cHAPTER 7

ALKYL HALIDES
 OUTLINES
1. Introduction to Alkyl Halides
2. Nomenclature: IUPAC and common name
3. Method of Preparation of Alkyl Halides
❑ Halogenation of alkanes
❑ Addition of HX to alkenes
4. Reactions of Alkyl Halides
❑Substitution: SN1 & SN2 reaction (mechanism, stereochemistry,
rate of reaction, steric hindrance)
❑Elimination Reactions: E1 & E2 (mechanism, rate of reaction)
❑Reduction of Alkyl Halides
❑Hydrolysis of Grignard Reagent
5. Uses
INTRODUCTION TO
ALKYL HALIDES
• Alkyl halides are organic molecules containing a halogen atom
bonded to an sp3 hybridized carbon atom.
• Alkyl halides are classified as primary (1°), secondary (2°), or
tertiary (3°)
Examples of 1°, 2°, and 3° alkyl halides

Examples Four types of organic halides (RX) having X near a π bond

5
NOMENCLATURE OF
ALKYL HALIDES
 CH3
5 4 3 2 1
CH3 CH2 CH CH CH3
CH3 I
CI
iodomethane 3-chloro-2-methylpentane

CH3 CH3 F
6 5 4 3 2 1
CH3 CH2 C CH2 CH CH3
Br
4-bromo-2,4-dimethylhexane fluorocyclohexane

I
Cl

Cl
iodobenzene 1,2-dichlorobenzene
Common names:
1. Naming the alkyl group followed by the name of the
halide.
2. Change the –ine to –ide for the halogen. For examples,
fluorine to fluoride, chlorine to chloride.
** Only for simple alkyl halides

CH3CH2F CH3CH2CH2CH2Cl
IUPAC name: fluoroethane IUPAC name: 1-chlorobutane
common name: ethyl fluoride common name: n-butyl chloride

Br I

CH3CHCH3
IUPAC name: 2-bromopropane IUPAC name: iodocyclohexane
common name: isopropyl bromide common name: cyclohexyl iodide
 PREPARATION
OF ALKYL HALIDES
 HALOGENATION OF ALKANES
Alkanes undergoes free radical substitution reaction to form
alkyl halide and halogen halide
ADDITION OF HYDROGEN HALIDE
(HX) TO ALKENES
• The hydrogen and halogen atoms add across the double
bond to form haloalkanes (alkyl halides).

• Follow Markovnikov’s rule.

• Reactivity of hydrogen halides : HF < HCl < HBr < HI

 EXAMPLE…
EXAMPLES:

H-I I
cyclopentene iodocyclopentane
Br
CH3CH=CHCH3 + H-Br CH3CH2CHCH3
2-butene 2-bromobutane
 Addition of hydrogen halide (HX)

When HBr (not HCl or HI) reacts with unsymmetrical alkene in

the presence of peroxides
✓ ANTI- Markovnikov’s rule

peroxide
CH3CH=CH2 HBr CH3CH2CH2Br
1-bromopropane
(major product)
anti-Markovnikov's orientation
 Addition of halogen in inert
solvent (Br2 & Cl2)
• Alkenes react with halogens at room temperature and in
dark.
• The halogens usually dissolved in an inert solvent such as
dichloromethane (CH2Cl2) and tetrachloromethane (CCl4).
 EXAMPLE…
CCl4 Br
Br2
Br
cyclohexene 1,2-dibromocyclohexane
Cl Cl
CH3CH=CH2 Cl2 CCl4
CH3CH CH2
propene 1,2-dichloropropane
CHEMICAL REACTIONS OF
ALKYL HALIDES
 The Polar Carbon-Halogen Bond
• The electronegative halogen atom in alkyl halides creates a
polar C—X bond, making the carbon atom electron deficient.

