm–1-3200 cm–1 will be missing and an intense band at 1715 cm–1
will appear.
What happens to O-H str position when 10 ml of carbon tetrachloride is added to 2 ml of
ethyl alcohol ?

39
 Unit-II Stereochemistry and Spectroscopy

Ans. Ethyl alcohol exhibits intermolecular hydrogen bonding and due to this, absorption band
occurs at 3200 cm–1. When carbon tetrachloride is added it, there is decrease in hydrogen
bonding and thus, the absorption position is raised.
How will you differentiate between o-salicyclic acid and m-salicylic acid?
Ans. In o-salicylic acid, intramolecular hydrogen bonding takes place. Therefore, the O—H str
shifts to some lower wave number. As it is intramolecular, change in concentration does not
cause any shift in O—H str absorption. In case of m-hydroxy benzoic acid, O—H str occurs at a
still lower value due to intermolecular hydrogen bonding. Moreover, the absorption band will be
broad and position of absorption shifts with dilution.

40
 Unit-II Stereochemistry and Spectroscopy

NMR spectroscopy
This technique is based on transitions between nuclear spin states by absorption of
electromagnetic radiations in the radiofrequency region of roughly 4 to 900 MHz by certain
organic molecules when they are placed in a strong magnetic field. Subatomic particles
(electrons, protons, and neutrons) can be imagined as spinning on their axes. In many atoms
(such as 12C) these spins are paired against each other, such that the nucleus of the atom has no
overall spin. However, in some atoms (such as 1H and 13C) the nucleus does possess an overall
spin (I).
How to determine value of I
1. Even numbers of both protons and neutrons: NO spin (I=0).
2. Odd numbers of both protons and neutrons: I=integer spin (i.e. 1, 2, 3)
3. Odd/even and even/odd Neutrons and protons: I=half-integer spin (1/2, 3/2, 5/2)
Motion of charged particle creates magnetic field. In absence of external influence,
magnetic poles (spin axis) randomly oriented. Add external magnetic field (Bo): spins align. Acc.
to Quantum mechanics:
possible orientations for a nucleus of spin I = 2I + 1.
for 1H, I = 1/2 , possible orientations = 2I + 1=2
In the absence of an external magnetic field, these orientations are of equal energy. If a magnetic
field is applied, then the energy levels split. Each level is given a magnetic quantum number, m.

Resonance: In NMR spectroscopy, resonance is the absorption of energy by a precessing

nucleus and the resulting “flip” of its nuclear spin from a lower energy state to a higher energy

41
 Unit-II Stereochemistry and Spectroscopy

state. The precessing spins induce an oscillating magnetic field that is recorded as a signal by the
instrument. Signal: A recording in an NMR spectrum of a nuclear magnetic resonance.
Nuclei in different environments (i.e. with different amounts of electron density around them)
will require different amounts of energy to “flip” to higher energy different spin state.

Larmor Equation
Energy difference is proportional to the magnetic field strength. DE = hn
!"#!
$"B
"! where, Gyromagnetic ratio, g, is a constant for each nucleus !"#"$%&'($#%! & "#' "#

42
 Unit-II Stereochemistry and Spectroscopy

Question: In a 12 T magnetic field, calculate the frequency at which radiation comes into
resonance with proton spin.
&! '($)*
!"#"$%&'(H$," * #$- #$
)B."/H$," * #$- #$H$)(*
)"#
)HM.$1
B #$
'/$$H$, - '/$$234.
NMR Spectrum = plot of photon energy versus photon quantity

Information from NMR spectra

• Number of signals =number of nonequivalent proton groups in molecule
• Position of signals (chemical shift)= magnetic environment of protons
• Relative intensity of signals (integration)= ratio of equivalent proton types
• Splitting of signals (spin-spin coupling)= proton neighbors
Equivalent protons = Hydrogens that have the same chemical environment.
Nonequivalent protons = Hydrogens that don’t have the same chemical environment.

