Woodward–Fieser Rules for Diene
Ø Woodward (1941) predicted λmax values only for the lowest energy
transition (π è π*) from HOMO to LUMO.
Base values:
Ø Base value for an unsubstituted, conjugated, acyclic or
heteroannular diene 214 nm
Ø Base value for an unsubstituted, conjugated, homoannular diene 253 nm
Increments for:
Each extra double bonds in conjugation + 30 nm
Exocyclic double bond (effect is two fold if the bond is exocyclic to
two rings) + 5 nm
Substituent effect:
A. -OCOR or –OCOAr + 0 nm
B. Simple alkyl substituents or ring residue + 5 nm
C. Halogen (-Cl, -Br) + 5 nm
D. OR (R=Alkyl) + 6 nm
E. SR (R=Alkyl) + 30 nm
F. NR2 (R=Alkyl) + 60 nm
Woodward–Fieser Rules for Diene
1 2
3
EtO
Woodward–Fieser Rules for Diene
1
2
3
1
2 3
Woodward–Fieser Rules for Diene
R
2
3
1
4
5
HOOC
2
5 4 3
AcO
Woodward–Fieser Rules for Diene
2
3
4
5
Woodward-Fieser Rule for Enones
Rules of Enone & Dienone Absorption
Base values:
Ø Acyclic α,β-unsaturated ketones 215 nm
Ø 6-membered cyclic α,β-unsaturated ketones 215 nm
Ø 5-membered cyclic α,β-unsaturated ketones 202 nm
Ø α,β-unsaturated aldehydes 210 nm
Ø α,β-unsaturated carboxylic acid & esters 195 nm
Increments for:
Double bond extending conjugation (DEC): +30
Exocyclic double bond: + 5
Homodiene component: +39
CH-‐521
Course
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Molecular
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Instructor:
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Kaliappan
28
Woodward-Fieser Rule for Enones
Increments for:
Alkyl group/ring residue: α +10
β +12
γ & higher +18
Polar groups: -OH: α +35
β +30
δ +50
-OAc: α,β,γ + 6
-OMe: α +35
β +30
γ +17
δ +31
-SAlk: β +85
-Cl: α +15
β +12
-Br: α +25
β +30
-NR2: β +95
CH-‐521
Course
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Molecular
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Course
Instructor:
Krishna
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Kaliappan
29
Woodward-Fieser Rule for Enones
O 1 β'
2
CH3 β
β
O 3 5
4
β
OH
HO β β α
α
O
O
Woodward-Fieser Rule for Enones
O
CH3
α OCOCH3 O
β δ
γ
O
O
Br
Woodward-Fieser Rule for Enones
O O
O
O
Aromatic Compounds
Parent chromophore: Ar = C6H5
Ar-CO-R 246 nm
Ar-CHO 250 nm
Ar-COOH or Ar-COOR 230 nm
Increment for each substituent on Ar:
Alkyl or ring residue o, m + 3 nm
p + 10 nm
OH, OCH3, OAlk o, m + 7 nm
p + 25 nm
NH2 o, m + 13 nm
p + 58 nm
NHCOCH3 o,m + 20 nm
p + 45 nm
NHMe p + 73 nm
NMe2 o, m + 20 nm
p + 85 nm
Cl o, m + 0 nm
p + 10 nm
Br o, m + 2 nm
p + 15 nm
CH-‐521
Course
on
Interpreta2ve
Molecular
Spectroscopy;
Course
Instructor:
Krishna
P.
Kaliappan
33
Aromatic Compounds
MeO
Cl
CO2Et
OH O
OMe
MeO
O
CH,CH,C H
B
(CH,),C-CH-C-OH
~CH,
OH
(A) (B)
(A) B)
(A) (B) (C) (D)
(a)
(A) (B) (C) (D)
(6)
(A) (B) (C) (D)
(a)
(c)
CH,COOCH==CHCH=CHCI
CH,CH,CBr çcoOH
(6) CH,CH,CH-CBrCOCH,
ÓH
(c) -CH,
Aco
^CH3
ÇHO
(g)
(h)
CH,
OH
NO ÇH,CHO
