Reaction Coordinate Diagrams for the Two Benzene Reactions

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1 Electrophilic Addition vs. Substitution ( LEAVES!) Electrophilic Aromatic Substitution δ δ E E Y Y Reaction Coordinate Diagrams for the Two Benzene Reactions δ δ E E Y Y Electrophilic aromatic substitutions include: Nitration Sulfonation alogenation Friedel-Crafts Alkylation Friedel-Crafts Acylation Nitration of Benzene Sulfonation of Benzene N 2 2 S 4 N 2 2 S 2 heat S 2 2 Nitrobenzene (95%) Benzenesulfonic acid (100%)

2 alogenation of Benzene Friedel-Crafts Alkylation of Benzene 2 Fe 3 2 (C 3 ) 3 CClCl C(C 3 ) 3 Cl omobenzene (65-75%) tert-butylbenzene (60%) Friedel-Crafts Acylation of Benzene C 3 C 2 CClCl CC 2 C 3 Cl Mechanistic Principles of Electrophilic Aromatic Substitution 1-Phenyl-1-propanone (88%) Step 1: attack of electrophile on π-electron system of aromatic ring Step 2: loss of a proton from the carbocation intermediate E E E E highly endothermic carbocation is allylic,, but not aromatic highly exothermic this step restores aromaticity of ring

3 E Nitration of Benzene E E Nitration of Benzene Step 1: attack of nitronium cation on π-electron system of aromatic ring N 2 2 S 4 N 2 2 N 2 N 2 Electrophile is nitronium ion N Step 2: loss of a proton from the carbocation intermediate N 2 N 2 Sulfonation of Benzene

4 Sulfonation of Benzene Step 1: attack of sulfur trioxide on π-electron system of aromatic ring S 2 heat Several electrophiles present: a major one is sulfur trioxide S S 2 2 S 3 S 3 Step 2: loss of a proton from the carbocation intermediate Step 3: protonation of benzenesulfonate ion S 3 S 3 2 S 4 S 3 S 3 alogenation of Benzene

5 alogenation of Benzene The 2 -Fe 3 Complex 2 Fe 3 2 Lewis base Fe 3 Lewis acid Complex Fe 3 Electrophile is a Lewis acid-lewis base complex between Fe 3 and 2. The 2 -Fe 3 complex is more electrophilic than 2 alone. Step 1: attack of 2 -Fe 3 complex on π-electron system of aromatic ring Step 2: loss of a proton from the carbocation intermediate Fe 3 Fe 4 Question Which set of reagents is best to chlorinate benzene? A) Cl, peroxides B) Cl 2, hv C) Cl 2, CCl 4 D) Cl 2, FeCl 3 Friedel-Crafts Alkylation of Benzene

6 Friedel-Crafts Alkylation of Benzene Role of (C 3 ) 3 CCl C(C 3 ) 3 Cl (C 3 ) 3 C acts as a Lewis acid to promote ionization of the alkyl halide Cl (C 3 ) 3 C Cl Electrophile is tert-butyl cation 3 C 3 C C C 3 (C 3 ) 3 C Cl Rearrangements in Friedel-Crafts Alkylation Carbocations are intermediates. Therefore, rearrangements can occur (C 3 ) 2 CC 2 Cl C(C 3 ) 3 Rearrangements in Friedel-Crafts Alkylation Isobutyl chloride is the alkyl halide. But tert-butyl cation is the electrophile. (C 3 ) 2 CC 2 Cl C(C 3 ) 3 Isobutyl chloride tert-butylbenzene (66%) Isobutyl chloride tert-butylbenzene (66%) Rearrangements in Friedel-Crafts Alkylation Reactions Related to Friedel-Crafts Alkylation 3 C C C 3 C 2 Cl 2 S 4 3 C C C 3 C 2 Cl Cyclohexylbenzene (65-68%) Cyclohexene is protonated by sulfuric acid, giving cyclohexyl cation which attacks the benzene ring

7 Alkylation of benzene by an alkene Friedel-Crafts Acylation of Benzene Friedel-Crafts Acylation of Benzene C 3 C 2 CCl Electrophile is an acyl cation CC 2 C 3 Cl can be used instead of acyl chlorides Acid Anhydrides C 3 CCC 3 CC 3 Acetophenone (76-83%) C 3 C 2 C C 3 C 2 C C 3 C Question Which set of reagents would convert benzene into acetophenone (shown) in the highest yield? Acylation-Reduction A) B) C) D)

8 RCCl Acylation-Reduction Permits primary alkyl groups to be attached to an aromatic ring. Reduction of aldehyde and ketone carbonyl groups using Zn(g) and Cl is called the Clemmensen reduction. CR Zn(g), Cl C 2 R (C 3 ) 2 CCCl Acylation-Reduction Zn(g) Cl CC(C 3 ) 2 C 2 C(C 3 ) 3 Why is it important and useful? Reduction of aldehyde and ketone carbonyl groups by heating with NN 2 2 and K is called the Wolff-Kishner reduction. RCCl Acylation-Reduction Permits primary alkyl groups to be attached to an aromatic ring. CR 2 NN 2, K, triethylene glycol, heat C 2 R Example: Prepare Isobutylbenzene (C 3 ) 2 CC 2 Cl C 2 C(C 3 ) 3 No! Friedel-Crafts alkylation of benzene using isobutyl chloride fails because of rearrangement.

9 It is not possible to obtain good yields of desired certain alkylbenzenes if rearrangements can occur Question Which combination of reactants will yield n- propylbenzene as the major product when reacted with benzene? A) C 3 C 2 C(=), B) C 3 C 2 C 2 Cl, C) C 3 C 2 C(=)Cl, followed by Zn(g), Cl D) C 3 C 2 C 3,

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