Enantiotopic protons- If replacement of one hydrogen at a time in separate models creates

enantiomers, the hydrogens are enantiotopic. Enantiotopic protons have the same chemical shifts.
Diastereotopic protons- If replacement of hydrogens in separate models creates diastereomers,
the hydrogens are diastereotopic. Diastereotopic protons have different chemical shifts.

43
 Unit-II Stereochemistry and Spectroscopy

C " " C
!"#!"$!"$!"#% ! !
!"#!"$ !"# !"#!"$ !"#

Number of signals
The number of NMR signals ~ the number of different types of 1Hs.

44
 Unit-II Stereochemistry and Spectroscopy

Chemical shift
A signal in the spectrum is referred to as a resonance. The frequency of a signal is known as its
chemical shift. The chemical shift in absolute terms is defined by the frequency of the resonance
expressed with reference to a standard compound which is defined to be at 0 ppm. The scale is
made more manageable by expressing it in parts per million (ppm) and is indepedent of the
spectrometer frequency. It is often convenient to describe the relative positions of the resonances
in an NMR spectrum. Increasing chemical shift is plotted from left to right. Most protons absorb
between 0-10 ppm.
The terms “upfield” and “downfield” describe the relative location of peaks. Upfield means to
the right. Downfield means to the left.
NMR absorptions are measured relative to the position of a reference peak at 0 ppm on the δ
scale due to tetramethylsilane (TMS). TMS is a volatile inert compound that gives a single peak
upfield from typical NMR absorptions.

#$%
$%# !" #$%
#$%

TMS has following advantages as the reference compound:

• It is chemically inert and non-toxic.
• It is volatile ([Link] 27oC) and soluble in most organic solvents.
• It gives a single sharp peak as it has 12 equivalent hydrogens.
• 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.
C'()*H(,H-.
/'M1(234C'()*H5H
CSM2*T%1M*MTH)TM89M,2:H(,H#-.
!"! "#$
H#$% ;<=!
!%

Question. What is the shift of the resonance from TMS of a group of nuclei with δ = 3.50
and an operating frequency of 350 MHz?

45
 Unit-II Stereochemistry and Spectroscopy

! " !!"#
! "# $%&!
!$
! $! $
! " !!"# =
%&!
'()&$')&"$%&! "*H
"#
%&!
#%,,)"*H

Factors affecting chemical shift

1. Deshielding by electron withdrawing groups and shielding by electron donating groups.
2. Anisotropic fields usually due to pi-bonded electrons in the molecule.
3. Deshielding due to hydrogen bonding.
Shielding and deshielding: The electrons around the nucleus are induced to circulate in a
magnetic field and create a magnetic field that opposes the applied field. Since this reduces the
field experienced at the nucleus, the electrons are said to shield the proton.
• Electron donating groups tend to increase the electron density and shield the nucleus.
• Electron withdrawing groups tend to draw the electron density towards them and deshield
the nucleus.
deshielding increases with the electronegativity of atom X

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 Unit-II Stereochemistry and Spectroscopy

Anisotropic effect: Anisotropic" means "non-uniform“ and magnetic anisotropy means a "non-
uniform magnetic field". Electrons in π systems (e.g. aromatics, alkenes, alkynes etc.) interact
with the applied field which induces a magnetic field that causes the anisotropy. As a result, the
nearby protons will experience 3 fields: the applied field, the shielding field of the valence
electrons and the field due to the π system. Depending on the position of the proton in this third
field, it can be either shielded (smaller δ) or deshielded (larger δ).

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 Unit-II Stereochemistry and Spectroscopy

Acetylenic protons: shielding effect, d=2.5 Vinylic protons: deshielding effect d=5-7
Hydrogen bonding: Hydrogen bonding lengthens the O-H bond and reduces the valence
electron density around the proton. It is deshielded and shifted downfield in the NMR spectrum.
Effect of dilution will be observed for intermolecular H-bonding causing a decrease in extent of
H-bonding while intramolecular H-bonding will remain the same.

