Reaction Map: Reactions of Benzene And Related Aromatic Compounds https://www.MasterOrganicChemistry.

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Amide Reduction Nitro Sulfonyl

Protection Amine
H SO3H
N R NH 2 NO 2
18 9 10
O
Hydrolysis Not shown, but
Not as activated as (NaOH, H 2O) 17 Sulfonylation is
a free amino group SN Ar via can return to benzene
from aryl halide by reversible!
aryne* Sulfonylation
*also from making Grignard and
19 Diazonium aryl bromides then adding acid 6
F Cl
salt formation and iodides
8 Nitration Desulfonylation
7

25 20 1
Diazonium
Salt Br Benzene
N 21 2
N
X Friedel-Crafts Alkylation
3 5 (watch out for rearrangements!)
22
Nitrile 24
N I Alkyl Benzylic Alkyl Halide
C
Friedel-Crafts H H Bromination Br H
23 4
Acylation
R 14 R

13 Too many
H 3O+ gives Baeyer- reactions to
carboxylic acid 12
Villiger Sidechain depict! See
Phenol Ester Ester Ketone O 15
from nitrile Oxidation 11 Oxidation alkyl halide
Hydrolysis Ketone sheet
(acidic hydrolysis) OH O R Reduction
16 R
(e.g. NaOH, O
H 2O)

Grignard formation w/ CO2 Carboxylic Acid

(Mg, CO2, then acidic workup) O
*works with all aryl
OH
Typical Notes halides except the fluoride
Reaction Name Conditions

Chlorination Cl2, FeCl 3 Catalytic in FeCl 3 Nitro group reduction Pd-C, H 2 Catalytic hydrogenation
1 10 O
(can use other Lewis acids, (or Pt-C, or Ni) Amide formation "Schotten-Baumann"
18 + base
like AlCl3, ZrCl4, etc.) R Cl conditions
Bromination Br 2, FeBr 3
2 Catalytic in FeBr 3 Wolff-Kishner reduction KOH, NH 2NH 2 Basic, requires high heat (or anhydride)
11
HOCH 2CH2OH, heat
Iodination I 2, oxidant Stoichiometric oxidant required 19 Diazonium salt HNO 2, H 2SO4 Can use NaNO 2 and strong
3 Clemmensen reduction Zn(Hg) Requires acidic conditions formation
e.g. CuBr2, HNO 3 /H2SO4 12 acid, which will make HNO 2
H+ (or NaNO 2, H 2SO4)
O
Friedel-Crafts Acylation AlCl3 No rearrangements occur Requires high pressures; only 20 Chlorination CuCl –
4 R Cl Fails when meta-directing 13 Catalytic hydrogenation Pd-C
works for benzylic ketones (Sandmeyer)
substituents present (too deactivating) H2

Friedel-Crafts Alkylation Rearrangements can occur Br 2 Only attaches to benzylic 21 Bromination CuBr –
5 R Cl AlCl3 14 Benzylic bromination
with primary alkyl halides position. (Sandmeyer)
peroxides
Can also use alkene + strong acid
22 Iodination NaI (or KI) Or KI
Sulfonylation H 2SO4 – Sidechain oxidation KMnO 4 Benzylic carbon must have at
6 SO3 15
least one C–H bond
acid
(can also use H 2CrO4)
23 H 2O H 2SO4, H 2O, heat can also use Cu2O, H 2O
Desulfonylation H 2SO4, heat Allows use of SO3H as
7
blocking group RCO 3H RCO 3H is a peroxyacid
16 Baeyer-Villiger oxidation
(e.g. m-CPBA) 24 Cyanation CuCN –
Nitration Makes NO 2+ in solution, which (Sandmeyer)
8 HNO 3, H 2SO4
is the key electrophile SN Ar via aryne NaNH 2 Elimination gives an aryne
17
intermediate, which can be 25 Fluorination HBF 4 –
Reduction of nitro group with NH 3 , –30°C
trapped with dienes (Diels-
Nitro group reduction Zn, HCl Alder)
9 metal and acid; can also use
Fe, Sn, or SnCl2