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© www.chemsheets.co.uk A2 1026 21-Dec-2021
+ HNO3
+ H2O
conc HNO3
conc H2SO4
50C
NITRATION – Electrophilic substitution
© www.chemsheets.co.uk A2 1026 21-Dec-2021
Aromatic NITRO compounds - USES
TNT (trinitrotoluene)
Aromatic NITRO compounds - USES
Making primary amines
(used to make azo dyes)
e.g. a yellow azo dye
electrophile = NO2
+ (nitronium ion)
HNO3 + 2H2SO4  NO2
+ + 2HSO4
– + H3O+
- H+
NO2
NITRATION – Electrophilic substitution
© www.chemsheets.co.uk A2 1026 21-Dec-2021
e.g. 1 methylbenzene + conc HNO3 & conc H2SO4 at 50C to make 2-nitromethylbenzene
Electrophilic
substitution
+ HNO3
+ H2
O
HNO3 + 2H2SO4  NO2
+ + 2HSO4
– + H3O+
- H+
NO2
© www.chemsheets.co.uk A2 1026 21-Dec-2021
e.g. 2 methylbenzene + conc HNO3 & conc H2SO4 at 50C to make 4-nitromethylbenzene
Electrophilic
substitution
HNO3 + 2H2SO4  NO2
+ + 2HSO4
– + H3O+
+ HNO3
+ H2
O
- H+
NO2
© www.chemsheets.co.uk A2 1026 21-Dec-2021
e.g. 3 1,3-dimethylbenzene + conc HNO3 & conc H2SO4 at 50C to make 2-nitro-1,3-dimethylbenzene
Electrophilic
substitution
HNO3 + 2H2SO4  NO2
+ + 2HSO4
– + H3O+
+ HNO3
+ H2
O
- H+
NO2
© www.chemsheets.co.uk A2 1026 21-Dec-2021
AlCl3
Acyl chloride /
acid anhydride
FRIEDEL-CRAFTS ACYLATION –
Electrophilic substitution
+ HCl
© www.chemsheets.co.uk A2 1026 21-Dec-2021
USES of Friedel-Crafts reactions
VERY useful in organic synthesis as it is a way
of adding C atoms onto an aromatic ring.
© www.chemsheets.co.uk A2 1026 21-Dec-2021
electrophile = RCO+ (acylium ion)
FRIEDEL-CRAFTS ACYLATION
Electrophilic substitution
+ AlCl3
+ AlCl4
-
- H+
AlCl4
– + H+  AlCl3 + HCl
© www.chemsheets.co.uk A2 1026 21-Dec-2021
electrophile = RCO+ (acylium ion)
FRIEDEL-CRAFTS ACYLATION
Electrophilic substitution
Cl3
Al
_
+ AlCl3
_
- H+
AlCl3
Cl3
Al
_
+ H+
© www.chemsheets.co.uk A2 1026 21-Dec-2021
e.g. 4 methylbenzene with ethanoic anhydride and AlCl3 to make 2-methylphenylethanone
Electrophilic substitution
Cl3
Al
_
+ AlCl3
- H+
AlCl3
Cl3
Al
_
+ H+
© www.chemsheets.co.uk A2 1026 21-Dec-2021
e.g. 5 methylbenzene with propanoyl chloride and AlCl3
Electrophilic substitution
+ HCl
+ AlCl3
+ AlCl4
-
- H+
AlCl4
– + H+  AlCl3 + HCl
© www.chemsheets.co.uk A2 1026 21-Dec-2021
e.g. 6 nitrobenzene with ethanoyl chloride and AlCl3
Electrophilic substitution
AlCl4
– + H+  AlCl3 + HCl
+ HCl
+ AlCl3 + AlCl4
-
- H+
© www.chemsheets.co.uk A2 1026 21-Dec-2021
e.g. 7 1,3-dimethylbenzene with ethanoic anhydride and AlCl3
Electrophilic substitution
Cl3
Al
_
+ AlCl3
- H+
AlCl3
Cl3
Al
_
+ H+
© www.chemsheets.co.uk A2 1026 21-Dec-2021
FRIEDEL-CRAFTS ACYLATION
WARNING! - do not mix
Friedel-Crafts acylation & other acylations
(needs AlCl3)
Swap H on benzene ring
for acyl group
H
H N
H
R
H O R
Swap H on O/N
for acyl group
© www.chemsheets.co.uk A2 1026 21-Dec-2021

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Chemsheets-A2-1026-Reactions-of-aromatics.pptx

