厦门大学化学化工学院：《有机化学》课程教学资源（课件讲稿，双语版）Chapter 15 Reactions of Aromatic Compounds（15.10-15.13）Effect of Substituents on Reactivity and Orientation

ORGANIC CHEMISTRY Chapter 15 15.10 Effect of substituents on Reactivity and orientation Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 15 15.10 Effect of Substituents on Reactivity and Orientation

ORGANIC CHEMISTRY Chapter 15 HNO NO H2SO4 NO2 NO z=oh Me CI NO, CN o(%)4059306 17 p(%)603769<12 (%)<14 93 81 Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 15 Z HNO3 H2SO4 Z Z Z NO2 NO2 NO2 + + o- p- m￾Z＝ OH Me Cl NO2 CN o(%) 40 59 30 6 17 p(%) 60 37 69 <1 2 m(%) <1 4 1 93 81

ORGANIC CHEMISTRY Chapter 15 CH NO An activating group An deactivating group Ortho-para director Meta director More reactive than benzene Less reactive than benzene toward electrophilic substitution toward electrophilic substitution An deactivating group Ortho-para directors Less reactive than benzene toward electrophilic substitution Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 15 CH3 An activating group More reactive than benzene toward electrophilic substitution NO2 An deactivating group Less reactive than benzene toward electrophilic substitution Ortho-para director Meta director X An deactivating group Less reactive than benzene toward electrophilic substitution Ortho-para directors

ORGANIC CHEMISTRY Chapter 15 g Ortho-para directors NR2-NHR一NH2-OH-OR一 NHCOR OCOR-R-C6H5 -X g Meta directors NR3-NO2-CCI3 -CN SO3H CHO-COR-CO2R-CONH2 Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 15 Ortho-para directors NR2 NHR NH2 OH R OR OCOR NHCOR C6H5 X Meta directors NR3 NO2 CCl3 CN CO2R SO3H CHO COR CONH2

ORGANIC CHEMISTRY Chapter 15 15.11 Theory of Substituent Effects on Electrophilic Aromatic Substitution Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 15 15.11 Theory of Substituent Effects on Electrophilic Aromatic Substitution

ORGANIC CHEMISTRY Chapter 15 Q Reaction 8++E+→→(8+)—-(+ is faster Q releases E H E H electrons Q Reaction +E is slower E H E H Q withdraws electrons Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 15 δ+ Q δ− δ− δ− δ δ − − Q δ+ δ+ δ+ δ+ Q releases electrons Q withdraws electrons + E + E δ E H Q E H Q δ E H Q E H Q Reaction is faster Reaction is slower

ORGANIC CHEMISTRY Chapter 15 R R R E E H H H R R R R +e EH EHEH R R R H H E E Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 15 + E+ R R E H R E H R E H R R R E H E H E H R R R H E H E H E

ORGANIC CHEMISTRY Chapter 15 NO2E NO NO E E H H H NO2 NO NO2 NO + +E EHEH EH NO NO2 NO ◇ H E Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 15 + E+ NO2 NO2E H NO2E H NO2E H NO2 NO2 NO2 E H E H E H NO2 NO2 NO2 H E H E H E

ORGANIC CHEMISTRY Chapter 15 C H H H H Cl Cl +C E EH EH E HE H H H H E E Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 15 + E+ Cl Cl E H Cl E H Cl E H Cl Cl Cl E H E H E H Cl Cl Cl H E H E H E Cl E H Cl E H

ORGANIC CHEMISTRY Chapter 15 Orientation of disubstituted benzenes CH CH HNO NO2 HoSO 4 NO NO CH CH FeCl Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 15 Orientation of Disubstituted Benzenes CH3 NO2 HNO3 H2SO4 CH3 NO2 NO2 CH3 Cl CH3 Cl CH3 Cl Cl2 FeCl3 Cl Cl +