ORGANIC CHEMISTRY 1

CHM 207

CHAPTER 5
ALKYL HALIDES AND
ARYL HALIDES
NURUL’ AIN BINTI JAMION
 Nomenclature and structures of alkyl halides.
 Classification of alkyl halides.
 Physical properties of alkyl halides.
 Reactions of alkyl halides.
 Uses of alkyl halides
 Alkyl halides also known as haloalkanes.
 Alkyl halides:
- organic compounds in which one or more hydrogen atoms
of an alkane have been substituted by halogen atoms (F, Cl,
Br, I).
- General formula for monosubstituted alkyl halides:
CnH2n+1X where n = 1,2,… and Xis halogen or RX (R = alkyl
group)
- Examples: fluoroethane, bromomethane
 Aryl halides:
- the halogen atom is attached directly to the benzene ring.
- General formula of monosubstituted aryl halide: Ar-X (Ar
= the phenyl group, X = halogen)
- Examples: bromobenzene, chlorobenzene
 Functional group: halogen, -X (X = F, Cl, Br, I)
i) IUPAC: named as derivatives of the corresponding
alkanes, cycloalkanes or aromatic compounds.
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
ii) Common name:
- naming the alkyl group followed by the name of the
halide.
- 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

I
Br
CH3CHCH3
IUPAC name: 2-bromopropane IUPAC name: iodocyclohexane
common name: isopropyl bromide common name: cyclohexyl iodide
i) Primary alkyl halides (1°) H H
- the halogen-bearing carbon H C X H C X
is bonded to none or one
carbon atom H R

ii) Secondary alkyl halides (2°) H

- the halogen-bearing carbon
is bonded to two carbon
R' C X
atoms R

iii) Tertiary alkyl halides (3°)

- the halogen-bearing R''
carbon is bonded to three R' C X
carbon atoms
R
 BOILING POINTS
- molecules with higher molecular weight have
higher boiling points.
- reasons: the molecule is heavier, slower
moving, have greater surface area, have larger
London attractions, resulting higher boiling
points.
- example:
CH3F CH3Cl CH3Br CH3I
RMM 34 50.5 95 142
bp (°C) -78 -24 4 42
- compounds with branched have more spherical shapes,
have smaller surface area, resulting lower boiling points.

CH3
CH3 CH3 C Cl
CH3CH2CH2CH2Cl CH3CH2CHCl CH3
bp 78 oC bp 67 oC bp 52 oC

- alkyl halides with more carbon atoms have

higher boiling points.

CH3Cl CH3CH2Cl CH3CH2CH2Cl

bp -24oC o
bp 12 C bp 47oC
 Substitution (SN1 and SN2 reactions)
 Elimination (E1 and E2 reactions)
 Formation of alcohol
 Formation of ether
 Formation of amino compound
 Formation of cyano compound
 Formation of alkane -Wurtz reaction
 SUBSTITUTION REACTIONS
- -
C C + Nuc: C C + X:
H X H Nuc Leaving group
Nuc = nucleophile

• The halogen atom on the alkyl halide is replaced with another

group – substitution reaction.

• The alkyl halides is called the substrate, meaning the compound is

attacked by the reagent.

• Since the halogen is more electronegative than carbon, the C-X

bond breaks heterolytically and halide ion (X-) leaves.

• The halogen atom can leave with its bonding pair of electrons to
form a stable halide ion (halide ion is a good leaving group).

• The group replacing X- is a nucleophile.

 Nucleophile:
- a species (ion or molecule) that attacks a
positively charged carbon atom by donating an
electron pair to form a dative covalent bond.

