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UV Spectros

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The Woodward-Fieser rules provide a method to calculate the maximum absorption wavelength (λmax) of conjugated dienes and polyenes based on their structure. The rules assign base values depending on whether the double bonds are in the same ring or different rings. Increments are then added based on features like exocyclic double bonds, substituents, and ring size. The rules can be used to distinguish between isomers and predict λmax values that often match observed wavelengths closely.

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UV Spectros

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getashishkm
79 views13 pages
The Woodward-Fieser rules provide a method to calculate the maximum absorption wavelength (λmax) of conjugated dienes and polyenes based on their structure. The rules assign base values depending on whether the double bonds are in the same ring or different rings. Increments are then added based on features like exocyclic double bonds, substituents, and ring size. The rules can be used to distinguish between isomers and predict λmax values that often match observed wavelengths closely.

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UV Spectroscopy

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The Woodward-Fieser rules provide a method to calculate the maximum absorption wavelength (λmax) of conjugated dienes and polyenes based on their structure. The rules assign base values depending on whether the double bonds are in the same ring or different rings. Increments are then added based on features like exocyclic double bonds, substituents, and ring size. The rules can be used to distinguish between isomers and predict λmax values that often match observed wavelengths closely.

Copyright:

© All Rights Reserved
Download as PPTX, PDF, TXT or read online from Scribd
Download as pptx, pdf, or txt
79 views13 pages

UV Spectros

Uploaded by

getashishkm
The Woodward-Fieser rules provide a method to calculate the maximum absorption wavelength (λmax) of conjugated dienes and polyenes based on their structure. The rules assign base values depending on whether the double bonds are in the same ring or different rings. Increments are then added based on features like exocyclic double bonds, substituents, and ring size. The rules can be used to distinguish between isomers and predict λmax values that often match observed wavelengths closely.

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Woodward - Fieser Rules

Woodward-Fieser Rules for Calculating the λmax of


Conjugated Dienes and Polyenes

Empirical Rules for Absorption Wavelengths of


Conjugated Systems

Homo annular Ring


Base Value = 260 / 253
Double bonds present in the same ring and
* Represents that the carbon has Exocyclic double
bond
Hetero
Base Value = 215
Annular Exocyclic double bonds
Double bond extending from ring to another
Two exocyclic double bonds
Each exocyclic double bond adds 5 nm. Substituent and Influence

*When a homoannular (same ring) a base value of R- (Alkyl Group) .... +5


260 nm should be choosen. nm RO- (Alkoxy Group) ..
+6 X- (Cl- or Br-) .........
*When a hetero annular (different ring) a base +10
value of 215 nm should be choosen. RCO2- (Acyl Group) .... 0
RS- (Sulfide Group) .. +30
λmax (calculated) = Base (215 or 260) + Substituent Contributions R2N- (Amino Group) ..
+60

Further π -Conjugation
C=C (Double Bond) ...
+30 C6H5 (Phenyl Group) ...
+60
Distinguishing Isomers

Base value 215


4 X alkyl subst. 20
exo DB 5
Total 240
Obs 238
HO2C

Base value 260


2Xalkyl subst 10
Total 270
273
HO2C Obs
Woodward-Fieser Rules for Dienes
Homoannular Heteroannular
(cisoid) (transoid)

=214 nm
Parent =253 nm
=217 (acyclic)
Increments for:
Double bond extending conjugation 30 30
Alkyl substituent or ring residue 5 5
Exocyclic double bond 5 5
Polar groupings:

-OC(O)CH3 0 0
-OR 6 6
-Cl, -Br 5 5
-NR2 60 60
-SR 30 30
Example 1:

Transoid: 217 nm
Alkyl groups or ring residues: 3x5= 15 nm
Calculated: 232 nm
Observed: 234 nm

Hetero annualr: 214 nm


Alkyl groups or ring residues: 3x5= 15 nm
Exocyclic double bond: 5 nm
Calculated: 234 nm
Observed: 235 nm
Woodward's Rules for Conjugated Carbonyl Compounds

Base values:
X=R

=215 nm
Six-membered ring or acyclic parent enone

Five-membered ring parent enone =202 nm

X=H =208 nm

X = OH, OR =195 nm

Increments for:

Double bond extending conjugation 30

Exocyclic double bond 5

Endocyclic double bond in a 5- or 7-membered ring for X = OH, OR 5

Homocyclic diene component 39

Alkyl substituent or ring residue  10

 12

 or higher 18
Polar groupings:
-OH  35
 30
 50
-OC(O)CH3  6
-OCH3  35

 30
 17
 31
-Cl  15
 12
-Br  30
 25
-NR2  95
* Solvent shifts for various solvents:

Solvent  max shift (nm)


water +8
chloroform -1
ether -7
cyclohexane - 11
dioxane -5
hexane - 11
Acyclic enone: 215 nm
-Alkyl groups or ring residues: 10 nm
-Alkyl groups or ring residues: 2 x 12 = 24 nm
Calculated: 249 nm
Observed: 249 nm

Five-membered ring parent enone: 202 nm


-Alkyl groups or ring residues: 2 x 12 = 24 nm
Exocyclic double bond: 5 nm
Calculated: 231 nm
Observed: 226 nm
Six-membered ring or alicyclic parent enone: 215 nm
Extended conjugation: 30 nm
Homocyclic diene component: 39 nm
-Alkyl groups or ring residues: 18 nm
Calculated: 302 nm
Observed: 300 nm

Five-membered ring parent enone: 202 nm


-Br: 25 nm
-Alkyl groups or ring residues: 2 x 12 = 24 nm
Exocyclic double bond: 5 nm
Calculated: 256 nm
Observed: 251 nm

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