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 Unit-II Stereochemistry and Spectroscopy

SPIN-SPIN SPLITTING
Often a group of hydrogens will appear as a multiplet rather than as a single peak. This happens
because of interaction with neighboring hydrogens and is called SPIN-SPIN SPLITTING.
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.
Signal splitting: Splitting of an NMR signal into a set of peaks by the influence of neighboring
nonequivalent hydrogens.
(n + 1) rule: If a hydrogen has n neighboring hydrogens in same chemical environment, signal is
split into (n + 1) peaks. It is also known as multiplicity.

Rules for splitting

• Equivalent protons do not split each other.
• Protons bonded to the same carbon will split each other if they are nonequivalent.
• Protons on adjacent carbons normally will split each other.
• Protons separated by four or more bonds will not split each other.
• The relative intensities of the lines in a coupling pattern is given by a binomial expansion
or more conveniently by Pascal's triangle.

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 Unit-II Stereochemistry and Spectroscopy

Coupling constant J
It is the distance (measured in Hz) between the peaks in a multiplet and is not dependent on
strength of the external field. J is a measure of the amount of interaction between the two sets of
hydrogens creating the multiplet.

Vicinal coupling-between hydrogens on adjacent carbon atoms.

Integral
Not only does each different type of hydrogen give a distinct peak in the NMR spectrum, but we
can also tell the relative numbers of each type of hydrogen by a process called integration.
Integration = determination of the area under a peak- S-shaped curve
The area under a peak is proportional to the number of hydrogens that generate the peak.
!"#$%&'()'! '*%H'()',&(H(-* .%/0NH'/-'##'()'/-H%0&23')(&'! '*%H'()',&(H(-*
4
!"#$%&'()'" '*%H'()',&(H(-* .%/0NH'/-'##'()'/-H%0&23')(&'" '*%H'()',&(H(-*

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 Unit-II Stereochemistry and Spectroscopy

Heights of integral: 2 cm, 3 cm and 3 cm

The ratio of the peak areas =[Link].

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 Unit-II Stereochemistry and Spectroscopy

Question: Distinguish between CH3COCH3 and CH3COCH2CH3

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 Unit-II Stereochemistry and Spectroscopy

Question: Discuss splitting of NMR signals

Question: A compound has molecular formula C8H8O. Assign the structure if the proton NMR
has three peaks:
1. singlet at δ 2.2 (3H),
2. singlet at δ 10 (1H)
3. two doublets centred around δ 7.6.
SOLUTION:
1. The doublets centered at δ = 7.6 -aromatic region
2. Two doublets -1,4-disubstituted aromatic compound.
3. The peak at d = 2.2 -methyl group adjacent a mildly electronegative group.
4. The singlet at d = 10 -aldehydic protons.

4-methylbenzaldehyde
Question: Two isomeric has molecular formula C10H14. Assign the structure if the proton NMR
has following peaks:
1. A isomer- δ 1.3 (9H,s), δ 7.28 (5H,s)
2. B isomer- δ 0.88 (6H,d), δ 1.86 (1H,m), δ 2.45 (2H,d), δ 7.12 (5H,s)
SOLUTION:
A isomer- δ 7.28 (5H,s) – phenyl ring
δ 1.3 (9H,s) –tert. Butyl group
B isomer-
δ 7.28 (5H,s) – phenyl ring

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 Unit-II Stereochemistry and Spectroscopy

δ 2.45 (2H,d) – doublet means attached to another carbon having proton

δ 0.88 (6H,d) –doublet means attached to another carbon having proton
δ 1.86 (1H,m) –multiplet means many neighbouring H atoms

Question: A compound has molecular formula C5H10O. Assign the structure if the proton NMR
has three peaks:
1. singlet at δ 2.10 (3H),
2. doublet at δ 0.95 (6H)
3. multiplets at δ 2.43 (1H).
SOLUTION:
1. multiplets at δ 2.43 (1H)- –CH group with many neighbouring H atoms
2. doublet at δ 0.95 (6H) –two methyl groups attached at one –CH group
3. singlet at δ 2.10 (3H)- one methyl group isolated.

54