(芳香化合物亲电取代.pptVIP

Common substituent groups and their effect on reactivity in EAS: -NH2, -NHR, -NR2 -OH -OR -NHCOCH3 electron donating -C6H5 -R -H -X -CHO, -COR -SO3H -COOH, -COOR electron withdrawing -CN -NR3+ -NO2 increasing reactivity Electron donating groups activate the benzene ring to electrophilic aromatic substitution. electron donating groups increase the electron density in the ring and make it more reactive with electrophiles. electron donation stabilizes the intermediate carbocation, lowers the Eact and increases the rate. * Chapter 8 Electrophilic Aromatic Substitution (芳香化合物的亲电取代 Ar-H = aromatic compound 1. Nitration Ar-H + HNO3, H2SO4 ? Ar-NO2 + H2O Sulfonation Ar-H + H2SO4, SO3 ? Ar-SO3H + H2O Halogenation Ar-H + X2, Fe ? Ar-X + HX Friedel-Crafts alkylation Ar-H + R-X, AlCl3 ? Ar-R + HX Friedel-Crafts alkylation (variations) Ar-H + R-X, AlCl3 ? Ar-R + HX Ar-H + R-OH, H+ ? Ar-R + H2O c) Ar-H + Alkene, H+ ? Ar-R toluene faster than the same reactions with benzene nitrobenzene slower than the same reactions with benzene Substituent groups on a benzene ring affect electrophilic aromatic substitution reactions in two ways: reactivity activate (faster than benzene) or deactivate (slower than benzene) orientation ortho- + para- direction or meta- direction -CH3 activates the benzene ring towards EAS directs substitution to the ortho- para- positions -NO2 deactivates the benzene ring towards EAS directs substitution to the meta- position Common substituent groups and their effect on EAS: -NH2, -NHR, -NR2 -OH -OR -NHCOCH3 -C6H5 -R -H -X -CHO, -COR -SO3H -COOH, -COOR -CN -NR3+ -NO2 increasing reactivity ortho/para directors meta directors If there is more than one group on the benzene ring: The group that is more activating (higher on “the list”) will direct the next substitution. You will get little or no