REACTIONS of BENZENE
Benzene
REACTION
REAGENTS
Cl2, FeCl3 catalyst
ELECTROPHILE
PRODUCT
(Cl+)- chlorine doesnt
actually have a
positive charge
Chlorobenzene, HCl, (FeCl3)
HALOGENATION
Br2, FeBr3 catalyst
COMMENTS
Electrophile formed by
Lewis Acid removing X-,
where X is a halogen.
Catalyst regenerates
itself.
Br+
Bromobenzene, HBr, (FeBr3)
NITRATION
SULFONATION
HNO3, H2SO4
catalyst
NO2+
SO3/ H2SO4
Conc. H2SO4, heat
SO3, +SO3H
(sulfonium ion)
Nitrobenzene
, water, (sulphuric acid)
Benzenesulf
onic acid, water,
RCOCl is an acyl halide
RCO2COR, AlCl3,
water
RCO2COR is an acid
anhydride
Reversible (heat + acid)
Electrophile is formed by
removing Cl-, HCl is a
product
RCOCl, AlCl3
catalyst, water
FRIEDEL-CRAFTS
ACYLATION
Dehydration reaction
electrophile formed by
loss of water from nitric
acid
RCO+
(acylium ion)
Ketone
Electrophile is formed by
removing RCO2-,
carboxylic acid product
REACTIONS of BENZENE
REACTION
FRIEDEL-CRAFTS
ALKYLATION
REAGENTS
RCl, AlCl3 catalyst
ELECTROPHILE
PRODUCT
COMMENTS
Alkylbenzene, acid,
Many other alkylation
methods. Straight chain
alkane cannot be added
to the benzene ring
because of carbocation
rearrangement.
R+
CATALYTIC
HYDROGENATION
CLEMMENSEN
REDUCTION
WOLFF-KISHNER
REDUCTION
H2, Pd/C
Zn(Hg)
HCl, heat
Reducing agent:
Reducing agent:
hydrazine (N2H4),
OH, heat
Not important for
now
Only works on ketones
directly attached to a
benzene ring (contain
benzylic hydrogen)
DO NOT USE ON
ALCOHOLScauses
substitutionreduces all
carbonyl groups on
molecule
Good for acid sensitive
molecules (i.e. pyrrole)
and high MW
compounds reduces all
carbonyl groups
REACTIONS of BENZENE
Substituted Benzenes
REACTION
REAGENTS
PRODUCT
COMMENTS/ EXAMPLE
A halogen substituted on a benzene ring will now allow it to
undergo SN1/SN2 reactions, and E1 and E2 reactions as well.
For the elimination reactions, use t-BuO-/t-BuOH
ALKYLATION of
SUBSTITUENTS
Substituted benzene,
Light energy (hv)
Halogen gas (Br2, Cl2)
Halo-substituted alkyl group on
benzene ring (example: 1-bromo-1phenylethane)
REDUCTION
REACTIONS
Decrease number of CO, C-N, C-X bonds,
increase number of C-H
bonds
Substituted benzene
with halogen group
attached to substituent
t-BuO-/t-BuOH
Substituents with double bonds (or alkenes) can undergo
different kinds of reactions, including other reduction reactions
Benzene ring with alkene
substituent (example: 1phenylpropene)
REACTIONS of BENZENE
Also shown in the reduction of a nitro group to an amino group.
Another alternative can be SnCl2, HCl, OH-.
Styrene or other
alkene-substituted
benzene
H2, Pd/C
Alkane substituted benzene (i.e.
ethyl benzene)
REDUCTION
REACTIONS
CONTD
Raney Nickel can be used for the hydrogenation of alkenes
and alkynes as well. VERY useful for reducing C-S bonds to
C-H bonds.
Benzonitrile
2 moles hydrogen gas
Raney Nickel catalyst
(Raney Ni)
Benzylamine
Benzenes unusual stability allows this.
-
Benzene
3 moles hydrogen gas
Nickel
250C
25 atm
Cyclohexane
REACTIONS of BENZENE
REACTIONS
REAGENTS
PRODUCTS
COMMENTS/EXAMPLES
Not matter what the length of the alkyl chain is,
it will always be oxidized into a carboxylic acid
group. A benzylic hydrogen must be
attached to the substituent group.
KMnO4
Heat
HCl
Toluene (or some
kind of alkyl
benzene)
A carboxylic acid (in this case,
benzoic acid)
Importance of benzylic hydrogen. These
reagents can also oxidize benzylic alcohols to
benzoic acid.
OXIDATION REACTIONS
-
Na2Cr2O7
HCl
Heat
Alkyl substituted
benzene
Carboxylic acid groups
A milder oxidizing agent.
-
MnO2
Heat
Alkyl substituted
benzene
Aldehydes or ketones, depending
on substituents attached.
REACTIONS of BENZENE
EFFECTS of SUBSTITUENTS on REACTIVITY
Substituents can donate electrons, and activate the benzene ring (increases reaction rate)
Substituents can withdraw electrons from the ring and deactivate it (decreases reaction rate)
Inductive Electron Withdrawal
-
Substituent has to be more electron withdrawing than H
o Look for a positive charge
Example: NH3
Electron Donation Hyperconjugation
-
Alkyl substituents are more electron donating because of hyperconjugation
o More electron donating than hydrogen
Resonance Electron Donation and Withdrawal
-
If substituent has lone pair on atom directly attached to benzene,
lone pair can donate electrons by resonance
o NH2, OH, OR, Cl donate by resonance
If a substituent is double/triple bonded to the benzene ring by an
atom more electronegative than itself, electrons can be withdrawn
inductively
o C=O, CN, SO3H, NO2
ACTIVATING GROUPS
NH2
NHR
NR2
Strong
OH
activating
OR
groups
NHC=OR
OC=OR
R
Ar
CH=CHR
Mod activating
Weak activating
All are O/P directors
Ortho/para
DEACTIVATING GROUPS
F
Cl
Br
Weak deactivating groups, O/P directors
I
C=OH
C=OR
OC=OR
COOH
C=OCl
CN
SO3H
NH3, 1 amine
2, 3 amines
NO2
Mod deactivating groups
Meta directors
Mod deactivating groups
REACTIONS of BENZENE
SYNTHESIS of BENZENES from ARENEDIAZONIUM SALTS
Many compounds can be synthesized from arenediazonium salts because the leaving group (NN) can easily be displaced, as it forms the very
stable N2 gas.
How to Make Arenediazonium Salt
Arenediazonium salt
Aniline
Nitrous acid (HNO2)NaNO2 works too
Aqueous solution of HCl/HBr
Cold temperatures (0C)
Nucleophiles CN, Cl-, Br- will replace leaving group if
appropriate copper (I) salt (MUST be copper salt) is
addedSandemeyer reactions.
CuCN, CuCl, and CuBr are all required to add cyano,
chloro, or bromo groups, respectively. Products include
substituted benzene and N2 gas.
These reactions are good for making para-substituted
benzenes because NN is an ortho-para director
To add iodo group, need KI
To add fluoro group, need heat and fluoroboric acid
(HBF4) ... BF3 and N2 are the products
To add hydroxyl group and make it a phenol, requires
heat and water
To add nitro group, need Cu (I) and NaNO2
To add hydrogen, need hypophosphorous acid
(H3PO2) when to use: when an amino or nitro group is
used for directing purposes and eventually needs to be
removed.
