Chapter 6

Alkyl Halides

NEPHAR 109 Organic Chemistry I

Assist.Prof. Banu Keşanlı
 Alkyl Halides
ÎThe polarity of a carbon-halogen bond leads
to the carbon having a partial positive charge

ÎIn alkyl halides this polarity causes the

carbon to become activated to substitution
reactions with nucleophiles

Chapter 6 2
¾ Carbon-halogen bonds get less polar, longer and
weaker in going from fluorine to iodine

Chapter 6 3
 Nomenclature of Alkyl Halides
ÎIn IUPAC nomenclature halides are named as
substituents on the parent chain
• Halo and alkyl substituents are considered to
be of equal ranking

Chapter 4 4
• Common nomenclature of simple alkyl halides
is accepted by IUPAC and still used

Chapter 4 5
 Classification of Hydrogen Atoms

ÎHydrogens take their classification from the

carbon they are attached to

Chapter 6 6
• If the carbon is attached to one other carbon
that carbon is primary (1o) and the alkyl halide
is also 1o
• If the carbon is attached to two other carbons,
that carbon is secondary (2o) and the alkyl
halide is 2o
•If the carbon is attached to three other
carbons, the carbon is tertiary (3o) and the alkyl
halide is 3o

Chapter 6 7
 Reactions and Their Mechanisms
There are four general types of organic
reactions

• Addition Reactions
Two reactants add together to form a single new product
with no atoms “left over”

Chapter 3 8
 • Elimination Reactions
Single reactant splits into two products

Chapter 3 9
• Substitution Reactions
Two reactants exchange parts to give two new products

• Rearrangement Reactions
Single reactant undergoes a reorganization of bonds and
atoms to yield an isomeric product

Chapter 3 10
 Cleavage of Covalent Bonds
Homolysis

¾ Symmetrical bond breaking leading to

radical reactions
Heterolysis

¾ Unsymmetrical bond breaking leading

to polar reactions Chapter 3 11
 Radical Reactions
ÎHomolytic bond cleavage of relatively weak
bonds such as O-O or X-X bonds can occur
with addition of energy in the form of heat or
light leading to the formation of radicals
(also called free radicals)

ÎRadicals are highly reactive, short-lived

species
• Single-barbed arrows are used to show
the movement of single electrons

Chapter 3 12
 Reactions of Radicals
ÎRadicals tend to react in ways that lead to
pairing of their unpaired electron
• Hydrogen abstraction is one way a
halogen radical can react to pair its
unshared electron

Example of a Radical Reaction

Chapter 3 13
¾ Heterolytic reactions almost always occur at
polar bonds
ÎThe reaction is often assisted by formation
of a new bond to another molecule

Chapter 3 14
Heterolysis of Bonds to Carbons: Carbanions and
Carbocations

z Reaction can occur to give a carbocation or

carbanion depending on the nature of Z

Chapter 3 15
zCarbocations have only 6 valence electrons
and a positive charge

Chapter 3 16
• Carbanions have 8 valence electrons and a
negative charge

Chapter 3 17
Nucleophilic Substitution Reactions (SN)
ÎIn this reaction a nucleophile is species with
an unshared electron pair which reacts with
an electron deficient carbon
ÎA leaving group is substituted by a
nucleophile

ÎExamples of nucleophilic substitution

Chapter 6 18
 Nucleophile
ÎThe nucleophile reacts at the electron
deficient carbon

ÎA nucleophile may be any molecule with an

unshared electron pair

Chapter 6 19
 Leaving Group
ÎA leaving group is a substituent that can
leave as a relatively stable entity
ÎIt can leave as an anion or a neutral species

Chapter 6 20
 SN2 Reactions
¾ Rate determining step is bimolecular
¾ Methyl and 1° alkyl halides undergo SN2 type
nucleophilic substitutions

