ARYL HALIDES

CLASSIFICATION OF ARYL HALIDES

Contain at least one benzene ring and one halogen atom in the molecule.

Nuclear halogen compounds Side- Chain halogen Compound

Directly attached halogen atoms to the Side chain attached with halogen. There may
benzene ring. be more than one halogen in the side chain.
NOMENCLATURE OF ARYL HALIDES

Termed as haloarenes in IUPAC as well as common system.

If there is only one halogen group bonded For dihalogen derivatives containing same type
directly to benzene ring, it is numbered as of halogen, the prefix o- (ortho) m-(meta) and
one position and written as prefix followed p-(para) are used in common system. If the two
with benzene as main ring. For example group are located in neighboring position the
Chlorobenzene or aryl chloride. All six two groups are ortho to each other. If there is a
position of benzene are equivalent. Hence gap of one position, the groups are meta to
monohalogen compounds could be each other and if the gap is of two position the
represented by attaching the halogen to any groups are para to each other. However in
of the six position. IUPAC nomenclature of dihalogen derivatives,
numerical prefixs 1,2 , 1,3 , 1,4 are used to
assigned the position of halogen.
In the presence of two different halogen For naming trihalogen compounds, we use
group attached to benzene ring, halogen the number system. Number 1 is given to the
numbered alphabetically and written in the position of the groups and then the other
same way. For eg. If there are two halogen groups are numbered accordingly. Clockwise
groups like bromo and fluoro bonded to direction is followed for this purpose.
benzene ring bromo group will be writren
first followed by fluoro group.

Side chain halogen compounds are named as follows :

METHODS OF FORMATION OF ARYL HALIDES

Direct halogenations of benzene - Chlorination and bromination is very conveniently

carried out at ordinary temperature in the absence of light and in the presence of metallic
iron or lewis acids such as chlorides or bromides of Fe, Al, Sb. Fluorination and Iodination
of benzene, are rarely performed because fluorine is too reactive to control the reaction and
iodine is too unreactive for a favourable equilibrium constant.

This reaction stops at the monosubstituted stage due to the deactivating influence of the
halogen atom on the aromatic ring.
However, if chlorine is used in excess, further substitution takes place and a mixture of o-
and p-dichlorobenzene is obtained.

When aromatic compounds contain strongly deactivating group such as –NO2, -COOH
etc., high temperature is required and the halogen enters then meta position.
Decomposition of aryl Diazonium salts (Sandmeyer’s reaction)- This is an important
method for the preparation of aryl halides, specially those which cannot be prepared by the
direct halogenations.

Aryl amines when treated with acidified sodium nitrite at low temperature (0-5oC), result
in the formation of Aryldiazonium salts.
Gattermann Reaction:

Gattermann reaction is the modified form of above mentioned reactions. This reaction
requires the diazonium salt to be warmed in presence of copper powder when it
decomposes to give the halobenzene.

Schiemann reaction:

This is a good method for introducing fluorine atom in the ring. Addition of
fluoroborate, to aryldiazonium salt solution gives the insoluble diazonium
fluoroborate, which on gental heating gives the aryl fluoride.
Aryl iodides are obtained by warming the diazonium salt solution with potassium iodide
Solution

When aromatic compounds contain highly activating group such as –OH, -NH2 etc.
They undergo halogenation in the absence of halogen carrier and halogen enters the
ortho and para position.
From phenols – Reaction of phenol with From silver salt of benzoic acid (
PCl5 yields aryl chloride. Hunsdiecker reaction ) :
REACTIONS OF ARYL HALIDES

The reactions of aryl halide are due to the halogen atom (nucleophilic substitution
reactions) and the aromatic ring (Electrophilic substitution reaction).

Nucleophilic substitution reactions

Aryl halides are relatively unreactive towards nucleophilic substitution reactions. For
example Chlorobenzene is essentially inert to aqueous sodium hydroxide at room
temperature. To proceed reaction at reasonable rate temperature over 300ºC are required.

Aryl halides are less reactive than alkyl halide in nucleophilic substitution reaction. This
lack of reactivity is due to several factors. In aryl halide the carbon chlorine bond is σ
bond. However, one of the p-orbital of chlorine having a pair of electrons is parallel to
the delocalized p-orbitals of the benzene nucleus. This p-orbital of chlorine can also
overlap with the delocalized p-orbitals of benzene nucleus. Thus the bond between
carbon and chlorine becomes strong.
The delocalized π MO gives partial double bond character to C-Cl bond in aryl halides.

Another reason for the low reactivity of aryl halide towards nucleophilic substitution
reaction is the π electron cloud in aromatic ring with which does not allow the
nucleophile to attack easily on benzene ring.
 Aryl halides cannot proceed through SN1-type processes because carbon- halogen bonds of
aryl halides are too strong, and aryl cations formed during the reaction are highly unstable
due to high in energy.

Aryl halides also cannot be proceeding through SN2-type process, because the aromatic
ring blocks the approach of the nucleophile to carbon at the side opposite the bond to the
leaving group. Inversion of configuration is impossible.
Nucleophilic substitution in nitro substituted aryl halides (SNAr)

Aryl halides consists of strong electron withdrawing group such as a nitro group ortho or
para to the halogen undergo nucleophilic substitution readily
Aryl fluorides undergo nucleophilic substitution reaction when ring bears an o- or a p- nitro
group.

