Reactions With Benzene 2g683k

Reactions With Substituent Effects Electrophilic Aromatic Substitutions

c ccc cc

c c cc c cc c ccc cc General Mechanism

c c c cc c ccc cc c c à c c c c c c ! "# c $ c %c ! "# c c c c c c

cc

c c

? Halogenation & cc'cc!'c( )cc'c cc c(

c# cc*)c c cV c c c c!'c cc c cc c cc

c c(

)ccc

c cc

c c

c c c c+c c

c c

c c

c, c c c c cccc cc

c c cc

c c Nitrationc & ccà-ccà- c c c

c c-.cccccc c cV c c c cà-c c $cccc cc cc c c c c c, c cc c c c c cc ccà-c c c c

c-.c

c

c c c c c

cc

c c

c cc

c c cSulfonation²c & cc-ccà- c( c c )c c c

c cà-.c c cV c c c c-c c $cccc cc ccà- c c cc, c c ccc ccc c/cc, c c c c c c c c c ccc c c c

cc c c

c c cc

c cccccccccccccccccccccccccccccccccccccccc cccccccc

c& ccc c cc c0 c c 1cHighc0!1dcforwardc c c +c c cDilutec0!1dcreversec c c cc+c

c c

c c

c c


2c 3c c

c c c cc*c c4 c c cc c c c c cc cR-X and AlX3 where X is either Br or Cl cV c cc $ c c

cccccc c c

ccccccccccccccccc

c

c $ c ccc5 c5 cc5ccc cc ccc

c(c6cc6cc6c#à)c c c cccc $ c c c( c c cc c c )c cc "c Mayccccmorec c#(.)ccc cc c "c Sometimescccequallyc c#(.)cccc cc "c Noc cc c#(.)c clessc c c cc c c c c c c c c

c c

c c

c c

c

c



c

c c

c c

cc

c c

ccR-OH and H+c c( c c )cc, ccc c c7c c cc c c +c cccc cc c c c c c cc cV c cc c c c c/cc c c cccc c cc ccc c cc c c c cc c cc

c c cAlkene, H+ cV c cc $c c c c $c c c c c cc c cc c cc c

c "c c( )c cc c cc c cc c cc c c cc( c )c ccc c

c "c 89 ccc c c cc c ccc c " cc(cc c#:-)cccc cc("à cà& c"&)c

c c

c c

c c

"c

c c c c c c c c cc c c( cc c )cc c $ c

c2cc c c c

%cFriedel-Crafts Acylationcc & ccc c c(&"#:-"')cc 'c c c c

c c&"#:-.c c c V c c c c 'c cc c c c cc c c c cc

c cc c cc cc cc c

c c c c c cccc c( ' .)cc c c c c

c c c c+c c

c c c c c

c

c c

c c

c

c

c c

c c

c c

Electrophilic Addition of Styrenes c c c B c

c 2 $cc $cÉccc

c(Éccc +c cc c )cc cc c c c cc c ccc c +c c&cc$ c c $c

c

c c cc c Reagents7cà-.c(à..cà-) cà' cc'c c ; c< c c

c

c

c c c c c c c c c

c c

c c

c c

Substituent Effects of Styrenes

c

c

c

c c c c c c c c c c c c c c

c c

c c

c c

Base-Catalyzed Hydrolysis of Benzoate Esters c #cc c cc c c c c

c c c Reagents7c-àc(-à") cà-c =cc/ c ccc c

c

c c c

c c

cc

c c

ý cBcc

c c c c c c c c c c c c c c c c c c c c

c c

c c

c c

Reactions Without Substituent Effects Nucleophilic Aromatic Substitution c *+c c cc c c c 7c c -c ccc>;ccc c -c ccc cc(

c )c c c cc"c c c>;cc c

c

Reagent:c#à-"c.c(

)c c V

c

c

c c

c c

c c

Benzyne Reactionc c c c c*+c c c < ccc cc(

cc cc c )c c àccc c cc c cc c

c c Reagents7c ccc

c& c c Strong Base Electrophilic Reagent àc( )cà"c à*c( c )c " -àc(-à )c 'c à-.c

c ? c " c c(?8)c c c c c " / cc ( c $/ c cc

c c cc )c c àc( c )cà""c c c c c c c c c c c c

c c

c

c c

c c

V

c

c

c c

c c

c c

c

c

c c

c c

c c

c c

c c

c c

c

c c c( c cc)cbut meta is major c c c cc c c c c c c c c Oxidation of Substituents on Benzene Rings -/ cc c c c(# )c c c "c 8c c cc càc@c cc c-

c c Two types of oxidationscc+ c c c À<- c

c c

c * c

c c KMnO< Oxidationc c c/ cc+ c c c4 c ccc c ccàc c

c

c c

c c

c c

c c

/ c

c c c c c cc c/ +c ccnot oxidize × bonds of benzene ringsc c

coxidize alkene/alkynes to produce diols

c c c c

c c

c c

NBS Oxidationc c c/ cc+ @

cc c c ccàc c c cc c c cc+ @

c cc c & c& cc c c c " cc c c ccc c = " ccc c cc @ c c ccc c c 3c c c c c c c " cc c c ccc c

< c c

c

c c c c c c c

c c

c c

c c



c c

c

c c c c

c c

c c

c

Reaction Energy Diagram

Stability of carbocation radicals •c

c cc•c+ c •c

c6c•c+ c BUT c cc c c c5 c5 cc5cc c c

c c

c c

c c

Kinetic Reaction (under kinetic conditions) Major Product2c c 2 cc c c c c cc c c c c c( cο;്)c c c÷• allylic bromidec c cmajor kinetic productc( c c c c

)c c c Thermodynamic Reaction (under thermodynamic conditions) Major Product2 c c c cc

cc c c c c c1• allylic bromide c cmajor thermodynamic productcc c cc disubstituted alkenecc c Reduction of Substituents on Benzene Ringsc c Reductionc c c c c cccc càc@cc c cccc c-c c

c c Three types of reduction c # cà c& 7cà()cc c c(= cc=)c c

c

c c

c c

c c

c # c& c( c )c& 7cA cà# cc cà# c

c c c c c > "À c(* c )c& 7cà+ c(à"à)ccÀ-àc

cccccccc c c c >c c c c c c cc Bc c 1?c Catalytic hydrogenation c &c+ c cc cc c &c $cc $c ÷?c Clemenson Reduction c &c+ c cc cc c à# cc c c $cc $c c

c c 3?c Wolf-Kishner c &c+ c cc cc c À-àcc c c(" +)cc c c c

c c

c c

c c

c c

c

c

c c

c c

c c

c

c c c c c c c c c c c c c c

c c

c c

c c