Benzene Reactions (EAS and NAS)

Bromination

Benzene + Br₂ + FeBr₃ (forms Br⁺ and FeBr₄^-)

Chlorination

Benzene + Cl₂ + AlCl₃

Iodination

Benzene + I₂+ CuCl₂

Fluorination

Benzene + Selectfluor (F⁺ is too reactive for EAS)

Nitration

Benzene + HNO₃ + H₂SO₄

Sulfonation

Benzene + SO₃ + fuming H₂SO₄ (contains H₂O)

Nitro reduction (NO₂ to NH₂)

1) Fe, Sn, or SnCl₂ H₃O⁺ 2) NaOH

Friedel-Crafts Alkylation

Alkyl group attached to Cl + AlCl₃

Friedel-Crafts Acylation

Acyl (carbonyl) group attached to Cl + AlCl₃ + heat

Friedel-Crafts Limitations

1. Primary alkyl halides can rearrange, forming BRANCHED product instead of the desired product

2. Only sp³ alkyl halides (2º or 3º) can be used

3. Adding alkyl groups activates the ring, which can lead to multiple additions (new ring is more reactive than original)

4. Reactions do NOT OCCUR on rings substituted with STRONG EWGs or amines

Aryl alkyl ketone reduction (must be DIRECTLY ATTACHED to benzene)

H₂/Pd

Forms carboxylic acid (benzylic oxidation)

KMnO₄ + H₂O OR Na₂Cr₂O₇ + H₂SO₄ + H₂O

Benzylic bromination

NBS + light + CCl₄ adds bromine to carbon substituent

H₂/Pd + EtOH

Reduces substituents to alkene (H adds in syn). Does NOT reduce benzene or other substituents

H₂ (excess) + Pt catalyst + 130 atm

Hydrogenates ring (NO REMAINING PI BONDS)

Nucleophilic Aromatic Substitution (NAS)

Good leaving group + nucleophile + ortho/para benzene