Organic Chemistry II

Lectures N15-16

Aryl Halides

I. Structure, nomenclature, isomers

Aryl halides are halides in which the

halogen is attached directly to an
aromatic ring.
Nomenclature
Br
CH 3

NO2
Cl

1-chloro-3-methylbenzene 1-bromo-3-nitrobenzene

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Structure and Bonding
In aryl halides, the carbon to which the halogen is attached is sp2
hybridized.
The bond is stronger and shorter than the carbon-halogen bond in
aliphatic compounds where the carbon is sp3 hybridized.

Hence it is more difficult to break this bond and aryl halides resist
the typical nucleophilic substitution reactions of alkyl halides. 3
Structure and Bonding

The reason for more strong bonding is that C-X bonds in aryl
halides have more double bond character than C-X bonds in
alkyl halides:

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II. Physical properties

- essentially insoluble in water

- less polar than alkyl halides

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III. Synthesis
1. Halogenation of arenes

2. The Sandmeyer reaction

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III. Synthesis
3. The Schiemann reaction

4. Reaction of aryl diazonium salts with iodide ion

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IV. Chemical properties

1. Electrophilic aromatic substitution

Br Br Br
HNO3, H2SO4 NO2
+

Br NO2
SO3H
H2SO4,SO3
+ Br SO3H

Br Br
Br2,Fe Br
+

Br
Br
CH2CH3
CH3CH2-Br, AlCl3
+ Br CH2CH3
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1. Electrophilic aromatic substitution (cont.)

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2. Formation of aryl Grignard reagents

Mg
Br MgBr
anhyd. Et2O

Mg
Cl MgCl
THF

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3. Nucleophilic Aromatic Substitution

Ar must contain strongly electron withdrawing groups ortho

and/or para to the X.

Cl NH2
NO2 NO2
+ NH3

NO2 NO2

Br OCH3
O2N NO2 O2N NO2
+ NaOCH3

NO2 NO2

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3. Nucleophilic Aromatic Substitution (cont.)
The more strongly electron withdrawing groups ortho and/or
para to the X the easy the substitution.

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3. Nucleophilic Aromatic Substitution (cont.)
The more strongly electron withdrawing groups ortho and/or
para to the X the easy the substitution.

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3. Nucleophilic Aromatic Substitution (cont.)
Without electron withdrawing groups ortho and/or para to
the X the substitution needs very high temperature.

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3. Nucleophilic Aromatic Substitution (cont.)

Mechanism:

SN1 not reasonable because:

1) C—Cl bond is strong; therefore, ionization
to a carbocation is a high-energy process
2) aryl cations are less stable than alkyl cations

SN2 not reasonable because ring blocks

attack of nucleophile from side opposite bond
to leaving group
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3. Nucleophilic Aromatic Substitution (cont.)

Mechanism:

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3. Nucleophilic Aromatic Substitution (cont.)

In some reaction conditions not activated substrates

(without –NO2, -CF3, -CN, etc.) do undergo substitution:

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3. Nucleophilic Aromatic Substitution (cont.)

Mechanism:

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3. Nucleophilic Aromatic Substitution (cont.)

Mechanism:

Step 1 - Elimination

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3. Nucleophilic Aromatic Substitution (cont.)

Mechanism:

Step 2 - Addition

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3. Nucleophilic Aromatic Substitution (cont.)

Mechanism:

Step 3 - Protonation

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3. Nucleophilic Aromatic Substitution (cont.)

14C labeling indicates that the high temperature reaction of

chlorobenzene with NaOH proceeds via benzyne.

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3. Nucleophilic Aromatic Substitution (cont.)

Phenylation via benzyne.

Acetoacetic esters and malonic esters can be phenylated by

benzyne generated in situ from bromobenzene

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4. The Diels-Alder Reaction via benzyne formation

Convenient method for the preparation of benzyne:

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4. The Diels-Alder Reaction via benzyne formation (cont.)

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4. The Diels-Alder Reaction via benzyne formation (cont.)

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4. The Diels-Alder Reaction via benzyne formation (cont.)

In the absence of dienes benzyne undergoes dimerization

and trimerization:

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