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ULTRAVIOLET AND VISIBLE SPECTROSCOPY

LECTURE NOTES: DR. CYRIAC MATHEW


Lecture notes: Dr. Cyriac Mathew

All organic compounds absorb light in the visible or UV region of the electromagnetic spectrum. Absorption
of visible or UV light by molecules will occur only when the energy of the incident radiation is the same as that of the
possible electronic transition in the molecules involved. Such absorption of energy is termed electronic excitation
and correspond to promotion of an electron from the ground state to a higher excited electronic state. In the course
of such high energy transitions it must be expected that the vibrational energy rotational energy (for gaseous
Lecture notes: Dr. Cyriac Mathew

systems) of the molecule will also change. Therefore, the electronic transition
result in broad absorption or emission bands. These bands always contain a
number of fine structure.

absorption
For organic chemists UV spectroscopy is mainly concerned with
electronic transition in conjugated systems. The position and intensities of
Lecture notes: Dr. Cyriac Mathew

absorption band maxima depend to a large extent on the particular system


under consideration. The electronic transitions are very sensitive to structural
changes and reflect the strain imposed on the system by steric and electronic
interactions. Unlike IR spectrum it is not possible to assign functional group max
absorption to fixed and specific region of the UV-visible wavelength scale and
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considerable experience is required in the interpretation of the spectra. However, there exist a large volume of data
covering most structural types which absorb in the UV and visible region between wavelength of 200 nm to 800
nm. Within any family of compounds, it is usually possible to correlate changes in spectra with changes in structure
with fair degree of success. With some class of compounds empirical rules have been worked out which allow one to
calculate with some degree of accuracy the absorption maxima of particular structures and these can be used to
Lectrue notes Dr. Cyriac Mathew

distinguish between and/or confirm structural features.


It is convenient to divide the UV spectrum into two regions: the near UV between 190 nm and 400 nm and
the far UV or vacuum UV below 190 nm. The reason for this arbitrary division is mainly due to the fact that
atmospheric oxygen begins to absorb around 190 nm. Therefore, oxygen must be removed from the
spectrophotometer either by vacuum instruments or by filling with nitrogen, which absorb strongly at about 150 nm
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and below. The technique of using an evacuated spectrophotometer enable the range below 200 nm to be studied.
This region is frequently called the vacuum ultraviolet region. Since glass does not transmit UV radiation well, cells
for holding sample are normally made of quartz. Therefore, the near UV region is also called quartz UV region,
between 200 and 380 nm.
THE ABSORPTION PROCESS: BEER-LAMBERTS LAW
The amount of incident radiation absorbed by a translucent medium can be related to the amount of
medium by two empirical relationships. Beers law relates the absorption to the concentration of the absorbing
solute, and Lamberts law relates the total absorption to the optical path length.
Beers law: The fraction of the incident monochromatic light absorbed by a homogeneous medium is proportional to
the quantity of the absorbing medium.
Lamberts law: The proportion of the monochromatic light absorbed by homogeneous medium is independent of
the intensity of the incident light and each successive layer absorbs an equal fraction of the light incident upon it.
That is path length.
When dealing with solutions it is clear that the amount of absorption depends on the concentration of the
solution and thickness of the layer is the path length of the light. By combining Beers and Lamberts Laws the
Lecture notes: Dr. Cyriac Mathew

fraction of the incident light absorbed is related to the concentration and path length through the solution as
I0
follows: log cl A . Where, I0 is the intensity of the incident monochromatic light, I is the intensity of the
I
transmitted light, is the molar absorptivity (molar extinction coefficient), c is the concentration in mol L 1 of the
absorbing solute in non-absorbing solvent, l is the thickness of the solution in cm (path length) and A is the
1
absorbance or optical density. Rearranging the equation and putting the dimensions length (L) and quantity (mol)
leads to:
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A 1 L2
3
cm 2 mol 1 . Thus, molar absorptivity has the dimensions of area/mol and could be
cl molL L mol
regarded as the photon capture cross section for a mole of the absorbing material at any particular wavelength.
Usually, by convention the units are never expressed. The intensity of an absorption band in the UV-vis spectrum is
usually expressed as the molar absorptivity at maximum absorption, max or log max. Absorptions with max value 104
Lecture notes: Dr. Cyriac Mathew

is a high intensity absorption. Low intensity absorptions correspond to max values less the 103. The intensity of
absorption may also be expressed as transmittance T. T = I/I0.
THE ELECTRONIC EXCITATION
The electronic (UV-vis) absorption spectra result from the interaction of light quanta with electrons. These
interactions under favourable conditions raise the potential energy of the electrons, and the system containing such
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an electron is said to be in the excited state. The energy thus acquired is dissipated largely by collisions with other
molecules. Since the electrons in a molecule are not identical in energy it follows that the energy absorbed in the
excitation process may bring about one or more transitions according to the type of electrons involved. The different
types of electrons involved in promotion to higher excited states are
*
electrons from sigma, pi and non-bonding molecular orbitals. These
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higher energy states are described by molecular orbitals that are


vacant in the ground or unexcited state and are commonly called
ant-bonding orbitals. Anti-bonding orbitals associated with -bonds
are designated as *-orbitals and that of -bond as *-orbitals. As
n-electrons do not form bonds, no anti-bonding orbitals are *
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associated with them. The different types of electronic transitions


involved in UV-visible spectroscopy are: *, n *, *
and n * transitions. E
In general, -electrons are most firmly bound to nuclei and n
hence require a great deal of energy to undergo transition. The -
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and n- electrons require less amount of energy. The n-electrons


usually require less energy than -electrons. The * transition
fall in the vacuum ultraviolet region (below 200 nm). The *
and n * transitions appear at longer wavelengths, near the
borderline of near and far UV region. But n * transition occur at
still longer wavelength coming well in the near UV and visible

