HALOALKANES AND HALOARENES - NOTES

▪ The replacement of hydrogen atom(s) in a hydrocarbon, aliphatic or aromatic, by halogen

atom(s) results in the formation of alkyl halide (haloalkane) and aryl halide (haloarene),
respectively.

▪ Haloalkanes contain halogen atom(s) attached to the sp3 hybridised carbon atom of an alkyl
group whereas haloarenes contain halogen atom(s) attached to sp2 hybridised carbon atom(s)
of an aryl group.

▪ CLASSIFICATION - On the Basis of number of Halogen Atoms

▪ Haloalkanes and haloarenes may be classified as mono, di, or polyhalogen (tri-,tetra-, etc.)

▪ Monohalo compounds may further be classified according to the hybridisation of the carbon
atom to which the halogen is bonded.

COMPOUNDS CONTAINING sp3 C-X BOND

(a) Alkyl halides or haloalkanes (R—X)

▪ In alkyl halides, the halogen atom is bonded to an alkyl group (R).

▪ They form a homologous series represented by CnH2n+1X.

▪ They are further classified as primary, secondary or tertiary according to the nature of carbon to
which halogen is attached.

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(b) Allylic halides
These are the compounds in which the halogen atom is bonded to an sp3 hybridised carbon atom next
to carbon-carbon double bond (C=C)

(c) Benzylic halides

These are the compounds in which the halogen atom is bonded to an sp3-hybridised carbon atom next
to an aromatic ring.

Nomenclature

▪ Alkyl halides

▪ Common names of are derived by naming the alkyl group followed by the halide.

▪ In the IUPAC system of nomenclature are named as halosubstituted hydrocarbons

• The dihalo-compounds having same type of halogen atoms are further classified as geminal
halides (halogen atoms are present on the same carbon atom) and vicinal halides (halogen
atoms are present on the adjacent carbon atoms).
In common name system, gem-dihalides are named as alkylidene halides and vic-dihalides are
named as alkylene dihalides.
In IUPAC system, they are named as dihaloalkanes.

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Aryl halides

• Haloarenes are the common as well as IUPAC names.

• For dihalogen derivatives, the prefixes o-, m-, p- are used in common system. In IUPAC system,
the numerals 1,2; 1,3 and 1,4 are used.

Nature of C-X Bond

▪ Since halogen atoms are more electronegative than carbon, the carbon halogen bond of alkyl
halide is polarised; the carbon atom bears a partial positive charge whereas the halogen atom
bears a partial negative charge.

▪ Since the size of halogen atom increases as we go down the group in the periodic table.
Consequently the carbon-halogen bond length also increases from C—F to C—I.

Physical Properties

Melting point, boiling point and solubility

- Higher the molar mass higher will be the boiling point – greater dispersion/ London forces
- If molar masses are almost equal – R – X will have higher b.p as there is dipole -dipole forces
- Branching decreases b.p. as surface area of the molecule decreases which decreases
intermolecular attraction.
- For same alkyl group boiling points of alkyl halide are in the order: RI˃ RBr˃ RCl ˃RF
- Among isomeric halides boiling point decreases with increase in branching in alkyl group.
- Alkyl halides are insoluble in water due to their inability to form hydrogen bonds with water
- Boiling points of isomeric dihalobenzenes are very nearly the same.
- The para-isomers are high melting as compared to their ortho and meta-isomers because of
the symmetrical arrangement in the lattice.

Methods of Preparation

▪ From Hydrocarbons

(a) By free radical halogenation

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 (b) By electrophilic substitution

▪ From Alcohols

HCl/ZnCl2 – Lucas test to distinguish alcohols

NaI/KI cannot be usea as H2OS4 oxidizes I- to I2

Good yields of R—I may be obtained by

heating alcohols with sodium or potassium
iodide in 95% orthophosphoric acid.

