Chapter 6

Alkyl halides
 Content
• Application

• Nomenclature

• Properties

• Preparation

• Reactions
 Introduction
- Organohalogen compounds: halogen as
functional group

Alkyl halides
Vinyl halides Alyl halides

Aryl halides Benzyl halides

 Application

Chloroform Freon, CCl2F2 DDT

(solvent) (refrigerant, propellant) (pesticides)

Teflon – insulator

Trichloroethylene – dry cleaning

Polyvinyl chloride (PVC) – Raincoat, toys, plastics

 Nomenclature

1° 2° 3°

vicinil geminil
 Nomenclature

Common : ethyl fluoride

IUPAC : fluoroethane
Common : isopropyl chloride
IUPAC : 2-chloropropane

Common : sec-butyl bromide

IUPAC : 2-bromobutane

Common : cyclohexyl iodide

IUPAC : 1-iodocyclohexane
 Properties
1. Boiling points
- molecular mass, alkyl branch

2. Solubility
- Immicible in water

3. Density
- denser than H2O (except R—Cl)
 Preparation

1. Alkane
 Preparation

2. Alkene
 Preparation

3. Alkyne
 Preparation

4. Alcohol

SOCl2
+ SO2 + HCl

PX3
+ P(OH)3 + X2

PX5
+ POX3 + HX

HX
+ H2O
 Reactions

1. Reduction

2. Grignard reagent

3. Substitution

4. Elimination
1. Reduction
2. Grignard reagents
Substitution and Elimination
3. Substitution
 3.1 Neuclophilic Substitution
Bimolecular (SN2)

- rate = k [R—X] [Nu¯]

- products: Walden inversion
- stearic effects
- Requires STRONG neuclophiles
- reactivity towards alkyl halides; 1° > 2° > 3°
 3.2 Neuclophilic Substitution
Unimolecular (SN1)
slow
Step 1:

fast
Step 2:

- rate = k [R—X]
- formation of carbocation
- products: inversion + retention 🡪 rasemic mixtures
- Requires WEAK neuclophiles
- reactivity towards alkyl halides; benzyl > alyl > 3° > 2° > 1°
 Comparison SN2 & SN1

SN2 SN1
Kinetics 2nd rate order 1st rate order
(molecularity) (bimolecular) (unimolecular)
Stereochemistry
inversion rasemic mixtures
(Products)
benzyl > alyl > 3° >
R─X reactivity 1° > 2° > 3°
2° > 1°
Neuclophiles Strong Weak
 SN2- Steric factor
• A different structure of alkylhalide will give a different rate of reaction
toward SN
SN2
• In SN2, Nu must attack R-X from opposite site to the LG. Primary RX is
least crowded with CH3 group make it easier for Nu to approach C
compare to tertiary RX which is most crowded – steric factor
• In SN2: relative rates: methyl > 1° > 2° > 3°
 SN1-racemic mixture
the nucleophile attacks with equal
probability from either face of the planar
carbocation intermediate
 Leaving Group (LG)
the best leaving groups measured by the ability of a LG as a
stable anion after leaving the group or classified as weak
bases after they depart.
C-I is a weakest bond , so, Iodide is the best LG in the
series of halogens.
OH-, RO-, and NH2- are such poor LG that they are rarely if
ever displaced in nucleophilic substitution reactions
 4. Elimination

STRONG base: KOH, NaOH, RbOH, LiOH,

t-butoxide
WEAK base: NH3, CH3NH2, Ph–NH2
 4.1 Elimination Bimolecular
(E2)

- rate = k [R—X] [B¯]

- Requires STRONG base
- reactivity towards alkyl halides; 3° > 2° > 1°
 4.2 Elimination Unimolecular
(E1)

Step 1:

Step 2:

- rate = k [R—X]
- Requires WEAK base
- reactivity towards alkyl halides; benzyl > alyl > 3° > 2° > 1°
 Comparison E2 & E1

E2 E1
2nd rate order 1st rate order
Kinetics
(bimolecular) (unimolecular)
benzyl > alyl > 3° >
R─X reactivity 3° > 2° > 1°
2° > 1°
Base Strong Weak
Substitution and Elimination
 Factors affecting SN & E reactions

1. Alkyl halides
2. Type of neuclophiles
3. Concentration / molarity of neuclophiles
4. Solvents
5. Temperatures
 1. Alkyl Halides

1° 2° 3°

SN2 ( strong Nu¯) SN2 (strong Nu¯) E2 (strong base)

E2 (strong base) E2 (strong base) SN1 (weak Nu¯)

SN1 + E1 (weak Nu¯ E1 (weak base)

in polar protic
solvent)
Methyl- X (CH3-X)
- Will undergo SN2 ( strong Nu¯)
2. Type of neuclophile / base

Strong Nu¯ = SN2

Strong base = E2

Weak Nu¯ / base = SN1 + E1

3. Neuclophiles Concentration

SN2 = concentration , rate

E2 = concentration , rate

SN1 + E1 = concentration , rate

 4. Solvents

Protic (contains —OH):

H2O, alcohol, carboxylic acid SN1
S N1 + E1
(helps solvent carbocations)

Aprotic (no —OH):

DMF, DMSO SN2
•
The Solvent
Protic solvent: a solvent that contains an -OH group

• Aprotic solvent:does not contain an -OH group

 5. Temperature

Temperature = SN2, E2, SN1, E1

 Summary of S vs E for Haloalkanes

for methyl and 1°haloalkanes

Summary of S vs E for Haloalkanes
for 2° and 3° haloalkanes
 Visual tests (1)
- Reagent : AgNO3
- Purpose :
distinguish alkyl chloride, bromide, iodide (time & colour)

3°, 2° , 1°
reacts faster = white ppt.
= pale yellow ppt.
= pale yellow ppt.

- NOT applicable on aryl / vinyl halides

 Visual tests (2)
- Reagent : NaI
- Purpose :
distinguish 1°, 2° & 3° alkyl bromide (time)

1° 2° 3°
Increasing reactivity time of ppt
(slow / medium / fast)

- NOT applicable on aryl / vinyl halides

Try yourself…