Spectroscopy

It is the branch of science that

deals with the study of interaction of
electromagnetic radiation with
matter.
Spectroscopy is used in physical and analytical
chemistry to detect, determine, or quantify the
molecular and/or structural composition of a sample.
Each type of molecule and atom will reflect, absorb,
or emit electromagnetic radiation in its own
characteristic way.

Matter: Anything which occupies space in universe

and having mass is called matter.
 Beer-Lambert’s Law:
It state that, when monochromatic radiations are
passed through homogeneous sample solution, then
the absorbance of sample is directly proportional to
the concentration and path length of the sample.

A= ɛcl

Where A is the absorbance, c is the concentration of the

molecule in mol/l or Molarity (M), and l is the path length
of sample cell in cm and ɛ is the molar absorptivity
coefficient in cm2mol-1 or cm-1M-1.
Also, Absorbance is logarithm of the reciprocal of
transmittance. So,

A = log10 (1/T) = log10 (Io/I)

Where I0 is the intensity of incident light, I is the

intensity of transmitted light and T is transmittance.

The equation A = Log Io/I = Ɛcl

shows linear relationship between absorbance and
concentration of the absorbing molecule (or
chromophore).
Numericals
Q1. A compound having concentration 10-3 g/l
resulted absorbance value 0.20 at λmax 510 nm
using 1 cm cell. Calculate its absorptivity and
molar absorptivity values. Molecular weight of
compound is 400.
Ans: Given: c = 10-3 g/l; l= 1 cm; A = 0.20
A = Ɛcl
Ɛ = A/cl = 0.20/10-3 x 1 = 200 gl-1cm-1
Molecular wt. of compound = 400
Molar conc. cM = 10-3 / 400 = 0.25 x 10-5 mol/l
A = Ɛm cM l or Ɛm= A/ cM l
= 0.20/ 0.25 x 10-5 x 1 = 8 x 104 l mol-1cm-1
Q2: The molar absorption coefficient of tyrosine in
water is 1280 M-1cm-1 at 280 nm. Calculate the
concentration of a tyrosine solution in water if the
absorbance of the solution is 0.34 in a 1 cm path
length cell.
Ans: Given:

λ = 280 nm; ε = 1280 M-1cm-1; l = 1 cm; A = 0.34

From Beer-Lambert Law,

A = εcl
c = / = 0.32/ (1280 M-1 cm-1 × 1 cm)
= 0.00025 M = 250 μM
Q3: Calculate absorbance if (%T) i.e. percentage
transmittance of a solution is 80.
Ans. A = log (1/T) = log(Io/I) = log 100/80 = 0.097

Q4: When U.V. Light is passed through a solution,

the radiant power is reduced to 50%. Calculate the
absorbance.
Ans: Let radiant power of U.V. Light passed through
the solution be Po.
So, if P is the radiant power of emitted light then,
P = 50/100 Po
P = 0.5 Po
Therefore, Absorbance will be given by,

A = log Po
P

= log Po
0.5 Po

= log 2

= 0.301
Ultra Violet- Visible Spectroscopy
UV-visible spectroscopy is concerned with the study of
absorption of UV-visible radiations which ranges from
200 to 800 nm (200-400nm- UV, 400-800 nm- visible).
UV region is divided into:

Type of electrons in a molecule Orbitals involved

Near UV 250 nm – 400 nm
Far UV region 190 nm – 250 nm
Vacuum UV region < 190 nm

Ordinary UV-Visible measurements are carried out from about

200nm to 800 nm. Below 200nm, the measurements are done
under vacuum to avoid absorbance signals from air components
like CO2. Therefore, region below 200 nm is called vacuum UV.
Various Electronic transition on molecule

• Various transitions that are possible in a compound on absorption of

follows:

1. σ→ σ* transition:
 σ → σ* transition is a high energy process.
 σ electrons are strongly held, so require high energy for transitio

 lies in the vacuum UV region.

 electron from σ orbital is excited to corresponding
• anti-bonding orbital σ*.
 Chromophore
Generally, the part of a molecule responsible for
imparting colour, is known as chromophore.
Chromophores are the functional groups
containing multiple bonds, which are capable of
absorbing radiations above 200 nm due to n → π*
& π → π* transitions.
They may or may not impart the colour to the
molecule but absorbs the radiations between 200- 800
nm. e.g. NO2, N=O, C=O, C=N, C≡N, C=C, C=S, etc.
 Auxochrome:

