[理学]有机化学波谱.ppt

一、 Background Ultraviolet spectroscopy involves the absorption of ultraviolet light by a molecule causing the promotion of an electron from a ground electronic state to an excited electronic state. Ultraviolet light: wavelengths (l) between 200 and 400 nm Types of Transitions There are several types of electronic transitions available to a molecule including: s to s* (alkanes) p to p* (alkenes, carbonyl compounds, alkynes, azo compounds) h to s* (oxygen, nitrogen, sulfur, and halogen compounds) h to p* (carbonyl compounds) Not all transitions that are possible will be observed. Some electronic transitions are forbidden by certain selection rules. However, even forbidden transitions can be observed, but these are usually not very intense. Chromophore lmax _____________________________ Alkanes ~ 150 __________________________ Chromophore lmax ______________________ Alkenes ~ 175 Alkynes ~ 170 Carbonyls ~ 188 ________________________ Chromophore lmax ______________________ alcohols, ethers ~ 185 Amines ~ 195 sulfur compounds ~ 195 _________________________ Chromophore lmax __________________________ Carbonyls ~ 285 _____________________ 四、 紫外吸收带及其特征 (1) R带[来自德文Radikalartig(基团)] 起源：由n-π＊跃迁引起。或者说，由带孤对电 子的发色团产生。例如： (2) K带[来自德文Konjugierte(共轭)] 起源：由π-π＊跃迁引起。特指共轭体系的π-π＊跃迁。 K带是最重要的UV吸收带之一，共轭双烯、α,β－不饱和醛、酮，芳香族醛、酮以及被发色团取代的苯（如苯乙烯）等，都有K带吸收。例如： (3) B带和E带 起源：均由苯环的π-π＊跃迁引起。是苯环的UV特征吸收。 特点： ①B带为宽峰，有精细结构 (苯的B带在230－270nm) εmax偏低：200＜ε＜3000 (苯的ε为215)； ② E1带特强，(εmax ＜10000) ； E2带中等强度，(2000＜εmax ＜10000) ③ 苯环上引入取代基时，E2红移，但一般不超过210nm。如果E2带红移超过210nm，将衍变为K带。 七.Measurement of the Spectrum The UV spectrum is usually taken on a very dilute solution (1 mg in 100 ml of solvent). A portion of this solution is transferred to a silica cell. A matched c