MECHANISMS

For Final Exam

Electrophilic Aromatic Substitution

Br

H H H Br
Br Br Br -HBr
Br

Electron Donating Groups Electron Withdrawing Groups

alkyl OR NR2 acyl CN NO2 SO3H

SR meta directors

ortho-para directors X ortho-para director

Nucleophilic Aromatic Substitution

Cl Cl OH Cl OH Cl OH
O2N NO2 O2 N NO2 O2N NO2 O2N NO2
NaOH

NO2 NO2 NO2 NO2

Carbonyl Addition Reactions

Acid Catalyzed Hydration acid activates the carbonyl making it more reactive
(more electrophilic) so water can add

H H2O H
O HA O A
HO O H HO OH

more
electrophilic

Base Catalyzed Hydration hydroxide is a more reactive nucleophile than

water and can add more readily to the carbonyl

OH H2O
O O OH HO OH

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Gregory R Cook page  Chem 
Exam  Mecahnisms

North Dakota State University
Mechanism for Imine Formation

H2N R H H H Up to here this is

O HA H O H O H A identical to a hydration
N O N
R R with amine as
nucleophile instead of
Hemiaminal water

HA

R H H H
N H N R -H2O
A N O N
R H R
imine
resonance structures

Mechanism for Enamine Formation

HN R R H R
O HA H O H O H A
R N O N
R R

Hemiaminal

HA

R R R H R
N R N R -H2O
A N O N
H R H R
enamine
resonance structures

The only difference is this last step. There is no

proton on the nitrogen to come off, so a proton
is taken off of the alpha carbon

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Gregory R Cook page
Chem 
Exam  Mecahnisms

North Dakota State University
Mechanism for Acetal Formation

H Up to here this is
O HA H O H O H A identical to a
O O O
R R hydration with alcohol
as nucleophile
Hemiacetal instead of water

HA

H R OH R H
O -H2O
O O O O O
R R R H R

resonance structures
A

O O
R R

Acyl Substitution Reactions

Fischer Esterification
H
O HA OH R'OH HO OR' A HO OR'

R OH R OH R OH R OH

HA

O A OH HO OR' HO OR'

R OR' R OR' R R OH
H

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Gregory R Cook page  Chem 
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North Dakota State University
 Acid Catalyzed Hydrolysis

H H H
O HA O O H2O H O O H A H O O H
OCH3 OCH3 OCH3 OCH3 OCH3

HA

O A H H H O O H
O O
OH OCH3
OH OH
H

Base Catalyzed Hydrolysis (Saponification)

O OH O O
O OH + OCH3 + HOCH3
OCH3 OCH3 OH O

Acid Catalyzed Hydrolysis of Amides

H H H
O HA O O H2 O H O O H A H O O H
NH2 NH2 NH2 NH2 NH2

HA

O H H H O O H
A O O
OH NH2
OH OH
H

©

Gregory R Cook page  Chem 
Exam  Mecahnisms

North Dakota State University