 It is a group which itself does not act as a

chromophore but when attached to a chromophore, it
shifts the adsorption towards longer wavelength along
with an increase in the intensity of absorption.
 All auxochromes have one or more non-bonding
pairs of electrons.
 If an auxochromes is attached to a chromophore, it
helps is extending the conjugation by sharing of non-
bonding pair of electrons.
Some commonly known auxochromic groups
are: -OH, -NH2, -OR, -NHR, and –NR 2 .
For example:
Benzene: λmax = 255 nm
Phenol: -OH group attached to benzene,
λmax = 270 nm
Aniline: -NH2 group attached to benzene,
λmax = 280 nm
 ABSORPTION AND INTENSITY SHIFTS:
1. Bathochromic Shift (Red Shift)

 When absorption maxima (λmax) of a compound

shifts to longer wavelength, it is known as
bathochromic shift or red shift.
 The effect is due to presence of an auxochrome or
by the change of solvent. e.g. an auxochrome
 Group like –
OH, -OCH3
causes
absorption of
compound at
longer
wavelength.
2. Hypsochromic Shift (Blue Shift)

 When absorption maxima (λmax) of a compound

shifts to shorter wavelength, it is known as
hypsochromic shift or blue shift.
 The effect is due to removal of an auxochromic
group which causes the
removal of conjugation
or by the change of
solvent. e.g.: Aniline
shows blue shift in
acidic medium, since it
loses conjugation.
3. Hyperchromic Effect:

 When absorption intensity (ε) of a compound is

increased, it is known as hyperchromic shift.
 If Auxochrome introduces to the compound, the
intensity of absorption increases.
4. Hypochromic Effect:

 When absorption intensity (ε) of a compound is

decreased, it is known as hypochromic shift.
 This is caused by the introduction of a group which
distorts the chromophore by forcing the rings out of
coplanarity resulting in the loss of conjugation.
Summary of different shift in Absorption spectra
Factors responsible for shifts in UV-Vis spectroscop

1. Conjugation: The higher the extent of conjugation,

the more is the bathochromic shift. This results in the
bathochromic shift.
Auxochrome:
 Auxochromes are the chemical groups that
result in a bathochromic shift when attached to a
chromophore.
 They exhibit bathochromism by extending
conjugation through resonance.

Solvents effect:
 The solvents used in any spectroscopic method
should ideally be transparent (non-absorbing) to
the electromagnetic radiation being used.
 The polarity of solvents is an important factor in
causing shifts in the absorption spectra. This is
because polar solvents stabilize all the three
molecular orbitals (n, π, and π*).
 Nonbonding orbital (n) stabilizes more than
antibonding π* orbital and bonding π orbital as
shown in the following figure.
 Following is the order of decrease in energy of
respective molecular orbital in polar solvent.
∆Eπ < ∆Eπ* < ∆En
 Thus two electronic transitions π → π* and n →
π* respond differently to the changes in polarity.
APPLICATIONS OF UV - Vis SPECTROSCOPY

 Qualitative & Quantitative Analysis:

 It is used for characterizing aromatic compound and
conjugated olefins.
 It can be used to find out molar concentration of the
solute under study.
 Detection of impurities: It is one of the important
method to detect impurities in organic solvents.

 Detection of isomers are possible.

 Determination of molecular weight using Beer’s law .
Woodward Fieser Rule
 Applicable for conjugated diene
 Applicable to conjugated carbonyl compound

1. Type of conjugated diene

Acyclic diene Base value: 217 nm

or

Homoannular Diene Heteroannular Diene

Base Value = Base Value
253 nm = 214 nm
2. Type of double bond characteristic Endocyclic
double bond: Any double
bondwhere both thecarbon is
a part ofring orcyclic
structure
concerned called endocyclic double
Exocyclic Double
bond.
bond: Any double
bond where only
one of carbon is a
part of ring or the
concerned cyclic
structure is called
endocyclic double
bond.
3. Alkyl group or Ring residue:
Carbon atom of the ring system or functional group
connected to the carbon of conjugated diene moiety of
the molecule.