- known as nucleophilic reagents

- Lewis bases

- negative ions or molecules that have at least one

lone pair of electrons.
 Neutral or negatively charged Lewis base.
 Reaction increases coordination at nucleophile:
◦ Neutral nucleophile acquires positive charge
◦ Anionic nucleophile becomes neutral
 Basicity: the equilibrium constant for abstracting a
proton (H).
 Nucleophilicity: the rate of attack on an electrophilic
carbon atom.
 The nucleophile or base will forms a new bond.
 If the new bond is to a proton, it has reacted as a base.
 If the new bond is to a carbon, it has reacted as a
nucleophile.
Basicity

Keq
B H A B H A

Nucleophilicity

kr
B C X B C X
 Nucleophilic strength:
 Stronger nucleophiles will react faster.
 Strong bases are strong nucleophiles, but not all strong
nucleophiles are basic.
 Trends in nucleophilicity:
 A species with negative charge is a strong nucleophile than a similar
neutral species. A base is a stronger nucleophile than its conjugate
acid:
OH- > H2O, NH2- > NH3
 Nucleophilicity decreases from left to right in the periodic table,
following the increase in electronegativity. More electronegative
atoms less likely to form new bond:
OH- > F-, NH3 > H2O, R3P > R2S
 Nucleophilicity increases down the periodic table, following the
increase in size and polarizability:
I- > Br- > Cl-
SOME COMMON NUCLEOPHILES, LISTED IN DECREASING
ORDER OF NUCLEOPHILICITY IN HYDROXYLIC SOLVENTS
SUCH AS WATER AND THE ALCOHOLS

STRONG NUCLEOPHILES
MODERATE NUCLEOPHILES

WEAK NUCLEOPHILES
 SUBSTRATE (ALKYL HALIDES)
 The reactivity of alkyl halides towards nucleophilic
substitution depend on the halogen.
 Halide ion is a good leaving group because they are
conjugate base for strong acid.
 In the nucleophilic substitution reaction to alkyl
halides, iodide ion is easy to substitute compare to
bromide ion and chloride ion. Fluoride ion is not
easy to substitute with other atom or group.
 Reason: C-X bond become stronger from I to F
 The rate of reaction decrease in the order:
R-I > R-Br > R-Cl > R-F
(most reactive) (least reactive)
 Examples:
CH3CH2 Br NaOH CH3CH2 OH NaBr
ethyl bromide ethyl alcohol

CH3 I CH3CH2 O Na+ CH3 O CH2CH3 Na+ I-

methyl iodide sodium ethoxide ethyl methyl ether

CH3CH2 Br H-NH2 CH3CH2 NH2 HBr

ethyl bromide ethylamine (primary amine)

(CH3)2CHCH2CH2-Cl NaCN (CH3)2CHCH2CH2-CN NaCl

1-chloro-3-methylbutane 4-methylpentanenitrile
 S = substitution
 N = nucleophilic
 1 = a first order (unimolecular) reaction
 2 = a second order
= both nucleophile and substrate in
characteristic step (bimolecular)
 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.

 The incoming nucleophile approaches from a direction

180° away from the leaving halide ion, thereby inverting
the streochemistry at carbon.

 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.
 • Example: hydrolysis of iodomethane (primary alkyl halides).
- 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.

H δ+ δ- H
HO C I δ- δ+ δ- H
H HO C I HO C I-
nucleophile H H
H H H
electrophile
(substrate) transition product leaving
state (methanol) group
• 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]

Example: hydrolysis of iodomethane

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).
 STRENGTH OF THE NUCLEOPHILE

- need strong nucleophile rather than weak

nucleophile.
- example: the methoxide ion (CH3O-) reacts
with electrophiles in the SN2 reaction about 1
million times faster than methanol. Methoxide
ion is a stronger nucleophile while methanol is
a weak nucleophile.
 STERIC EFFECTS ON THE SUBSTRATE
 Steric hindrance:
 repulsive interactions of the electron-cloud between two bulky
groups that are so close together.

 SN2 - Nucleophile approaches from the back side.

 The SN2 reaction depends on steric accessibility to the halide-

bearing carbon.

 Bulky substrates, in which the halide-bearing carbon atom is

difficult to approach, react much more slowly than those in which
the carbon is more accessible.

