S5 CHEMISTRY 29/NOV/2021

Alkyl halides

Aerosol cans used to Fire extinguishers contain

Aerosol being dispensed
contain alkyl halides as alkyl halides
propellants
Did you know that alkyl halides have been and are still around us?

Introduction
 Alky halides
(i) are also called haloalkanes or halogenoalkanes.
(ii) are derivatives of alkanes that possess at least one halogen atom in their
molecules.
(iii) have carbon-halogen bond as the functional group.
 Monoderivatives
(i) have the general formula 𝐶𝑛 𝐻2𝑛+1 𝑋, where X = F, Cl, Br, I; and n= 1, 2, 3,…
They are sometimes simply represented by the general formula R−X where R
represents an alkyl group.
(ii) can be classified as:
(a) primary; 𝑅 − 𝐶𝐻2 𝑋 e.g. CH3Cl, CH3CH2Br and CH3CH2CH2I

(b) secondary;

(c) tertiary;
R, RI and RII may be identical or not.

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 Polyhalides are alkyl halides which contain more than one halogen atom.
For example;
(a) Dihalides contain two halogen atoms and maybe vicinal dihalides; where the two
halogen atoms are attached to adjacent carbon atoms in a molecule or geminal
dihalides; where the two halogen atoms are attached to the same carbon atom in a
molecule.

Vicinal dihalide Geminal dihalide

(b) Tetrahalides contain four halogen atoms per molecule.

For example, 𝐶𝐶𝑙4 , 𝐶𝐹2 𝐶𝑙2, 𝐶𝐻2 𝐹𝐶𝐹3 , 𝐶𝑙2 𝐶 = 𝐶𝐶𝑙2 e.t.c.

Nomenclature of haloalkanes
 Halooalkanes are named as halo−substituted alkanes.
 Where necessary, the longest chain is chosen and numbered in such a way that the
halogen atom gets the lowest number as possible.
 The position(s) of the halogen atom(s) and substituent(s) are indicated as before.
Examples are:
CH3Br; bromomethane CH3CH2Cl; chloroethane CH3CHBr2; 1,1−dibromoethane

(CH3)3CCl; 2−chloro−2 −methylpropane

Activity 1:
1. Name the following;

2. Write the structural formulae of the following compounds.

(a) Trichloromethane (h) 2-iodo-2-methylpropane
(b) 1,2-dichloroethane (i) 1-bromo-2,2-dimethylbutane
(c) 1-bromobutane (j) 1-chloro-2-methylpropane

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 (d) Chloroethene (k) 2-fluoro-2-methylpropane
(e) 3–chloro–3–methylheptane (l) 2–bromo–4,4–dimethyloctane
(f) 1–bromopent–2–yne (m) 4–chloropent–2-ene
(g) 1-iodobutane (n) 2–bromo–2–methylpentane

Isomerism in haloalkanes
 Higher haloalkanes exhibit chain isomerism and position isomerism.
Activity 2:
1. Draw the non–cyclic isomers of a compound whose molecular formula is C4H9Cl. In
each case give the IUPAC name and state the class of the alkyl halide.
2. An organic compound Z on analysis was found to contain 30.30% carbon, 5.56%
hydrogen and the rest being iodine. The molecular mass of Z was found to be
197.9.
(a) Determine the molecular formula of Z.
(b) Write the names and the structures of all possible isomers of Z.
3. Draw the possible isomers of C3H6Br2 and in each case give the IUPAC name of
the isomer.
4. Draw the possible isomers of C3H7I and in each case give the IUPAC name of the
isomers.
5. A bromolkane Q with general formula, CnH2n+1Br was found to contain 58.39% by
mass bromine.
(a) Determine the molecular formula of Q.
(b) The bromoalkane burns with non-sooty flame. Write the names and structural
formula of all the possible isomers of Q.
6. An organic compound T on analysis was found to contain 35.04% carbon, 6.56%
hydrogen and the rest being bromine. The vapour density of T was found to be
68.
(a) Calculate the empirical of T.
(b) Determine the molecular formula of T.
(c) Write the names and the structural formulae of all possible isomers of T.

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Physical properties of haloalkanes
 The carbon-halogen bond in haloalkanes is polar; since the halogen atom is more
electronegative than the carbon atom.

Thus, molecules of alkyl halides are polar. This makes the individual molecules to
associate via dipole-dipole attractions.
 Alkane molecules are non-polar and the individual molecules associate via van der Waals
forces of attraction.
 Because dipole-dipole interactions in haloalkanes are stronger than the van der Waals
forces of attraction in alkanes, haloalkanes are less volatile than alkanes of
comparable/similar relative molecular mass.
 For haloalkanes with corresponding alkyl groups, the boiling points increase with
increase in molecular mass. Branching in the molecules affects their boiling points as
already in alkanes.
For example;
Haloalkane Chloromethane Bromomethane Iodomethane
Boiling point −24 5 43

Reason
The increase in molecular mass increases the strength of the intermolecular forces
(van der Waals forces). Hence, a lot of energy must be supplied to separate the
molecules for boiling to occur.
 Alkyl halides are insoluble in water. This is because they cannot form hydrogen bonds
with water molecules. However, they soluble in organic solvents.
Activity 3:
Copy and complete the table below that gives the boiling points of some haloalkanes.
Compound Molecular formula Boiling point (oC) Molecular mass
Chloromethane −24
Bromomethane 5
Iodomethane 43
Chloroethane 12.5
Bromoethane 38
Iodoethane 72
1−chloropropane 47
1−bromopropane 71
1−iodopropane 102

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 (a) Carefully look at the table above and the deduce trend in the boiling points of
alky halides? Predict reason(s) for your observed trend.
(b) Why do you think the boiling points of alky halides are generally higher those of
the corresponding hydrocarbons of comparable molecular masses?
(c) 1–chlorobutane boils at 78oC while 2–chloro–2–methylpropane boils at 51oC; yet
the two compounds have the same molecular mass. Give reason(s) to support this
statement.