• Electrostatic potential maps of four simple alkyl halides

illustrate this point.
The Polar Carbon-Halogen Bond
 1. NUCLEOPHILIC
SUBSTITUTION OF ALKYL
HALIDES,
SN 1 & S N 2
General Features of Nucleophilic
Substitution
Three components are necessary in any substitution reaction.
EXAMPLE…
General Features of Nucleophilic
Substitution

PRODUCTS

NEUTRAL NEUTRAL
POSITIVE
- No Proton - Proton CHARGE
transfer Transfer
• Negatively charged nucleophiles like HO¯ and HS¯ are used as
salts with Li+, Na+, or K+ counterions to balance the charge.

• When a neutral nucleophile is used, the substitution product

bears a positive charge.
 CONTINUE…
• When the substitution product bears a positive charge and
also contains a proton bonded to O or N
✓ the initially formed substitution product readily loses a
proton in a BrØnsted-Lowry acid-base reaction, forming
a neutral product.
 THE LEAVING GROUP
• In a nucleophilic substitution reaction of R—X, the C—X bond
is heterolytically cleaved,
✓ the leaving group departs with the electron pair in that
bond, forming X:¯.
• The more stable the leaving group X:¯, the better able it is to
accept an electron pair.
THE LEAVING GROUP

Weak bases
THE LEAVING GROUP

Strong bases
 NUCLEOPHILE
• Nucleophiles and bases are structurally similar:
✓ both have a lone pair or a  bond.
✓ They differ in what they attack.
NUCLEOPHILE Vs. BASICITY
Basicity is a measure of how readily an atom
donates its electron pair to a proton. It is
characterized by an equilibrium constant, Ka
in an acid-base reaction.

Nucleophilicity is a measure of how readily an

atom donates its electron pair to other atoms.
It is characterized by a rate constant, k.
 NUCLEOPHILE Vs. BASICITY
• Nucleophilicity does not parallel basicity when steric hindrance
becomes important.
• Steric hindrance is a decrease in reactivity resulting from the
presence of bulky groups at the site of a reaction.
• Steric hindrance decreases nucleophilicity but not basicity.
• To serve as a nucleophile, an ion or molecule must get in close
to a carbon atom to attack it.
 NUCLEOPHILE Vs. BASICITY
• Bulky groups on the nucleophile hinder this close approach
and they slow the reaction rate. Therefore this bulky groups
is a weaker nucleophile.
NUCLEOPHILE
 NUCLEOPHILE
STRONG MODERATE WEAK
NUCLEOPHILE NUCLEOPHILE NUCLEOPHILE
 MECHANISM OF NUCLEOPHILIC
SUBSTITUTION

In a nucleophilic substitution:
 CONTINUE…
[1] Bond making and bond breaking occur at the same time.

Mechanism: 1 step.
Reaction: Bimolecular reaction,
Rate: concentration of both reactants
Rate Equation: second order.
 CONTINUE…
[2] Bond breaking occurs before bond making.

Mechanism: 2 steps.
Reaction: Unimolecular reaction
Rate: concentration of R-X
Rate Equation: First order.
 S N2
(SUBSTITUTION NUCLEOPHILIC
BIMOLECULAR)
MECHANISM
GENERAL FEATURES
 1) ONE STEP MECHANISM
• The processes of bond breaking and bond forming occur
simultaneously (one bond is forming, one bond is breaking).

• The mechanism involves only one step without

intermediates.
 EXAMPLES…
• OH- ion is attacked C-I bond from the back side
followed by the breaking of C-I bond and forming of
C-OH bond to form methanol.

• This process is occured simultaneously.

δ+ δ-
δ- δ+ δ-

nucleophile electrophile transition state product leaving

(substrate) (methanol) group
 2) RATES OF REACTIONS
• Bimolecular: the transition state of the rate-limiting step
involves the collision of two molecules.

• A second order reaction.

• The rate of reaction depends in the concentration of two

substances i.e. alkyl halide and nucleophile.

• Rate = k[alkyl halide][Nucleophile]

 EXAMPLES…

Kinetic data show that the rate of reaction depends on the

concentration of both reactants, which suggests a
bimolecular reaction with a one-step mechanism
 EXAMPLES…
CH3I + OH- → CH3OH + I-

❖ Rate equation = k[CH3I][OH-]

❖ Both iodomethane and the OH- are involved in the rate-

limiting step.

