Ashwini somayaji

1st M.pharm
pharmacology

1
 INTRODUCTION

 RULE FOR CONJUGATED DIENES

 RULE
FOR CONJUGATED CARBONYL
COMPOUND

 RULE FOR ACYL BENZENES

 APPLICATIONS

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 In 1945 Robert Burns Woodward gave certain
rules for correlating λmax with molecular
structure

 In 1959 Louis Frederick Fieser modified these

rules with more experimental data, and the
modified rule is known as Woodward-Fieser
Rules.

 It is used to calculate the position and λmax for a

given structure by relating the position and
degree of substitution of chromophore.
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 Woodward rules work well for dienes
and polyenes with upto 4-double
bonds or less.

 Thefieser rule must be applied for

certain plant pigments such as
cartenoids have even more than 4-
conjugated double bonds and
extended rules to conjugated
aldehydes and ketones.

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 These sets of rules to calculate the wavelength of
maximum absorption or λmax of a compound in the
ultraviolet-visible spectrum, based empirically have
been called the Woodward-Fieser rules or Woodward’s-
rules.

This may be differs from observed value by

4-5nm.

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 Conjugated dienes and polyenes are found in
most organic compounds.

 Longer the conjugated system,greater the

wavelength of absorption maximum.

 According to Woodward’s rules the λmax of the

molecule can be calculated using a formula:

λmax = Base value + Σ Substituent

Contributions + Σ Other Contributions.

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 Eachtype of diene or triene system is having
a certain fixed value at which absorption
takes place; this constitutes the Base value
or Parent value

 The first step in predicting the

wavelength of maximum UV absorption
for conjugated dienes is to determine
wheather it lies in an s-trans or s-cis
conformation.
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 If it lies in the s-trans conformation, its base
wavelength is 217nm.
 If it lies in the s-cis conformation,its base
wavelength is 253nm.

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 the base value depends upon whether the
diene is a linear or hetero-annular or
transoid diene, or whether it is a cyclic or
homo-annular diene.

 The sum of all substituent contributions are

added to the base value to obtain the
wavelength of maximum absorption of the
molecule.

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 This type of diene generally involves the
attachment of trans dienes .

 Since the two double bonds attached are

trans, it leads to a linear diene which is also
called a hetero-annular diene.

 The base value for a hetero-annular diene

system is 215 nm according to the
Woodward-Fieser rules.

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 Transoid / Heteroannular Diene With an
Example

In the above example, it can be seen that one of the

double bonds belongs to ring A while the other double
bond belongs to ring B, hence making the double bond
hetero-annular.

 Since both double bonds are trans with respect to

substituents making the diene a transoid diene. In
general, hetero-annular dienes are transoid. If the diene
is not a part of a ring then it is just transoid.

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 Thistype of diene involves the conjugation
of two cis dienes.

 Sincethe double bonds are cis to each other,

the molecule often tends to form a closed
ring system and therefore also called a cyclic
or homo-annular diene.

 The base value for homo-annular diene

system is 253 nm according to the
Woodward-Fieser rules.
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 Cisoid / Homo-annular Diene With An
Example

In the above example, it can be seen that both the

double bonds belong to ring B making this type of diene
a homo-annular diene.
Since both double bonds are cis with respect to
substituents making the diene a cisoid diene.
 In general, homo-annular dienes are cisoid. If the
diene is not a part of a ring (i.e. the green bonds do not
exist) then it is just a cisoide. If a molecule has both a
homo-annular diene and a hetero-annular diene , then
the homoannular diene as the core chromophore.

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 Only the substituents attached directly to the
double bond diene systems can influence the
ultraviolet visible absorption of the molecules.

 If the substituents are not directly attached to

the carbons of the diene system, it will not
affect the UV-Visible absorption spectrum of the
molecule.

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 Transoid and Cisoid Dienes with
substituents highlighted in red.

The figure above highlights possible substituents in red

given by the different -R groups.
 In the above examples 1 and 2, assignment of
substituents must be given to all the atoms which are
directly connected to the diene.
 Hence even though the structure has no substituents,
the core carbon atoms have yet to be considered as
alkyl-substituents.
This is known as RING RESIDUE.
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Ring residue & alkyl substituent

these are the influences of a neighbouring

saturated carbon on a double bond or at a site
of un staturation.

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EXTENDED CONJUGATED DOUBLE BOND:
 two double bonds separated by the single bond is
conjugated.

 If a third double bond is separated from one of the

original pair of a double bonds by a single bond, the
three double bonds represents an extended conjugated
double bonds.

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1] Exocylcic Double Bonds:
 Exocyclic doube bond by definition is a double
bond where one of the participating carbon
atoms is a part of a ring, while the other carbon
atom is not part of the same ring.

 From the name we can understand that exo-

cyclic would stand for a double bond outside the
ring and endo-cyclic would stand for a double
bond within the ring.

