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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

12 25. 12.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. d a. b. g and higher a. b. g and higher a. 18 35. b b 10. g. 18 35.Woodward-Fieser Rules . 30. 17. 30 95 5 39 . b. 30. d a. 31 6 15. b a.

b or b. esters and carboxylic acids have different base values than ketones Unsaturated system Aldehyde With a or b alkyl groups With a.Enones Aldehydes.b alkyl groups Group value – exocyclic a.b double bond Group value – endocyclic a.b alkyl groups Acid or ester With a or b alkyl groups With a.b bond in 5 or 7 membered ring 208 217 +5 +5 Base Value 208 220 230 242 3 .Woodward-Fieser Rules .b alkyl groups With a.b or b.b.

600 13.400 7.000 11.400 9.400 8.400 7.600 11.800 7.480 1.450 1.800 lmax 254 261 264 261 270 269 280 271 273 e 204 225 190 192 1.000 970 -CH3 -Cl -Br -OH -OCH3 -NH2 -CN C(O)OH -C(O)H -C(O)CH3 -NO2 Electron withdrawing 4 .Substituent Effects on aromatic compounds Primary Substituent -H Electron donating Secondary lmax 203.900 6.5 207 210 210 211 217 230 224 230 250 224 269 e 7.000 7.200 6.430 1.

-O-Ring -O-Cl -Br -NH2 -NHC(O)CH3 -NHCH3 -N(CH3)2 G . -OH.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 O 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.