Alkyl Halides

What Is an Alkyl Halide?

An organic compound containing at least one carbonhalogen bond (C-X)
o X (F, Cl, Br, I) replaces H

Can contain many C-X bonds

Some uses
Solvent
Refrigerants
Pharmaceuticals and precursors

Alkyl halides
Alkyl halides are organic molecules containing a halogen
atom directly bonded to an sp3 hybridized carbon atom.
Alkyl halides are classified as primary (1), secondary
(2), or tertiary (3), depending on the number of
carbons bonded to the carbon with the halogen atom.
H

H
H

Methyl halide

One R group
1

C
R

Two R groups Three R groups

2
3

The halogen atom in halides is often denoted by the symbol X.

Types of halides
CH2CH3
CH3CH2CH2

Cl

Cl

3 chloride

2 chloride

CH2CH3

CH3
CH3

C CH2Cl

H
1 chloride

CH 3

CH 3

2 chloride

Cl

CH3

There are other types of organic halides. These include vinyl halides, aryl halides,
allylic halides and benzylic halides.

Vinyl halides
alkene.

halogen atom (X) bonded to sp2 carbon of

H

H
C

C
X

Types of halides
Aryl halides

X directly bonded to a benzene ring.

X

Allylic halides
X bonded to the carbon atom
adjacent to a C=C double bond.
H
H
C
H

C
CH2

Benzylic halides
X bonded to the carbon atom
CH2X
adjacent to a benzene ring.

Naming Alkyl Halides

Name is based on longest carbon chain
o (Contains double or triple bond if present)
o Number from end nearest any substituent (alkyl or
halogen)

Naming with Multiple

Halides
If more than one of the
same kind of halogen is
present, use prefix di, tri,
tetra

If there are several

different halogens,
number them and list
them in alphabetical
order

Naming if Two Halides or Alkyl Are Equally Distant

from Ends of Chain
Begin at the end nearer the substituent whose
name comes first in the alphabet

Many Alkyl Halides That Are Widely Used Have

Common Names

Chloroform
Carbon tetrachloride
Methylene chloride
Methyl iodide
Trichloroethylene

Cl

Cl

H
Dichloromethane

Cl

Cl
H

Cl

Cl

D
Deuterated chloroform

Structure of Alkyl Halides

C-X bond is longer as you go down periodic table
C-X bond is weaker as you go down periodic table
C-X bond is polarized with slight positive on carbon
and slight negative on halogen

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Quick Review Questions

Preparing Alkyl Halides

Alkyl halide is from addition of HCl, HBr, HI to
alkenes to give Markovnikov product
Alkyl dihalide from anti addition of bromine or
chlorine

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 It is usually not a good idea to plan a synthesis that

uses this method

Why?

Reaction of Alkanes with

Halogens

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Preparing Alkyl Halides from Alcohols

Reaction of tertiary C-OH with HX is fast and effective
o Add HCl or HBr gas into ether solution of tertiary alcohol

Primary and secondary alcohols react very slowly and

often rearrange, so alternative methods are used

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Preparation of Alkyl Halides from Primary and

Secondary Alcohols
Specific reagents avoid rearrangements of
carbon skeleton
Thionyl chloride converts alcohols into alkyl
chlorides (SOCl2 : ROH RCl)
Phosphorus tribromide converts alcohols into
alkyl bromides (PBr3: ROH RBr)

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Reactions of Alkyl Halides: Grignard

Reagents
Reaction of RX with Mg in ether or THF
Product is RMgX an organometallic compound
(alkyl-metal bond)
o R is alkyl 1, 2, 3, aryl, alkenyl
o X = Cl, Br, I

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Reactions of Grignard
Reagents
Many useful reactions
o RMgX behaves as R- (adds to C=O)
o RMgX + H3O+ R-H

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Alkyl Halides React with Nucleophiles and Bases

Alkyl halides are polarized at the carbon-halide bond,
making the carbon electrophilic
Nucleophiles will replace the halide in C-X bonds of many
alkyl halides(reaction as Lewis base)
Nucleophiles that are Brnsted bases produce elimination

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Good Base

Quick Review Questions

The Nature of
Substitution

Substitution, by definition, requires that a "leaving group",

which is also a Lewis base, departs from the reacting
molecule.
A nucleophile is a reactant that can be expected to
participate effectively in a substitution reaction.

