ORGANIC CHEMISTRY

CHM 207

Chapter 5
Alkyl Halides
Upon completion of this topic, students should be able to:

1. Interpret the properties of alkyl halides compounds as

well as it’s IUPAC name, chemical structure, reaction &
mechanism (LO1, C3).

2. Explain the properties of alkyl halides compounds as well

as it’s IUPAC name, chemical structure, physical
properties, reaction and mechanism of alkyl halides (SN1
& SN2, E1 & E2) (LO2, C6).

3. Write comprehensive information on the uses of

aromatic compounds in commercial industrial
applications (LO3, A4).
 5.1)
Nomenclature Content
5.2) Classification
and physical
properties Alkyl 5.4) Uses
halides

1) Formation of alkanes (Wurtz reaction)

2) Nucleophilic substitution reaction:
5.3) Reaction - Formation of alcohol,
of alkyl halides - Formation of ether (Williamson synthesis)
- Amine synthesis
- Nitrile synthesis compounds
- Mechanism of nucleophilic substitution reactions.
- Types of nucleophilic substitution reaction:
SN1 and SN2 reaction.
3) Elimination reaction (dehydrohalogenation of
alkyl halides).
- E1 and E2 reactions.
 5.1) IUPAC Name of ALKYL HALIDES

➢ Also known as haloalkane.

➢ General formula: CnH2n+1X where n = 1,2,… and X (halogen).

➢ Contain halogen atom as functional group:

 halogen, -X (X = F, Cl, Br, I).

➢ Naming alkyl halides:

 - same as nomenclature of alkanes

CH3 CH3 CH3

5 4 3 1 6 5 4 3 2 1
2 CH3 CH2 C CH2 CH CH3
CH3 CH2 CH CH CH3
CH3 I
CI Br
iodomethane 3-chloro-2-methylpentane 4-bromo-2,4-dimethylhexane
 5.2) Classification & Physical Properties
of alkyl halides
o
a) Primary (1 )
no. of alkyl groups: none or one

H H
H C X H C X
H R
o
b) Secondary (2 )
no. of alkyl groups: 2

H
R' C X
R
o
c) tertiary (3 )
 R' C X
5.2) Classification & Physical Properties
of alkyl halides
R
o
c) Tertiary (3 )
no. of alkyl groups: 3

R''
R' C X
R
 5.2) Classification & Physical Properties
of alkyl halides
 A) 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
o
bp 78 C bp 67 oC o
bp 52 C

- alkyl halides with more carbon atoms have higher

boiling points.

CH3Cl CH3CH2Cl CH3CH2CH2Cl

bp -24oC o
bp 12 C
o
bp 47 C
• b) DENSITIES

- alkyl fluoride and alkyl chlorides (with one Cl atom) are less dense
than water.

- alkyl chloride with two or more chlorine atoms are denser than
water.

- all alkyl bromides and alkyl iodides are denser than water.
5.3) REACTIONS OF ALKYL
HALIDES
 Formation of alkanes (Wurtz reaction)
 Equation:
2R-X + 2Na → R-R + 2NaX

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

 Most suitable for preparation of higher alkanes

containing an even number of carbon atoms.
 ➢ Alkanes containing an odd number of carbon atoms
can be prepared by using a mixture of two different
alkyl halides.

➢ This reaction produces only low yields due to the

formation of other alkanes as by-products.

dry ether
CH3I + 2Na + CH3CH2I CH3CH2CH3 + 2NaI + CH3CH2-CH2CH3 + CH3CH3

by-products
 5.3) Reactions of alkyl halides
 Two types of reactions:
i) substitution reactions
ii) elimination reactions

a) nucleophilic substitution

- -
C C Nuc X
C C
H X
H Nuc

b) elimination

- -
B C C B-H X
C C
H X
i) NUCLEOPHILIC SUBSTITUTION REACTIONS

In nucleophilic substitution, nucleophile (Nu:-) replaces X,

using its lone pair of electrons to form new bond to
carbon atom.

Halogen is good leaving group (EWG).

The reaction must be reflux in ethanol.