region.
* transition: The excitation of strongly bound -electrons to
antibonding * orbitals require relatively larger energies and correspond to absorption in the far UV or vacuum UV
region. Organic compounds in which all the valency shell electrons are involved in the
formation of -bonds shows such transitions. For eg. saturated hydrocarbons like methane,
propane etc. shows absorption near 150 nm. An exception is cyclopropane which shows a
max of 190 nm while propane shows a max of 135 nm. In cyclopropane, the hybridized
orbitals of carbon are not pointing towards one another in the same straight line and
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consequently there is a loss of overlap. This loss of overlap give rise to instability and the
cyclopropane molecule is in a state of strain due to bent bonds (Bayer strain).
n * transition: This type of transition take place in saturated compounds containing one or more hetero atoms
(like O, S, N or halogens) with unshared pair of electrons (n-electrons). Some compounds undergoing this type of
transition are saturated halides, alcohols, ethers, amines etc. Such transitions require comparatively less energy than
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that required for * transitions; consequently, molecules containing non-bonding electrons usually exhibit
absorption in the ordinary UV region. Some examples are: n * for water at 167 nm, methyl alcohol 174 nm,
Lecture notes: Dr. Cyriac Mathew

methyl chloride at 172 nm, dimethyl ether at 185 nm, methyl iodide at 258 nm etc.
In saturated alkyl halides, the energy required for n * transition decreases with decrease in
electronegativity of the atom. Thus, methyl chloride absorbs around 172 nm while methyl iodide absorbs at
relatively longer wavelength of 258 nm. This is because the n-electrons of iodine are more loosly bound than that of
the chlorine atom.

Lecture notes: Dr. Cyriac Mathew

Trimethyl amine shows an absorption maximum of 227 nm max


vapour
due to n * transition. But when the
spectrum of the same compound determined in aqueous acid show no absorption due to n * transition because
the protonated amine contain no non-bonding electrons. n * transition is very Hetero
max (nm)
sensitive to hydrogen bonding also. Saturated compounds containing oxygen absorb substituent
below 200 nm region. As polarizability of the hetero atom increases the absorption -OH
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184
maximum moves to longer wavelengths as shown in the table. -NH2 190
The absorption maximum in compounds containing more than one hetero -SH 210
atom is very sensitive to steric effects. A significant higher wavelength shift (red shift) is observed where overlap of
non-bonding orbitals can occur. Eg. CH3I (258 nm), CH2I2 (292 nm), CHI3 (349 nm).
* transitions: Molecules that contain double or triple bonds or aromatic rings can undergo transition in which
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a -electron is excited to an antibonding * orbital. These transitions require still - (CH = CH)n - max
lower energy as compared to n * transitions and therefore absorption occurs at n = 1 162
longer wavelengths. Alkenes, alkynes, arynes, carbonyl compounds, cyanides azo 2 217
compounds etc. show * transitions. Although ethene itself does not absorb 3 258
strongly above 165 nm conjugated -electron system are generally of lower energy 4 296
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5 335
and absorb in the accessible spectral region. Increasing conjugation generally moves
6 415
absorption to longer wavelengths and finally to visible region. 8 415
n * transitions: These transitions involve the excitation of an electron in a non- 11 470
bonding orbital (unshared electrons on O, N, S or halogens) to an anti-bonding * 15 547
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew

orbital associated with an unsaturated centre in the molecule. The transitions occur with compounds possessing
double bonds involving hetero atoms, eg. C = O, C = S, N = O, etc. Transitions of this type requires the least amount
of energy out of all the transitions discussed above and hence occur at longer wavelengths. These absorptions are of
low intensity. A familiar example is the low intensity absorption in the 285 300 nm region of saturated aldehydes
and ketones.
CHROMOPHORES
An isolated functional group which is not in conjugation with any other group and exhibits absorption of a
characteristic nature in the UV or visible region is said to be a chromophore. Chromophores such as ethene, ethyne
etc. contain -electrons and they undergo * transitions. But chromophores such as carbonyls, nitriles, azo,
nitro compounds etc. contain both -electrons and n-electrons. They undergo both * and n * transitions.
Absorptions caused by * transitions are of high energy and occur only in the vacuum UV region and are of
little use to the quantitative interpretation of the spectrum.
AUXOCHROMES
Auxochromes are groups that do not in themselves show selective absorption above 200 nm but which
when attached to a given chromophoric system usually cause a shift in the absorption to longer wavelength and
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increased intensity of the absorption peak. Common auxochromic groups are hydroxyl, amino, sulphydril (-SH or
thiols) and some of the halogens. All these groups contain n-electrons and transition involving these electrons are
responsible for the shift in the absorption. For example, benzene shows an absorption maximum of 255 nm with max
230; while aniline shows an absorption maximum of 280 nm with max 1430. Thus, introduction of amino group
enhances max by 25 nm and high increase in intensity. The shift in max to higher wavelength is called bathochromic
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shift and to lower wavelength is called hypsochromic shift. Shift in max to higher value is called hyperchromic shift
and to lower value is called hypochromic shift.
Lecture notes: Dr. Cyriac Mathew

UV-VIS ABSORPTIONS OF SIMPLE ISOLATED CHROMOPHORES


Class Transition max (nm) log Class Transition max (nm) log
R OH n * 180 2.5 R NO2 n * 271 <1
ROR n * 180 3.5 R CHO * 190 2
R NH2 n * 190 3.5 n * 290 1
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R2C = CR2 * 175 3.0 R2CO * 180 3