δ− δ−
HO- + CH3 Cl HO CH3 Cl HO CH3 + Cl-
Transition state

Chapter 6 21
Kinetics of a Nucleophilic Substitution
Reaction: An SN2 Reaction
• The rate equation reflects this
dependence
• SN2 reaction: substitution,
nucleophilic, 2nd order (bimolecular)

Chapter 6 22
 A Mechanism for the SN2 Reaction

ÎA transition state is the high energy state of

the reaction
• It is an unstable entity with a very brief
existence (10-12 s)

ÎIn the transition state of this reaction bonds

are partially formed and broken
• Both chloromethane and hydroxide are
involved in the transition state and this
explains why the reaction is second order
»

Chapter 6 23
 A Mechanism for the SN2 Reaction
Mechanism of a Reaction: The events that are
postulated to take place at the molecular level as
reactants become products

Chapter 6 24
 The Stereochemistry of SN2 Reactions

ÎStereochemistry can be controlled in SN2

reactions
• Backside attack of nucleophile results in an
inversion of configuration

Chapter 6 25
¾ In cyclic systems a cis compound can react
and become trans product

Chapter 6 26
Transformations Using SN2 Reactions

Chapter 6 27
 SN1 Reactions
¾ Rate determining step is unimolecular
¾ Tertiary halides show SN1 type nucleophilic
substitution reactions

slow +
(CH3)3CCl (CH3)3C + Cl-

+ H2 O (CH3)3COH + H3O +
(CH3)3C

Chapter 6 28
6.10 The Reaction of tert-Butyl Chloride with
Hydroxide Ion: An SN1 Reaction
Îtert-Butyl chloride undergoes substitution
with hydroxide
ÎThe rate is independent of hydroxide
concentration and depends only on
concentration of tert-butyl chloride

Chapter 6 29
¾ SN1 reaction: Substitution, nucleophilic, 1st
order (unimolecular)

¾ The rate depends only on the concentration

of the alkyl halide

¾ Only the alkyl halide (and not the

nucleophile) is involved in the transition
state of the step that controls the rate

Chapter 6 30
 6.11 A Mechanism for the SN1 Reaction

ÎStep 1 is rate determining (slow) because it

requires the formation of unstable ionic
products

ÎIn step 1 water molecules help stabilize the

ionic products

Chapter 6 31
Chapter 6 32
 Carbocations
ÎA carbocation has only 6 electrons, is sp2
hybridized and has an empty p orbital

ÎThe more highly substituted a carbocation

is, the more stable it is and the easier it is to
form

Chapter 6 33
ÎHyperconjugation stabilizes the carbocation by
donation of electrons from an adjacent carbon-
hydrogen or carbon-carbon σ bond into the
empty p orbital
• More substitution provides more opportunity
for hyperconjugation

Chapter 6 34
The Stereochemistry of SN1 Reactions
ÎWhen the leaving group leaves from a
stereogenic center of an optically active
compound in an SN1 reaction, racemization
will occur
• This is because an achiral carbocation
intermediate is formed
Racemization: transformation of an optically
active compound to a racemic mixture

Chapter 6 35
Chapter 6 36
 Solvolysis

ÎA molecule of the solvent is the nucleophile

in a substitution reaction
• If the solvent is water the reaction is a
hydrolysis

Chapter 6 37
 Factors Affecting the Rate of SN1 and SN2
Reactions

• The Effects of the Structure of the Substrate

z SN2 Reactions
ÎIn SN2 reactions alkyl halides show the
following general order of reactivity

Chapter 6 38
ÎSteric hinderance: the spatial arrangement of
the atoms or groups at or near a reacting site
hinders or retards a reaction
• In tertiary and neopentyl halides, the reacting
carbon is too sterically hindered to react

Chapter 6 39
• SN1 reactions
ÎGenerally only tertiary halides undergo SN1
reactions because only they can form
relatively stabilized carbocations

Chapter 6 40
Solvent Effects on SN2 Reactions: Polar Protic and
Aprotic Solvents
Polar Protic Solvents
• Polar solvents have a hydrogen atom attached
to strongly electronegative atoms
• They solvate nucleophiles and make them less
reactive