4. Addition conjugated double bond:

Look for the additional double bond which extend the
conjugation of double bonds.
Contribution to λmax of otherBase
factorvalue =
Acyclic diene
217 nm
Base value = 253
Homoannular diene nm
Base value =
Heteroannular diene
214 nm
Increment for
Alkyl substituent or ring residue 5 nm
Exocyclic double bond 5 nm
Double bond extending conjugation 30nm
Polar functional group attached to diene part of
molecule
-OCOCH3 (Acetate) 0 nm
-OR (Ether) 6 nm
-Cl 5 nm
-Br 5 nm
Steps for calculation of λmax using
Woodward Fieser rule

 Identify the type of diene species present in

molecule. If a molecule has both homoannular
diene and heteroannular diene in same molecule,
then always consider homoannular diene for base
value = 253 nm.
 Calculate the alkyl substituents or ring residues
which are directly attached to the carbon atoms
making conjugated system within the compound.
 Calculate the number of exocyclic double bond
 Calculate the number of extended double bond in
conjugation to dienes
Example:

Base value = 253 nm

Ring residue/alkyl group = 6 x5 nm = 30 nm
Exocyclic double bond = 1 x 5 nm = 5 nm
Extended double bond =1 x 30 nm= 30 nm
conjugated to diene

Thus calculate λmax = 318 nm

 Base value = 214 nm
Ring residue/alkyl group = 7 x5 nm = 35 nm
Exocyclic double bond = 2 x 5 nm = 10 nm
Extended double bond =1 x 30 nm= 30 nm
conjugated to diene

Thus calculate λmax = 289 nm

Infrared Spectroscopy
It is also known as Vibrational Spectroscopy

Emol = Eel + Evib + Erot

It is the study of Vibrational transition in molecule

which occur via excitation of electron from vibrational
ground state to vibrational excited state by absorption
light in infrared radiation.

It is mainly used in structure elucidation to determine

the functional groups
Hooke’s law and frequency of vibration
Each vibration in molecule can be treated as a spring
where spring vibrate with frequency (ν) mentioned
below. These vibration in molecule can be explained
by Hooke's law which state that force acting on atom
during vibration is directly proportion to the
displacement given below.

2
 Type of Molecular Vibration:
There are 2 types of vibrations:
 Stretching vibrations
 Bending vibrations

1. Stretching vibrations: Vibration or oscillation

along the line of bond is called stretching vibration.
There occurs a change in bond length.

2. Bending vibrations: Vibration are not along the

line of bond. Bond angle changes during vibration
which results in the deformation of molecule.
Stretching vibrations are of two types:
 Symmetric stretching: The bonds increase or
decrease in length simultaneously. i.e. either
both the atoms approach central atom or moves
away from it.
 Asymmetric stretching: in this, one bonds
length is increased and other is decreased. i.e.
on of the two atoms approaches the central
atom and the other moves away from it.
a) In plane bending

 Scissoring: This is an in-plane blending in

which two atoms approach each other and bond
angles decreases or vice versa.
 Rocking: Change of angle between two bonds
due to movement of atoms take place in the
same direction.
b) Out plane bending
 Wagging: 2 atoms move to one side of the plane.
They move up and down the plane.
 Twisting: One atom moves above the plane and
another atom moves below the plane.
Symmetric Stretching Scissoring Twisting

Asymmetric Stretching Rocking Wagging

Different types of vibration mode

Summary of different type of vibration mode
Selection rule for vibrational spectroscopy:
(a) Molecule should have permanent dipole moment
or should create dipole moment during vibration

(b) Vibrational Quantum Number change ∆ν = ±1

Functional Group Region (4000-1500 cm-1):

 The most common application of IR spectroscopy is
perhaps to identify the functional groups. This is
possible because different functional groups vibrate
at different frequencies allowing their identification.
 The frequency of vibration, however, depends on
additional factors such as delocalization of
electrons, H-bonding, and substitutions at the
nearby groups.
 Region from 4000-1500 cm-1 in an IR spectrum is
useful for identification of functional groups.
 This region shows the absorption due to
stretching mode.
Functional group vibrational frequency
Wavenumbe
Bond Molecule
r (cm-1)