RN=NR n * 340 <1 n * 280 1.5
RCN n * 160 <1 RCOOH n * 205 1.5
RCONH2 n * 210 1.5
ALLOWED AND FORBIDDEN TRANSITIONS
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Transitions in which the value of the extinction coefficient (max) is high (usually above 104) are called allowed
transitions. The probability of such transitions are higher and hence the absorption bands are intense. For eg. in 1,3-
butadiene the absorption at 217 nm has an max value of 21000. This is an allowed transition which arises due to
* transitions. The forbidden transitions arise as a result of the excitation of one electron from the lone pair present
on a hetero atom to an anti-bonding * orbital. Eg., n * transition near 300 nm in carbonyl compounds with max
Lecture notes: Dr. Cyriac Mathew

value in the range 10 to 100. Low max value shows low probability and hence of low intensity. Usually n *
transitions are of low intensity with low max values.
An explanation for the above observation can be given on the basis of the symmetries of the orbitals
involved in the transition. The bonding -orbital and the anti-bonding *-orbital lie in the same plane whereas the
non-bonding orbital in an orthogonal plane. Hence promotion of an electron from the non-bonding orbital is not
Lectrue notes Dr. Cyriac Mathew

possible without a significant change in the geometry of the molecule. The weak intensity is due to non-symmetrical
vibration that slightly deform the molecule and lowers its symmetry allowing n * transition to acquire a finite
probability. But n * transitions are allowed transitions and hence have high intensity. The n-electrons and -
electrons are in the same plane.
AROMATIC COMPOUNDS
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Benzene shows three characteristic absorption bands: 184 nm (max = 60,000), 204 nm (max = 7,900), and 256
nm (max = 200). These bands originate from * transitions. The intense band at
184 nm arise from an allowed transition whereas the weaker bands at 204 and 256 nm E1u
results from forbidden transitions in the highly symmetrical benzene molecule.
Different notations have been used to designate the absorption bands of benzene. The b1u
strong band at 184 nm is characteristic of benzenoid system of three ethene bonds
204 nm (forbidden)

which are in closed cyclic conjugation and is called E-band (or E1 band). The band at 256
nm is called B-band (benzenoid band). The band at 204 nm is called K-band (or E2
band). The absorption band at 256 nm shows a series of fine structure between 230 b2u
256 nm (forbidden)

184 nm (allowed)

and 270 nm, which arise due to the vibrational effects on the * transitions. In
vapour phase this vibrational fine structure is marked but tend to vanish in solution.
Substitution of alkyl groups on benzene ring produces a bathochromic shift (red
shift) of the B-band. But the effect of alkyl substituents on E-band is not clearly defined.
The bathochromic shift is attributed to hyperconjugation in which the -electron of an a1g
alkyl C H bond participate in resonance with the ring. The methyl group is more
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Energy states of benzene


effective in hyperconjugation than other alkyl groups. The addition of a second alkyl
group to the molecule is most effective in producing a red shift if it is in para position. The para isomer absorbs at
the longest wavelength with largest max. The ortho isomer generally absorbs at the shortest wavelength with
reduced max. This effect is attributed to steric interaction between the ortho substituent, which effectively reduces

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hyperconjugation. Substitution on the benzene ring of auxochromic groups (OH, NH2, etc.) shifts the E- and B- bands
to longer wavelengths frequently with intensification of B-band.
Lecture notes: Dr. Cyriac Mathew

STERIC INHIBITION OF RESONANCE:


For conjugated systems, the intensities and positions of the * transition depends upon the length of
the conjugated system. The longer such systems are the longer the wavelength of absorption and larger will be the
extinction coefficient. When the -electron system is prevented from achieving coplanarity the degree of overlap of
the -electron system will be diminished and results in a marked effect on the spectrum. For example, consider
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biphenyl and substituted biphenyls. For biphenyl max is 250 nm (max = 16,300). But in the case of 2-methylbiphenyl
max is 237 nm (max = 10,000) and for 2,2-dimethylbiphenyl max is 262 nm (max = 700). For hexamethyl biphenyl max
is 266 nm (max = 545). Its value is same as that for 1,3,5-trimethyl benzene, max = 266 nm (max = 305).
Lecture notes: Dr. Cyriac Mathew

ma x = 250 nm ma x = 237 nm ma x = 262 nm ma x = 266 nm


Biphenyl is not completely coplanar due to the steric repulsion between ortho-ortho hydrogens. This is mainly
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observed in solution while in crystalline state it is coplanar. In solution, the two rings are at an angle of
approximately 230 (in heptane solution) and in vapour phase at an angle 43 0. In 2-substituted derivatives the two
rings are pushed even further out of coplanarity. This reduces the -orbital overlap resulting in shifting max to lower
value accompanied by a decrease in intensity.
When more methyl groups are attached the absorption maximum shows effects due to methyl groups. Thus
2,2-dimethyl biphenyl shows an absorption maximum 262 nm which is similar to that of o-xylene. Similarly,
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hexamethyl biphenyl shows absorption maximum similar to that of 1,3,5-trimethyl benzene (mesitylene).
In the case of compounds having geometrical isomers the cis form is expected to achieve coplanarity of the
-electron system more readily. Therefore, generally in trans isomers the * transition occurs at longer
wavelength and has a larger extinction coefficient than that of cis isomer. For example, consider trans cinnamic acid
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and cis cinnamic acid.

ma x = 280 nm ma x = 295 nm
ma x = 10,500 ma x = 27,000
ma x = 272 nm ma x = 268 nm
ma x = 15,900 ma x = 10,700 cis-stilbene trans-stilbene
Similarly, cis-stilbene absorbs at a shorter wavelength than trans stilbene.
SOLVENT EFFECTS
The position and intensity of an absorption band may shift when the spectrum is recorded in different
solvents. Conjugated dienes and aromatic hydrocarbons experience very little solvent effects. The absorption
maxima for polar compounds is usually shifted with change in polarity of the solvents. Polar solvents stabilize , *
and n orbitals by hydrogen bonding or electrostatic interaction with the polar solvent. The stabilization of the n-
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orbitals is more pronounced by hydrogen bonding. *-orbitals are more stabilized by solvation than -orbitals
because *-orbitals are more polar. This could be expressed in the form of an energy level diagram. The *
transition require less energy polar solvents and the absorption shifts to longer wavelength (red shift). But the n
* transition requires more energy in polar solvents and the absorption shifts to shorter wavelengths (blue shift).
The magnitude of the shift in the former case is not usually as large as the that in the latter.
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- unsaturated carbonyl compounds show two different shifts: (a) n * and (b) *. In polar solvents
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n * shifts to shorter wavelengths. In the case of carbonyl compounds the ground state is more polar compared
to excited state. In the ground state carbonyl group contain an
*
important contribution from the more polar form. In the excited
state carbonyl group is believed to have contribution from the s*
less polar form. Therefore, the n-electrons in the ground state are
Lecture notes: Dr. Cyriac Mathew