Chapter 6 41
¾Larger nucleophilic atoms are less solvated and
therefore more reactive in polar protic solvents

¾Larger nucleophiles are also more polarizable

and can donate more electron density

*Relative nucleophilicity in polar solvents:

Chapter 6 42
ÎPolar Aprotic Solvents
• Polar aprotic solvents do not have a
hydrogen attached to an electronegative
atom

Chapter 6 43
•Polar aprotic solvents solvate cations well but
leave anions unsolvated because positive centers
in the solvent are sterically hindered

Chapter 6 44
• Polar aprotic solvents lead to generation of
“naked” and very reactive nucleophiles

• Trends for nucleophilicity are the same as for

basicity

• They are excellent solvents for SN2 reactions

Chapter 6 45
z The Nature of the Leaving Group
ÎThe best leaving groups are weak bases
which are relatively stable
• The leaving group can be an anion or a
neutral molecule
ÎLeaving group ability of halides:

ÎOther very weak bases which are good

leaving groups:

Chapter 6 46
ÎThe poor leaving group hydroxide can be
changed into the good leaving group water
by protonation

Chapter 6 47
 Summary SN1 vs. SN2
ÎIn both types of reaction alkyl iodides react
the fastest because of superior leaving group
ability

Chapter 6 48
 Elimination Reactions of Alkyl Halides
Dehydrohalogenation
ÎUsed for the synthesis of alkenes
• Elimination competes with substitution
reaction
• Strong bases such as alkoxides favor
elimination

Chapter 6 49
Chapter 6 50
 The E2 Reaction

ÎE2 reaction involves concerted removal of

the proton, formation of the double bond,
and departure of the leaving group

ÎBoth alkyl halide and base concentrations

affect rate and therefore the reaction is 2nd
order

Chapter 6 51
E2 Reaction Mechanism

Chapter 6 52
 The E1 Reaction
ÎThe E1 reaction competes with the SN1
reaction and likewise goes through a
carbocation intermediate

Chapter 6 53
E1 Reaction Mechanism

Chapter 6 54
Chapter 6 55
Reaction Types of Alkyl Halides
A Summary of Substitution and Elimination Reactions

Halide SN1 SN2 E1 E2

Type
RCH2X Does not Highly Does not Occurs
(primary) occur favored occur when
strong
bases are
used
R2CHX Can occur Occurs in Can occur Favored
(secondary) with competitio with when
benzylic n with E2 benzylic strong
allylic reaction and allylic bases are
halides halides used
R3CX Favored in Does not Occurs in Favored
(tertiary) hydroxylic occur competitio when
solvents n with SN1 bases are
reaction used

Chapter 6 56
 Preparation of Alkyl Halides
¾ From radical halogenation of alkenes
e.g. allylic bromination with N-bromosuccinimide
(NBS) and light

H Br
C C hν, NBS
C C C
CCl4 C

¾From alkenes by addition of HBr and HCl

H Br
C C + HBr C C
Chapter 6 57
Conversion of Alcohols into Alkyl Halides

Î Hydroxyl groups are poor leaving groups,

and as such, are often converted to alkyl
halides when a good leaving group is needed

Î Three general methods exist for conversion

of alcohols to alkyl halides, depending on the
classification of the alcohol and the halogen
desired

Î Reaction can occur with phosphorus

tribromide, thionyl chloride or hydrogen
halides

Chapter 6 58
¾From alcohols
• Reaction with HX, where X=Cl, Br, I
OH X
HX
C H Ether C H

Reactivity order 3°>2°>1°

• Reaction of 1° and 2° alcohols with SOCl2
OH Cl
SOCl2
C H Pyridine C H

• Reaction of 1° and 2° alcohols with PBr3

OH Br
PBr3
C H C H
EtherChapter 6 59
 Examples
• By using hydrogen halides, HX

Chapter 6 60
• By using PBr3

Chapter 6 61
• By using SOCl2

Chapter 6 62