Methods of preparing haloalkanes

Haloalkanes can be obtained in several ways.
A. From direct halogenation of alkanes
Refer to the reactions of alkanes for details.
This method is not employed to make fluoroalkanes since the reaction is highly
exothermic and, both fluorine and hydrogen fluoride are difficult to handle.
B. From alkenes

Refer to the reactions of alkenes for details.

C. From alkynes

Refer to the reactions of alkynes for details.

D. Chlorination of carbonyl compounds
The reaction involves replacement of the oxygen atom by two chlorine atoms.

For example
𝑃𝐶𝑙5 𝑃𝐶𝑙5
𝐶𝐻3 𝐶𝐻𝑂 → 𝐶𝐻3 𝐶𝐻𝐶𝑙2 + 𝑃𝑂𝐶𝑙3 ; (𝐶𝐻3 )2 𝐶 = 𝑂 → (𝐶𝐻3 )2 𝐶𝐶𝑙2 + 𝑃𝑂𝐶𝑙3

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 Activity 4:
(a) Write equation(s) to show how
(i) propene can be converted in 2,2-dichloropropane.
(ii) 2-chloropropane can be obtained from propane.
(iii) 1-chloropropane can be converted into propyne.
(iv) 2-methylpropanioc acid can be prepared from 2-chloropropane.
(v) ethanol can be converted into ethyne.
(b) Outline the mechanism for reaction leading to the formation of 2-chloropropane
in (a)(ii) above.

E. From alcohols
This involves replacement of the hydroxyl group (−OH) in alcohols by a halogen atom
(−X); X=Cl, Br or I.
The process can be effected as follows;

Comments about the reaction above reaction scheme

 The evolution of hydrogen chloride gas in route 1 and route 2 is used in organic
chemistry to identify the presence of hydroxyl group (−𝑂𝐻) in a compound.
Observations: Misty fumes are evolved. (This is due to hydrogen chloride gas
evolved).
Pyridine in route 2 serves to absorb hydrogen chloride as it is formed.
The use of route 2 is better than route 1 because all the minor products are
gaseous. Thus, much purer products are obtained.
 The use of 𝑋2 /red P and reflux in route 3 is preferred for X= Br or I; because 𝑃𝐵𝑟5
is not readily available and 𝑃𝐼5 does not exist.
A mixture of 𝑋2 /red P first gives 𝑃𝑋3 (X=Br or I), which then, reacts with the
alcohol to give the haloalkane..

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  In route 4, KX or NaX first reacts with hot concentrated sulphuric acid to
generate HX(g) needed for the reaction according to the following reaction.
ℎ𝑒𝑎𝑡
2NaX(s) + H2SO4(l) → Na2SO4(s) + 2HX(g); X= Cl, Br or I
The gaseous HBr and HI formed are powerful reducing agents. Thus, they are
readily oxidised by the unreacted hot acid to evolve the corresponding molecular
halogens.
Thus;
NaBr/KBr + conc H2SO4(l) ⟶ gives mainly Br2 not HBr
NaI or KI + conc H2SO4(l) ⟶ gives mainly I2 not HI
To avoid to formation of the molecular halogens, sometimes, non-oxidizing
concentrated phosphoric acid is employed in place of concentrated sulphuric acid.
3KI + H3PO4 → 3HI + K3PO4
 In route 5, a mixture of anhydrous zinc chloride and concentrated hydrochloric
acid is called Lucas reagent.
The reaction of Lucas reagent with alcohols depends on the class of the alcohol.
Thus, Lucas reagent is used to distinguish between the classes of alcohols as
follows:
 Primary alcohols give no observable change at room temperature.
 Secondary alcohols give a cloudy solution within 5-10 minutes.
 Tertiary alcohols give a cloudy solution immediately.

Note:
Classes of alcohols can be identified in a similar way like the classes of
haloalkanes.

Activity 5:
1. Ethanol can be converted into chloroethane when treated with sodium
chloride in the presence of hot concentrated sulphuric acid whereas
treatment of ethanol with sodium iodide under similar conditions gives no
iodoethane. Explain this observation.
2. Write equations to show how propene can be converted to 2,2-
dichloropropane.
3. Name one reagent that can be used to distinguish between the following pairs
of compounds. In each case, state what would be observed if each member of
the pair is separately treated with the reagent you have named.

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 4. State the application of the following reagents in organic chemistry analysis.
(a) Anhydrous zinc chloride in the presence of concentrated hydrochloric
acid.
(b) Bromine water.
(c) A solution of silver(I) nitrate in excess ammonia solution.
(d) Phosphorus(V) chloride
5. The following reagents are used to distinguish between classes of organic
compounds. In each case, name the class(es) of organic compounds and state
what would be observed if a member of the class is separately treated with
the reagent.
(a) Bromine in carbon tetrachloride
(b) Ammoniacal copper(I) chloride solution
(c) Anhydrous zinc chloride in the presence of concentrated hydrochloric
acid.

Chemical Properties of haloalkanes

 Because the carbon−halogen bond is polar, alkyl halides are fairly reactive compounds.
The partial positive charge on the carbon atom, makes its susceptible to attack by
nucleophiles (electron deficient species).
 Thus, haloalkanes majorly undergo nucleophile substitution reactions; the nucleophile
attacks the electron deficient carbon atom.

