SRI ADICHUNCHANAGIRI INDEPENDENT PU COLLEGE, SHIMOGA

II PUC - Online Classes

SUBJECT : CHEMISTRY
Topic : Haloalkanes and Haloarenes
For II PU Board Examination: 6M [ 1M + 5M]
Definitions:
 The replacement of hydrogen atom(s) in aliphatic hydrocarbon, by halogen atom(s) results in the
formation of haloalkane.

 The replacement of hydrogen atom(s) in aromatic hydrocarbon, by halogen atom(s) results in the
formation of haloarene.

Applications:
Name Uses
Chloramphenicol produced by soil microorganisms is very effective for the treatment of typhoid fever.
Thyroxine the deficiency of this hormone causes a disease called goiter.
Chloroquine is used for the treatment of malaria
Halothane is used as an anaesthetic during surgery

Classification:Haloalkanes and haloarenes may be classified as follows

 On the Basis of Number of Halogen Atoms: These may be classified as mono, di, or
polyhalogen (tri-,tetra-, etc.)compounds depending on whether they contain one, two or more halogen
atoms in their structures.
For Example:

Monohalo compounds may further be classified according to the hybridisation of the carbon atom to which
the halogen is bonded. They are as follows

Compounds Containing sp3 C—X Bond (X= F, Cl, Br, I) :

(a) Alkyl halides or haloalkanes (R—X) :In these compounds, the halogen atom is bonded to an alkyl
group (R).
 They are generally represented by CnH2n+1X or R-X.
 They are further classified as primary(10), secondary (20 ) and tertiary(30) 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) i.e. to an allylic carbon.

(c) Benzylic halides :These are the compounds in which the halogen atom is bonded to an sp3hybridised
carbon atom next to an aromatic ring.

Compounds Containing sp2 C—X Bond:

(a)Vinylic halides:These are the compounds in which the halogen atom is bonded to an sp2hybridised
carbon atom of a carbon-carbon double bond (C = C).

(b) Aryl halides or Haloarenes: These are the compounds in which the halogen atom is directly bonded
to an aromatic ring.

 Dihaloalkanes:The dihalo-compounds having same type of halogen atoms are further classified as
1. Geminal halides or alkylidene halides: Both halogen atoms are present on the same carbon atom.

common name:Ethylidene chloride

H3C CH Cl
IUPAC name: 1,1-Dichloroethane
Cl

2. Vicinal halides or alkylene dihalides: Both halogen atoms are present on the adjacent carbon atoms.
common name:Ethylene dichloride
Cl CH2 CH2 Cl
IUPAC name: 1,2-Dichloroethane

Nomenclature:
 The common name of these compounds are alkyl halides and are derived by naming the alkyl group
first followed by the name of halide.
 According to IUPAC system, these compounds are called haloalkanes in which halogen is a prefix and
followed by the name of the alkane.
 The longest continuous carbon chain containing halogen atom is selected as parent alkane.
 The carbon chain is numbered in such a way that the carbon carrying substituent (it may alkyl or
halogen) gets lowest number.
 If multiple bond is present , then it is given the least preference in numbering the carbon chain.
 When different kinds of substituents are present then alphabetical order is followed.
 If same kinds of substituents are present then labelled with Greek numerical prefix such as di, tri, tetra
etc .

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Nomenclature for Haloarenes
 For mono halogen substituted derivatives of benzene, common and IUPAC names are the same.
 For dihalogen derivatives, the prefixes o-, m-, p- are used in common system but in IUPAC system, the
numerals 1,2 ; 1,3 and 1,4 are used.
 When different halogen atoms are present on the ring halogen atoms are named in an alphabetical order
after their proper numbering is done.

Note: Halogen substituent and alkyl substituent have equal priority but in case of Tie halogen takes
priority over alkyl group.