1) Formation of alcohol

R-X OH R-OH X
nucleophile
example
CH3CH2 Br NaOH CH3CH2 OH NaBr
ethyl bromide ethyl alcohol

2) Williamson ether synthesis

R-X R'O R-O-R' X

nucleophile

example
CH3 I CH3CH2 O Na+ CH3 O CH2CH3 Na+ I-
methyl iodide sodium ethoxide ethyl methyl ether

CH3CH2 OH Na CH3CH2 O Na+

sodium ethoxide
3) Amine synthesis

R-X NH3 R-NH2 HX

nucleophile

example
CH3CH2 Br H-NH2 CH3CH2 NH2 HBr
ethyl bromide ethylamine (primary amine)

HBr(g) + NH3 (g) NH4Br (s)

amine are also act as nucleophile (more reactive than ammonia)
C2H5Br H N C2H5 (C2H5)2NH + HBr
H diethylamine
(secondary amine)

C2H5Br (C2H5)2NH (C2H5)3N + HBr

triethylamine
(tertiary amine)

+ -
C2H5Br (C2H5)3N (C2H5)4N Br
tetraethylammonium bromide
(quaternary salt)
4) Nitrile synthesis

R-X CN R-CN X
cyanide nitrile
(nucleophile)

H2O/H+
R-COOH (hydrolysis)
R-CN H2/Ni
R-CH2NH2 (reduction)
180oC

example
(CH3)2CHCH2CH2-Cl NaCN (CH3)2CHCH2CH2-CN NaCl
1-chloro-3-methylbutane 4-methylpentanenitrile

H2O/H+
(CH3)2CHCH2CH2-COOH
(CH3)2CHCH2CH2-CN H2/Ni
180oC
(CH3)2CHCH2CH2-CH2NH2
Mechanism of nucleophilic substitution reactions

-
H Nu H
δ+ δ-
R C X R C Nu X-
H H

EXAMPLE

-
H OH H
δ+ δ-
CH3 C Br CH3 C OH Br-
H H
formation of alcohol
 Type of nucleophilic substitution reactions:
SN1 and SN2 reactions

 S = substitution
 N = nucleophilic
 1 = a first order (unimolecular) reaction
 2 = a second order (bimolecular) reaction
 SN1 (Substitution, Nucleophilic, unimolecular) reactions

➢ Unimolecular : rate determining step involves only one reactant.

rate = k [RX]

➢ Two steps are involve in the mechanism.

➢ Example: the reaction between aqueous NaOH and tertiary alkyl

halides will produce alcohol.
➢ The reaction is first order and the rate depends only on the
concentration of the tertiary alkyl halides.
 Rate = k[(CH3)3CBr]

➢ The concentration of OH- does not have any effect on the rate of
reaction.

➢ OH- does not involved in the rate-limiting step.

 Carbocation rearrangement in SN1 reactions
➢ Rearrangement of the carbon skeleton will take place if a more
stable carbocation can be formed in the process.
➢ For example, hydrolysis of the secondary alkyl bromide, 2-bromo-3-
methylbutane, yields the tertiary alcohol, 2-methyl-2-butanol.

CH3 H CH3 H
SN1
CH3 C C CH3 -
CH3 C C CH3 Br
H2O
H Br H slow step
o
2-bromo-3-methylbutane (2 carbocation)

shift of H

CH3 H CH3 H
H-OH
CH3 C C CH3 fast
CH3 C C CH3

H OH H
o 2-methyl-2-butanol
(3 carbocation)
Reactivity towards SN1 substitution mechanisms
follows the stability of carbocations:

SN1 reactivity: CH3X < 1o < 2o < 3o

More
reactive
 SN2 (Substitution, Nucleophilic, bimolecular)
reactions

➢ Bimolecular: rate determining step involves 2 reactants.

 rate: k [RX] [Nu-]
➢ The processes of bond breaking and bond forming occur
simultaneously (one bond is forming, one bond is breaking).
➢ The mechanism involves only one step.
➢ For example, hydrolysis of iodomethane (primary alkyl halides)

H H
slow
HO C I fast H
-
H HO C I HO C I
H H
H H H
iodomethane transition state methanol
 or
HO CH3 I HO CH3 I HOCH3 -
I
rate-limiting
iodomethane transition state methanol step

➢ A second order reaction

➢ Rate equation = k[CH3I][OH-]
➢ Both iodomethane and the OH- are involved in the rate-limiting step.
➢ SN2 reactivity: 3o < 2o < 1o < CH3

➢ Factor that determines the order of reactivity in SN2 reactions is the steric
effect.
➢ A steric effect is one in which the rate of chemical reaction depends on the
size or spatial arrangement of the groups attached to, or near to, the
reaction site of the molecule.
3o < 2o < 1o < CH3 X
Less reactive More reactive
(More R, (Less R,
More steric effect) Less steric effect)
 Relative reactivities of primary, secondary, and
tertiary alkyl halides

➢ The reactivity of alkyl halides towards nucleophilic

substitution depend on the halogen.

