理学取代基效应.pptxVIP

CH3COOH ClCH2COOH Cl2CHCOOH Cl3CCOOH pKa 4.76 2.86 1.29 0.65;取代基效应;Inductive effects are those that occur through the sigma system due to electronegativity effects.? These too can be either electron donating (e.g. -Me) where sigma electrons are pushed toward the functional group or electron withdrawing (e.g. -CF3, +NR3) where sigma electrons are drawn away from the functional group. ;;特征： 分子链（单、双、叁键） 强度：取决于取代基的电负性与距离。电负性差值越大，强度越高；距离越大，强度越弱。;1. 同周期元素（-I）：F OH NH2 CH3;取代基诱导效应的结果： 使官能团的电子云密度升高或下降，反应活性改变。;二.共轭体系与共轭效应 Resonance effects (conjugation effects) ;1.1、π - π 共轭体系;1.2、p - π 共轭体系;2.1、共轭效应特点： 共轭效应受距离的影响较小;Y为吸电基－吸电子共轭效应 (-C), X为供电基－供电子共轭效应 (+C).; 3、共轭效应的强度：取决于取代基中的中心原子的电负性与半径。;p - π共轭体系（+C效应）:;静态时： （分子未参加反应）;4、共振论 （Resonance Theory） · Electrons in σ bonds have a fixed location and so they are said to be localized.  · In contrast,? π electrons that can be drawn in different locations are said to be delocalized. · In certain cases, molecules can be represent by more than one reasonable Lewis structure that differ only in the location of π electrons.  · Collectively these Lewis diagrams are then known as resonance structures.  · The real structure has characteristics of each of the resonance structures, and is often represented as the resonance hybrid.? In a way, the resonance hybrid is a mixture of the contributors. ;O=C=O、CH2=CHCH=O 的共振结构;三. 超共轭效应 (Hyperconjugation); R: Me3C Me2CH Et Me H 110 180 290 340 1;当C－H键与双键直接相连时， C－H键的强度减弱，H原子的 活性增加。; C－H键上的σ电子发生 离域，形成σ－π共轭。σ 电子已经不再定域在原来的 C、H 两原子之间，而是离域 在C3－C2之间，使H原子容易 作为质子离去，这种共轭强度远弱于π-π和p-π共轭。;使分子的偶极距增加：;;四. 场效应 (Field effect);酸性：;五. 空间效应 (Steric effect);12.6 kJ/mol higher;2. 空间效应对质子酸 酸性的影响;pKao pKap;3. 空间效应对亲核取代反应活性的影响;;形成碳正离子是SN1反应的一步（速控步） 键角的扩张缓解了基团的拥挤程度 ;4. 空间效应（面张力）对Lewis酸碱性的影响;两者在相互接近过程中，基团位阻导致相互排斥作用－F－张力(Face - Strain);60° ;Topic 1:取代基对材