Structure Common Name IUPAC

CH3CH2CH(Cl)CH3 sec-Butyl chloride 2-Chlorobutane
(CH3)3CCH2Br neo-Pentyl bromide 1-Bromo-2,2-dimethylpropane

(CH3)3CBr tert-Butyl bromide 2-Bromo-2-methylpropane

CH2 = CHCl Vinyl chloride Chloroethene

CH2 = CHCH2Br Allyl bromide 3-Bromopropene

CH2Cl2 Methylene chloride Dichloromethane

CHCl3 Chloroform Trichloromethane

CHBr3 Bromoform Tribromomethane

CCl4 Carbon tetrachloride Tetrachloromethane

CH3CH2CH2F n-Propyl fluoride 1-Fluoropropane

CH3CH(Cl)CH3 Isopropyl chloride 2-chloropropane
CH3CH(CH3)CH2Cl Isobutyl chloride 1-chloro-2-methyl propane
Br

Bromobenzene Bromobenzene

Br

m-Dibromobenzene 1,3-Dibromobenzene

Br

For additional IUPAC names solve example 10.2 and 10.1 intext questions in NCERT textbook.

 Nature of C—X bond:Since halogen atoms are more electronegative than carbon, the carbon atom
bears partial positive charge whereas the halogen atom bears partial negative charge, hence the resulting
bond is polar covalent bond.

 As we go down the group in the periodic table, the size of halogenatom increases. Fluorine atom is the
smallest and iodine atom is thelargest.

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 Competitive Corner
Bond Bond length/pm C-X Bond enthalpies/ kJmol -1
Dipole moment/Debye
CH3–F 139 452 1.847
CH3–Cl 178 351 1.860
CH3–Br 193 293 1.830
CH3–I 214 234 1.636

METHODS OF PREPARATION:

1. From Alcohols: Alkyl halides are best prepared from alcohols.

a) Using halogen acids/hydracids/Grooves process:Alcohols are treated with hydrogen halides in
presence of zinc chloride to form haloalkanes.

Alcohol hydrogen halides alkyl halide water

 Preparation of alkyl chloride: when alcohol is heated with HCl alkyl chloride is obtained. The
reactions of primary and secondary alcohols with HCl require the presence of a catalyst, ZnCl2. With
tertiary alcohols, the reaction is conducted by simply shaking with concentrated HCl at room
temperature.

Eg:
 Preparation of alkyl bromide: Constant boiling with HBr (48%) in the presence of H2SO4 is used for
preparing alkyl bromide.
H2SO4
R-OH +HBr R-Br + H2O
Or

Alcohol Sodium Bromide Sulphuric acid Alkyl bromide sodium bisulphate

 Preparation of alkyl iodide: Good yields of R—I may be obtained by heating alcohols with sodium or
potassium iodide in 95% phosphoric acid.

Competitive Corner
 The order of reactivity of Alcohols are 30> 20 > 10
 The order of reactivity of Hydrogen Halides are HI>HBr>HCl>HF

b) Using phosphorus halides:Alcohols when treated with PX3 or PX5 (X= Cl, Br) forms alkyl halides.

Alcohol phosphorous trihalides alkyl halide phosphorous acid

Alcohol phosphorous pentachloride alkyl chloride phosphorous oxychloride

 Phosphorus tribromide and triiodide are usually generated in situ (produced in the reaction mixture)
by the reaction of red phosphorus with bromine and iodine respectively.

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c) Using thionyl chloride/ Darzen’s method: Alkyl chloride can be obtained by heating alcohol with
thionyl chloride in the presence of pyridine as catalyst.

Competitive Corner:
 Thionyl chloride is best method for the preparation of alkyl chloride because since both the
byproducts (SO2 and HCl) are gaseous and escape easily.
 Alkyl bromide and alkyl iodide cannot be prepared from this method because thionyl bromide is
unstable and thionyl iodide doesnot exist.

2. From Hydrocarbons
i. From alkanes (By free radical halogenations): When alkanes react with halogens in the presence of
diffused sunlight, alkyl halides are formed.
Sunlight
CH4+ Cl2 CH3Cl +HCl.