 For each exocyclic double bond, we must add +5

nm to obtain the λmax.
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In example 1, the double bond present within ring A is
exocyclic to ring B as it is attached to an atom which is
shared between ring A and ring B, while the double bond
present in ring B is not connected to any ring A atoms and
is within just one ring, hence making it endocyclic.

In example 2, both double bonds are present within

ring B with connections to shared carbon atoms with ring
A, making both the double bonds exocyclic.
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In example 3, there is a single double bond which is
exocyclic at two points to two different rings. In such
a case, the influence would be 2 times + 5 nm (i.e +
10 nm).

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 Parent value for buta diene system
or a cyclic conjugated diens 217mμ
 Acyclic triene 245mμ
 Homo annular conjugated dienes 253mμ
 Heteroannular conjugated diene 215mμ
Increment for each substituents
 alkyl substituent or ring residue 5mμ
 Exocyclic double bond 5mμ
 Double bond extending conjugation 30mμ
Auxochromes
 -OR +6mμ
 -SR +30mμ
 -Cl, -Br +5mμ
 -NR2 +60mμ
 OCOCH3 0 mμ
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Example:
1. Calculate the absorption maxima in the uv spectrum of
2,4-hexadiene.

CH₃-CH=CH-CH=CH-CH₃

Solution:
The basic unit in 2,4 hexadiene is butadiene .

Basic value =217mμ

2 alkylsubstituents =2X5 =10 mμ
Calculated value =227 mμ
The observed value =227mμ

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 3-methoxy-10-methyl-
2,7,8,9,10,11,12,13,14,15,16,17-
Name of Compound
dodecahydro-1H-
cyclopenta[a]phenanthrene
Woodward Component Contribution

Core- Transoid/Heteroannular Diene + 215 nm

Substituents- 3 alkyl groups 3 x 5 = + 15 nm

1 alkoxy group + 6 nm

Other Effects- Exocyclic Double Bond + 5 nm

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Calculated λmax 241 nm
 10,13-dimethyl-
2,3,9,10,11,12,13,15,16,17-
name of Compound
decahydro-1H-
cyclopenta[a]phenanthrene
Woodward Component Contribution

Core-Transoid/Heteroannular + 215 nm

Substituents- 5 alkyl groups 5 x 5 = + 25 nm

1 Double bond extending conjugation + 30 nm

Other Effects- 3 Exocyclic Double

+ 15 nm
Bond

Calculated λmax 285 nm

Observed λmax 283 nm
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Note- In this example the molecule contains both, a homoannular diene
system and a heteroannular diene system. In such a molecule the core
chromophore is considered to be the homoannular system .

Component Contribution

Core- Homoannular/Cisoid diene + 253 nm

Substituents– 5 alkyl substituents 5 x 5 = + 25 nm

Double bond extending conjugation + 30 nm

Other Effects- 3 Exocyclic double

3 x 5 = + 15 nm
bonds
Calculated λmax 323 nm
Observed λmax n/a
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3. Calculated absorption maximum for the compound
.Homoannular conjugated Diene =253 mμ
3 Ring residues(3X5nm) =15 mμ
1 Exocylic double bond =5 mμ
Calculated value =273 mμ
Observed value found to be =274 mμ

4.Calculated the λ max for compound

Hetroannular conjugated Diene = 215 mμ
2 Ring residues(2X5nm) =10 mμ
1 Exocylic double bond =5mμ
Calculated value =230 mμ
Observed value =232 mμ

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Bicylic system

 If a Diene system is present in a bicylic compound,then due to strain

correction , the value of absorption maximum is-
 For the 2,3 dimethylene bicylo[2,2,1] heptane.
 Basic value =217mμ
 2Ring residue(2X5nm) =10mμ
 2Exocylic double bonds(2X5nm ) =10mμ
 Bicylo system(strain correction) =15mμ
 Calculated value =252mμ
 Observed value =254mμ

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Core Chromophores With Base Values:
 As Woodward and Fieser have listed, α,β-
unsaturated carbonyl compounds have a range of
influence on the λmax of the molecule
depending upon:

 1] The type of carbonyl functionality present.

For example, α,β-unsaturated aldehyde
contribute 210 nm while α,β-unsaturated
ketones contribute 215 nm and α,β-
unsaturated esters contribute 195 nm.

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 2]
If the core is a part of a cyclic ring. For
example, cyclopentenone contribution is
202 nm whilecyclohexenone is 215 nm.

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 3]If the conjugation is extended to γ,δ-positions to
form dienes. For example, in such cases, a simple
addition of 30 nm to the base value of the α,β-
unsaturated carbonyl compound gives appropriate
estimates to the observed influences.

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 According to Woodward, in case of α,β-
unsaturated carbonyl compounds, the location of
the substituent is significant in determining the
influence on the wavelength of maximum
absorption.

 Substituents can be located on either α, β

positions.

 If the conjugation is extended to γ and δ

positions, then substitutions at these position
also play a vital role in determining the practical
λmax.
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1] Exocyclic Double Bonds

 In general exocyclic double bonds add an

additional + 5 nm to the base value.