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 The type of substitution mechanism depends on the class of the alkyl halide (i.e. the
structure of the molecule).
(a) Primary alkyl halides undergo substitution nucleophilic bimolecular (SN2) mechanism
in substitution reactions.
SN2 refers to a reaction in which two molecules are involved in the transition state
of the rate–determining step (activated complex formation).

The transition state shows partial C−nucleophile bond formation and partial
C−halogen bond cleavage
Why SN2 mechanism in primary alkyl halides?
 The electron deficient carbon atom is less sterically hindered. This allows the
existence of five bonds on the same carbon atom in the intermediate.
 They form very unstable carbocations as intermediates.

Or simply as follows:

Experiments show that this reaction follows second order kinetics. That is the rate
of reaction is dependent upon the concentration of both the haloalkane and the
nucleophile.
The rate law/rate equation can be written as:
𝑅𝑎𝑡𝑒 = 𝑘 [𝑅𝐶𝐻2 − 𝑋][𝑁𝑢− ]; where 𝑘 is called the velocity constant or rate constant
and [ ] denotes concentration in moles per dm3.

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 The energy profile diagram for the reaction taking place is as below:

The question that now arises is why the shape of the graph above?
To help answer the question on the shape of the above graph, you should recall that
breaking a bond requires energy while forming a bond releases energy.
Explanation
The potential energy of the system initially rises along AB because more energy is
used to break the carbon−halogen bond than what is released during
carbon−nucleophile bond formation. At B, a maximum potential is reached when
carbon−halogen bond is partially broken and carbon−nucleophile bond is partially
formed. This state is called the transition state or activated complex. The energy
barrier, 𝐸𝑎 , which must be overcome in order that the transition state is reached,
is called the activation energy of the reaction. The potential energy of the system
then falls along BC owing to energy released due to completion of formation of the
carbon−nucleophile bond.
(b) Tertiary alkyl halides undergo substitution nucleophilic unimolecular (SN1)
mechanism in substitution reactions.
SN1 refers to a reaction in which one molecule is involved in the rate determining
step (activated complex formation).

Why SN1 mechanism in tertiary alkyl halides?

 The electron deficient carbon atom is sterically hindered. Thus, the halogen
atom must leave before the nucleophile attacks.
 They form very relatively very carbocations as intermediates.

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 Experiments show that this reaction follows a first order kinetics. That’s is the
rate of the reaction is dependent upon the concentration of only the haloalkane.
The rate law can be expressed as: 𝑅𝑎𝑡𝑒 = 𝑘[ℎ𝑎𝑙𝑜𝑎𝑙𝑘𝑎𝑛𝑒]

Research work
Draw a potential energy against reaction co–ordinate for substitution reactions in
tertiary alkyl halides.

(c) Secondary alkyl halides are intermediate in behaviour between primary and
tertiary; with SN2 mechanism predominating.

 The order of reactivity for the same alkyl group towards nucleophiles is such that
𝑖𝑜𝑑𝑜𝑎𝑙𝑘𝑎𝑛𝑒𝑠 > 𝑏𝑟𝑜𝑚𝑜𝑎𝑙𝑘𝑎𝑛𝑒𝑠 > 𝑐ℎ𝑙𝑜𝑟𝑜𝑎𝑙𝑘𝑎𝑛𝑒𝑠.
For example, iodomethane reacts faster than bromomethane which in turn reacts
faster chloromethane.
Reason
The order of reactivity depends on the carbon−halogen bond strength which in turns
depends on both the atomic radius and the electronegativity of the halogen atoms.
Atomic radius of the halogen atom increases from chlorine atom to iodine atom. The
carbon−halogen bond length increases in the order 𝐶 − 𝐶𝑙 < 𝐶 − 𝐵𝑟 < 𝐶 − 𝐼 and hence,
carbon−halogen bond strength decreases in the order 𝐶 − 𝐶𝑙 > 𝐶 − 𝐵𝑟 > 𝐶 − 𝐼. The
iodine atom is more easily substituted followed by the bromine atom and the chlorine
atom is the least easily substituted in a molecule. Hence, the observed trend.
Also, the more electronegative the halogen atom is, the greater the separation of
charges between the carbon atom and halogen atom (i.e. the more polar the
carbon−halogen atom) and the stronger the carbon−halogen bond.
The bond length and energy for the 𝐶 − 𝑋 bond are:
Bond 𝐶 − 𝐶𝑙 𝐶 − 𝐵𝑟 𝐶−𝐼
Bond length (nm) 0.177 0.194 0.214
−1
Bond energy (kJ mol ) 338 276 238

 Alkyl halides also specifically undergo nucleophilic substitution reactions because the
halogen atoms are good leaving groups.
 Examples of substitution reactions in haloalkanes are:
A. Hydrolysis (alcohol formation)
Hydrolysis of primary or secondary alkyl halides can effected by use of hot aqueous
sodium (potassium) hydroxide solution.

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 The reaction according to the following mechanism:

Rate law/rate equation for the hydrolysis of primary alkyl halides is

𝑅𝑎𝑡𝑒 = 𝑘 [𝑅𝐶𝐻2 − 𝑋][𝑂𝐻 − ]
Examples:
ℎ𝑒𝑎𝑡
CH3−Br + NaOH(aq) → CH3−OH + NaBr
𝑟𝑒𝑓𝑙𝑢𝑥
CH3CH2Cl + 𝑂𝐻 − (𝑎𝑞) → CH3CH2OH + 𝐶𝑙 − (𝑎𝑞)
ℎ𝑜𝑡 𝐾𝑂𝐻(𝑎𝑞)
(CH3)2CHI → (CH3)2CHOH + KI

Hydrolysis of tertiary alkyl halides is done by water alone; no base is needed.

