[理学]5alicyclic hydrocarbons.ppt

Chapter 5 脂环烃alicyclic hydrocarbons 本章重点讲解： 1. 环烷烃的分类与命名——掌握 2. 环烷烃的结构——理解 3. 环烷烃的化学性质——掌握 4. 环己烷及其衍生物的构象——掌握 5.1 脂环烃的分类与命名 在单环体系中分为：小环(C3-C4) 普通环(C5-C7) 五环和六环最普遍 中环(C8-C11) 大环(≥C12) 5.1 脂环烃的分类与命名 5. 2 脂环烃的化学性质 5.3 环烷烃的结构与稳定性 5.4 环己烷及其衍生物的构象 Conformational Inversion chair-chair interconversion (ring-flipping) rapid process (activation energy = 45 kJ/mol) all axial bonds become equatorial and vice versa Methylcyclohexane Source of crowding is close approach to axial hydrogens on same side of ring. Crowding is called a 1,3-diaxial repulsion and is a type of van der Waals strain. Fluorocyclohexane Crowding is less pronounced with a small substituent such as fluorine. Size of substituent is related to its branching. tert-Butylcyclohexane Crowding is more pronounced with a bulky substituent such as tert-butyl. tert-Butyl is highly branched. tert-Butylcyclohexane 1,4-Dimethylcyclohexane Stereoisomers Trans stereoisomer is more stable than cis, but methyl groups are too far apart to crowd each other. Conformational analysis ofcis-1,4-dimethylcyclohexane Conformational analysis oftrans-1,4-dimethylcyclohexane 1,2-Dimethylcyclohexane Stereoisomers Analogous to 1,4 in that trans is more stablethan cis. Conformational analysis ofcis-1,2-dimethylcyclohexane Conformational analysis oftrans-1,2-dimethylcyclohexane 1,3-Dimethylcyclohexane Stereoisomers Unlike 1,2 and 1,4; cis-1,3 is more stable than trans. Conformational analysis ofcis-1,3-dimethylcyclohexane Conformational analysis oftrans-1,3-dimethylcyclohexane 5.5 十氢化萘构象 20 20 20 Less than 0.01% Greater than 99.99% C(CH3)3 C(CH3)3 van der Waalsstrain due to1,3-diaxialrepulsions 2) 二取代环己烷的构象 试比较顺式和反式 1,4-二甲基环己烷的稳定性。 ea键型 ee键型 甲基ee键型异构体比甲基ea键型异构体稳定。 cis trans CH3 5219 kJ/mol 5212 kJ/mol less stable more stable H3C H H H3C CH3 H H CH3 H3C H H Two equivalent conformations; each has one axial methyl group and