❖ When the concentration of CH3I is added double, the reaction

rate will become doubles (the reaction will become faster).

❖ Similarly, if the concentration of OH- is added double, the

reaction rate will become doubles (the reaction become
faster).
 3) STEREOCHEMISTRY
• The incoming nucleophile approaches from a direction 180° away from
the leaving halide ion, thereby inverting the stereochemistry at
carbon.

• All SN2 reactions proceed with backside attack of the nucleophile,

resulting in inversion of configuration at a stereogenic center.

• In the transition state, the new Nu-C bond is partially forming at the
same time the old C-X bond is partially breaking, and the negative
charge is shared by both incoming nucleophile and the outgoing
leaving group.
EXAMPLES…
EXAMPLES…
Two examples of
SN2 inversion of configuration:
The Walden Inversion.
FACTOR AFFECTING SN2
REACTIONS…
 1. STERIC HINDRANCE

✓ Methyl & 1° alkyl halides undergo SN2 reactions with ease.

✓ 2° Alkyl halides react more slowly.
✓ 3° Alkyl halides do not undergo SN2 reactions.
→ Steric hindrance - bulky R groups
→ makes nucleophilic attack from the backside more difficult,
slowing the reaction rate.
Electrostatic potential maps illustrate the effects of steric
hindrance around the carbon bearing the leaving group in a
series of alkyl halides.
• Increasing the number of R groups on the carbon with the
leaving group increases crowding in the transition state,
thereby decreasing the reaction rate.

• The SN2 reaction is fastest with unhindered halides.

 2. SOLVENTS
• Polar aprotic solvents
✓ Does not contain O-H or N-H molecule
✓ do not form hydrogen bonds with nucleophile
✓ form weaker interactions with substrate
• may enhance the strength of weak nucleophiles.
✓ permit faster reaction.
• Examples: O
O
C CH3
H N
CH3 C N C
CH3
acetonitrile H3C CH3
dimethylformamide
acetone
(DMF)
CHARACTERISTIC OF THE SN2
MECHANISM
 SN1
(SUBSTITUTION NUCLEOPHILIC
UNIMOLECULAR)
MECHANISM
GENERAL FEATURES
 1) TWO STEPS MECHANISM
➢ SN1 mechanism is a two steps mechanism.
i) Step 1: slow ionization to form a carbocation.

ii) Step 2: A fast attack on the carbocation by a

nucleophile.

➢ Carbocation is a strong electrophile; it reacts very fast

with both strong and weak nucleophiles.
➢ Loss of proton to solvent to give the final uncharged
product.
 EXAMPLES…
(CH3)3C-Br + H2O (CH3)3C-OH

Step 1
+ -
(CH3)3C Br (CH3)3C + Br

Step 2
+
(CH3)3C + H O H (CH3)3C O H
H
+
(CH3)3C +O H + H O H (CH3)3C O H + H3O
H
EXAMPLES…
 2) REARRANGEMENTS
❑ Carbocations can rearrange to form a more stable
carbocation.

❑ Hydride shift: H- on adjacent carbon bonds with C+.

❑ Methyl shift: CH3- moves from adjacent carbon if no

hydrogens are available.
 i) HYDRIDE SHIFT
Br H H
CH3 C C CH3 CH3 C C CH3
H CH3 H CH3

H H
CH3 C C CH3 CH3 C C CH3
H CH3 H CH3

H H Nuc
CH3 C C CH3 Nuc
CH3 C C CH3
H CH3 H CH3
 i) METHYL SHIFT
Br CH3 CH3
CH3 C C CH3 CH3 C C CH3
H CH3 H CH3

CH3 CH3
CH3 C C CH3 CH3 C C CH3
H CH3 H CH3

CH3 CH3 Nuc

CH3 C C CH3 Nuc
CH3 C C CH3
H CH3 H CH3
 EXAMPLE…
Hydrolysis of the secondary alkyl bromide, 2-bromo-3-
methylbutane, yields the tertiary alcohol, 2-methyl-2-
butanol.