The mechanism of the above reaction is as follows:

Examples:
𝑟𝑜𝑜𝑚 𝑡𝑒𝑚𝑝 𝑜𝑟 𝑏𝑜𝑖𝑙
(CH3)3C−Br + H2O → (CH3)3C−OH + HBr(aq)

Hydrolysis reaction is used in organic chemistry to prepare alcohols.

The different classes of haloalkanes give better yields of alcohols when hydrolysed
using hot moist silver(I) oxide.

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 Activity 6
1. 1.64 g of bromoalkane, T (CnH2n+1Br) was heated with excess sodium hydroxide
solution. The resultant solution was cooled, acidified with dilute nitric acid
and diluted to 100 cm3.
10.0 cm3 of the acidified solution required 13.0cm3 of 0.1 M silver nitrate
solution for complete reaction.
T reacts with hot sodium hydroxide solution according to the following
equation.
CnH2n+1Br(l) + NaOH(aq) → CnH2n+1OH(aq) + NaBr(aq)
(a) State what was observed when the resultant solution was treated with
silver nitrate solution. Give a reason for your answer.
(b) Calculate the molecular mass of T.
(c) Deduce the molecular formula of T. (𝐵𝑟 = 80)
(d) Write the structural formulae and IUPAC names of all the possible
isomers of T.
(e) Write equation to show how T can be
(i) obtained from ethanol.
(ii) converted to poly(propene).
2. Complete the following equations and in each case outline a mechanism for the
reaction.

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 B. Nitrile formation
The process can be effected as follows:

Aqueous alcohol serves as a solvent; the water component dissolves the alkali metal
cyanide and the alcohol dissolves the haloalkane.
In this case, the nucleophile is the cyanide anion, 𝑁 ≡ 𝐶 − or simply −𝐶 𝑁
The nitriles are useful compounds in organic synthesis and can be used as follows:

Nitrile formation is used in organic synthesis to increase the length of the carbon
chain.

C. Formation of higher alkynes

Refer to preparation of alkynes for details.

Activity 7
1. Complete the following equation and outline a mechanism for the reaction.

2. Write equations to show how the following conversions can be effected.

(a) Pent-2-yne can be obtained from calcium carbide.
(b) Ethene can be converted in pentane.
(c) Propan-1-ol can be converted into but-2-ene.

D. Ether formation (Williamson’s synthesis)

Ethers are organic compounds with the structure, 𝑅 − 𝑂 − 𝑅 ′ .
They formed when the haloalkane is refluxed/boiled with alcoholic solution of
sodium (or potassium) alkoxide.
For example;

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 The nucleophile is the alkoxide ion, 𝑅 ′ 𝑂− .

Note:
 𝑅 ′ 𝑂− 𝐾 + 𝑎𝑛𝑑 𝑅 ′ 𝑂− 𝑁𝑎+ are called potassium alkoxide and sodium alkoxide
respectively. The alkoxides are made by dissolving the alkali metal in excess
of the appropriate alcohol.
For example:
CH3CH2OH(l) + Na(s) → 𝐶𝐻 ⏟ 3 𝐶𝐻2 𝑂− 𝑁𝑎+ (𝑙) + ½H2(g)
Sodium ethoxide
CH3OH(l) + K(s) → ⏟
𝐶𝐻3 𝑂− 𝐾 + (𝑙) + ½H2(g)
Potassium ethoxide
 Alkyl halides also form ethers when reacted with dry silver(I) oxide (Ag2O).
For example: 2CH3CH2Br + Ag2O(s) → CH3CH2−𝑂 −CH2CH3 + 2AgBr
 This reaction is used in organic chemistry for preparation of both
symmetrical and unsymmetrical ethers.

Activity 8
Complete and outline the mechanism for each of the following reactions.

E. Ester formation
It involves reacting the haloalkane with silver(I) salt of a carboxylic acid in an
alcohol as a solvent.
Silver(I) halide is precipitated in this reaction.

The reaction proceeds according to the following mechanism.

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 Activity 9
Complete and outline the mechanism for each of the following reactions.

F. Formation of amines
A mixture of amines is formed when alkyl halides are heated with alcoholic solution
of ammonia in a sealed tube at 100oC. A mixture of products is formed because
products formed are more reactive than ammonia.
For example:
CH3CH2Br + NH3 → ⏟ 𝐶𝐻3 𝐶𝐻2 𝑁𝐻2 + HBr
1° amine

⏟ 3 𝐶𝐻2 )2 𝑁𝐻 + HBr
CH3CH2Br + CH3CH2NH2 →(𝐶𝐻
2° amine

CH3CH2Br + (CH3CH2)2NH →(𝐶𝐻

⏟ 3 𝐶𝐻2 )3 𝑁 + HBr
3° amine

CH3CH2Br + (CH3CH2)3N →(𝐶𝐻

⏟ 3 𝐶𝐻2 )3 𝑁 + 𝐵𝑟 −
𝑠𝑎𝑙𝑡

The mechanism for this reaction can be outlined as below:

Note:
Ammonia molecules are neutral nucleophiles which initiate the reaction.

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 Activity 10
(a) Predict the formulae of the products of the reaction between excess
bromopropane and hot alcoholic ammonia. Give reason(s) for your answers.
(b) Complete the following reaction.
ethanol
CH3Br + hot excess NH3 →
(c) Outline the reaction mechanism and give a reason for the choice of product in
the reaction in (b) above.
(d) Complete and outline the mechanism for the following reaction.

Elimination reactions of alkyl halides

 Alkyl halides also undergo elimination reactions which involve the removal of hydrogen
and halogen atoms from adjacent carbon atoms. An alkene is formed.