Alcohol, ethers,
C-O 1300-1000
esters, carboxylic
acid etc

Alcohol, Ketones,
C=O 1750-1680
esters, carboxylic
acid
C=O Amide 1680-1630
N-H
Amine, Amides 3500-3100
(stretching)
-N-H Amine, Amides
1640-1550
(bending)
O-H Alcohols 3650-3200
C-N Amine 1350-1000
 Factor effecting vibrational frequency:

1. Bond order: Bond order affects the position of

absorption bands. Higher the bond order larger is the
band frequency
2. Electronic Effects: Resonance and Inductive
Inductive effect
The effect on electron density in one portion of a
molecule due to electron-withdrawing or electron-
donating groups elsewhere in the molecule.
Resonance
effect
Hydrogen Bonding:

 The presence of hydrogen bonding changes the

position and shape of an infrared absorption band.
 Stronger the hydrogen bonding, greater is the
absorption shift from the normal values which result
in red shift in IR spectra.
 The two types of hydrogen bonding
(intramolecular and intermolecular) can be
differentiated by the use of infrared spectroscopy.
 Application of IR Spectroscopy
 Qualitative Analysis: Main application of IR
spectroscopy is compound identification.
 Determination of Purity of a sample.
 To identify cis and trans isomers of a
compound. IR absorption of a trans isomer is very
weak and of cis is stronger.
 Distinguish between inter and intra molecular H
bonding.
 Structural information: IR spectra provides
valuable information regarding molecular symmetry,
dipole moments, bond strength, characteristic
absorption etc.
Q.4 Two isomers X and Y having molecular formula
C3H6O give IR band near 3550 cm-1 and 1717 cm-1
respectively. Assign structural formula to X and Y
consistent with their IR absorption band.
Sol: Two isomers X and Y have molecular formula
C3H6O.
Double bond equivalence in isomer 1 and isomer 2
= C - H/2 + 1 = 3 – 6/2 + 1 = 1
So; X and Y isomer may have one double bond thus
possibilities are C=C or C=O.
1) The peak at 3550 cm-1 corresponds to alcoholic
group (-OH). So, structural formula is CH2=CH-
CH2OH.
2) The peak at 1717 cm-1 corresponds to –C=O
group stretching frequency (ketone group). So,
structural formula is CH3COCH3.
What is Nuclear Magnetic Resonance
Spectroscopy
Nuclear magnetic resonance spectroscopy, commonly
known as NMR spectroscopy or magnetic resonance
spectroscopy (MRS), is a spectroscopic technique to
observe local magnetic fields around atomic nuclei

 It is based on the absorption of electromagnetic

radiation in the radiofrequency region ranging from
4 to 900 MHz by nuclei of the atoms.

 NMR has become the preeminent technique for

determining the structure of organic compounds.
Principle of NMR Spectroscopy

1. The principle behind NMR is that many nuclei have spin and
electrically charged. If an external magnetic field is applied, an
possible between the lower energy to a higher energy level

2. The energy transfer takes place at a wavelength that corresponds

frequencies and when the spin returns to its lower level, energy
same frequency.

3. The signal that matches this transfer is measured in many ways

order to yield an NMR spectrum for the nucleus concerned.
Magnetic:

o All nuclei with odd number

of protons
o All nuclei with odd number
of neutrons

Nonmagnetic:

o Nuclei with even number of

both protons and neutrons

88
 Shielding effect
 Shielding determines how nuclei interact with the magnetic field
and the Chemical shift of the signal
 The electron cloud surrounding a nucleus opposes the applied
field
 The more electrons, the greater the shielding around a proton,
so the field is more strongly opposed
 As a proton becomes deshielded, it is shifted further downfield,
as the magnetic field is able to affect it more
 Electronegative atoms (eg. oxygen or chlorine) will draw electron
density away from the protons, deshielding them
 Less electronegative atoms like carbon will not pull electron
density, leaving the proton shielded, so it is not shifted.
• As the proton’s electron cloud reduces, the nucleus
is exposed to more of the external magnetic field
(B0)
• The energy gap increases causing magnetic
resonance frequency to change. This changes the
emissions frequency from relaxation
• This results in a greater chemical shift and the
signal appears further downfield
Downfield Upfield

Chemical shift
Nuclear shielding and deshielding
 The external magnetic field is uniform over the entire
molecule and therefore cannot differentiate to the
different types of the proton. However the induced
magnetic field generated by the e- around the nucleus
is not uniform, this situation makes the different spin
active nuclei proton) to be non-equivalent. Thus each
proton in the different electronic environment show
slightly different magnetic field due to the circulation of
e- in the neighboring bond.