CH3 H CH3
H O H
CH3 C C CH3 CH3 C CH2CH3
H Br OH
Step 1: Formation of carbocation and rearrangement

CH3 H CH3 H

CH3 C C CH3 CH3 C C CH3 Br-

H Br H slow step
o
(2 carbocation)

shift of H

CH3 H

CH3 C C CH3
(3o carbocation)
H
 Step 2: Solvent attack and loss of proton

CH3 CH3 CH3

fast
CH3 C CH2CH3 CH3 C CH2CH3 CH3 C CH2CH3
H O H H O H OH

H O H
H3O+
 3) RATES OF REACTIONS
• Unimolecular: The reaction is first order

• The rate depends only on the concentration of the alkyl

halides.

• Rate = k[alkyl halide]

 EXAMPLE…
Hydrolysis of tert-butyl bromide

(CH3)3C-Br + H2O (CH3)3C-OH

✓ Rate = k[(CH3)3CBr]

✓ The concentration of H2O does not have any effect on the

rate of reaction.

✓ H2O does not involved in the rate-limiting step.

 4) STEREOCHEMISTRY
✓ Nucleophilic attack can occur from either side producing
mixtures of configuration if the carbon is chiral

✓ Configuration
➢ Retention
➢ Inversion
✓ Retention: Attacks from the front side
✓ Inversion: Attack from the back side

✓ The SN1 reaction produces mixtures of enantiomers. There

is usually more inversion than retention of configuration.
 EXAMPLE…
CH3 H3C
CH2CH3 H2O CH3CH2
Cl C C OH
ethanol
CH2CH2CH2CHCH3 CH3CHCH2CH2CH2
CH3 CH3
(R)-6-chloro-2,6-dimethyloctane 60% S
(inversion)

CH3
CH2CH3
HO C

CH2CH2CH2CHCH3
CH3
40% R
(retention)
 EXAMPLE…

H3C Br H3CO CH3

CH3OH
(R)-3-bromo-3-methylhexane (S)-3-methoxy-3-methylhexane (50%, inversion)

H3C OCH3

(R)-3-methoxy-3-methylhexane (50%, retention)

FACTOR AFFECTING SN1
REACTIONS…
 1) CARBOCATION STABILITY
✓ Carbocations are classified as primary (1°), secondary (2°),
or tertiary (3°), based on the number of R groups bonded to
the charged carbon atom.

✓ As the number of R groups increases, carbocation stability

increases.
 2) SOLVENTS
• Polar protic solvent.
✓ the solvent will stabilized the carbocation in the
transition state – through HYDROGEN BONDING
 3) NUCLEOPHILES

✓ weak nucleophile promotes the SN1 reaction if

the substrate is secondary or tertiary.
 4) EFFECT OF SUBSTRATE
✓ Order of reactivity follows stability of carbocations
(opposite to SN2)

✓ 3° > 2° > 1° >> CH3X

✓ More stable carbocation requires less energy to form.

FACTOR CONSIDERED TO
IDENTIFY SN1 or SN2
MECHANISM
1) STRUCTURE OF ALKYL HALIDE
 2) NUCLEOPHILE
•Strong nucleophiles (usually bear a negative charge) present
in high concentrations favor SN2 reactions.

•Weak nucleophiles, such as H2O and ROH favor SN1

reactions by decreasing the rate of any competing SN2
reaction.
The strong nucleophile favors an SN2 mechanism

The weak nucleophile favors an SN1 mechanism.

 3) LEAVING GROUP
A better leaving group increases the rate of both SN1 and SN2
reactions.
 4) NATURE OF SOLVENT
• Polar protic solvents like H2O and ROH favor
✓ SN1 reactions because the ionic intermediates
(both cations and anions) are stabilized by
solvation.