 Conditions for the reaction are; KOH, excess alcohol (ethanol/methanol) and heat
(reflux)
 In this reaction,
(i) 𝐶𝐻3 𝐶𝐻2 𝑋 (X=Cl, Br or I) gives poor yield of ethene.
(ii) much better yields of alkene can be obtained from secondary, tertiary or higher
primary alkyl halides.
 Elimination reactions proceed either via E1 or E2 mechanism depending on the
structure of the alkyl halide (i.e. whether the alkyl halide is 1o, 2o or 3o).
 E1 mechanism; means elimination unimolecular, referring to a reaction in which only one
molecule is involved in the rate determining step (slowest step of the reaction).
Experiments show that this type of reaction mechanism is mainly followed by tertiary
alkyl halides.
For example;

The rate of reaction being dependent upon the concentration of only the haloalkane.
Thus, we can say the reaction follows a first order kinetics.
The mechanism of the reaction can be outlined as follows:

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 Step 1: This involves heterolytic cleavage of carbon−halogen bond. It is the
slowest step and the rate determining step of the reaction.

Step 2: The ethoxide ion abstracts a proton from the carbonium ion formed in
step 1 with formation of carbon−carbon double bond.

 E2 mechanism means elimination bimolecular. It refers to a reaction in which two

molecules are involved in the rate determining step of the reaction. Thus, it is a
one−step reaction.
This reaction follows a second order kinetics; meaning that the rate of reaction is
dependent upon the concentration of both the base and the alkyl halide.
Experiments show that this type of reaction mechanism is mainly followed by primary
alkyl halides.
For example:

The mechanism of the reaction can be outlined as follows:

 Secondary alkyl halides are intermediate in behaviour; thus, they can either follow E1
or E2.

Activity 11
Complete and outline the mechanism for each of the following reactions.

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Concurrent substitution and elimination

 Elimination reaction usually occurs in competition with substitution reaction. Thus, we

have E1 versus SN1 and E2 versus SN2.
 The percentage yield of the product depends on a number of factors namely:
(i) Temperature at which the reaction is carried out; higher temperatures favour
elimination reaction. Thus if substitution product is desired, the reaction
temperature should be low
(ii) The type of alkyl halide used in the reaction; sterically hindered substrate
favours the elimination product. Thus, elimination reaction becomes
progressively more important in the order
primary haloalkane < secondary haloalkane < tertiary haloalkane
(iii) Solvent used.
 The effect of solvent used can be best illustrated by treating the alkyl halide with an
alkali; hydroxide ions.
(a) In aqueous solution i.e. 𝐾𝑂𝐻(𝑎𝑞), 𝑁𝑎𝑂𝐻(𝑎𝑞) 𝑜𝑟 𝑂𝐻 − (𝑎𝑞)
Primary haloalkanes undergo substitution reaction while tertiary haloalkanes
undergo elimination reaction.
This explains why hydrolysis of tertiary haloalkanes to form alcohols can be best
done using water alone. This is because water is a much weaker nucleophile than the
hydroxide ions.
(b) In alcoholic solution i.e. 𝐾𝑂𝐻/𝑎𝑙𝑐𝑜ℎ𝑜𝑙 , 𝑁𝑎𝑂𝐻/𝑎𝑙𝑐𝑜ℎ𝑜𝑙 𝑜𝑟 𝑂𝐻 − /𝑎𝑙𝑐𝑜ℎ𝑜𝑙
Lower primary haloalkanes (particularly those with two carbon atoms) undergo
substitution reaction while higher primary haloalkanes under elimination reaction.
Tertiary haloalkanes undergo elimination reaction.
 Illustration of competition between SN2 and E2 in CH3CH2X is as follows:

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Other reactions of haloalkanes
 The Wurtz reaction
Alkyl halides react with sodium metal in dry ether to yield alkanes.
dry ether
For example: 2CH3CH2−Br + 2Na → CH3CH2CH2CH3 + 2NaI
Refer to alkanes for details.
 Formation of Grignard reagents
Haloalkanes react with magnesium turnings/granules in dry ether to form useful
synthetic reagents called Grignard reagents or alkyl magnesium halides.
Mg/dry ether
𝑅−𝑋 → 𝑅 − 𝑀𝑔𝑋
⏟ ; where R is an alkyl group
𝑎𝑙𝑘𝑦𝑙 𝑚𝑎𝑔𝑛𝑒𝑠𝑖𝑢𝑚 ℎ𝑎𝑙𝑖𝑑𝑒
 The alkyl magnesium halides are very reactive and are readily converted into alkanes,
alkenes, alcohols, aldehydes, ketones and carboxylic acids.

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 Aqueous ammonium chloride is used in the hydrolysis to the tertiary alcohol as the
presence of an acid causes dehydration of the alcohol formed to an alkene.

Activity 12
Show by means of equation(s) how the following conversions can be effected. In each
case indicate suitable reagents and reaction conditions.
(a) Ethanol to butane.
(b) Bromomethane to 2–methylpropan–2–ol.
(c) Methanol to ethanol.
(d) Cyclohexene to cyclohexanol.
(e) Cyclohexanol to cyclohexanoic acid (cyclohexanecarboxylic acid).

Testing for aliphatic haloalkanes

 Alkaline hydrolysis of aliphatic haloalkanes provides a useful means to identify aliphatic
haloalkanes in the laboratory.