 Tertiary halides are more hindered than secondary halides, which

are more hindered than primary halides.
ethyl bromide (1°) isopropyl bromide (2°) tert-butyl bromide (3°)
attack is easy attack is possible attack is impossible

SN2 reactivity: CH3 X > 1o > 2o > 3o

 SOLVENTS

 Polar protic solvents, i.e. solvents that have O-H or N-H:

- reduce the strength of the nucleophile.
- Reason: 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 of polar protic solvent is alcohols, water and
carboxylic acids.
 Polar aprotic solvents (no O-H or N-H):
- do not form hydrogen bonds with nucleophile.
- form weaker interactions with substrate.
- may enhance the strength of weak nucleophiles.
- permit faster reaction.
 Examples of polar aprotic solvents:

O
CH3 C N
acetonitrile C
H3C CH3
O acetone
O O
C CH3
H N
CH3 S P
N(CH3)2
H3C CH3 (H3C)2N
dimethylformamide N(CH3)2
(DMF) DMSO HMPA
Dimethyl Sulfoxide Hexamethylphosphoramide
Polar protic solvents Polar aprotic solvents
 The leaving group serve two proposes in the SN2
reaction:
i) it can polarize the C-X bond – making the
carbon atom electrophilic.
ii) it leaves with the pair of electrons that once
bonded it to the electrophilic carbon atom.
 The good leaving groups are:
- Electron-withdrawing, to polarize the carbon
atom.
- Stable (not a strong base) once it has left.
- Polarizable, to stabilize the transition state.
- examples: weak bases such as I-, Br-, Cl-
 Predict the compound in each pair that will
undergo the SN2 reaction faster:

a) Cl or
Cl

b) or
Cl I
 Unimolecular : only one molecule involved in the
transition state of the rate-limiting step.

 SN1 mechanism is a multistep process.

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.
iii) Final step: Loss of proton to solvent to give the final
uncharged product.
Example:
(CH3)3C-Br + H2O (CH3)3C-OH

Step 1: Formation of carbocation (slow) – rate limiting

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

Step 2: Nucleophilic attack on the carbocation (fast)

+
(CH3)3C + H O H (CH3)3C O H
H
Final step: Loss of proton to solvent (fast)

+ +
(CH3)3C O H + H O H (CH3)3C O H + H3O
H
 The reaction is first order and 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.
1.
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)
 2.
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)

 SOLVENTS
 Requires polar protic solvent.
- Reason: it can solvate both ions (carbocation and anion)
strongly through hydrogen bonding or the solvent will
stabilized the carbocation in the transition state and
lowering the activation energy for their formation (reaction
become faster).
- the solvent may be heated to reflux (boiling) to provide
the energy needed for ionization.
 STRENGTH OF THE NUCLEOPHILE
- weak nucleophile promotes the SN1
reaction if the substrate is secondary or
tertiary.

 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.
 SN1 SN2
Rate of reaction First order Second order
Rate = k[alkyl halide] Rate
= k[alkyl halide][Nuc]
Stereochemistry Racemic mixture Inversion at chiral
(mixture of inversion carbon
and retention)
Substrate (alkyl 3º > 2º (1° and CH3X are CH3X > 1º > 2º (3° is
halides) unlikely) not suitable)
Nucleophiles Weak nucleophiles Strong nucleophiles
Solvent Polar protic solvent Polar aprotic solvent
Rearrangements Rearranged products No rearrangements
 Point out the mechanism of the following reactions as SN1 or
SN 2 :
i) CH3CH2I + NaCN → CH3CH2CN + NaI

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

Answers:
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)3Br is tertiary alkyl halide
- CH3OH (methanol) that was used as a solvent is a weak
nucleophile
 ELIMINATION REACTIONS
(DEHYDROHALOGENATION OF ALKYL
HALIDES)
- -
C C + B: C C + X: + HB
H X B- = base

 The alkyl halide loses halogen as a halide ion,

and also loses H+ on the adjacent carbon to a
base.
 A pi bond is formed. Product is alkene.
 Also called dehydrohalogenation (-HX).
 Dehydrohalogenation will yield an alkene that
has the larger number of alkyl groups as the
main product (Saytzeff product).
 The elimination reaction is occurred when the
reaction used strong base for examples,
t-butoxide ion ((CH3)3CO-) or OH- ion and
heated at high temperature.