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Substitution Mechanisms

SN1
o Two steps with carbocation intermediate
o Occurs in 3, allyl, benzyl

SN2
o Two steps combine - without intermediate
o Occurs in primary, secondary

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Two Stereochemical
Modes of Substitution
Substitution with inversion:

Substitution with retention:

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The SN2 Reaction

Reaction is with inversion at reacting center

Follows second order reaction kinetics
Nomenclature to describe characteristic step:
o S=substitution
o N (subscript) = nucleophilic
o 2 = both nucleophile and substrate in characteristic
step (bimolecular)

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SN2 Process

The reaction involves a transition state in which

both reactants are together

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SN2 Transition State

The transition state of an SN2 reaction has a

planar arrangement of the carbon atom and
the remaining three groups

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Characteristics of the SN2 Reaction

Sensitive to steric effects

Methyl halides are most reactive
Primary are next most reactive
Secondary might react
Tertiary are unreactive by this path
No reaction at C=C (vinyl halides)

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Steric Effects on SN2

Reactions

The carbon atom in (a) bromomethane is readily accessible

resulting in a fast SN2 reaction. The carbon atoms in (b) bromoethane
(primary), (c) 2-bromopropane (secondary), and (d) 2-bromo-2-methylpropane
(tertiary) are successively more hindered, resulting in successively slower SN2
reactions.
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Order of Reactivity in SN2

The more alkyl groups connected to the reacting carbon,
the slower the reaction
o Difficult for nucleophile to approach, steric strain in T.S.

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The Nucleophile
Neutral or negatively charged Lewis base
Reaction increases coordination at nucleophile
o Neutral nucleophile acquires positive charge
o Anionic nucleophile becomes neutral
o See Table 7-1 for an illustrative list

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Relative Reactivity of Nucleophiles

Depends on reaction and conditions
More basic nucleophiles react faster
Anions are usually more reactive than neutrals

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The Leaving Group

A good leaving group reduces the barrier to a reaction
Stable anions that are weak bases are usually excellent
leaving groups and can delocalize charge

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Poor Leaving Groups

If a group is very basic or very small, it is prevents
reaction

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The SN1 Reaction

Tertiary alkyl halides react rapidly in protic solvents by

a mechanism that involves departure of the leaving
group prior to addition of the nucleophile
Called an SN1 reaction occurs in two distinct steps
while SN2 occurs with both events in same step
If nucleophile is present in reasonable concentration
(or it is the solvent), then ionization is the slowest step

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SN1 Energy Diagram

k1

k-1

k2

Rate-determining step is
formation of carbocation

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Step through highest

energy point is ratelimiting (k1 in forward
direction)
V = k[RX]

Rate-Limiting Step
The overall rate of a reaction is controlled by the
rate of the slowest step
The rate depends on the concentration of the
species and the rate constant of the step
The highest energy transition state point on the
diagram is that for the rate determining step
(which is not always the highest barrier)
This is the not the greatest difference but the
absolute highest point

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Stereochemistry of SN1
Reaction
The planar
intermediate
leads to loss of
chirality
o A free
carbocation
is achiral

Product is
racemic or has
some inversion

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Delocalized Carbocations
Delocalization of cationic charge enhances
stability
Primary allyl is more stable than primary alkyl
Primary benzyl is more stable than allyl

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Characteristics of the SN1 Reaction

Tertiary alkyl halide is most reactive by this
mechanism

o Controlled by stability of
carbocation

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Allylic and Benzylic Halides

Allylic and benzylic intermediates stabilized by
delocalization of charge
o Primary allylic and benzylic are also more reactive in
the SN2 mechanism

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Effect of Leaving Group on SN1

Critically dependent on leaving group
o Reactivity: the larger halides ions are better leaving groups

In acid, OH of an alcohol is protonated and leaving group

is H2O, which is still less reactive than halide
p-Toluensulfonate (TosO-) is excellent leaving group

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