1718344030

Haloalkanes &
Haloarenes
Telegram/ @padhleakshay
Introduction
The replacement of hydrogen atom in an aliphatic hydrocarbon by halogen atom
results in the formation of alkyl halide also known as haloalkane.
The replacement of hydrogen atom in an aromatic hydrocarbon by a halogen atom
results in the formation of haloarene.
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Remember
Classification of Halogen Derivatives

On the bases of No. of Halogen atoms present , this can be classified as mono,
di, tri, tetra etc.
CH 2 X CH 2 X
C 2 H5 X CH 2 X
CH 2 X
Monohaloalkane
CH 2 X
dihaloalkane
Trihaloalkane YouTube/@padhleakshay
On the basis of the nature of the carbon to which halogen atom is attached,
halogen derivatives are classified as 1 o ,2 o ,3o , allylic, benzylic, vinylic
and aryl derivatives.

(a) Alkyl halides or halo alkanes (R—X)
H R’ R’
R’ C X R” C X R” C X
H H R”’
Primary(1 o ) Secondary(2 o ) Tertiary(3 o )
(b) Benzylic halides: The structure in which halogen atom is attached to an sp3 -
hybridised carbon atom next to an aromatic ring.
R’
CH2 X X
R”
(c) Vinylic halides: The structure in which halogen atom is bonded to an sp2-
hybridised carbon atom of a carbon-carbon double bond (C = C).
X
X
H2 C
(d) Aryl halides: The structure in which halogen atom is bonded to the sp2-
hybridised carbon atom of an aromatic ring.
YouTube/@padhleakshay
Nomenclature
The common names of alkyl halides are derived by naming the alkyl group
followed by the halide.
Alkyl halides are named as halo substituted hydrocarbons in the IUPAC system of
nomenclature.
The carbon containing double or triple bond is given the least number.
Place the suitable suffix like di, tri, tetra for 2, 3, 4 halogen atoms respectively.
Name the compounds as halo alkanes, halo alkenes or halo alkynes.
Example:
Numerical prefixes (1,2) ; (1,3) ; (1,4) for [for positions of the compound with
respect to halogen atom.
Example:
Remember
Structure Common Name IUPAC Name
Nature of C-X Bond
What
The nature of the C-X bond depends on both the nature of carbon in the
aromatic ring and the halogen attached.
Halogens are generally denoted by “X”.
The carbon atom of the alkyl halide possesses a partial positive charge. The
halogen atom on the other hand possesses a partial negative charge.
The carbon-halogen bond length increases from C—F to C—I due to the increase in
the size of halogen atom while going down the group in a periodic table from
fluorine to iodine atom.
Example:
δ+ δ-
C X
Remember
Methods of Preparation of
haloalkanes
Allylic halogenations:
Br
H H
Allylic Hv
Br2
Position
By halogenations of alkanes in presence of light, catalyst or

heat:
Ethane ChloroEthane
By halogenations of alkenes with HX :
Hunsdiecker reactions:
The Hunsdiecker reaction is an instance of a halogenation reaction which involves
an organic between silver salts of carboxylic acids and halogens resulting in the
formation of organic halides.
Preparation of alkyl halides from alcohols:

Treatment of alcohol with HCl in the presence of anhydrous ZnCl2 phosphorous
pentachloride, PX3(P4 + X2)or SOCl2 leads to the preparation of alkyl halide.
Remember
1 and 2 degree alcohols require anhydrous ZnCl2 while alcohols do not require
ZnCl2. Mixture of conc. HCl and anhydrous ZnCl2 is called Lucas reagent.
Primary and secondary alkyl chlorides are prepared from their respective alcohols
by using HCl gas and anhydrous ZnCl2.
Physical Properties of
Haloalkanes
Exist in various physical states (gases, liquids, or solids) at room temperature, YouTube/@padhleakshay
depending on the specific haloalkane and its molecular structure.
Higher boiling and melting points compared to their parent alkanes with the same
number of carbon atoms due to stronger intermolecular forces.
Generally less soluble in water but soluble in nonpolar and organic solvents.
May have distinct odors, which can vary depending on the specific haloalkane.
Chemical Properties of
Haloalkanes
Contain polar carbon-halogen bonds due to electronegativity differences.
Display reactivity in nucleophilic substitution and elimination reactions:
1. SN1 Reaction: Unimolecular nucleophilic substitution reaction.
2. SN2 Reaction: Bimolecular nucleophilic substitution reaction.
E1 Reaction: Unimolecular elimination reaction.
E2 Reaction: Bimolecular elimination reaction.
Can undergo reactions with metals or other reagents to form organometallic
compounds.
Certain haloalkanes, such as chlorofluorocarbons (CFCs), have been implicated
in ozone depletion and are regulated internationally.
May exhibit structural isomerism based on the arrangement of atoms in the
molecule.
Substitution reaction in
haloalkanes
Nucleophilic substitution reactions are most common reactions of alkyl halides.