more stabilized by hydrogen bonding. For example, the -


unsaturated ketone, mesityl oxide, shows a max of 329 nm (max =
41) in hexane and a max of 305 nm (max = 60) in water, due to n n
* transitions. Thus, the n * transition is shifted by 24 nm
to shorter wavelength in more polar solvents. In the case of ns
* > s s*
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* transitions the absorption moves to n * < ns s*


longer wavelength by the increase in
polarity of the solvent. The dipole-dipole s
less polar solvent more polar solvent
interaction with the solvent molecule lower
mesityl oxide the energy of the energy of excited state more than that of ground state. Thus, the absorption
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shifts to longer wavelength in polar solvents. Thus the * transition of mesityl oxide show a max of 230 nm (max
= 12,600) in hexane and a max of 243 nm (max = 10,000) in water. Thus the * transition shifts to longer
wavelength by 13 nm with increase in solvent polarity. This indicates that
in this transition the excited state is more polar than the ground state. Phenol in alcohol
Another effect of the change of solvent polarity is the smoothing Phenol in hexane
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out of the spectrum. That is, the fine structure of the spectrum
frequently vanishes as the solvent changes from non-polar to polar. For
eg. the spectrum of phenol in hexane and in alcohol shown in the
following figure demonstrates this effectively. The fine structure of the
UV spectrum is best observed in the vapour phase where intermolecular
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interactions are minimized. Even in non-polar solvent the fine structure


is further eliminated by solvent-solute interaction.

EMPIRICAL RULES FOR CALCULATING max
1. Woodward-Fieser Rules:
a. Conjugated dienes (non-aromatic)
The absorption maximum of diene system is affected by substituents and Woodward found that the position
of the absorption depends on their number and type. As a result, Woodward developed a set of empirical rules for
computing max which was later modified by Fieser.
Constituents values in nm, and example
Base value for parent diene:
a. Homo annular diene 253

b. Hetero annular diene 214

c. Acyclic diene 217


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Increments for:
a. each alky group or ring residue 5
3 ring residues and one alkyl group

6
b. each exocyclic double bond 5
A C
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c. each double bond exocyclic to two rings 10


simultaneously
d. each double bond that extends conjugation 30
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Each polar group


- OCOCH3 0
- OR 6
- SR 30
- Cl, Br 5
- NR2 60
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Calculated max(EtOH) nm
NB: A homo annular diene preferred as a parent diene to a hetero annular diene.
Examples:
Q. Calculate the UV absorption maximum for 2,4-hexadiene.
Base value 217
CH3 CH = CH CH = CH CH3
2 alkyl substituents 10
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max 227 nm

Q. Calculate max(EtOH) for exomethylene-4-isopropyl cyclohex-2-ene


Base value 217
2 ring residues 10
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1 exocyclic double 05
bond
max(EtOH) 232 nm

Q. Calculate max(EtOH) for the following compound Base value 217


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If a diene system is present in a bicyclic compound, due to the 2 ring residues 10


strain in the molecule 15 nm is added as ring strain correction to 2 exocyclic double 10
the calculated value. max(obs) = 254 nm bonds
Ring strain correction 15
max(EtOH) 252 nm
Q. Calculate max(EtOH) for the following compound
This is an example of a cross conjugated system. max Base value 217 217
value is calculated taking the highly substituted diene 2 ring residues 10 10
system. Usually in such systems poor correlations are 1 exocyclic double 05 05
observed. bond
1 alkyl group 05 -

max(EtOH) 237 nm 232 nm

Q. Calculate max(EtOH) for the following compound


Base value (homo annular diene) 253
5 ring residues 25
Lecture notes: Dr. Cyriac Mathew

3 exocyclic double bonds 15


2 double bonds extend conjugation 60
-OAc substituent 00
max(EtOH) 353 nm

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Q. Calculate max(EtOH) for the following compounds

Base value (acyclic) 217 Base value 253


Lecture notes: Dr. Cyriac Mathew

2 ring residues 10 4 ring residues 20


Ring strain correction 15 2 exocyclic C = C 10
max(EtOH) 242 nm -OCH3 06
(a) (b) max(EtOH) 289 nm
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Q. The following triene on partial hydrogenation gave three products which are separated by GLC. How UV
spectroscopy can be utilized to identify the products?

H2 (1 equi.)
Pt
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ma x = 273 nm = 234 nm < 200nm


b. - Unsaturated Carbonyl Compounds

C C C C C

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Woodward-Fieser Rules:
Parent system X = R, alkyl or X=H X = OH, Polar groups nm
ring residue OR 1. OH : 35, : 30, : 50
Acyclic, 215 207 193 2. OCH3 : 35, : 30, : 17, : 31
3. Cl : 15, : 12
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Six-membered 215 4. Br : 25, : 30


ring, 5. NR2 : 95
Five-membered 202
ring,
Solvent correction nm
Structural increments for parent system: nm
11
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1. Hexane
1. each exocyclic double bond 05 2. Dioxane 05
2. each double bond that extends conjugation 30 3. Chloroform 01
3. homo annular diene 39 4. Methanol 00
5. Ether 07
Increments for each carbon nm 6. Water + 08
substituent
1. at -carbon 10 Absorption values commonly given for - unsaturated
2. at -carbon 12 ketones and aldehydes are for 95% ethanol solution. To obtain the
3. at -carbon 18 position of this band when another solvent is used the given
4. at , ( +1), ( +2) . 18 solvent corrections are used.
Base value 215
Q Find the max(EtOH) for the following compounds 2, Extending conjugation 60
Homo annular diene 39
1 exocyclic double bond 05
(+2)
Base value 215 , ring residue 12
(+1) 18
1, -alkyl group 10 (+1) alkyl
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1, ring residue 12 (+2) alkyl 18


max (EtOH) 237 nm (+2) ring residue 18
max(EtOH) 385
a. b.