This method is preferred as biproducts are gases

(d) From alkenes

(i) By addition of HX (Markovnikov’s rule)

Anti-Markovnikov’s rule is applicable only for H – Br

in presence of a peroxide (Benzoyl peroxide)

(ii) Addition of halogens:

Sandmeyer’s reaction
When a primary aromatic amine, dissolved or suspended in cold aqueous mineral acid, is treated with
sodium nitrite, a diazonium salt is formed.
Mixing diazonium salt with cuprous chloride or cuprous bromide results in the replacement of the
diazonium group by –Cl or –Br.

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Replacement of the diazonium group by iodine does not require the presence of cuprous halide and is
done simply by shaking the diazonium salt with aq. potassium iodide.

Halogen Exchange Reactions

▪ Alkyl iodides are often prepared by the reaction of alkyl chlorides/bromides with NaI in dry
acetone. This reaction is known as Finkelstein reaction

▪ The synthesis of alkyl fluorides is best accomplished by heating an alkyl chloride/bromide in the
presence of a metallic fluoride such as AgF, Hg2F2, CoF2 or SbF3. The reaction is termed as
Swarts reaction

REACTIONS OF ALKYL HALIDES

The reactions of haloalkanes may be divided into the following categories:

(i) Nucleophilic substitution (ii) Elimination reactions (iii) Reaction with metals

I. NUCLEOPHILIC SUBSTITUTION REACTIONS

Since X- can be replaced (substituted) by electron rich reagents (nucleophiles), they undergo
nucleophilic substitution reaction.

CN- is ambident
nucleophile -
cyanide group is a
hybrid of two
contributing
structures and
therefore can act
as a nucleophile in
two different ways
[C≡N ↔ :C=N, i.e.,
linking through
carbon atom
resulting in alkyl
cyanides and
through nitrogen
atom.

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Molecularity: The number of particles taking part in the rate determining step (slowest step)

SN2 mechanism: It take place in a single step. The attacking nucleophile approaches from the side
opposite to the leaving halogen

Since it’s a single step reaction and two particles are in the rate determining step, molecularity is 2 and
reaction is referred as SN2.

Primary alky halides prefer this reaction because of two reasons:

- Steric hindrance is less as the groups surrounding the carbon joined to halogen are smaller
groups.
- The stability of 1o carbocation is lesser as +I (Inductive) effect is very low and low
hyperconjugation.

SN1 mechanism: It takes place in 2 steps. A slow rate determining step1 and a fast step 2

Since rate is determined by slower step the molecularity will be 1 and therefore this reaction is called SN1
reaction.

Tertiary alky halides prefer this reaction because of two reasons:

- Steric hindrance is more as bulkier groups surrounding the carbon joined to halogen are bigger
groups
- The stability of 3o carbocation is more as +I (Inductive) effect is very high and high
hyperconjugation effect.

Due to the stability of carbocation, the allylic and benzylic halides show high reactivity towards the SN1
reaction. The carbocation thus formed gets stabilized through resonance as shown below:

Vinyl chloride is less reactive than allyl

chloride – partial double bond due to
resonance

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For a given alkyl group, the reactivity of the halide, R-X, follows the same order in both the mechanisms
R–I> R–Br>R–Cl>>R–F. As iodine is a better leaving group because of its large size, it will be released at a
faster rate in the presence of incoming nucleophile.

Evidence for the mechanism

Optical activity

When ordinary light pass through a through Nicol prism plane polarized light is produced.

Certain compounds rotate the plane polarised light when it is passed through their solutions. Such
compounds are called optically active compounds.

The degree of rotation is measured using a Polari meter

If the compound rotates the plane polarised light to the right, i.e., clockwise direction, it is called
dextrorotatory or the d-form and is indicated by placing a positive (+) sign before the degree of rotation.

If the light is rotated towards left (anticlockwise direction), the compound is said to be laevo rotatory or
the l-form and a negative (–) sign is placed before the degree of rotation.

Such (+) and (–) isomers of a compound are called optical isomers and the phenomenon is termed as
optical isomerism.