 Thus the effective magnetic field for the different spin

active nuclei can be calculated through the following
equations: H effect = H0 – H induced
H effect = H0 – H induced
Form the above equation the shielded and deshielded proton
concept can be given as:

For shielding: For deshielding:

Proton in the electron Proton in the

rich environment electron deficient
↓ environmen
High H induced t
↓ ↓
Low H effect Low H induced
↓ ↓
Low frequency absorption High H effect
in NMR spectra ↓
↓ High frequency
Low chemical shift absorption in NMR
spectra
↓
High chemical shift
NMR Chemical Shift Values
Internal standard for NMR spectroscopy:
That compound which is used as a reference standard to
represent the NMR/PMR signal of the compounds is
known as internal standard for the NMR or PMR
spectroscopy.
In case of PMR spectroscopy Tetramethylsilane (TMS)
used as a internal standard due to the following reasons:

Tetramethylsilane
Why TMS ?

1. Due to the more shielded nature of the proton of

TMS in compare to the protons of most of the
organic compound.

2. It is chemically inert and miscible with large range

of solvent.

3. It does not take part in intermolecular association

with the sample.

4. Due to the volatile nature of TMS.

Splitting patterns
 In the spectrum below, there is a signal for each
environment, however, they appear split.
 These split peaks are multiplets.
 The number of peaks in a multiplet provides
information about neighbouring protons.
 Splitting is caused by the interaction between
inequivalent protons, called coupling
 Proton-proton coupling usually takes place 3 bonds
away from each other
 The number of peaks, or multiplicity, comes from the
number of protons interacting
 The number of peaks follows an n+1 pattern, where
n is the number of protons in the interacting
environment
 The number of peaks observed is the multiplicity
 The intensity of the peaks in a multiplet follows the
pattern of Pascal’s triangle
  eg. If a group of protons has 2 neighbouring equivalent
protons, it will be split into a triplet.

0 neighbouring protons Singlet

1 neighbouring proton Doublet

2 neighbouring protons Triplet

3 neighbouring protons Quartet

 This is known as Pascal's triangle.

Instrumentation of Nuclear Magnetic
Resonance (NMR) Spectroscopy

1. Sample holder: Glass tube with 8.5 cm long, 0.3

cm in diameter.
2. Permanent magnet: It provides a homogeneous
magnetic field at 60-100 MHZ
3. Magnetic coils: These coils induce a magnetic
field when current flows through them
4. Sweep generator: To produce an equal amount of
magnetic field pass through the sample
Instrumentation of Nuclear Magnetic
Resonance (NMR) Spectroscopy