• Polar aprotic solvents favor

✓ SN2 reactions because nucleophiles are not well
solvated, and therefore, they are more
nucleophilic.
 CONTINUE…
• Polar protic solvents (O-H or N-H)
• Reduce the strength of the nucleophile.
✓ energy is required to “strip off” some of the solvent
molecules.
✓ Hydrogen bonds must be broken before nucleophile
can attack the carbon.
✓ makes the SN2 reactions become slower
• Examples: alcohols, water and carboxylic acids.
SUMMARY
SUMMARY FOR SN1
AND SN2
MECHANISM
 SN1 SN2
Substrate (alkyl 3º > 2º (1° and CH3X are CH3X > 1º > 2º (3° is not
halides) unlikely) suitable)

Nucleophiles Weak nucleophiles Strong nucleophiles

Solvent Polar protic solvent (more Polar aprotic solvent
polar solvent) (less polar solvent)

Leaving group Good LG important to Not as important but

form C+ enhances reaction

Rate of reaction First order Second order

Rate = k[alkyl halide] Rate = k[alky halide][Nu]

Stereochemistry Racemic mixture (mixture of Inversion at chiral carbon

inversion and retention)

Rearrangements Rearranged products No rearrangements

EXAMPLE…
 EXERCISES…
Point out the mechanism of the following reactions as
SN1 or SN2 :

i) CH3CH2I + NaCN → CH3CH2CN + NaI

ii) (CH3)3CBr + CH3OH → (CH3)3COCH3 + HBr

 ANSWER…
i) SN2 mechanism
Reasons:
- the alkyl halide i.e. CH3CH2I is primary alkyl halide
- NaCN will produced CN- - strong nucleophile

ii) SN1 mechanism

Reasons:
- substrate (alkyl halide) i.e. (CH3)3CBr is tertiary alkyl
halide
- CH3OH (methanol) that was used as a solvent is a weak
nucleophile
NUCLEOPHILIC SUBSTITUTION
& ORGANIC SYNTHESIS
2. ELIMINATION OF
ALKYL HALIDES,
E1 & E2
• Elimination reactions involve the loss of elements from the
starting material to form a new  bond in the product.
 EXAMPLE…
In both reactions a base removes the elements of an acid, HX,
from the organic starting material.
 EXAMPLE…
• Removal of the elements HX is called dehydrohalogenation.
• Dehydrohalogenation is an example of  elimination.
• The curved arrow formalism shown below illustrates how
four bonds are broken or formed in the process.
• The most common bases used in elimination reactions are
✓ negatively charged oxygen compounds, such as HO¯
✓ alkyl derivatives, RO¯, called alkoxides.
 DRAWING PRODUCT

To draw any product of dehydrohalogenation

➢ Find the  carbon.
➢ Identify all  carbons with H atoms.
➢ Remove the elements of H and X from the  and 
carbons and form a  bond.
EXAMPLE…
Mechanisms of elimination:

• There are two mechanisms of elimination—E2 and

E1, just as there are two mechanisms of substitution,
SN2 and SN1.
• E2 mechanism—bimolecular elimination
• E1 mechanism—unimolecular elimination
• The E2 and E1 mechanisms differ in the timing of
bond cleavage and bond formation, analogous to the
SN2 and SN1 mechanisms.
• E2 and SN2 reactions have some features in
common, as do E1 and SN1 reactions.
 MECHANISM
OF ELIMINATION, E2
GENERAL FEATURES
➢ Bimolecular elimination
→Reaction between two molecules occurs
simultaneously.
→The reaction is concerted—all bonds are broken and
formed in a single step.

➢ E2 reactivity: 3o > 2o > 1o

➢ It exhibits second-order kinetics

→both the alkyl halide and the base appear in the rate
equation, i.e.,
→rate = k[(CH3)3CBr][¯OH]
 MECHANISM
• The most common mechanism for dehydrohalogenation is
the E2 mechanism.