The spatial arrangement of four groups (valencies) around a central carbon is tetrahedral and if all the
substituents attached to that carbon are different, such a carbon is called asymmetric carbon or
stereocenter or chiral.

The objects which are non-superimposable on their mirror image (like a pair of hands) are said to be
chiral and this property is known as chirality. While the objects, which are, superimposable on their
mirror images are called achiral.

The stereoisomers related to each other as non-superimposable mirror images are called enantiomers

A mixture containing two enantiomers in equal proportions will have zero optical rotation, as the
rotation due to one isomer will be cancelled by the rotation due to the other isomer. Such a mixture is
known as racemic mixture or racemic modification.

Using optical activity to justify SN1 or SN2 mechanism

Retention of optical activity:

Since the Nu: had joined on the same side where the leaving
group left, optical activity is retained.

Since the Nu: had joined on the opposite side where the leaving
Inversion: group left, optical activity is inverted.

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Racemization: If the product contain equal amount of retained and inverted products, then the net
optical rotation will be zero and this is called racemization .

SN2 Mechanism:

Since the Nu: (OH-) had joined on the opposite side, the optical activity will be ………………………………

SN1 Mechanism

Since the intermediate is a planar carbocation, the Nu: can join either through the same side or through
the opposite side. Chances are 50-50.

Thus, the product will have 50% retention and 50% inversion – a racemic mixture will be formed.

II. ELIMINATION REACTION (beta elimination) – Important in conversions

When a haloalkane with β-hydrogen atom is heated with alcoholic solution of potassium hydroxide,
there is elimination of hydrogen atom from β-carbon and a halogen atom from the α-carbon atom. As a
result, an alkene is formed as a product.
Haloalkanes react with KCN to form alkyl cyanides as main
product while AgCN forms isocyanides as the chief product
because AgCN is mainly covalent in nature and nitrogen is
free to donate electron pair forming isocyanide as the main
product while in KCN……………………………………………………
Zaitsev rule: In dehydrohalogenation reactions, the preferred product is that alkene which has the
greater number of alkyl groups attached to the doubly bonded carbon atoms.

This reaction is very useful in conversion – 1-Bromopropane to 2-Bromopropane

- First dehydrohalogenation using alc. KOH and then Markovnikov’s addition

III. REACTION WITH METALS – Formation of organo-metallic compounds.

a) Grignard Reagent – R – Mg – X

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The carbon-magnesium bond is covalent but highly polar, help to make C -ve

Grignard reagent is used in the preparation of 10, 20 and 30 alcohols form aldehydes and ketones (next
chapter)

Even water, alcohols, amines are sufficiently acidic to convert them to corresponding hydrocarbons.
Therefore, its important to keep Grignard reagent away from water (kept in anhydrous conditions)

Wurtz reaction: Alkyl halides react with sodium in dry ether to give hydrocarbons containing double the
number of carbon atoms present in the halide. This reaction is known as Wurtz reaction.

Note1: Converting an alkyl halide to an alkyne

R – X + NaC CH → R – C CH

Alkyl halide + Sodium ethynide gives an alkyne with 2 more carbons as the alkyl halide.

Note2: Conversion of alkane to a carboxylic acid with one more C (Step up reaction)

R – X + KCN (aq) → R – CN The nitriles on hydrolysis give a carboxylic acid with one more carbon

The nitriles on reduction with LiALH4/ NaBH4 gives an amine

Note 3 – Converting alkanes to an alkane with double number of carbons – halogenation followed by
Wurtz reaction.

2-Chloropropane to 2,3-dimethylbutane

Reactions of Haloarenes

I. Nucleophilic substitution – Replace halogen by a nucleophile

Aryl halides are extremely less reactive towards nucleophilic substitution reactions due to the
following reasons
1. Resonance effect : In haloarenes, the electron pairs on halogen atom are in conjugation with
π-electrons of the ring and the following resonating structures

2. Difference in hybridization of carbon atom in C—X bond: In haloalkane, the carbon atom
attached to halogen is sp3 hybridised while in case of haloarene, the carbon atom attached
to halogen is sp2 -hybridised. The sp2 hybridised carbon with a greater s-character is more
electronegative and can hold the electron pair of C—X bond more tightly than sp3 -
hybridised carbon in haloalkane with less s- character. Thus, C—Cl bond length in haloalkane
is 177pm while in haloarene is 169 pm.