Test
The aliphatic haloalkane is treated with aqueous sodium hydroxide solution and the
mixture is refluxed/heated/boiled, and cooled. To the resultant mixture is added
excess dilute nitric acid followed by silver nitrate solution.
Observations
The formation of
(i) a white precipitate indicates a chloride ion hence a chloroalkane.
(ii) a pale yellow precipitate indicates a bromide ion hence a bromoalkane.
(iii) a yellow precipitate indicates an iodide ion hence an iodoalkane.
The general equations for the reactions that occur are:
𝑏𝑜𝑖𝑙
𝑅 − 𝑋 + 𝑂𝐻 − (𝑎𝑞) → 𝑅𝑂𝐻 + 𝑋 − (𝑎𝑞)
⏟ then, 𝐴𝑔+ (𝑎𝑞) + 𝑋 − (𝑎𝑞)
⏟ → 𝐴𝑔𝑋(𝑠)
𝑓𝑟𝑒𝑒 ℎ𝑎𝑙𝑖𝑑𝑒 𝑖𝑜𝑛 𝑓𝑟𝑒𝑒 ℎ𝑎𝑙𝑖𝑑𝑒 𝑖𝑜𝑛
𝑖𝑛 𝑡ℎ𝑒 𝑚𝑖𝑥𝑡𝑢𝑟𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑚𝑖𝑥𝑡𝑢𝑟𝑒
For example:
boil
CH3CH2CH2CH2Br + 𝑂𝐻 − (aq) → CH3CH2CH2CH2OH + 𝐵𝑟 − (aq)
Then; 𝐴𝑔+ (𝑎𝑞) + 𝐵𝑟 − (𝑎𝑞) → 𝐴𝑔𝐵𝑟(𝑠)

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 Activity 13:
1. Give reasons for each of the following procedures in testing for aliphatic
haloalkanes.
(a) Heating the alky halide with aqueous sodium hydroxide solution.
(b) Addition of excess dilute nitric acid.
(c) Why dilute hydrochloric or dilute sulphuric acid is not used in place of dilute
nitric acid.
2. State what would be observed and write equations for the reactions that would
take place if aqueous sodium hydroxide solution followed by dilute nitric acid and
silver nitrate solution were separately treated with:
(a) 1-chlorobutane (b) 1-iodopropane (c) bromocyclohexane
3. To about 3 drops of each of chloroethane, bromoethane and iodoethane in
separate test tubes, was added aqueous sodium hydroxide solution. Each of the
test tubes was warmed in water bath kept at 55oC for some minutes and treated
with an equal amount of acidified solution of silver nitrate. The test tubes were
left to stand and the time taken for the reaction to take place in the test tubes
noted. The results in the test tubes were summarised as below:

Table of results
Test tube Reaction mixture Observations
I chloroethane + sodium hydroxide white precipitate after 20
solution + acidified silver nitrate minutes
II bromoethane + sodium hydroxide pale yellow precipitate after 7
solution + acidified silver nitrate minutes
III iodoethane + sodium hydroxide immediate yellow precipitate
solution + acidified silver nitrate

(a) What name given to the type of the reaction that took place in each of the
test tubes?
(b) Explain why the reaction in test tube I took a longer time whereas that in test
tube III took the shortest time.
(c) Write equation and outline the mechanism for the reaction that took place in
test tube II.
(d) The reaction in (c) is exothermic. Sketch a labelled potential energy versus
reaction co−ordinate diagram for the reaction that took place in (c).
(e) Write equation(s) to show how bromoethane can be converted into
(i) butane. (ii) butanone. (iii) propan-1-ol. (iv) 2-methylbutan-2-ol.
4. Discuss the difference in the reactivity of 2−bromo−2 −methylbutane and
1−bromopentane with aqueous sodium hydroxide solution.

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 5. An aliphatic iodoalkane, Q contains 74.7% by mass iodine.
(a) Determine the molecular formula of Q.
(b) Write down the possible isomers of Q and in each case identify the class of
the compound.
(c) Q doesn’t does not undergo SN1 reaction.
(i) State what SN1 means. (ii) Identify the Q.
(d) Identify the type of reaction similar to SN1 that compound Q identified in
(c)(ii) undergoes and state the difference between the type of reaction you
have identified and the SN1 reaction.
6. Write short notes on the how haloalkanes cause global warming.
7. The boiling points of 2−chlorobutane and 2−iodobutane are 68℃ and 119℃
respectively. Explain this observation.
8. Discuss the reactions of iodoethane with
(a) benzene. (b) potassium hydroxide.
(Include mechanisms for the reactions)
9. (a) Complete and outline the mechanism for the following reactions.
ℎ𝑜𝑡 𝐾𝑂𝐻(𝑎𝑞) reflux
(i) CH3CH2Cl → (ii) CH3CH2CH2Br + 𝑂𝐻 − (aq) →
(b) Sketch a well labelled energy profile diagram for reaction in (a)(i) above.
Explain the shape of the graph.
(c) Write the rate law for the reaction in (a)(i) and state what would happen to
the rate of the reaction if the concentration of potassium hydroxide is
(i) halved. (ii) doubled.
Assume in both cases the concentration of CH3CH2Cl is kept constant.
10. Consider the conversion scheme below:

(a) Identify A and B.

(b) State the conditions and reagents at I, II, III and IV.
(c) Outline the mechanism at stage III.
11. (a) Write the structural formulae of the possible isomers of C2H4Cl2.
(b) Discuss briefly how one of the isomers above reacts with potassium
hydroxide. Indicate the equation (s) of reactions and mechanism for the
reaction.

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 12. Explain what is meant by each of the following:
(You answers should examples and where applicable the acceptable mechanisms
for the reactions)
(a) Elimination reactions. (c) Substitution reactions.
(b) Substitution unimolecular reaction. (d) Elimination unimolecular reaction.
13. Show by means of equations only show how the following conversions can be
effected. Indicate reagents and conditions for the reactions.