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2. Fieser-Kuhn Rules for Polyenes

Woodward-Fieser rules work well for conjugated dienes and polyenes with up to four double bonds or less.
Lecture notes: Dr. Cyriac Mathew

Certain plant pigments such as carotenoids have even more than four conjugated double bonds. For conjugated
polyenes having more than four double bonds, the Fieser-Kuhn rules must be applied in order to obtain the
wavelength of maximum absorption. According to the Fieser-Kuhn rule the following equation can be used to solve
for the wavelength of maximum absorption, max and also maximum absorptivity, max .
max = 114 + 5M + n(48 1.7 n) 16.5 Rendo 10Rexo
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where,

max is the wavelength of maximum absorption M is the number of alkyl substituents / ring residues in the
conjugated system
n is the number of conjugated double bonds
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Rendo is the number of rings with endocyclic double bonds in the conjugated system
Rexo is the number of rings with exocyclic double bonds in the conjugated system.
max = (1.74 104) n
max is the maximum absorptivity and n is the number of conjugated double bonds.
Lecture notes: Dr. Cyriac Mathew

Thus, using the above equations, one can get the wavelength of maximum absorbance (max) and the maximum
absorptivity (max).
Example 1: -carotene
-carotene is a precursor of vitamin A which is a terpenoid derived from several isoprene units. The observed max of
-carotene is 452 nm, while the observed max is 15.2 x 104. Let us therefore use Fieser-Kuhn rules to calculate the
max and the max for -carotene.
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Base value 114


No of ring residue and alkyl groups 10
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No. of conjugated double bonds 11


-carotene Rendo 02
Rexo 00
max(EtOH) 453.3 nm

Endo
-carotene
Endo
max = 114 + 5M + n (48 1.7 n) 16.5 Rendo 10Rexo = 114 + 510 + 11(48 1.7 11) 16.5 2 - 100 = 453.30
max(observed) = 452 nm.
max = (1.74 104) n = 1.74 104 11 = 19.14 104
max(observed) = 15.2 x 104.
Example 2: Lycopene
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Lycopene

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Base value = 114
No. of alkyl substituents/ring residue, M = 8
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No. of conjugated double bonds, n = 11


Rendo = Rexo = 0
max = 114 + 5M + n (48 1.7 n) 16.5 Rendo 10Rexo = 114 + 5 8 + 11 (48 1.7 11) 16.5 0 10 0 = 476.30 nm
max(observed) = 474 nm
max = (1.74 104) n = 1.74 104 11 = 19.14 104
Lecture notes: Dr. Cyriac Mathew

max(observed) = 18.6 x 104.


Lycopene (all-trans-lycopene) is a bright red carotenoid pigment found in tomatoes and other red fruits and
vegetables. However, lycopene has no vitamin A like activity.
Example 3: Retinol
Retinol is an animal form of vitamin A and is essential for vision.
Lecture notes: Dr. Cyriac Mathew

Base value 114


No of ring residue and alkyl groups 05
No. of conjugated double bonds 05
Rendo 01
endo Rexo 00
Retinol
Lecture notes: Dr. Cyriac Mathew

max(EtOH) 320 nm

max = 114 + 5M + n (48 1.7 n) 16.5 Rendo 10Rexo = 114 + 5 5 + 5 (48 1.7 5) 16.5 1 10 0 = 320 nm.

max(observed) = 325 nm
max = (1.74 104) 5 = 8.7 104
Lectrue notes Dr. Cyriac Mathew
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew
Lecture notes: Dr. Cyriac Mathew

10
CHIROPTIC PROPERTIES IN CHIRAL MOLECULES
Lecture notes: Dr. Cyriac Mathew

We know that light waves consist of oscillating electric and magnetic fields. These fields are always
at right angles to each other as well as to the direction of propagation. For simplicity, we ignore the
magnetic field, which is perpendicular
Z
to the electric field. The following
figure shows the electric field of a light
wave traveling along y- direction. If
Lecture notes: Dr. Cyriac Mathew

you imagine that you could see the light X Y


waves coming towards you, you would
see the electric field as a vertical line; ie
the electric field oscillates only in one
plane. We say that the light is plane
Lecture notes: Dr. Cyriac Mathew

polarized.
Light coming from an ordinary lamp is not plane polarized. The electric field of the light waves from
the lamp is arranged in many planes. However, if we pass the light through a piece of Polaroid it become
plane polarized. When plane Polaroid
polarized radiation passes
Lecture notes: Dr. Cyriac Mathew

through samples of certain


kinds of matter the plane of
polarization is rotated. This
property is known as optical
activity.
Lectrue notes Dr. Cyriac Mathew

A wave of plane Plane polarized light wave


polarized light may be
considered to be made up of
two types of circularly Some of the electric fields
polarized light. In circularly of light waves from the lamp
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew

polarized light the electric


fields (and magnetic fields, both remain perpendicular) at different points along the direction of propagation
rotates continuously. That is, the field spirals around the direction of propagation. If the rotation is towards
right it is called right circularly polarized and if towards left it is called left circularly polarized. The electric
field of a right circularly polarized wave may be described as a right-handed screw or helix twisting around
the direction of propagation where as a left circularly polarized wave describes a left-handed screw or helix.
The arrays of arrows in the following figure show the view of electric field when looking toward the
oncoming ray.
The plane-polarized beam may be regarded as a superposition of two oppositely rotating circularly
polarized components. It is the resultant of the two that appears as oscillation in a plane.