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 3. Instability of phenyl cation: In case of haloarenes, the phenyl cation formed as a result of
self-ionisation will not be stabilised by resonance and therefore, SN 1 mechanism is ruled
out.
4. Because of the possible repulsion, it is less likely for the electron rich nucleophile to
approach electron rich arenes.

Chlorobenzene can be converted into phenol by heating in aqueous sodium hydroxide

solution at a temperature of 623K and a pressure of 300 atmospheres.

Effect of substituents on nucleophilic reaction

Q. The presence of an electron withdrawing group (-NO2 ) at ortho- and para-positions increases the
reactivity of haloarenes. Explain with diagram to support your answer.

Draw resonance

The presence of nitro group at ortho- and para-positions withdraws the electron density from the
benzene ring and thus facilitates the attack of the nucleophile on haloarene. The carbanion thus formed
is stabilised through resonance. The negative charge appeared at ortho- and para- positions with respect
to the halogen substituent is stabilised by –NO2 group while in case of meta-nitrobenzene, none of the
resonating structures bear the negative charge on carbon atom bearing the –NO2 group. Therefore, the
presence of nitro group at meta- position does not stabilise the negative charge and no effect on
reactivity is observed by the presence of –NO2 group at meta-position.

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II. Electrophilic substitution reactions

Benzene has 3 double bond – Its rich in electron – Therefore ……………………… reagents will be attacking
benzene.

The different types of electrophilic reactions.

A. Halogenation
B. Nitration
C. Sulphonation
D. Friedel Craft alkylation
E. Friedel Craft acylation

Q. How does halogen influence electrophilic substitution reactions in haloarenes?

Although chlorine is an electron withdrawing group, yet it is ortho-, para- directing in electrophilic
aromatic substitution reactions - Chlorine withdraws electrons through inductive effect and releases
electrons through resonance. Through inductive effect, chlorine destabilises the intermediate
carbocation formed during the electrophilic substitution.

Through resonance, halogen tends to stabilize the carbocation and the effect is more pronounced at
ortho- and para- positions. The inductive effect is stronger than resonance and causes net electron
withdrawal and thus causes net deactivation. The resonance effect tends to oppose the inductive effect
for the attack at ortho- and parapositions and hence makes the deactivation less for ortho- and
paraattack. Reactivity is thus controlled by the stronger inductive effect and orientation is controlled by
resonance effect.

III. Reactions with metals

1. Fittig reaction

2. Wurtz-Fittig reaction

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SOME IMPORTANT POINTS IN CONVERSION

1. Alkane to another alkane with double the no. of C

First – free radical halogenation and then Wurtz reaction

Convert propane to hexane

2. Alkane to another an amine or a carboxylic acid of one C more

First halogenation, then reaction with aq. KCN to get nitrile – The reduction with LiAlH4 to
get amine and hydrolysis to get carboxylic acid

Convert CH4 to CH3NH2

Convert CH4 to CH3COOH

3. Alkane to an alkyne with 2 more carbon – halogenation and then reaction with sodium
ethynide
Convert Ethane to but-1-yne

4. Alkane to an alkene
Halogenation followed by dehydrohalogenation by alc. KOH

Convert propane to propene

2-chloropropane to 1-chloropropane

5. Conversion of benzene to m-nitrochlorobenzene – first nitration followed by chlorination

6. Conversion of benzene to p-nitrochlorobenzene – first chlorination followed by nitration

Halogen compounds

Uses and environmental effects of - dichloromethane, trichloromethane, tetrachloromethane, iodoform,

freons, DDT.

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