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2] Solvent Effects
 Since carbonyl functional groups have polarity, solvents
play an important role in how the electronics of the
structure play out. The rules are simple and straight
forward:

Solvent Influence:
 Water = – 8 nm
 Methanol/Ethanol = – 1 nm
 Ether = + 6 nm
 Hexane / Cyclohexane = + 7 nm

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3] Homoannular Cyclohexadiene

In a special case where you have α,β-γ,δ-

diene carbonyl compound and both the double bonds
are present within one ring system you get a
homoannular or homocyclic cyclohexadiene carbonyl
compound.

In such a case you must add an additional 35 nm to

the system.

O
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The structure increments for estimating λmax for a given αβ-
unsaturated compound are as follows:
→ For each exocyclic double bond : +5 mμ
→ For each double bond endocyclic

In 5 or7 numbered ring except : +5 mμ

Cyclo-pent-2enone .
→ For each alkyl substituent or ring
Residue at the,
α-position :+10 mμ
β-position :+12 mμ
γ or δ- or higher position :+18 mμ
→ For each double bond extending conjugation :+30 mυ
→ For homoannular conjugated diene :+39 mμ
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chromophore Increment in mυ for a position w.r.t carbonyl group
α β γ δ

-OH +35 +30 - +50

-Oac +6 +6 +6 +6

-Cl +15 +12 - -

-Br +25 +35 - -

-OR +35 +30 17 31

-SR - +85 - -

-NR2 - +95 - -

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1.Calculate λ max for given compound

O
H3C
C CH3
H3C H

 ά-β unsaturated ketone =215 mμ

 2 β alkyl substituents(2X12 =24 mμ
 Calculated value = 239 mμ
 Observed value =237 mμ

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2.Calculated absorption maximum in UV Spectra for
following compound.

 Basic value = 215 mμ

 2 β ring residue(2X12nm) =24 mμ
 1Exocylic double bonds =5 mμ
 calculated value =244 mμ
 Observed value =241 mμ

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4. Calculated the λ max for compound
O

H3C

 ά-β unsaturated Cyclopentane =202 mμ

 1 β alkyl substitution =12 mμ
 1 Exocylic double bond =5 mμ
 double bond with extending conjugation =30 mμ
 1γ ring residue =18 mμ
 1δ ring residue =18 mμ
 Calculated value =285 mμ
 Observed value =285 mμ
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 5.Calculated the λ max for the following compound

 Basic value =215mμ

 ά-ring residue =10mμ
 δ-ring residue =18mμ
 1 Exocylic double bond =5mμ
 1Homoannular conjugated diene =39mμ
 1 Double bond with extended conjugation =30mμ
 Calculated value =317mμ
 Observed value =319mμ
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Rules for calculating absorption maximum for derivatives of
acyl benzenes
 Like Woodward fieser rules, Scott devised a set of rules for
calculating the absorption maximum for the derivatives of Acyl
benzenes, These rules help in estimating the position of
absorption maximum in ethanol in a number of mono
substituted aromatic ketones aldehydes and acid esters.
 For the compound of the type 1.The basic value is 246 mμ if X
is an alkyl group acyclic residue.
 2. If X is hydrogen atom, the basic value becomes 250 mμ
 3. The basic value is 230 mμ if, X is OH and 245 mμ if X is
OR
O

C X
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 The structural increments in nm for further substation
on the aromatic ring in the ortho meta & para
position are given in the table
Auxochrome Incriment in mυ position of substituent

Ortho meta para

alkyl +3 +3 +10
OH, OR +7 +7 +25
Cl 0 0 +10
Br +2 +2 +15
NH2 +13 +13 +58
NHAc +20 +20 +45
NR2 +20 +20 +85
O- +11 +20 +75

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Calculating the absorption maximum for the following
compound
 Basic value =246mμ
 OH- substation at para position = 25mμ
 OH - substation at meta position =7mμ
 Calculated value =278 mμ
 Observed value =281mμ
O

C CH3

HO
OH
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 Detection of conjugation:
It helps to show the relationship between the different
groups particularly with respect to conjugation; it may
be between two or more carbon- carbon double bond ,
between cabon-carbon and carbon-oxygen double bond
or between double bond or aromatic ring.

 Determination of geometrical isomers. Trans isomers

exhibit λmax at slightly longer wavelength. And have
larger extinction coefficient than cis isomers.

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 Detection of functional group.
It is possible to detect the functional group with the help of uv
spectrum.

 Identification of unknown compound.

A unknown compound can be identified by comparing the
spectrum with the known spectra.
 Examination of polynuclear hydrocarbons
 Identification of compound in different solvent.
 Determination of strength of hydrogen bonding.
 Elucidation of the structure of vitamin A and K

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REFERENCES:
 ChatwalGR, Anand SK,; Instrumental
methods of chemical analysis-5th edition.PG
.NO:2.163-2.167

 YR.sharma, elimentary organic spectroscopy

PG.NO:36-48

 Internet source

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