(Looking from the source along the


direction of propagation of the beam)

Lecture notes: Dr. Cyriac Mathew

Source

Right circularly polarized light Left circularly polarized light


11
Ref. https://en.wikipedia.org/wiki/Circular_polarization
A plane polarized light entering a
Lecture notes: Dr. Cyriac Mathew

Resultant electric
sample can be regarded as the field, E
superposition of two counter rotating
circularly polarized components.
According to quantum theory a ray of Right circularly
frequency consists of a stream of
Lecture notes: Dr. Cyriac Mathew

Polarized, ER
photons, each one of which has energy
E = h.. Photons may also be polarized. A
plane-polarized ray of light consists of
plane-polarized photons and a circularly Left circularly Plane of polarization
Lecture notes: Dr. Cyriac Mathew

polarized ray consists of circularly Polarized, EL


polarized photons. Refractivity of a (Looking towards the oncoming beam
medium relates to the speed of light in that as a receiver)
medium. The lower the speed the higher
the refractivity. The index of refraction is the ratio of the speed of light in vacuum to that in the medium.
Lecture notes: Dr. Cyriac Mathew

When a light ray enters a transparent medium, with parallel surfaces, normal to one of the faces the ray
slows down and when it emerges from the other side it continues in the same direction at the original speed.
If on the other hand, light (for eg. monochromatic) strikes the surface at an angle other than 90 0, it is
refracted. This is true for substances that are optically isotropic. These include amorphous substances and
crystals belonging to cubic system. In crystals of the other systems a ray of light is split in to two rays that
Lectrue notes Dr. Cyriac Mathew

usually propagate at different velocities within the crystal. White light consists of photons of different
wavelength, vibrating along planes with different orientation in space. Monochromatic light consists of
photons of the same wavelength still vibrating along planes with different orientations. If either white light
or monochromatic light is passed through a crystal or other atomically or molecularly ordered substance
(such as a Polaroid sheet) only light whose vector (electric) is vibrating on a plane that can pass through the
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew

layer of atoms or molecules will emerge. ie polarization occurs. Because of their complex atomic structure
these substances can; (i) let polarized light to pass through (ii) let some light to pass through (iii) stop
polarized light (iv) rotate the polarization plane with either positive or negative helicity.
Molecular symmetry and chirality
A molecule can have only one mirror image. If the image is non-superimposable on the original, the
molecule and its mirror image form two distinct species called enantiomers. Such molecules are called
chiral. Chirality is a necessary and sufficient condition for the occurrence of enantiomerism and is
determined by the absence of rotation-reflection symmetry (Sn axis) in the molecule. All molecules
belonging to the point groups C1, Cn and Dn lack reflection symmetry and are chiral. Three terms have
almost been interchangeably used to describe molecules, which show enantiomerism asymmetric,
dissymmetric and chiral. The term chiral is synonymous with dissymmetry. The term asymmetric points to
molecules, which are chiral and lacks all symmetry element except the trivial C1 axis.

Present Achiral
Lecture notes: Dr. Cyriac Mathew

Sn
Molecule
Absent no Cn
Chiral, dissymmetric asymmetric
(C1, Cn, and Dn)
12
Lecture notes: Dr. Cyriac Mathew

OPTICAL ROTATORY DISPERSON (ORD)

As mentioned above, a wave of plane polarized light may be considered to be made up of two types
of circularly polarized light the right circularly polarized wave and the left circularly polarized wave. The
electric field of a right circularly polarized wave may be considered as a right-handed screw or helix
Lecture notes: Dr. Cyriac Mathew

twisting around the direction of propagation and the left circularly polarized wave describes a left-handed
screw or helix. The resultant of these two represents the linearly polarized wave. In linearly polarized light
the electric field vector changes its magnitude sinusoidaly in a plane along the direction of propagation. In
circularly polarized light the magnitude of the vector remain constant, but its direction changes continuously
in a helical manner. This can be explained using the following figures.
Lecture notes: Dr. Cyriac Mathew

ELP

ELP
ELCP ERCP
ELCP ERCP
Lecture notes: Dr. Cyriac Mathew

Plane of polarization
Lectrue notes Dr. Cyriac Mathew

ELCP ERCP
ELCP
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew

ERCP
ELCP ERCP
ELP (negative)

ELP

ELP: Electric field of linearly polarized light


ERCP: Electric field of right circularly polarized light
ELCP: Electric field of left circularly polarized light.
When a linearly polarized light enters an anisotropic medium the left and right circularly polarized
waves travel with different velocities. As a result, they have different refractive indices. Now the anisotropic
medium is said to be circularly birefringent. That is, it has unequal refractive indices for right and left

circularly polarized light. Since the velocity of a light in a medium is given by = , where c is the velocity
of light in vacuum and n is the refractive index of the medium, the result of circular birefringence is an
unequal rate of propagation of the left and right circularly polarized rays. For eg. If the right circularly
Lecture notes: Dr. Cyriac Mathew

polarized ray travels faster than the left circularly polarized ray, the result is that the light is still linearly
polarized but the plane of polarization is no longer in the xz-plane, instead it will make an angle with the
plane. That is the circularly birefringent medium has rotated the plane of polarization by an angle . The
situation is shown in the following figure. If the right circularly polarized ray travels faster is positive and

13
the medium is dextrorotatory, whereas if the left circularly polarized ray travels faster is negative and the

medium is levorotatory. The angle of rotation for unit path length is given by = ( ), Where nL

Lecture notes: Dr. Cyriac Mathew

and nR are the indices of refraction for the left and right circularly polarized light respectively. is the
vacuum wavelength of the light. A more convenient term specific rotation is
z
calculated using the following equation: [] = . It is calculated for a E

path length of 1 dm and c is the concentration of the sample in g/ml. The E L

Lecture notes: Dr. Cyriac Mathew

molar rotation is given by the equation; ER


[]

