LECTURE 15

SECTION 3B

3. ALKYL HALIDES, ALCOHOLS, PHENOLS, ETHERS, AND THEIR REACTIONS

 This section will deal with alkyl halides, alcohols, phenols, ethers and their reactions
(nucleophilic substitution and elimination reactions).
Objectives:
At the end of this topic the learner should be able to:
 Name alkyl halides, alcohols, phenols, and ethers according to the IUPAC system of
nomenclature.
 Describe reactions involved in the preparation of alkyl halides, alcohols, phenols, and ethers.
 Correlate the physical properties of alkyl halides, alcohols, phenols, and ethers with their
structures.
 Discuss the chemical reactions of alkyl halides, alcohols, phenols, and ethers.
 Predict the products of SN1 and SN2 reactions, including stereochemistry.
 Predict the products of E1 and E2 reactions, including stereochemistry and regiochemistry.
 Predict predominance of substitution or elimination reaction.
3.1 Alkyl halides
3.1a Review of definition, classification, and nomenclature
 Alkyl halides also known as haloalkanes or organohalides, are organic molecules containing
a halogen atom X (X = F, Cl, Br, I) (the functional group in this case) bonded to an sp3
hybridized carbon atom.
 They have a general molecular formula CnH2n+1X and are formally derived from an alkane
by replacing a hydrogen atom with a halogen atom.
 Alkyl halides are classified as primary (1o), secondary (2o), or tertiary (3o), depending on the
number of carbons bonded to the carbon bearing the halogen.

Examples:
 Classify each of the following alkyl halides as primary (1o), secondary (2o), or tertiary (3o):

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Exercise:
 Classify each of the following alkyl halides as primary (1o), secondary (2o), or tertiary (3o):

 An alkyl halide is named as an alkane with a halogen substituent-that is, as a halo alkane. To
name a halogen substituent, change the suffix -ine of the name of the halogen to the suffix-o
(fluorine → fluoro, chlorine → chloro, bromine → bromo, iodine → iodo).
Steps:
1. Apply all other rules of nomenclature.

Examples:

Exercise:
a) Give the IUPAC name for each of the following structures:

b) Give the structure corresponding to each of the following IUPAC names:

i. 3-chloro-2-methylhexane
ii. 1-3-dibromocyclopentane
iii. 1,1-3-trichlorocyclohexane

Uses
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  Organic halides are valuable as laboratory and industrial solvents eg dichloromethane and
trichloromethane (chloroform), refrigerants eg dichlorodifluoromethane (Freon-12), inhaled
anesthetics in medicine, pesticide and fumigants.

The character of Carbon-halogen bond

 Because halogens are more electronegative than carbons, the carbon-halogen bond is
polarized. As shown below, carbon atom has a partial positive charge, while the halogen
atom has a partial negative charge.

Boiling points of alkyl halides

 Alkyl halides have higher b.p than alkanes containing the same number of carbons. Two
types of forces: London dispersion and dipole-dipole interaction forces contribute to this
physical property. The boiling point also increases as a result of increasing the size of the
halogen, as well as increasing the size of the carbon chain.

Solubility

 Alkyl halides have little to no solubility in water in spite of the polar carbon-halogen bond.
This is because the attraction between the alkyl halide molecules is stronger than the
attraction between the alkyl halide and water.
 Alkyl halides are soluble in most organic solvents. The London Dispersion forces play a
dominant role in solubility

Chemical reactivity
 To react with the haloalkanes, the C-X bond has to be broken. Since that gets easier as we
move from fluoride to chloride to bromide to iodide, the compounds get more reactive in
that order.

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3.1b Preparation and importance of alkyl halides
a) From alcohols
 Most alkyl halides are formed (synthesised) in the laboratory from alcohols. The reaction is
carried out either by passing the dry H-X gas into the alcohol or heating the alcohol with
concentrated aqueous acid.

 However, the above method (using H-X) favours only the tertiary alcohols. Primary and
secondary alcohols are best converted into alkyl halides by treating them with phosphorus
tribromide (PBr3) or thionyl chloride (SOCl2).

b) Free radical halogenation of hydrocarbons

 Usually this method gives mixtures of mono-, di-, tri- etc halogenated compounds, thus, is
considered an inefficient method for the synthesis of a desired compound.
c) Addition of hydrogen halides to alkenes

d) Addition of halogens to alkenes and alkynes

e) Halide exchange

Uses
 Simple alkyl halides, especially chlorides and bromides, are versatile reagents in syntheses.

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 3.1.1 Reactions of alkyl halides
 Alkyl halides are chemically versatile. To react with the haloalkanes, the C-X bond has to be
broken.
 The halogen atom may leave with its bonding pair of electrons to give a halide ion which is
stable – a halide is called a good leaving group.
 If an atom replaces the halide the overall reaction is a substitution.
 If the halide loss is accompanied by the loss of another atom, the overall reaction is called an
elimination. Very often the other atom lost is a hydrogen (as H+).
 The elimination of H-X is common, and is called a dehydrohalogenation. Often substitution
and elimination reactions will occur in competition with each other.
3.1.1a Nucleophilic substitution reactions
 In a substitution reaction, the nucleophile Nu:¯ displaces the leaving group (producing X¯)
from the carbon atom by using its lone pair to form a new bond to the carbon atom.

 Based on the broad theory built by Edward Hughes and Christopher Ingold in 1935,
nucleophilic aliphatic substitution can proceed by two different mechanisms named SN1 and
SN2.
3.1.1b Elimination reactions
 In an elimination reaction, a new  bond is formed by the elimination of halide ion and
another atom (usually H+).
 In a dehydrohalogenation, the base B:¯ deprotonates the alkyl halide. Most nucleophiles can
also act as bases, therefore the preference for elimination or substitution depends on the
reaction
conditions and
the alkyl halide
used.

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