The most common nucleophiles are :
OH- , CN-, NO 2-, SH-, NH 2 -, OR- and RCOO-
Nucleophilic substitution may take place in two ways:

a) SN1 Mechanism
b) SN2 Mechanism
Example:
1. SN1 mechanism:
The SN1 reaction is a substitution nucleophilic unimolecular reaction.
It is a two-step reaction.
This reaction is carried out in polar protic solvents such as water, alcohol,
acetic acid etc. This reaction follows first order kinetics.
X- Nu-
R X R+ R Nu
Slow Fast
Remember
More stable will be the carbocation intermediate; faster will be the SN1
mechanism.
If the initial compound is chiral then SN1 reaction ends up with racemization
of the product.
Weaker bases being leaving group favor SN1 reaction.
Example:
SN1 reaction and conditions required for it:

SN1 reaction occurs faster if the carbocation intermediate is more stable and
has a lower activation barrier.
3̊ carbocation > 2̊ carbocation > 1̊ carbocation.

2. SN2 mechanism:
formation of another enantiomer is lead by SN2 reaction of an optically active
halide i.e. optical activity is retained but with opposite configuration.
Remember
The solvent is Protic or Aprotic.
To stabilize the intermediate stage.
In SN2 reaction the stereochemistry around carbon atom of the substrate
undergoes inversion and is known as walden inversion.
The rate of reaction depends on the steric bulk of the alkyl group.
Increase in the length of alkyl group decreases the rate of reaction. Alkyl
branching next to the leaving group decreases the rate drastically.
The alkyl is secondary and tertiary.
Methods of Preparation of
aryl halides YouTube/@padhleakshay
From phenol:
By Hunsdiecker reaction:
Sandmeyer reaction
Diazonium salts are highly reactive compounds used to prepare arene derivatives.
Gattermann reaction:
Haloarenes can also be prepared by reaction of benzene diazonium chloride with
copper powder in the presence of corresponding halogen acid.
This reaction is termed as Gattermann reaction.

Ye sab to padh hi
lena
Nuclear halogenations:
This method can be used to prepare aryl chlorides and bromides.
In the presence of halogen carrier like AlCl3, FeCl3 etc. at low temperatures. It is
an electrophilic substitution.
Comparison of E1 and E2:
1. E1 reaction is favored by polar protic solvent because it accelerates the
reaction by solvating halide ion forming carbonium ion .
2. E1 reaction requires little higher temperature.

3. E2 reaction is favored by strong base .
4. E2 reaction is decelerated by polar protic solvent.
Important:
Order of reactivity is same for both the reaction i.e. 3̊ > 2̊ > 1̊ .
Strong nucleophile & Weak