[] = . M is the molecular mass. (Since large numbers are usually y

obtained for molar rotation it is a common practice to divide the result by x
100).
Lecture notes: Dr. Cyriac Mathew

Since refractive index is related to polarizability, the circular birefringence can be correlated to some
dissymmetry of polarizability in the molecule. The dissymmetry of polarizability may arise in two ways or a
combination of the two. The first way may be explained by taking the molecule bromochloroiodomethane,
CHClBrI. Here dissymmetry of polarizability arises due to the differences in polarizability of the groups
attached to the asymmetric carbon atom. This is called atomic asymmetry. The second way is illustrated by
Lecture notes: Dr. Cyriac Mathew

methylethylpropylmethane. CH3CH2CH(CH3)CH2CH2CH3. In this case the dissymmetry of polarizability


arises due to spatial arrangement (conformation) of the groups in the molecule. This is called conformational
asymmetry and usually makes a larger contribution to molecular rotation than does atomic asymmetry.

CIRCULAR DICHROISM (CD)


Lectrue notes Dr. Cyriac Mathew

Just as dissymmetric media generally have different indices of refraction for right and left circularly
polarized light their intensity of absorption (absorption coefficient) also differ. Circular dichroism is the
difference in the absorption of left circularly polarised light (L-CPL) and right circularly polarised light (R-
CPL) and occurs when a molecule contains one or more chiral chromophores (light-absorbing groups).
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew

Circular dichroism = A() = A() LCPL - A()RCPL, where is the wavelength.

Circular dichroism (CD) spectroscopy is a spectroscopic technique where the CD of molecules is measured
over a range of wavelengths. Structural, kinetic and thermodynamic information about macromolecules can
be derived from circular dichroism spectroscopy. For eg. the following figure shows the CD spectra of the
two enantiomers of camphor sulphonic acid.
CD

CD

220 290 320 nm


220 290 320 nm
Lecture notes: Dr. Cyriac Mathew

(1S)-(+)- camphor-10- sulphonic acid


(1R)-()- camphor-10- sulphonic acid

The two enantiomers can be clearly distinguished from the spectra. Circular dichroism spectra are generally
suitable for advanced spectral analysis.

14
ORD Spectra
Lecture notes: Dr. Cyriac Mathew

Circular Dichroism (CD) is difficult to measure and it is more convenient to measure a combination
of circular dichroism and circular birefringence known as the Cotton effect. It may be studied by observing
the change of optical rotation with wavelength, called optical rotatory dispersion (ORD). there are three
types of rotator dispersion curves: (a) Plain curves (b) Single Cotton effect curves (c) multiple Cotton effect
Lecture notes: Dr. Cyriac Mathew

curves.

(a) Plain curves: These show no maximum or minimum and are smooth curves. They may be positive
or negative according as the rotation become more positive or negative as the wave length changes
from longer to shorter values. Plain curves are also referred to as normal curves.
Lecture notes: Dr. Cyriac Mathew

peak
(+)
(+) Positive cotton curve
[]
[]
()
Lecture notes: Dr. Cyriac Mathew

() Negative cotton curve


trough
300 nm 700 nm 300 nm 700 nm
Plain curves Single Cotton effect curves
Lectrue notes Dr. Cyriac Mathew

(b) Single Cotton effect curves: These are anomalous dispersion curves which show a maximum and a
minimum which occur in the region of maximum absorption. The curves are said to be positive or
negative according as the peak or trough occurs in the longer wave length. The above figure shows
both positive and negative cotton curves. The vertical distance between the peak and trough is called
the amplitude and the horizontal distance is the breadth of the cotton curve. The point at which
curves crosses the zero axis of rotation corresponds very closely to UV absorption region.
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew

(c) Multiple Cotton effect curves: Multiple cotton effect curves show two or more peaks and
corresponding number of troughs. Such curves are generally obtained in the case of complicated
molecules.
Applications of CD and ORD curves

CD and ORD curves are extremely useful for providing structural and configurational information.
Two procedures are generally adopted: (i) a comparison method in which the dispersion curve of a
compound of unknown configuration is compared with those of reference compounds of similar structure
with known absolute configuration (ii) a semi-quantitative approach based on comparison of experimental
parameters such as sign of Cotton effect, its amplitude and position with those estimated from certain
empirical or semi-empirical rules.

Use of plain curves: optical rotation of chiral compounds is generally represented for wavelength of 589 nm
(sodium D-line) which is quite far from UV region where electronic transition of most organic compounds
takes palace. As a result, the values of specific rotations at this wavelength are not usually high. In some
cases, the rotation at D-line of sodium is so small that it cannot be detected; however, it is usually greater in
Lecture notes: Dr. Cyriac Mathew

the UV region. Some compounds on the other hand may remain optically inactive throughout the accessible
region and thus may constitute a racemic mixture.

15
Plane curves may be of importance in making configurational assignments in cases where the rotator
dispersion curve crosses the zero axis of rotation. (iodophenoxy)propionic acid is an example.
Lecture notes: Dr. Cyriac Mathew

(+)
ortho
Lecture notes: Dr. Cyriac Mathew

(0) para

(iodophenoxy) ()
propionic acid 400 nm
The ortho isomer shows laevorotation at longer wavelengths, crosses the zero-rotation axis and
Lecture notes: Dr. Cyriac Mathew

become dextrorotatory at shorter wavelengths. But all the three have the same absolute configuration R.
below about 400 nm all three isomers of same configuration have same sign of rotation. Thus, we can
distinguish between the ortho and other isomers.

Curves with Cotton effect: Curves which exhibit cotton effects are much more useful and give information
Lecture notes: Dr. Cyriac Mathew

on structure, configuration and conformation of the molecules. Studies on the ORD curves of steroid and
terpenoid skeleton showed that the sign, magnitude and overall shape of the Cottton effect curve can be
closely correlated with the immediate structural and stereochemical environment of the carbonyl group and
are little affected by the structural changes away from this group.

