Introduction Definitions

Choice of solvents
Rules for dienes and trienes absorption Rules for , unsaturated aldehydes and ketones

Rules for conjugated carbonyl compounds

Absorption for mono & di-substituted benzene

derivatives Rules for polyenes

 The absorption maximum of a dienes system is

affected by substitution and WOODWARD (1942) found that the position of the absorption maximum depends on their number and type of dienes.
As a result WOODWARD developed a set of

empirical rules (later modified by fieser,1948) for calculating max from the molecular structure of the compound.

 Longer the conjugate system, greater is the

wavelength of absorption.
With the increase in the length of

chromophore, the intensity of absorption increases.

The conjugated polyene system appears

coloured to the naked eye if there are more than five double bonds are in conjugation and absorption occurs around or above 400nm.
The presence of alkyl group on the double bond

also causes bathochromic shift.

 Spectroscopy
It is a measurement and interpretation of EMR.

Absorbance
The difference between the intensity of incident light and intensity of transmitted light.

Chromophore
The group which is responsible for absorption of the U.V radiation and may or may not impart the colour to the compound.

SOLVENTS WAVELENGTH Ethanol 210nm Hexane 210nm Methanol 210nm Cyclohexane 210nm Diethyl ether 210nm Water 205nm Benzene 280nm Chloroform 245nm Tetrahydrofuran 220nm Carbon tetra chloride 265nm

 Parent value for butadiene system or a

Cyclic conjugated diene

Acyclic diene Homoannular conjugated diene

217nm
245nm 253nm

Heteroannular conjugated diene

215nm

Increment for each substituteAlkyl substituent or ring residue Exocyclic double bond Double bond extending conjugation 5nm 5nm 30nm

Auxochrome
-OR - SR - Cl*, - Br* - NR2 -OCOCH3 + 6nm + 30nm + 5nm + 60nm 0nm

The calculated and experimental values of max match with in 5nm

Homoannular diene

Heteroannular diene
CH2

Acyclic diene

H2C

The double bond exocyclic to a ring

IN CASE OF ACYCLIC DIENES

1. Observed max -224 Calculated max base value 214 one alkyl substituent 05 219

H2C

H3C

CH3

2.

Observed max 232 What is the Calculated max ?

H3C

CH3

In case of Homoannular diene

1.

H3C

Base value 253 2-alkyl substitutions 10 2- ring residues 10 273

H3C

CH3
Calculate the max for the following compounds.

2.

H3C

H3C

CH3

IN CASE HETEROANNULAR DIENE

Observed max 235 Calculated max Base value 214 3-alkyj substituent s 15 1-exocyclic double bond - 05 234

 Woodward and fieser framed certain emrpical rules for estimating the

absorption maximum for , - unsaturated carbonyl compounds.

These rules were later modified by Scott and are as follows The basic value , - unsaturated ketone is taken as 215 nm.

The , - unsaturated ketone may be a cyclic or six membered. For a compound, = CH COX, basic value is taken as 215nm If X = alkyl group then the basic value is 215nm If X = H, then the basic value is 207nm If X = OH, then the basic value is 193nm membered ring (cyclopentanone), then for such an , - unsaturated ketone, the basic value becomes 202 nm (The Emax for such compounds are generally above 10,000)

If the double bond and the carbonyl group are contained in a five

 The structural increament for estimating max for a given

, - unsaturated carbonyl compounds are as follows

For each exocyclic double bond + 5nm For each double bond endocyclic in 5 or 7 membered Ring except cyclo-pent-2 enone + 5nm For each alkyl substituent or ring residue at the position + 10nm position + 12nm or position + 18nm For each double bond extending conjugation + 30nm For a Homoannular conjugated diene + 39nm

 Increments for various auxochromes in the various , , etc.,

positions are given below

Chromophore
carbonyl

-OH -OAc

+ 35 +6 + 15 + 25 + 35

Increment in nm for position with respect to the group - or higher + 30 +6 + 12 + 35 + 30 +6 17 + 50 +6 31

-Cl
-Br -OR

-SR
-NR2

+ 85
+ 95

HO

Observed max 247 Calculated base value 202 1- substituent 10 -OH 35 247

O
O CH3

Observed max 232 Calculated base value 1- substituent 1--Substituent

215 12 10 247

CH3 CH3
Calculate the max for following structures

CH3

Examples: 1
H3C O CH3 OH

H3C

CH3

H3C

CH3

Observed max 270 nm Calculated max base value R--alkyl substituent(-OH)215 14 35 274

Example 2

OH

Observed max - 255nm What is the calculated max ?

R-C6H4-COG

max (nm) 246 250 230 0-3 nm O,M-7 nm P-25 nm O 11 nm M 20 nm P 78 nm

Parent chromophore
G-Alkyl or Ring residue G=H G=OH or OR

Addition for R
Alkyl or ring residue -OH or Ome ,-O-Alkyl -O

R-C6H4-COG -Cl

max (nm) O,M -0 nm P 10 nm

-Br

O,M -2 nm P 15 nm

-NH2

P 58 nm O,M -13 nm

-NHAC

O,M -20 nm

P 45 nm
-NHMe O,M -20 nm P 45 nm -NHMe2 O,M 20 nm P 85 nm

Examples: 1.

Observed max 276 nm Calculated max parent value - 246 para-methoxyl - 25 ortho-ring residue 03 274

CH3

2.
H3C

H3C O

Observed max 278 What is the calculated max ?

 Woodwards Rules work well only for conjugated

system of 4 double bonds or less conjugated polyenes having more than 4 double bonds the fisher-kuhn rules are used.

 Gurdeep R. Chatwal, Instrumental methods of

chemical analysis , Himalaya publishing house, 5th edition ,2008. B.K.sharma,Instrumental methods of chemical analysis , Goe publication, 23rd Edition. www.bing.com www.google.com