Uses of alkyl halides

 Alkyl halides have wide range of uses some of which we have already mentioned.
 Alkyl halides are used:
(i) as solvents for oil and grease in the dry cleaning industry and metal surfaces
(e.g. CH2Cl2 and CCl2=CCl2 are used for this purpose while toxic CHCl3 and CCl4
have limited use for this purpose). Dichloromethane which is a chloroalkane has
low toxicity and is as an excellent solvent used as a paint stripper.
Chloroform is used as a solvent for organic synthesis and solvent extraction.
(ii) as fire–extinguishers since the compounds are non–flammable and denser; for
example CCl4 whose use has been replaced by dibromochlorofluoromethane
(CBr2ClF also known as BCF) because its forms phosgene (COCl2), a very
poisonous gas at very high temperatures.
(iii) as starting materials for synthesis of many important other organic compounds
including some plastics. Dichlorodifluoromethane, trichlorofluoromethane and

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 other chlorofluoro–derivatives of methane are used as refrigerants and
propellants for aerosols under the trade name of Freons.
CH2=CHCl is used as anaesthetic; since its cooling effect once sprayed
desensitises the nerve ending; 1–bromo–1–chloro–2,2,2–trifluoroethane
(CHBrClCHF3) is also for this purpose.
(iv) in the manufacture of plastics e.g. PVC and Teflon

Supplement
The chlorofluorocarbons, CFCS
 These are haloalkanes that only contain chlorine and fluorine atoms in addition to
carbon. No hydrogen atoms. Examples include; CFCl3, CF2Cl2 and CClF2CClF2.
 CFCs were widely used as aerosol propellants, refrigerants (to replace toxic
ammonia and sulphur dioxide) and solvents. Aerosols are used to dispense
insecticide, hairsprays, shaving cream, perfumes, deodorants, polishes and waxes.
Their use became wide spread up to around the year 1990, because they are
unreactive, non–flammable, odourless, stable, non–toxic and have low boiling
points.

Old refrigertors are sources of dangerous CFCs

 One major disadvantage of CFCs use in the environment is that they can’t be
removed from the atmosphere once released from the aerosol sprays or old
refrigerants or any other source. This is due to their unreactive nature and being
insoluble in commonly used solvents and water.
 While in the upper atmosphere (the stratosphere), a series of reactions occur in
the presence of ultraviolet light to convert ozone to molecular oxygen. These
reactions destroy the ozone layer which would help in absorbing the dangerous
ultraviolet radiations from the sun. This results into increase in skin cancer
among humans.

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 For example:
light
CCl3F → CCl2F• + Cl• (very reactive radical)
Then: Cl• + O3(g) → O2(g) + ClO• and ClO• + O• → Cl• + O2(g)
 In fact scientists have estimated that one free chlorine radical can remove one
million ozone molecules.
 Because of the above dangers of CFCs, friendly haloalkanes that contain at least
one hydrogen atom per molecule have been introduced. The friendly haloalkanes
include; CHClF2 used in air–conditioners, CHCl2CF3 used in blowing plastics foam,
and CH2FCF3 used in air–conditioners and refrigerators.

Aryl halides
Introduction
 Aryl halides are:
(i) also called hogenoarenes.
(ii) compounds in which the halogen atom(s) is/are directly bonded to the benzene ring.
 Examples are:

Chlorobenzene

1,2,4-trichlorobenzene

 Aromatic halides of the following form:

are not classified as aryl halides. They are

classified as phenyl substituted haloalkanes or ‘side−chain’ aryl halides. They
resemble aliphatic haloalkanes in many of their reactions.

Preparation of aryl halides

 Aryl halides are can be made using the following methods:
(a) Direct halogenation of benzene or other aryl compounds
Refer to the reactions of benzene for details
(b) Via nitrobenzene/phenylamine/diazonium salt
Refer the formation of nitrobenzene.

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Reactions of aryl halides
 Aryl halides undergo two kinds of reaction namely:
(i) Electrophilic substitution in the ring
For details refer to notes under aromatic compounds
(ii) Replacement of the halogen atoms (nucleophilic substitution of the halogens)
Under ordinary conditions, aryl halides do not undergo substitution reactions
similar those that occur in aliphatic haloalkanes or ‘side−chain’ aryl halides.
For example:

R, R’ and R’’ may be a hydrogen atom, an alkyl group or an aryl group. The alkyl
groups or aryl groups may be identical or not.

Reasons for the differences in reactivity of the two classes of halocompounds

can be explained as follows:
 The carbon−halogen bond in the aryl halides is less polar and stronger. The
lone pairs of electrons on the halogen atom interacts with the delocalised of
pi electrons of benzene ring. This makes the carbon−halogen bond stronger
and difficult to break (or This results into formation of a partial
carbon−halogen double bond which makes the bond stronger and difficult to
break). Thus, substitution reaction does not easily occur.
 Whereas in aliphatic haloalkanes or ‘side−chain’ aryl halides, the
carbon−halogen bonds are polar. This because the halogen atom is more
electronegative than the carbon atom. The halogen atom pulls/withdraws the
bonding electrons more towards itself and this makes the carbon atom
acquire partial positive charge and the halogen atom acquires partial negative
charge. Therefore, the carbon atom is easily attacked by the nucleophiles
and this leads to nucleophilic substitution of the halogen atom.
Note
In ‘side−chain’ aryl halides, the intervening methylene/other groups
prevent the interaction of the lone pairs of electrons on the halogen atom
with the delocalised pi electrons of the benzene ring.