The keto group absorbs in the UV region around 280 290 nm and this absorption generally leads to
Lectrue notes Dr. Cyriac Mathew

a Cotton effect. Thus, the position or configuration of a carbonyl group in a compound can be found by
comparing its cotton curve with those of suitable analogues.

OCTANT RULE
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew

The octant rule is an empirical rule which permits one to deduce the sign of the Cotton effect for a
considerable number of compounds from their structure, configuration, and conformation. This is generally
used in the case of ketosteroids. The compound to be studied is considered to be oriented in a three-
dimensional coordinate system as shown below.

z
3 3
z 4
4
-y 5
5
2
2
1
x 1 6
6
y y
Lecture notes: Dr. Cyriac Mathew

16
The midpoint of the C = O bond is taken as the origin of the system. The space around the C = O
group is divided into eight sectors (octants) with the help of three orthogonal planes A, B, and C defined by
Lecture notes: Dr. Cyriac Mathew

xz, xy and yz respectively. The vertical plane A bisects the cyclohexane chair and passes through C1, C2 and
O. The horizontal plane B contains the C = O moity and the two attached carbon atoms C 2 and C6. The C =
O double bond is made the x- axis with origin at the midpoint of the bond. The projection contains four back
octants. The sign of each octant is obtained from the sign of the product of the coordinates of any given
atom. For example, atom 3 has coordinates, x, y and +z. The product is +xyz. On the other hand, for atom
Lecture notes: Dr. Cyriac Mathew

5 the coordinates are x, +y, +z. The product is xyz. Since it is unusual for substituents to lie in front of the
oxygen atom, front octants are generally unoccupied.

The octant rule states that atoms lying in the back upper left and back lower right octants make
positive contribution to cotton effect, atoms in the back lower left and back upper right octants make
Lecture notes: Dr. Cyriac Mathew

negative contribution to cotton effect, and atoms lying in any of the three planes make no contribution. Since
the contribution from hydrogen atoms are insignificant they are ignored.

a a
Lecture notes: Dr. Cyriac Mathew

e 3 4 5 e
+ Upper Left Upper Right
e e Plane B (+) () Plane B
2 1 6
+
a Lower Left
Lectrue notes Dr. Cyriac Mathew

a Lower right

Plane A 4 () (+)
3 5
2 6 Plane A
1
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew

Contribution of the substituents lying in different sectors towards the sign of the Cotton effect are considered
according to the following rules:

1. Substituents lying in the coordinate planes contribute negligibly and are usually ignored.
2. Substituents lying in the (+) sectors make positive contribution and substituents lying in the ()
sectors make negative contribution to the Cotton effect. This is generally true for substituents which
are more polarisable than hydrogen atom. On the other hand, fluorine atom which is less polarizable
than hydrogen does not conform to octant rule.
3. The axial substituents on C2 and C6 contribute strongly to Cotton effect while equatorial substituents
on C2 and C6 do not contribute much as they lie in plane B.

Axial Haloketone Rule

When a halogen atom is introduced into the -position of a cyclohexanone, and if the orientation is
Lecture notes: Dr. Cyriac Mathew

equatorial, there will be no change in the sign of the ORD curve. But if it is in the axial position the sign of
the ORD curve changes. The Cotton effect of axial -halocyclohexanone may be predicted by viewing along
the O = C axis in a model so placed that the carbonyl group occupies the head of the chair (or boat) close to
the observer. If the halogen is now on the left of the line of view the compound will exhibit a negative cotton

17
effect and if it is on the right a positive Cotton effect will be observed. Fluoroketones do not follow axial
haloketone rule.
Lecture notes: Dr. Cyriac Mathew

+
1
6 2
3 +
Lecture notes: Dr. Cyriac Mathew

X
4
2

Positive cotton effect


Lecture notes: Dr. Cyriac Mathew

5
+
1
6 2
3 +
X X
4
2
Lecture notes: Dr. Cyriac Mathew

Negative cotton effect


Lectrue notes Dr. Cyriac Mathew

Applications

Conformation of (+) 3- methyl cyclohexanone: Since cyclohexanone does not contain a chiral centre let us
consider 3-methyl cyclohexanone, which has a chiral centre at C3. Two possible orientations are equatorial
and axial methyl. To apply octant-rule the two forms are drawn with carbonyl bond horizontal.
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew

5
3
4 4
5 3 4
6 2 3
1 5 6
2
1 2
1
6
R-(+) Methyl axial
Methyl equatorial

Me
5 4
3 4 5 3
Me +
2
Lecture notes: Dr. Cyriac Mathew

+ 6
+
2 + 6
Positive cotton curve. Negative Cotton curve

18
According to octant rule the equatorial conformer has a positive Cotton effect, as the Me group fall
in the positive sector. On the other hand, the axial conformer displays negative Cotton effect as the Me
Lecture notes: Dr. Cyriac Mathew

group fall in the negative sector. Thus, the sign of the ORD curve will be expected to be positive if methyl
group is equatorial and negative if axial. The observed sign is positive and so the orientation is equatorial.
Thus, if we know the sign of the ORD curve we can elucidate the conformation. However, since the
equatorial conformation is the preferred one, on this basis we can predict sign of ORD curve.
Lecture notes: Dr. Cyriac Mathew

Reference:

1. Stereochemistry D. Nasipuri, P 486 89


2. Stereochemistry of Organic compounds E. L. Eliel, P. 399 433
3. Organic chemistry I. L. Finar Vol.2 p. 550
4. https://en.wikipedia.org/wiki/Circular_polarization
Lecture notes: Dr. Cyriac Mathew

5. https://en.wikipedia.org/wiki/Circular_dichroism
6. http://www.photophysics.com/chiroscan
7. http://www.nsmbuffalo.edu/~jocher
Lecture notes: Dr. Cyriac Mathew
Lectrue notes Dr. Cyriac Mathew
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew
Lecture notes: Dr. Cyriac Mathew

19