103
LEAVING GROUP & SOLVENTS
 EFFECT OF ALKYL GROUP
• The SN2 and E2 mechanisms differ in how the R group affects
the reaction rate.
 CONTINUE…
• In the transition state, the double bond is partially formed.
✓ Increasing the stability of the double bond (30) with
alkyl substituents
➢ stabilizes the transition state (FASTER REACTION)
CONTINUE…
Summary E2 mechanism.
Saytzeff Rule
 Saytzeff Rule

• A reaction is regioselective when it yields predominantly or

exclusively one constitutional isomer when more than one
is possible.
• Thus, the E2 reaction is regioselective.
 MECHANISM
OF ELIMINATION, E1
➢ Unimolecular elimination
✓rate limiting transition state involves a single
molecular rather than a collision between two
molecules.

➢ E1 reactivity: 3o > 2o > 1o

✓The rate-limiting step is the formation of carbocation.
✓The reactivity order reflects the stability of
carbocations.
✓Order of reactivity follows stability of carbocations.
➢ The E1 reaction proceeds via a two-step mechanism:

i) The bond to the leaving group breaks

ii) Then the  bond is formed.

➢ An E1 reaction exhibits first-order kinetics:

✓rate = k[(CH3)3CCI]
MECHANISM
 EXAMPLE…
Br
CH3 C CH3 H2O CH2 C CH3
CH3 CH3
Step 1:
H Br H
H C C CH3 H C C CH3
H CH3 H CH3

Step 2:
H
H O H H CH3
+
C C + H3O
H C C CH3
H CH3
H CH3
 CONTINUE…
SN1 and E1 reactions have exactly the same first step, formation
of a carbocation BUT differ in what happens to the carbocation.
The E1 and E2 mechanisms both involve the same number of
bonds broken and formed. The only difference is timing.

E1, the leaving group E2, the leaving group

comes off before the  comes off as the 
proton is removed, and proton is removed, and
the reaction occurs in the reaction occurs in
two steps. one step.
FACTOR AFFECTING E1
REACTIONS…
 ALKYL GROUP (-R)
The rate of an E1 reaction increases as the number of R
groups on the carbon with the leaving group increases.
 CONTINUE…
• E1 reactions are regioselective,
✓ favoring formation of the more substituted, more stable
alkene.
• So, Saytzeff rule applies to E1 as well as E2 reactions.
SUMMARY ON E1 MECHANISM
FACTOR CONSIDERED TO
IDENTIFY E1 or E2
MECHANISM
Strong bases : E2 mechanism.
Weak bases : E1 mechanism.
SUMMARY FOR E1
AND E2
MECHANISM
 E1 E2
Rate of reaction First order Second order
Rate = k[alkyl halide] Rate = k[alkyl halide][base]
Reactivity 3o > 2o > 1o 3o > 2o > 1o
* 1o usually will not go E1
Base Weak base Strong base

Solvent Enhanced by polar protic Solvent polarity not important

solvent

Leaving group Good LG important to form C+ Good LG enhances reaction

Orientation of Saytzeff orientation Saytzeff orientation

elimination

Rearrangements Common Impossible

PREDICTING THE
MECHANISM
SN1, SN2, E1 OR E2
NUCLEOPHILES / BASES
Strong nucleophile Strong Base
SN2 E2
(OH-) (bulky group, OH-)

Weak Nucleophile Weak Base

SN1 E1
(H2O, CH3OH) (H2O, NH3)
 CONTINUE…
➢ Weakly basic species that are good nucleophiles –
substitution

➢ Examples: I-, Br-, Cl-, RS-, N3-, RCO2-, CN-

 CONTINUE…
Strongly basic nucleophiles – eliminations
- Examples: OH-, OR-, H2N-, R2N-

Bulky nonnucleophilic bases favor elimination over substitution.

