Woodward-Fieser Rules - Dienes The rules begin with a base value for lmax of the chromophore being observed:

acyclic butadiene = 217 nm

Group Extended conjugation Each exo-cyclic C=C Increment +30 +5 Heteroannular (transoid): Homoannular (cisoid):

Alkyl
-OCOCH3 -OR -SR -Cl, -Br

+5
+0 +6 +30 +5

base lmax = 214 e = 5,000 15,000

base lmax = 253 nm e = 12,000-28,000

-NR2

+60

Woodward-Fieser Rules - Enones

b a b C C C O

d g b a d C C C C C O
Increment Base 215 nm Base 202 nm Base 245 nm 30

Group 6-membered ring or acyclic enone 5-membered ring parent enone Acyclic dienone Double bond extending conjugation Alkyl group or ring residue -OH -OR -O(C=O)R -Cl -Br -NR2 Exocyclic double bond Homocyclic diene component a, b, g and higher a, b, g and higher a, b, g, d a, b, d a, b a, b b

10, 12, 18 35, 30, 18 35, 30, 17, 31 6 15, 12 25, 30 95 5 39

Woodward-Fieser Rules - Enones Aldehydes, esters and carboxylic acids have different base values than ketones
Unsaturated system Aldehyde With a or b alkyl groups With a,b or b,b alkyl groups With a,b,b alkyl groups Acid or ester With a or b alkyl groups With a,b or b,b alkyl groups Group value exocyclic a,b double bond Group value endocyclic a,b bond in 5 or 7 membered ring 208 217 +5 +5 Base Value 208 220 230 242

Substituent Effects on aromatic compounds

Primary
Substituent
-H
Electron donating

Secondary

lmax
203.5 207 210 210 211 217 230 224 230 250 224 269

e
7,400 7,000 7,400 7,900 6,200 6,400 8,600 13,000 11,600 11,400 9,800 7,800

lmax
254 261 264 261 270 269 280 271 273

e
204 225 190 192 1,450 1,480 1,430 1,000 970

-CH3 -Cl -Br -OH -OCH3 -NH2 -CN C(O)OH -C(O)H -C(O)CH3 -NO2

Electron withdrawing

Di-substituted and multiple group effects on aromatic compounds

Parent Chromophore R = alkyl or ring residue R=H R = OH or O-Alkyl

lmax 246 250 230 Substituent increment

R
G

o
3
7 11 0 2 13 20 20

m
3
7 20 0 2 13 20 20

p
10
25 78 10 15 58 45 73 85

Alkyl or ring residue

-O-Alkyl, -OH, -O-Ring -O-Cl -Br -NH2 -NHC(O)CH3 -NHCH3 -N(CH3)2