 Elimination reactions can be divided into two:

i) E1 reaction
ii) E2 reaction
• Unimolecular elimination – rate limiting
transition state involves a single molecular
rather than a collision between two
molecules.

• Also have SN1 products (mixture product).

• E1 reactivity: Benzyl > allyl > 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.
MECHANISM OF E1 REACTION
STEP 1: FORMATION OF THE CARBOCATION (RATE LIMITING)

C C C C X
H X H

STEP 2: A BASE ABSTRACTS A PROTON (FAST)

B C C B-H C C
H
 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

 Halide ion leaves, forming carbocation.

 Base (H2O) removes H+ from adjacent carbon.
 Pi bond forms.
 The rate-limiting state involves a single
molecular than a collision between two
molecules.
 A first order reaction.
 The rate of reaction is proportional to the
concentration of alkyl halide [RX] but not the
concentration of the base.
 Rate equation: k[RX]
• Requires a strong base. Most strong
nucleophiles are also strong bases.

• Halide leaving and proton abstraction

happens simultaneously - no intermediate.

• E2 reactivity: 3o > 2o > 1o

* One step of
mechanism
Example:
Br
CH3 C CH3 - H2O -
OH CH2 C CH3 Br
CH3 CH3

• Example of base are KOH or NaOH.

• Condition: alkyl halides is heated with a concentrated
ethanolic solution or alcoholic solution of NaOH

MECHANISM

H Br CH3
H -
H C C CH3 C C + H2O + Br
H H CH3
H CH3
O
• A second order reaction.

• The base and alkyl halide participating in

the transition state.

• The rate of reaction proportional to the

concentration of both alkyl halide [RX] and
the base.

• Rate equation: k[RX][Base]

 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 such as water Strong base such as OH-,
and CH3OH. CH3O-
Solvent Good ionizing solvent Solvent polarity not
such as water and important
alcohols
Orientation of Saytzeff orientation Saytzeff orientation
elimination
Rearrangements Common Impossible
 Type of alkyl halides
 Type of nucleophiles or bases
 Concentration of nucleophiles
 Solvents
 Temperature
 TYPES OF ALKYL HALIDES
Alkyl halides Reactions
Good Nu- RCH2Nu
SN2
1O RCH2X
Strong B-
* Unlikely undergo SN1 reaction alkene
Possibly E2

Strong Nu-/B- R2CHNu +

SN2 + E2 alkene

2O
R2CHX
Weak B- & good ionizing solvent R2CHNu +
alkene
SN1 + E1

Weak Nu- or weak base

3O R3CNu +
SN1 + E1 alkene
* Cannot undergo SN2
reaction R3CX

Strong B-
alkene
E2
 TYPES OF NUCLEOPHILES OR BASES
• Good nucleophiles, but weak bases such as Br- and
I-, favor substitution.
• Strength of the nucleophile determines order:
i) Strong nucleophiles (or base) – second-order
kinetics: either SN2 or E2.
ii) Weak nucleophiles or weak base such as water
and methanol – first-order kinetics: either SN1 or E1
• Bulky bases such as t-butoxide [-OC(CH3)3] favor
elimination.
• Strong nucleophiles or strong base such as OH- or
-OCH : S 2 or E2
3 N
• Weakly basic species that are good nucleophiles – substitution
- examples: I-, Br-, Cl-, RS-, N3-, RCO2-, CN-

• Strongly basic nucleophiles – eliminations

- examples: OH-, OR-, H2N-, R2N-
 CONCENTRATION OF NUCLEOPHILES

• 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.
 SOLVENTS

• Polar aprotic solvents:

- SN 2
• Polar protic solvents:
- SN1 or E1

TEMPERATURE
High temperature favors elimination.
1) Predict whether each of the following reactions proceed
predominantly by substitution (SN1 or SN2), elimination (E1 or E2),
or whether the two mechanisms compete. Write structural
formulas for the major organic product(s).

a) Cl
NaCN
methanol
SN2
Reasons:
- the alkyl halide is a 1° alkyl halide. 1° alkyl halide usually undergo
SN2 reaction
- NaCN will produced CN- - strong nucleophile but not very basic.