5. Radio frequency transmitter: A radio transmitter

coil transmitter that produces a short powerful
pulse of radio waves
6. Radio frequency receiver: A radio receiver coil
that detects radio frequencies emitted as nuclei
relax to a lower energy level
7. Read out systems: A computer that analyses and
records the data.
Applications of NMR Spectroscopy
NMR spectroscopy is the use of the NMR phenomenon to study
the physical, chemical, and biological properties of matter.
Application of NMR are as follows:
1. It is an analytical chemistry technique used in quality control.
2. NMR spectroscopy is used in research for determining
the molecular structure.
3. NMR can quantitatively analyze mixtures containing known
compounds.
4. NMR spectroscopy techniques are being used for the
determination of protein structure.
5. NMR spectroscopy techniques are used to probe molecular
dynamics in solution.
6. Solid state NMR spectroscopy is used to determine the
molecular structure of solids.
Problems on NMR Spectroscopy
Problem: How many protonic signals would be expected from
NMR spectra of the following:
a) ClCH2CH2Cl b) CH3OCH3 c) CH3CHClC2H5
d) CH3COCH3 e) CH3CH2CHO f) CH3COOCH3
Solution: a a
a) ClCH2CH2Cl 1 signal
a a
b) CH3OCH3 1 signal
a b c d
c) CH3CHClCH2CH3 4 signal
a a
d) CH3COCH3 1 signal
a b c
e) CH3CH2CHO 3 signal
a b
f) CH3COOCH3 2 signal
Numerical
Q1. A compound having molecular formula C6H10O2
gave the following 1H-NMR data- δ 1.30 (6H, s); δ 2.1
(3H, s); δ 2.6 (2H, s); δ 3.9 (1H, s).
Identify the compound.
Solution: Molecular formula of compound = C6H12O2
Double bond equivalence in compound
= C - H/2 + 1 = 6 – 12/2 + 1 = 1
Molecule will have one double bond
NMR data Reason Structure
δ 1.3 (6H, s); Since C6H12O2 molecule
δ 2.1 (3H, s); shows 2 signals,
δ 2.6 (2H, s); indicates 2 sets of
δ 3.9 (1H, s). protons present in the
molecule.
Q2. Two isomeric compounds A and
B have molecular formula C10H14. 1H-NMR
spectra of these gave the following data:
IsomerB:A:δδ0.88
Isomer 1.30(6H,
(9H,d);s);
δ δ 7.28
1.86 (5H,
(1H, m); s)
δ 2.45
(2H, d); δ 7.12 (5H, s)
Giving reasons assign the structures for the two
isomers. 2022-2023
Solution:
Double bond equivalence in isomer A and isomer B
= C - H/2 + 1= 10 – 14/2 + 1 = 4
Molecule will have three double bond and one ring
thus part of the molecule will have benzene ring
Solutio
n:NMR data Reason Structure
Isomer A: Since C10H14 molecule
δ1.30 (9H, s); shows 2 signals,
δ 7.28 (5H, s) indicates 2 sets of
protons present in the
molecule.
NMR data Reason Structure
Isomer B: • Since C10H14 molecule
δ 0.88 (6H, d); shows 2 signals,
δ 1.86 (1H, m); indicates 2 sets of
δ 2.45 (2H, d); protons present
δ 7.12 (5H, s) in the molecule.
Q3 Predict the number of
signals andsplitting patterns in 1H NMR
of CH3CCl2CH3 and CH3OCH2CH3. 2022-2023
Solution:
CH3CCl2CH3 : All protons are chemically equivalent
i.e. only one signal which will be a singlet
a b c
CH3OCH2CH3 : There are 3 chemically non
equivalent protons i.e. three signals
Ha : singlet
Hb : quartet
Hc : triplet
Q4 A compound having molecular formula C4H9Br gave
the following signals in its 1H NMR spectra :
δ 1.04 (6H,d), δ 1.95 (1H,m), δ 3.33 (2H,d)
Giving reasons assign the structures for the compound.
Solution: 2022-2023
Double bond equivalence
= C - H/2 + N/2 + 1 – X/2
= 4 – 9/2 + 0/2 + 1 – ½
=0
Now, δ = 1.04, there is a doublet for 6 hydrogens i.e there
are two CH3 groups. therefore, (CH3)2CH-
Also, δ = 1.95, there is a multiplet because if one hydrogen
i.e., a CH- group attached to other alkyl groups
And, δ = 3.33, there is a doublet due to two hydrogens i.e.
a -CH2 group attached to –CH
Stereoisomers – compounds with
the same connectivity, different
arrangement in space
Enantiomers – stereoisomers that are non-
superimposible mirror images; only properties that
differ are direction (+ or -) of optical rotation

Diastereomers – stereoisomers that are not mirror

images; different compounds with different physical
properties
 Stereocenters
 An asymmetric carbon atom is the most common
example of a chirality center.
 Chirality centers belong to an even broader group
called stereocenters. A stereocenter (or stereogenic
atom) is any atom at which the interchange of two
groups gives a stereoisomer.
 Asymmetric carbons and the double-bonded
carbon atoms in cis-trans isomers are the most
common types of stereocenters
 Geometrical Isomers
 Stereoisomerism ascribed to different directional arrangements
of specifically located groups in the molecule and usually
considered to be caused by prevention of free rotation in parts of
the molecule (as by a double bond or a ring).
 This type of isomerism most frequently involves in compounds
containing carbon-carbon double bonds with suitable
substituents. Rotation of these bonds is restricted, compared to
single bonds, which can rotate freely.
 This means that, if there are two different atoms, or groups of
atoms, attached to each carbon of the carbon-carbon double
bond, they can be arranged in different ways to give different
molecules.
Example of geometrical isomerism:
a. 1,2 dichlorto cyclopropane