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 This difference in reactivity of the two classes of compounds (aryl halides
versus aliphatic haloalkanes or ‘side-chain’ aryl halides) makes it possible to
distinguish between the two classes of compounds as follows:

Test:
The aryl halide and aliphatic haloalkane (or ‘side-chain’ aryl halide) is
separately treated with aqueous sodium hydroxide solution and the mixture is
refluxed/heated/boiled and cooled. To the resultant mixture is added excess
dilute nitric acid followed by silver nitrate solution.
Observations:
The formation of
(i) a precipitate in indicates a haloalkane (or ‘side-chain’ aryl halide)
(ii) no observable change indicates an aryl halide
Thus, the reagent is hot aqueous sodium hydroxide solution followed by dilute
nitric acid and silver nitrate solution.

Some of the important substitution reactions undergone by aryl halides are

summarised below:

Activity 14:
1. Show by means of equations only show how the following conversions can
be effected. Indicate reagents and conditions for the reactions.
(a) Propan-1-ol to butanoic acid. (i) Propene to 1-bromobutane.
(b) 1-chloropropane to butylamine. (j) Benzene to benzoic acid.

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 (c) Benzene to 1-phenylethan-1-ol. (k) Hexane from 1-bromopropane.
(d) But-1-ene from ethene. (l) 1,2-dibromoethane to ethanol.
(e) Iodomethane to ethanoic acid. (m) 2-bromobutane to butanone.
(f) Chlorobenzene can be converted into cyclohexene.
(g) Chlorobenzene can be converted into cyclohexanol.
(h) Ethene to phenol.
2. 2−bromo−2 −methylpropane reacts with hot water to form
2−methylpropan−2 −ol.
(a) Write the rate equation for the reaction.
(b) Draw the energy diagram for the reaction that took place.
(c) Outline the mechanism for the reaction that took place.
(d) State the:
(i) rate determining state for the reaction.
(ii) technique which was used to study the reaction.
3. 1-bromobutane undergoes nucleophilic substitution reaction when heated
with aqueous sodium hydroxide solution whereas bromobenzene does not
react under similar conditions. Explain this observation.
4. An organic compound P contains 35.04% carbon, 6.56% hydrogen and
58.04% bromine.
(a) Calculate the empirical formula of P.
(b) The vapour density of P was found to be 68.
(i) Determine the molecular formula of P.
(ii) Write the names and structural formulae of all the possible
isomers of P.
(c) When P was reacted with sodium hydroxide, a compound, Q was
formed. When a solution of anhydrous zinc chloride in concentrated
hydrochloric acid was added to Q, it turned cloudy within 10 minutes.
(i) Identify Q.
(ii) Write the mechanism for the reaction between P and sodium
hydroxide and state the condition(s) for the reaction to take place.
(d) Explain the difference in the reactivity of P and bromobenzene with
sodium hydroxide.
(e) Write equation(s) to show how P can be synthesised from butan-1-ol.
5. (a) 2-bromobutane was treated with sodium ethoxide in ethanol to
compound T. Write the equation and a mechanism for the reaction
between 2-bromobutane and ethoxide in ethanol.
(b) The compound, T formed in (a) can be synthesised from an alcohol.
Write the equation and include a mechanism for the reaction leading to
the formation of T form an alcohol.

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 6. (a) Discuss the reactions of bromoethane with potassium hydroxide.
[Include mechanisms for the reactions].
(b) (i) Briefly describe a test that can be carried out to distinguish
between bromoethane and bromobenzene.
(ii) Account for the difference(s) in reactivity of bromoethane and
bromobenzene.
(c) Write equation to show how:
(i) bromoethane can be prepared from ethanol.
(ii) bromobenzene can be prepared from benzene.
(d) Write the mechanism for the reaction in (c)(ii) above.
7. Compound Q, 𝐶7 𝐻7 𝐶𝑙 burns with a sooty flame.
(a) Write the structural formulae of all the possible isomers of Q.
(b) When Q was heated with aqueous sodium hydroxide, a primary alcohol,
Z was formed.
(i) Identify Q.
(ii) Write equation and outline a mechanism for the reaction
between Q and sodium hydroxide.
(c) Write equation to show how Q can be converted to 2-phenylethanol.
8. Compound X, 𝐶8 𝐻9 𝐵𝑟 burns with a sooty flame.
(a) Write the structural formulae of all the possible isomers of X.
(b) When X was heated under reflux with aqueous sodium hydroxide, a
primary alcohol, Q, 𝐶8 𝐻10 𝑂 was formed.
(i) Identify Q and X.
(ii) Write an equation and outline a mechanism for the reaction
leading to the formation of Q from X.
(c) Q was converted in a one-step reaction to an alkene. Write equation
and outline a mechanism for the reaction.
(d) The alkene in (c) was polymerised. Write the structural formulae of
the polymer.
(e) State
(i) the type of polymerisation involved in (d).
(ii) one used of the polymer formed in (d).
9. Name one reagent that can be used to distinguish between the following
pairs of compounds. In each case, state what would be observed if each
member of the pair is separately treated with the reagent you have
named.

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 10. The structural formula of a compound X is shown below.

When 2.49 g of X was heated under reflux with 24.90 cm3 of 1.0 M sodium
hydroxide solution and the mixture cooled, the resultant cooled mixture
required 1.0 M dilute sulphuric acid for complete reaction using
phenolphthalein indicator.
(a) Write equation for the reaction between
(i) X and sodium hydroxide solution.
(ii) dilute sulphuric acid and the resultant cooled mixture.
(b) Determine the volume of volume of dilute sulphuric acid required for
complete reaction with the resultant cooled mixture.
(c) Outline the mechanism for the reaction in (a).

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