Cl
CN
NaCN
methanol
b) Br
CH3CH2O Na
methanol
E1

Reasons:
- alkyl halide - 2° alkyl halide
-CH3CH2O- = strong nucleophile and weak base
- undergo either SN2 or E1 reactions
- solvent: methanol (polar protic solvent) – not suitable for
SN2 reaction
- the reaction is E1 reaction and the product is alkene, while
the major product is determined by the Saytzeff rule.
Br
CH3CH2O Na
methanol
 C2H5
c) H3C CH3
CH3CH2OH
ethanol
Cl

SN1 and E1
Reasons:
- reaction of 3° alkyl halide with weak nucleophile and weak
base i.e. CH3CH2OH undergo SN1 and E1 reactions.
- ethanol i.e. polar protic solvent is needed in SN1 and E1
reactions
- the products are mixture of substitution product and alkene.

C2H5 C2H5
H3C CH3 H3C CH3 H3C H
CH3CH2OH
ethanol H3C CH3
Cl OCH2CH3
SN1 E1
 C2H5
d) H3C CH3
CH3CH2O-Na+
CH3OH
Cl

E1
Reasons:
- alkyl halide - 3°
- CH3CH2O- = strong nucleophile and weak base
- CH3OH = polar protic solvent: SN1 or E1
- 3° alkyl halide cannot go SN2 reaction
- the mechanism is E1 reaction and the product is alkene.

C2H5 H3C H
H3C CH3
CH3CH2O-Na+
H3C CH3
CH3OH
Cl
E1
e) C2H5
H3C CH3
NaOH

Cl

E2
Reasons:
- alkyl halide - 3°
- OH- = strong base and strong nucleophile (second-order
reaction)
- 3° alkyl halide cannot go SN2 reaction
- the mechanism is E2 reaction and the product is alkene.

C2H5 H3C H
H3C CH3
NaOH
H3C CH3
Cl
E2
 Reactions of Alkyl Halides

Alkyl halides undergo two types of reactions:

substitution and elimination.
 Reaction with NaOH to Form Alcohol or
Alkene

• When an alkyl halide reacts with dilute

aqueous solution of sodium hydroxide, NaOH
under reflux at lower temperature, the main
product formed is an alcohol.

• This is a substitution reaction of haloalkanes.

Example:

CH3CH2Br + NaOH reflux

bromoethane

CH3CH2OH + NaBr
ethanol sodium
bromide

Halogen atom is replaced by a nucleophile, OH-.

• However, if alkyl halide reacts with alcoholic
solution of sodium hydroxide, NaOH or
potassium hydroxide, KOH under reflux, the
main product is an alkene.

• The reaction is an elimination reaction.

Example:

ethanol
CH3CH(Br)CH3 + NaOH
reflux
2-bromopropane
H2C CHCH3 + HBr
1-propene

Sometime is written as “ NaOH in alcoholic

solution”
• There can be more than one elimination
product if a haloalkane with more than three
atoms is used for the reaction.

• According to Zaitsev’s Rule, the major

product is obtained when a proton is
removed from the carbon that is bonded to
the least hydrogen.
Example:

ethanol
CH3CH(Cl)CH2CH3 + NaOH
reflux
2-chlorobutane

CH2 CHCH2CH3 + HCl

1-butene (minor)

CH3CH CHCH3 + HCl

2-butene (major)
 Reaction with Cyanide Ion to Produce Nitriles

• The reaction of haloalkanes with cyanide

(CN-) ions to form nitriles provides a way of
ascending the homologues series; by adding
1 carbon into the carbon chain.