➢ The rate of reaction decrease in the order

 R-I > R-Br > R-Cl > R-F
(most reactive) (least reactive)

➢ Reason: C-X bond become stronger from I to F

 Comparison SN1 and SN2 reactions

SN1 SN2

Rate of reaction First order Second order

Stereochemistry Racemic mixture Complete inversion

(mixture of inversion
and retention)
Reactivity 3o > 2 o > 1 o CH3X > 1o > 2o > 3o

Nucleophiles Weak nucleophiles Strong nucleophiles

(H-O-H) (OH-)
 QUICK CHECK….

a)

b)

c)
QUICK CHECK (ANSWER)
QUICK CHECK (ANSWER)
ii) Elimination reactions-dehydrohalogenation of alkyl
halides

 Elimination: loss of two atoms or groups from the

substrate to form a pi bonds.
• Dehydrohalogenation (removal of hydrogen and a
halogen atom) of alkyl halide to form alkene.

C C C C HX
H X
alkyl halide alkene
HX = HCl or HBr or Hl
➢ 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/reflux.

➢ Dehydrohalogenation will yield an alkene that has the larger

number of alkyl groups as the main product (Saytzeff’s rule).

➢ Elimination reactions can be divided into two:

i) E1 reaction : has a close analog to SN1
ii) E2 reaction : has a close analog to SN2
 E1(Elimination, unimolecular) reaction

➢ The rate-limiting state involves a single molecular

than a collision between two molecules.
➢ A first order reaction.

➢ Rate equation: k[RX]

➢ E1 reactivity: Benzyl > allyl > 3o > 2o > 1o

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
 E2(Elimination, bimolecular) reaction

➢ A second order reaction.

➢ Rate equation: k[RX][Base]

➢ E2 reactivity: 3o > 2o > 1o

➢ Mechanism:
B
H
C C -
C C B-H X
X
 Comparison E1 and E2 reactions

E1 E2

Rate of reaction First order Second order

Reactivity 3o > 2 o > 1 o 3o > 2 o > 1 o

Base Do not need strong Strong base

base, (NaOH, H-O-H)) (KOH, t-KOC(CH3)3
@ t-butoxide ion)
Alkyl halides Reactions

Nu-
1O RCH2X RCH2Nu
SN2

Nu- strong
R2CHNu +
SN2 + E2 alkene
2O
R2CHX
B- (strong)
alkene
E2

Nu- (weak)
3O R3CNu +
SN1 + E1 alkene
R3CX
B- (strong)
alkene
E2
 SOME COMMON NUCLEOPHILES

strong nucleophiles moderate nucleophiles weak nucleophiles

(CH3CH2)3P Br F
S-H NH3
H-O-H
I CH3-S-CH3
CH3 O H
(CH3CH2)2NH Cl
O
C N
CH3C O
(CH3CH2)2N
H-O
CH3-O
 QUICK CHECK….

1 ) What elimination products would you expect when the following

reactants was reacted with KOH/ethanol in reflux.

a) 2-bromobutane
b) 1-chloro-1-methyl cyclohexane

2) Write the complete E1 and E2 mechanism for the reaction of (a)

with hydroxide ion, in order to produce major product.
QUICK CHECK (ANSWER)
QUICK CHECK (ANSWER)
 5.4) USES OF ALKYL HALIDES

• 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.
OVERVIEW OF ALKYL HALIDE
 TUTORIAL 5

a)

b)
c)

c)
3.
Question 4
Predict the products of E1 elimination of the following compounds. Label the
major products.
Question 5
Question 6

a)

b)
Question 7

i) Give elimination product from the following reactant.

ii) What alkyl halide might the following alkenes have been made from?
Spot Quiz – Alkyl Halide

Show the complete E1 mechanism for the following reaction with hydroxide ion.