UV Spectroscopy - FQO紫外光谱-矿场业主联盟.ppt

* UV Spectroscopy Structure Determination Aromatic Compounds Substituent Effects Electron-donating and electron-withdrawing effects No matter what electronic influence a group exerts, the presence shifts the primary absorption band to longer l Electron-withdrawing groups exert no influence on the position of the secondary absorption band Electron-donating groups increase the l and e of the secondary absorption band * UV Spectroscopy Structure Determination Aromatic Compounds Substituent Effects Electron-donating and electron-withdrawing effects Primary Secondary Substituent lmax e lmax e -H 203.5 7,400 254 204 -CH3 207 7,000 261 225 -Cl 210 7,400 264 190 -Br 210 7,900 261 192 -OH 211 6,200 270 1,450 -OCH3 217 6,400 269 1,480 -NH2 230 8,600 280 1,430 -CN 224 13,000 271 1,000 C(O)OH 230 11,600 273 970 -C(O)H 250 11,400 -C(O)CH3 224 9,800 -NO2 269 7,800 Electron donating Electron withdrawing * UV Spectroscopy Structure Determination Aromatic Compounds Substituent Effects Di-substituted and multiple group effects With di-substituted aromatics, it is necessary to consider both groups If both groups are electron donating or withdrawing, the effect is similar to the effect of the stronger of the two groups as if it were a mono-substituted ring If one group is electron withdrawing and one group electron donating and they are para- to one another, the magnitude of the shift is greater than the sum of both the group effects Consider p-nitroaniline: * UV Spectroscopy Structure Determination Aromatic Compounds Substituent Effects Di-substituted and multiple group effects If the two electonically dissimilar groups are ortho- or meta- to one another, the effect is usually the sum of the two individual effects (meta- no resonance; ortho-steric hind.) For the case of substituted benzoyl derivatives, an empirical correlation of structure with observed lmax has been developed This is slightly less accurate than the Woodward-Fieser rules, but can usually predict