Chemistry Specialist: Alicia Hart

BENZENE RXNS UC Davis - SASC

Br

Br2
FeBr3
Cl Ex's: Sn, HCl or H2, raney Ni or Fe, HCl or Zn(Hg), HCl,
Cl2
AlCl3
O
NO2 NH2 O O or O
HNO3 red. agent HN R
R O R R Cl
H2SO4
pyridine
mCPBA
NaOH, H2O,
(aka RCO3H)
or
1. H3O+,
2. NaOH, H2O

SO3H

SO3 H+, H2O,

H2SO4
or
H2SO4,
CH2R
RCH2X Clemmensen
Issues?..polyalkylation and rearrangement Reduction
lewis acid catalyst

O R R
O or O O
1. R Cl Zn(Hg), HCl
R O R , AlCl 3
2. H3O+
Jones
Important things to note about benzene reactions: (p.750 and 22-2 in 6 ed.)

SO3, H2SO4 is used to block the para position of a ring w/ an EDG on it (only a small percentage of the product adds SO3H
ortho) forcing the next group to add exclusively ortho; remove the blocking group using acid and heat.

Activators (EDG's through resonance) have a lone pair on the atom directly attached to benzene (exception: alkyl groups do
not have a lone pair but are EDGs via induction)

Deactivators (EWG's through resonance) do NOT have a lone pair on the atom directly attached to benzene (exception:
halogens have a lone pair but withdraw via induction)
no lone pair but alkyl lone pair but halogens
EX's grps are the exception Cl are the exception O OH
OCH3
lone pair on the O no lone pair
on the C

Activator Activator Deactivator Deactivator

(EDG) (EDG) (EWG) (EWG)

Watch out for benzene rings with OH and NH2 grps on them; they are highly activated and need to be toned down prior to
adding another grp on the ring. If you do not convert them into less activating groups, you will get polysubstitution at both
ortho and para positions. To do this, use either an anhydride or acyl chloride: EX O
OH O
Cl O
Directing Effects - mD opA poX is a helpful mnemonic to remember that
pyridine
Deactivators direct meta, Activators direct ortho and para, and halogens (X)
direct ortho and para even though they are weakly deactivating.