• Once the nitrile is formed, it can be reduced

to an amine or hydrolyzed to carboxylic acid
Step 1: Formation of nitrile

ethanol
CH3Br + KCN CH3CN + KBr
reflux methanenitrile
bromomethane potassium
cyanide
(nucleophile)
Step 2: Hydrolysis of nitriles to carboxylic acid

O
2H 2O/H 2SO4
CH3CN CH3C O- NH4+
reflux
methanenitrile ethanoate ion ammonium ion
 Mechanism of the conversion
O
CH3CN H2O/H2SO4
CH3C NH2
reflux
methanenitrile ethanamide

H2O/H2SO4
(reflux)

O
CH3C O- NH4+
ethanoate ion and ammonium ion
Step 2: Reduction of nitriles to amine

H2/Ni
CH3CN o
CH3CH2NH2
180 C
methanenitrile ethylamine
 Reaction with Ammonia (NH3) to Produce Amines

When a concentrated solution of ammonia in

alcohol is heated with a haloalkane, alkylation
of the ammonia take place and primary amine
is produced.
 The Production of 1o, 2o and 3o Amines

General reaction:

alcohol
R-X + H-NH2 R-NH2 + HX
haloalkanes ammonia (NH3) primary amines

Ammonia reacts as a nucleophile

Example 1:

CH3CH2Br + H-NH2 alcohol

heat
bromoethane

CH3CH2NH2 + HBr
ethylamine
(primary)
Primary amine which produced in example 1
reacts and further substitute the haloalkanes
to form secondary and tertiary amines.
Example 2:

CH3CH2Br + CH3CH2NH-H alcohol

ethylamine
bromoethane (primary)

CH3CH2NH + HBr

CH2CH3
diethylamine
(secondary)
Example 3:

CH3CH2Br + CH3CH2NH alcohol

bromoethane
CH2CH3
diethylamine
(secondary)

CH3CH2N CH2CH3 + HBr

CH2CH3
triethylamine
(tertiary)
Reaction with Sodium Alkoxide to Produce
Ether (Williamson’s Synthesis)

• Ether is produced when a haloalkane reacts

with sodium alkoxide (R-O--Na+).

• This reaction is called Williamson’s synthesis.

86
 Organic reaction, forming an ether from an
organohalide and an alcohol.
 The general reaction mechanism is as follows

 An example is the reaction of sodium

ethoxide with chloroethane to form diethyl
ether and sodium chloride:

 Na+C2H5O− + C2H5Cl → C2H5OC2H5 +Na+Cl−

General reaction:

- + alcohol
R-X + R- O Na
haloalkane sodium
alkoxide

R-O-R' + Na+ X-
ether sodium halide

Alkoxide is a nucleophile
Example:

alcohol
CH3Br + CH3CH2 -O- Na+
bromomethane sodium ethoxide

CH3- O- CH2CH3 + Na+ Br -

ethyl methyl ether sodium bromide

Ethoxide ion is a nucleophile which attack the

carbon of C-halogen bond.
 FORMATION OF ALKANES
(WURTZ REACTION)
 Equation:
2R-X + 2Na → 2NaX + R-R

 Example:
dry ether
2CH3I + 2Na CH3-CH3 + 2NaI
reflux

 Most suitable for preparation of higher alkanes

containing an even number of carbon atoms.
 Solvents
- industrial and household solvents.
- carbon tetrachloride (CCl4) used for dry cleaning,
spot removing.
- methylene chloride (CH2Cl2) is used to dissolve the
caffeine from coffee beans to produce decaffeinated
coffee.

 Reagents
- as starting materials for making complex molecules.
- for example, the conversion of alkyl halides to
organometallic reagents (compounds containing
carbon-metal bonds) is important tool for organic
synthesis.
• Anesthetics
- examples: chloroform (CHCl3) and ethyl
chloride.

• Freons: Refrigerants and foaming agents

- Freons (called chlorofluorocarbons, or CFCs)
is used as a refrigerant gas.

• Pesticides
- example: DDT (Dichloro Diphenyl-
Trichloroethane) is used as insecticides.