Nucleophile
Strong nucleophile:
1. A strong nucleophile is a chemical species or ion that is highly reactive and
readily donates a pair of electrons to form a new covalent bond with an
electron-deficient atom or molecule.
2. Strong nucleophiles are important in various chemical reactions, particularly in
organic synthesis and mechanisms such as nucleophilic substitution and
nucleophilic addition reactions.
Example:
NaOR, RLi, NaOH or KOH, NaCN or KCN,
NaCCR, NaNH2, NaNHR, NaI, LiBr, KI, NaN3.
Weak Nucleophile:
1. Weak nucleophiles are chemical species or ions that have limited reactivity in
donating a pair of electrons to form new covalent bonds in nucleophilic
reactions.
2. These nucleophiles are less likely to participate in nucleophilic substitution or
addition reactions when compared to strong nucleophiles.
Example:
Water (H2O), ROH, NH3, RC≡N, Esters (RCOOR'),
RCOOH, Aldehydes and Ketones.
Polyhalogen Compounds
Carbon compounds containing more than one halogen atom are usually
referred to as polyhalogen compounds.
Example:
CFCl3,CH2Cl2
1. Dichloromethane (Methylene chloride): YouTube/@padhleakshay
a) Dichloromethane is a colourless, sweet-smelling, volatile liquid having low

boiling point. It is insoluble in water.
b) It is used as a solvent as a paint remover, as a propellant in aerosols, and
as a process solvent in the manufacture of drugs.
c) It is used as a metal cleaning and finishing solvent.
b) Exposure to lower levels of methylene chloride in air can lead to slightly
impaired hearing and vision.
2. Trichloromethane (Chloroform):
a) Chloroform is a sweet smelling, heavy and colorless liquid. It has a low B.P.
of 61o.
b) CHCl3 is manufactured by chlorination of methane followed by separation
by fractional distillation.
c) Chloroform was once used as a general anaesthetic in surgery. However, this
use has been discontinued, as there are a number of safer alternatives.
d) Breathing about 900 parts of chloroform per million parts of air
chloroform even for a short time, can cause dizziness, fatigue and headache.
e) Chronic chloroform exposure may cause damage to the kidneys and liver.
3. Tetrachloromethane (Carbon tetrachloride): YouTube/@padhleakshay

a) They are also used for the synthesis of chlorofluorocarbons, pharmaceutical
etc.
b) It was extensively used as cleaning agent in industry and as a degreasing
agent at home as well.
c) It is also used as a spot remover and fire extinguisher.
d) Exposure to CCl4 can adversely affect the heart beat and make it beat
irregularly or make it permanently stop.
e) Exposure to eyes can cause irritation.
f) Exposure to atmosphere can lead ozone depletion that may lead to rise in
the level of exposure to ultraviolet rays. This in turn leads to increased risk of
skin cancer, eye diseases and other disorders as well as weakened immune
system.
g) They are used in manufacturing refrigerants and propellants for aerosol
cans.
4. Triiodomethane (Iodoform):
a) Triiodomethane (or) iodoform, is a pale yellow, crystalline solid, has a

pungent, medicine-like odour.
b) Iodoform was used earlier as an antiseptic due to the liberation of free
iodine but due to its objectionable smell, it has been replaced by other
formulations containing iodine.
5. Freons:
a) Freons are chlorofluorocarbon derivatives of methane and ethane. They are
non-toxic, non-corrosive and easily liquefiable gases.
b) Dichloro difluoro methane or Freon-12 (CCl2F2) is one of the most common

