Alkyl Halides - 1

By: Isman Kurniawan

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Introduction
Organohalogen compounds
Alkyl halides
Vinyl halides
Aryl halides
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Nomenclature
Classification

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Common Uses of Alkyl

Halides
Solvents
Reagents
Anesthetics
Freon
Pesticides
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Structure of Alkyl
Halides

Electronegativity
Bond length
Dipole moment
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Structure of Alkyl
Halides

Molecular dipole moments of methyl

halides

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Physical Properties of
Alkyl Halides

Boiling points

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Preparation of Alkyl
Halides
1. Free radical halogenation of alkanes

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Preparation of Alkyl
Halides
2. Addition reaction of alkenes and alkynes

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Preparation of Alkyl
Halides
3. Substitution reaction of alcohols

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Reactions of Alkyl
Halides
1. Nucleophilic substitution

2. Elimination

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The SN2 Reaction

Reaction

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The SN2 Reaction

Mechanism

Reaction rate
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The SN2 Reaction

Energy diagram

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The SN2 Reaction

The order of reactivity
CH3X > 1o > 2o
o
3

alkyl halides cannot react by this

mechanism.

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Exercise
Draw the reaction mechanism between 1chloropropane and NaI to produce 1iodopropane.

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Factors Affecting SN2

Reactions

Strength of the nucleophile

A strong nucleophile is much more

effective than a weak one in attacking an

electrophilic carbon atom.

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Factors Affecting SN2

Reactions

Strength of the nucleophile

Trens in nucleophilicity

1. A species with a negative charge is

stronger nucleophile than a similar
neutral species.

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Factors Affecting SN2

Reactions
Strength of the nucleophile
Trens in nucleophilicity
2. Nucleophilicity decrease from left to
right in the periodic table.

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Factors Affecting SN2

Reactions
Strength of the nucleophile
Trens in nucleophilicity
3. Nucleophilicity increase down the
periodic table.

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Exercise
For each pair, predict the stronger
nucleophile in the SN2 reaction.

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Factors Affecting SN2

Reactions
Steric effects on nucleophilicity
The effect steric hindrance

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Factors Affecting SN2

Reactions
Solvent effects on nucleophilicity
Protic solvent : one that has acidic

protons, usually in the form of O-H or

N-H groups

Aprotic solvent : solvent without O-H or

N-H groups

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Factors Affecting SN2

Reactions

Solvent effects on nucleophilicity

An anion is more reactive in an aprotic
solvent.

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Reactivity of The
Substrate in SN2 Reactions
Leaving group effects on the substrate
Good leaving groups should be weak
bases

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Reactivity of The
Substrate in SN2 Reactions
Steric effects on the substrate

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Reactivity of The
Substrate in SN2 Reactions
Steric effects on the substrate

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Exercise
Rang the following compounds in

decreasing order of their reactivity toward

the SN2 reaction.

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The SN1 Reaction

Reaction

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The SN1 Reaction

Mechanism

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The SN1 Reaction

Energy diagram

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Exercise
Draw the reaction mechanism between 3bromo-3-methylpentane and ethanol.

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The SN1 Reaction

Substituent effects
The rates of S 1 reactions depend
N

strongly on carbocation stability

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Exercise
Choose the member of each pair that will
react faster by the SN1 mechanism.

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The SN1 Reaction

Leaving-group effects
A good leaving group is just as necessary
in the SN1 reaction as it is in the SN2.

Similar leaving groups are effective for

either reaction.

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The SN1 Reaction

Solvent effects
The S 1 reaction goes much more
N

readily in polar solvents that stabilize

ions.

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Rearrangements in SN1
Reactions
Reaction

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Rearrangements in SN1
Reactions
Hydride shift

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Friday, June 27, 14

Rearrangements in SN1
Reactions
Hydride shift

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Rearrangements in SN1
Reactions
Methyl shift

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Friday, June 27, 14

Exercise
Propose a mechanism involving an alkyl
shift for each solvolysis reaction.

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Comparison of SN1 and

SN2 Reactions

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Exercise
For each reaction, give the expected

substitution product, and predict whether

the mechanism will be predominantly first
order or second order.

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Assignment
(deadline June 30 2014)
Predict the mechanisms and product of the
following reactions.

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