b. 1,2 dimethyle cyclohexane

c. 1,2 dichlorto cyclopropane

Optical isomer without chiral carbon

 Atropisomerism

 Allenes

 Spiranes
1. Atropisomerism
Atropisomers are Stereoisomers obtained due to the
restricted rotation about carbon-carbon single bond
are called atropisomers and the phenomenon is called
atropisomerism. Such compounds also have the
chirality due to the axis.
Biphenyl shows the enantiomerism when the molecule
has the following properties
 Each ring must be unsymmetrically substituted. Each
of the rings should not contain any kind of symmetry
element

 Suitable substitution (at least one substitution) at

ortho- position must be there at each rings.
 othro- substituents must be larger in size (-Cl, -Br, -I, -
COOH, -NO2, -NHCOCH3, - SO3H, -R groups etc.).
Optical isomers without chiral center
BIPHENYL DERIVATIVES

c
 Optical Isomerism in achiral Spiro
Compounds
Example
4 3
1
2

4 2 1
3
View
1
3 2 4 R

3
4 1
2
1 2
3 4
View
1 S
4
2
3
2. Optical activity in spiranes
 Stereochemistry of Spiranes: When both the double
bonds in allenes are replaced with the ring system the
resulting compounds are known as spiranes or spiro
compounds
 The two rings of spiranes are
perpendicular to each other .

 Proper substitution on the terminal carbon will make

the molecule chiral and thus exhibit enantiomerism.
 Optical Isomerism in achiral Spiro Compounds
Example
3 1
2
4 3

View
4 1
2 R

3 1
2
4 3

View
R
4 1 2
3. Optical isomerism in allenes
 Allenes are compounds with two double bonds side-
by-side. Such bonds are called cumulated double
bonds.
 The central carbon of allene forms two sigma bonds
and two pi bonds.

 The central carbon is sp-hybridized and the two

terminal carbons are sp2 -hybridized.
 The two π-bonds attached to the central carbon are
perpendicular to each other.
 The two rings of spiranes are perpendicular to each other .
 Allene exhibit enantiomorphism, if each of the terminal sp2
carbon atoms contain non-identical substituent.
 Allenes cannot exhibit optical isomerism.

Example
Problem on Stereochemistry

Q : Asymmetrically substituted compounds having

even number of cumulative double bonds exhibit
optical isomerism whereas compounds having odd
number of cumulative double bonds exhibit
geometrical isomerism . Explain giving proper
reasons. 2022-2023
Cumulene exhibiting optical
isomerism

Cumulene analogous to Allene: it having cumulative

even number of double bond exhibit optical isomerism
 The alternate π-bonds attached to the carbon are
perpendicular to each other.
 This result in the group attached to terminal carbon
are not in one plane. Hence molecule have chiral
plane.
 Thus they exhibit optical isomerism (R-S
configuration).
Cumulene exhibiting geometrical
isomerism
Cumulene analogous to Alkene: it having
cumulative odd number of double bond and exhibit
geometrical isomerism
Since the alternate π-bonds attached to the carbon are
perpendicular to each other.
This result in the group attached to terminal carbon are
in one plane.

Thus they exhibit geometrical isomerism (E-Z isomers)

 CHIRAL DRUGS
 Chemical compounds that come as mirror-image
pairs are referred to by chemists as chiral or handed
molecules.

 Each twin is called an enantiomer. Drugs that

exhibit handedness are referred to as chiral drugs.

 Chiral drugs that are equimolar (1:1) mixture of

enantiomers are called racemic drugs and these are
obviously devoid of optical rotation.
Few examples of chiral drugs whose
enantiomers have vastly different
properties
Thalidomide Chiral Drug

 R- enantiomer is an effective sedative with a soothing effect that

relieves anxiety
 whereas S- enantiomer causes teratogenic birth defects.
Carvone Chiral Drug

 These two smells differently. R-carvone smells

like spearmint
 whereas S- carvone smells like caraway seed.
Ibuprofen Chiral Drug

 S-ibuprofen is a pain killer drug

 whereas R-ibuprofen is inactive.