  • 1. © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 2. + HNO3 + H2O conc HNO3 conc H2SO4 50C NITRATION – Electrophilic substitution © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 3. Aromatic NITRO compounds - USES TNT (trinitrotoluene)
  • 4. Aromatic NITRO compounds - USES Making primary amines (used to make azo dyes) e.g. a yellow azo dye
  • 5. electrophile = NO2 + (nitronium ion) HNO3 + 2H2SO4  NO2 + + 2HSO4 – + H3O+ - H+ NO2 NITRATION – Electrophilic substitution © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 6. e.g. 1 methylbenzene + conc HNO3 & conc H2SO4 at 50C to make 2-nitromethylbenzene Electrophilic substitution + HNO3 + H2 O HNO3 + 2H2SO4  NO2 + + 2HSO4 – + H3O+ - H+ NO2 © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 7. e.g. 2 methylbenzene + conc HNO3 & conc H2SO4 at 50C to make 4-nitromethylbenzene Electrophilic substitution HNO3 + 2H2SO4  NO2 + + 2HSO4 – + H3O+ + HNO3 + H2 O - H+ NO2 © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 8. e.g. 3 1,3-dimethylbenzene + conc HNO3 & conc H2SO4 at 50C to make 2-nitro-1,3-dimethylbenzene Electrophilic substitution HNO3 + 2H2SO4  NO2 + + 2HSO4 – + H3O+ + HNO3 + H2 O - H+ NO2 © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 9. AlCl3 Acyl chloride / acid anhydride FRIEDEL-CRAFTS ACYLATION – Electrophilic substitution + HCl © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 10. USES of Friedel-Crafts reactions VERY useful in organic synthesis as it is a way of adding C atoms onto an aromatic ring. © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 11. electrophile = RCO+ (acylium ion) FRIEDEL-CRAFTS ACYLATION Electrophilic substitution + AlCl3 + AlCl4 - - H+ AlCl4 – + H+  AlCl3 + HCl © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 12. electrophile = RCO+ (acylium ion) FRIEDEL-CRAFTS ACYLATION Electrophilic substitution Cl3 Al _ + AlCl3 _ - H+ AlCl3 Cl3 Al _ + H+ © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 13. e.g. 4 methylbenzene with ethanoic anhydride and AlCl3 to make 2-methylphenylethanone Electrophilic substitution Cl3 Al _ + AlCl3 - H+ AlCl3 Cl3 Al _ + H+ © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 14. e.g. 5 methylbenzene with propanoyl chloride and AlCl3 Electrophilic substitution + HCl + AlCl3 + AlCl4 - - H+ AlCl4 – + H+  AlCl3 + HCl © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 15. e.g. 6 nitrobenzene with ethanoyl chloride and AlCl3 Electrophilic substitution AlCl4 – + H+  AlCl3 + HCl + HCl + AlCl3 + AlCl4 - - H+ © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 16. e.g. 7 1,3-dimethylbenzene with ethanoic anhydride and AlCl3 Electrophilic substitution Cl3 Al _ + AlCl3 - H+ AlCl3 Cl3 Al _ + H+ © www.chemsheets.co.uk A2 1026 21-Dec-2021
  • 17. FRIEDEL-CRAFTS ACYLATION WARNING! - do not mix Friedel-Crafts acylation & other acylations (needs AlCl3) Swap H on benzene ring for acyl group H H N H R H O R Swap H on O/N for acyl group © www.chemsheets.co.uk A2 1026 21-Dec-2021