These reactions follow a second order rate law:

Rate = k[Aryl halide][Nucleophile]

Mechanism of second order nucleophilic aromatic substitution reaction (SNAr) can

be of following two types.

1) Addition/elimination mechanism
2) Elimination /addition mechanism
Addition /elimination mechanism
General schematic representation for addition elimination reaction: It is two step reaction.

Step I: In this step incoming nucleophile Step II: In second step the leaving group
attacks at the same position where the detached leading to regeneration of
leaving group is attached. Such attack is aromaticity in benzene ring.
known as ipso attack.
Elimination/ Addition mechanism
Elimination/Addition mechanism is proceeding via benzyne mechanism. The benzyne
intermediate has triple bond in benzene ring during the transition stage. Benzyne
intermediate is highly reactive and they rapidly undergo nucleophilic substitution reaction.
Aryl halides undergo substitution by the benzyne mechanism only in the presence of very
strong bases such as alkali metal amide and organolithium reagents or somewhat weaker
bases under vigorous conditions.

Elimination

In first step elimination of H and X (Halide) Loss of halide ion to form benzyne
occurs to give benzyne. Elimination itself
comprises of two steps. Abstraction of a
hydrogen ion by the strong base
Addition

In second step addition of nucleophile and Protonation of anion by reaction with acid,
H occurs to give overall substitution ammonia etc.
product.
Electrophilic substitution reaction of Aryl halides

Aryl halides are reactive towards the electrophilic aromatic substitution but they are less
reactive than benzene because halides are weak deactivators. The weak deactivation is
due to the electronegativity of the halogen making the intermediate cations less stable
than those produced when benzene undergoes substitution. Halides are o- or p- directing
groups.

Other reactions
Wurtz- Fittig reaction- When aryl halide is treated with ethereal solution of alkyl
halide, in the presence of sodium, we obtain an alkyl benzene.
When only aryl halide is treated with sodium diaryl are produced, this reaction is called
fittig reaction.

Reduction – Aryl halide are reduced by Nickel- Aluminium alloy in alkali or sodium
amulgum and aqueous alcohol in the presence of alkali.
Formation of Grignard reagent: When Aryl halides and Iodides are treated with
magnesium turnings in dry ether they form Grignard reagent. Aryl chloride form
Grignard reagent only when the reaction is carried out in dry tetra hydro furan (THF) as
solvent.
RELATIVE REACTIVITY OF ALKYL HALIDES vs ALLYL, VINYL AND
ARYL HALIDES

Aryl halide for example chlorobenzene has carbon atom in ring which has p-
orbital available for overlapping with p-orbital of chlorine atom and thus the p-
orbital carbon atom overlap with the p-orbital of attached Cl- atom. Hence the Cl-
atom is firmly attached with the C-atom of benzene ring.

Moreover the bond between the C-atom in the benzene ring has partial double
bond character due to delocalization of electrons in the benzene ring. All these
factors make it difficult for aryl halide to undergo SN1 or SN2 reactions and thus
they are least reactive in nature. In case of vinyl halide also the side wise
overlapping of the p-orbitals of carbon atom occurs with Cl- atom.

Thus there is sidewise overlapping in the vinyl halide which makes it difficult to
undergo SN1 or SN2 reactions and they are also less reactive. However in case of
alkyl halide carbon atom attached to halide atom does not have any unhybridised
p-orbital to overlap with the p-orbital of the Cl-atom and Hence it is easy for them
to undergo SN1 and SN2 substitution reactions.

The allyl cation has delocalization which decreases the energy of the system. This
makes it easier to remove a halide.
Synthesis of 1, 1-Bis (4-Chlorophenyl)-2, 2, 2-Trichloroethane, (DDT)

DDT is used as insecticide. DDT was initially used

by the military in World War II to control malaria,
typhus, body lice, and bubonic plague. DDT is still
used today in South America, Africa, and Asia for
this purpose. Farmers used DDT on a variety of
food crops in the United States and worldwide.
DDT was also used in buildings for pest control.
DDT was so widely used was because it is effective,
relatively inexpensive to manufacture, and lasts a
long time in the environment. DDT is slightly to
moderately acutely toxic to mammals, including
people, if eaten. DDT is poorly absorbed through
mammalian skin, but it is easily absorbed through
an insect’s outer covering known as an
exoskeleton.People exposed to DDT while working
with the chemical or by accidental exposure report a
prickling sensation of the mouth, nausea, dizziness,
confusion, headache, lethargy, in coordination,
vomiting, fatigue, and tremors .
Benzene hexa chloride:

For benzene hexa chloride eight isomers are possible but only seven are known. One of
these isomers is an insecticide called lindane, or Gammexane (γ- isomer). Gama Benzene
Hexachloride is used for the treatment, control, prevention, & improvement of the
contagious and itchy human head infection mites skin disease and lice skin disease.
There are various side effect of BHC as insomnia, paresthesia, giddiness, dizziness,
headache, nausea, vomiting, restlessness, skin irritation, contact dermatitis if used in
excess quantity.