有机化学Chapter6.Arenes粗砂全解.ppt

Directing substitution primarily to the meta position to themselves 6% 3% 91% 3. Ortho and para directing deactivators –X: 30% 69% 1% –I, +C Ortho- and para- directing activitors Ortho- and para- directing deactivitors Meta- directing deactivitors FIGURE 6.1 Classification of substituent effects in electrophilic aromatic substitution. 6.4.2 Substituent Effects in electrophilic Aromatic substitution Substituent Effects P157 Meta-directing deactivitors Electron-withdrawing Ortho- and para- directing activitors Electron-releasing Reactivity 1. Ortho and para directing activitors Activiting effect: Electron-releasing groups increase the density of electron could to favor electrophilic attack. stabilize the carbocation. Orientation effect: Ortho attack Para attack Meta attack Most stable resonance structure Para and ortho attacks are primary. P168, 2. Meta directing deactivitors Deactiviting effect: Electron-drawing groups decrease the density of electron cloud of aromatic ring. Making intermedias highly unstable Orientation effect: Ortho attack Para attack Meta attack Most unstable intermeidate Meta attack is primary 3. Halogens Halogen as a substituent on aromatic ring possesses both electron-drawing inductive effect(-I) and electron-releasing conjugative effect(+C). -I +C -I +C Inductive effect of halo-group deactivates aromatic ring. Halo-group stabilizes the inter- mediate relative to that from ortho and para attack deactivates aromatic ring by donating unshared pair of electrons in the same way as –OH. 6.5 Multiple Substituent Effects Further electrophilic substitution of a disubstituted bezene is governed by additivity(累加性) of effects. If the directing effects of the two groups reinforce( 增强) each other, there is no problem. 2. If the directing effects of the two groups are oppose each other, the activiting group has the dominant inf