✓ KOC(CH3)3, DBU, and DBN are too sterically hindered to attack
tetravalent carbon,
✓ but are able to remove a small proton, favoring elimination
over substitution
 Bulky nonnucleophilic bases

N N

O-
N
K+
1,5-Diazabicyclonon-5-ene (DBN) t-butoxide
N
N
N N

1,8-Diazabicycloundec-7-ene(DBU)
 CONTINUE…

✓ Sterically unhindered strongly basic nucleophiles –

substitution

✓ may occur depends on the classes of alkyl halides

➢ examples: OH-, CH3O-, H2N-
ALKYL HALIDE
CONTINUE…
SUMMARY
 SOLVENT
• Polar aprotic solvents:
- SN2
• Polar protic solvents:
- SN1 or E1

Higher temp. favors elimination over substitution

 RATE OF REACTION
• The rate of reaction of SN2 and E2 are proportional to the
concentration of nucleophiles or bases.
✓ If the concentration of the nucleophiles or bases are
added doubled, the rate of reaction of SN2 and E2 also
increase doubled.

• The changes of nucleophiles or bases concentration is not

effect the rate of reactions of SN1 and E1.
 EXERCISES
1) Predict the mechanisms for the following reaction. Write structural
formulas for the major organic product(s).
a) Cl
NaCN
SN2 methanol

Reasons:
- alkyl halide : 1° alkyl halide
- CN- : strong nucleophile and weak base
- Mechanism : SN2

Cl
CN
NaCN
methanol
b)

SN1 and E1

Reasons:
- alkyl halide : 3° alkyl halide i.e.
- CH3CH2OH : weak nucleophile and weak base
- Mechanism : SN1 and E1 reactions.
- Solvent : ethanol, polar protic solvent - SN1 and E1 reactions
e)

E2

Reasons:
- alkyl halide : 3°
- OH- : strong base and strong nucleophile
- 3° alkyl halide cannot go SN2 reaction
 3. REDUCTION OF ALKYL
HALIDES TO FORM ALKANES
Alkyl halides undergoes reduction to form alkanes.

ether H2O
R X Mg R MgX R H Mg(OH)X

H2O
R X 2Li R Li LiX R H LiOH

Example:

i) Mg, ether
CH3CH2Br CH3CH3 + Mg(OH)Br
ii) H2O
 4. SYNTHESIS OF GRIGNARD
REAGENTS
• A compound in which a metal atom or ion is bonded to an
organic group is called an organometallic compound.

• Grignard reagents: a class of organometallic compounds of

magnesium with general formula RMgX (R=alkyl or aryl
group, X = halogen).

• Examples of Grignard reagents: ethylmagnesium bromide

(C2H5MgBr) and phenylmagnesium chloride (C6H5MgCl).
 CONTINUE…
➢ Preparation of Grignard reagents:

Mg dry ether
R-X RMgX
(X = Cl, Br or I)

➢ Grignard reagents can be prepared from primary,

secondary and tertiary alkyl halides, vinyl halides and aryl
halides.
➢ The reactivity of alkyl halides with Mg decreases in order:
R-I > R-Br > R-Cl
 EXAMPLE…

ether
C H 3I Mg C H 3 M gI
ether
C H 3C H 2B r Mg C H 3C H 2M g B r

ether
Br Mg M gBr
USES OF
ALKYL
HALIDE
❑ Many simple alkyl halides make excellent solvents because
they are not flammable & dissolve in a wide variety of
organic solvents.
➢ Synthetic organic halides are also used in insulating
materials, plastic wrap, & coatings.

➢ For example Teflon & polivinyl chloride (PVC)

 Trifluoromethane [CFCl3, CFC 11, or Freon
11(trade name)] – is an easily vaporized
compounds extensively being used as a
refrigerant & aerosol propellant.

 CFCs slowly rise to the stratosphere, where

sunlight catalyzes their decomposition, a
process that contributes to the destruction of
the ozone layer, the thin layer of atmosphere
that shields the earth’s surface from harmful
ultraviolet radiation
 Insecticide DDT (dichlorodiphenyltrichloroethane)

 DDT is an organic molecule with valuable short-term

effects that caused long-term problems.

 DDT kills insects that spread diseases such as malaria &

typhus, & in controlling insect populations, DDT saved
millions lives worldwide.
THE
END