freons and is manufactured from tetrachloromethane by Swarts reaction.
c) Freon-12 useful in aerosol propellants, refrigeration and air conditioning.
d) Freon-12 and other chlorofluorocarbons are known to initiate radical chain
reactions that lead to the destruction of the ozone layer.
6. DDT( p,p'-Dichlorodiphenyltrichloroethane):
Sabse jada
puche jana wlaa
topic
a) It is used to prevent insect-transmitted human diseases, such as malaria,
spread by mosquitoes, and typhus, spread by lice.
b) DDT is toxic to many species of fish. . It is stored in the fatty tissues of the
body and is metabolised very slowly.
c) The use of DDT in agriculture has also lead to measurable DDT levels in
humans.
NCERT QUESTION
Q1. Write the structures of the following organic halogen compounds.
(i) 2 -Chloro-3 -methylpentane
(ii) p -Bromochlorobenzene
(iii) 1 -Chloro-4-ethylcyclohexane
(iv) 2 – (2 -Chlorophenyl) -1 -iodooctane
Ans:
(i).
(ii).
(iii).
(iv).
Q2. Which one of the following has the highest dipole moment?
(i) CH2Cl2
(ii) CHCl3
(iii) CCl4
Ans.
Q3. What are ambident nucleophiles? Explain with an example.
Ans. When there are two nucleophilic sites in a nucleophile, they are called
ambident nucleophile. These nucleophilic sites are sites through which they can
attack.
For ex- Nitrite ion
Q4. Write the structure of the major organic product in each of the following
reactions: YouTube/@padhleakshay
Ans: (i).
(ii).
(iii).
(iv).
(v).
(vi).
(vii).
(viii).
Q5. The treatment of alkyl chlorides with aqueous KOH leads to the formation
of alcohols but in the presence of alcoholic KOH, alkenes are major products.
Explain.
Ans. In an aqueous solution, KOH almost completely ionizes to give OH− ions.
OH− ion is a strong nucleophile, which leads the alkyl chloride to undergo a
substitution reaction to form alcohol.
On the other hand, an alcoholic solution of KOH contains alkoxide (RO−) ion,
which is a strong base. Thus, it can abstract a hydrogen from the β-carbon of
the alkyl chloride and form an alkene by eliminating a molecule of HCl.
Remember
OH− ion is a much weaker base than RO− ion. Also, OH− ion is highly solvated in
an aqueous solution and as a result, the basic character of OH− ion decreases.
Therefore, it cannot abstract a hydrogen from the β-carbon.
After studying from this notes you got
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Haloalkanes &

Classification of Halogen Derivatives

halogen derivatives are classified as 1 o ,2 o ,3o , allylic, benzylic, vinylic

and aryl derivatives.

Structure Common Name IUPAC Name

By halogenations of alkanes in presence of light, catalyst or

By halogenations of alkenes with HX :

Preparation of alkyl halides from alcohols:

by using HCl gas and anhydrous ZnCl2.

depending on the specific haloalkane and its molecular structure.

number of carbon atoms due to stronger intermolecular forces.

Display reactivity in nucleophilic substitution and elimination reactions:

1. SN1 Reaction: Unimolecular nucleophilic substitution reaction.

2. SN2 Reaction: Bimolecular nucleophilic substitution reaction.

E1 Reaction: Unimolecular elimination reaction.

E2 Reaction: Bimolecular elimination reaction.

Can undergo reactions with metals or other reagents to form organometallic

in ozone depletion and are regulated internationally.

May exhibit structural isomerism based on the arrangement of atoms in the

Nucleophilic substitution reactions are most common reactions of alkyl halides.

OH- , CN-, NO 2-, SH-, NH 2 -, OR- and RCOO-

Nucleophilic substitution may take place in two ways:

SN1 reaction and conditions required for it:

3̊ carbocation > 2̊ carbocation > 1̊ carbocation.

The solvent is Protic or Aprotic.

Haloarenes can also be prepared by reaction of benzene diazonium chloride with

copper powder in the presence of corresponding halogen acid.

This reaction is termed as Gattermann reaction.

Comparison of E1 and E2:

1. E1 reaction is favored by polar protic solvent because it accelerates the

reaction by solvating halide ion forming carbonium ion .

2. E1 reaction requires little higher temperature.

4. E2 reaction is decelerated by polar protic solvent.

Strong nucleophile & Weak

1. A strong nucleophile is a chemical species or ion that is highly reactive and

electron-deficient atom or molecule.

2. Strong nucleophiles are important in various chemical reactions, particularly in

organic synthesis and mechanisms such as nucleophilic substitution and

nucleophilic addition reactions.

donating a pair of electrons to form new covalent bonds in nucleophilic

a) Dichloromethane is a colourless, sweet-smelling, volatile liquid having low

3. Tetrachloromethane (Carbon tetrachloride): YouTube/@padhleakshay

a) Triiodomethane (or) iodoform, is a pale yellow, crystalline solid, has a

non-toxic, non-corrosive and easily liquefiable gases.

b) Dichloro difluoro methane or Freon-12 (CCl2​F2​) is one of the most common

After studying from this notes you got

Note: Important worksheet (question) of all typology with answeris

You might also like

b) Dichloro difluoro methane or Freon-12 (CCl2F2) is one of the most common