Competitive Corner
This method is least preferred for the preparation of alkyl halides because the yield of any one
compound is low, the mixture of products are obtained which is difficult to separate as pure
compounds
ii.From alkenes:
a.Addition of Hydrogen halides:When alkene reacts with halogen acids (HCl,HBr or HI )
corresponding alkyl halide is formed. Addition takes place according to Markovnikov’s rule.

b) Addition of halogens: When alkenes react with halogen in CCl4, dihaloalkane is formed. addition
of bromine in CCl4 to an alkene resulting in discharge of reddish brown colour of bromine
constitutes an important method for the detection of double bond in a molecule. The addition
results in the synthesis of vic-dibromides, which are colourless .

3. Halogen Exchange:
a) Finkelstein reaction: Alkyl iodides are often prepared by the reaction of alkyl chlorides/ bromides
with NaI in dry acetone. This reaction is known as Finkelstein reaction.

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b) Swarts reaction: alkyl fluorides are prepared by heating an alkyl chloride/ bromide in the presence
AgF. The reaction is termed as Swarts reaction.

Competitive Corner
 In Finkelstein reaction, NaCl or NaBr thus formed is precipitated in dry acetone. It facilitates the forward
reaction according to Le Chatelier’s principle.
 In Swarts reaction can also be carried out by using metallic fluroides such as Hg2F2, CoF2, SbF3.

METHOD OF PREPARATION OF HALOARENES:

1. By electrophilic substitution: Aryl chlorides and bromides can be easily prepared by
electrophilic substitution of arenes with chlorine and bromine respectively in the presence of Lewis
acid catalysts like iron or iron(III) chloride.

Competitive Corner
 The ortho and para isomers can be easily separated due to large difference in their melting points.
 Reactions with iodine are reversible in nature and require the presence of an oxidising agent (HNO3,
HIO4) to oxidise the HI formed during iodination.
 Fluoro compounds are not prepared by this method due to high reactivity of fluorine.

2. Sandmeyer’s reaction:Aniline is dissolved in dilute HCl, and treated with ice cold solution of sodium
nitrite to get benzene diazonium chloride, this reaction is called diazotisation.

Benzene diazonium chloride on warming with cuprous chloride (Cu2Cl2) forms chlorobenzene, this reaction
is called Sandmeyer’s reaction.

PHYSICAL PROPERTIES:
1. Physical state and Odour :
 Haloalkanes are colorless, sweet-smelling liquids.
 The lower members like methyl chloride, methyl bromide and ethyl chloride are colorless gases while
members having very high molecular masses are solids.
 Aryl halides are colourless liquids with pleasant smell.

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2. Boiling points and melting point:
 The boiling point and melting point depends on molar mass (vanderwaals force), Hence with increase in
the number of carbon atom in chain the boiling point also increases.
 The boiling point of halides increases in the order RI>RBr>RCl> RF.
 In the case of isomers, as the number of branches increases boiling point decreases due to decrease in
surface area.
 Boiling point of alkyl halides are higher than the corresponding hydrocarbons because of higher
intermolecular force of attraction (dipole-dipole interaction) in alkyl halides.
 In the case of Haloarenes isomers, para isomer has higher melting point compared to ortho and meta
due to symmetry in para isomer

3. Density:
 Density depends on molar mass increases in the order RI>RBr>RCl> RF.
 The density increases with increase in number of carbon atoms and halogen atoms.
 Alkyl bromides and iodides are denser than water and alkyl fluorides and chlorides are lighter than
water

4. Solubility:
Although haloalkanes are polar in nature, yet they are practically very slightly soluble in water because less
energy is released when new attractions are set up between haloalkanes and water molecules, these
force is not strong as hydrogen bond in water molecules.

CHEMICAL REACTIONS OF HALOALKANES :

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:

In this type of reaction, a nucleophile attacks the partial positive charged carbon atom in C—X bond , as a
result substitution reaction takes place forming a new C—Nu bond and the halogen atom leaves as
halide ion.

Ex:
1. CH3Cl + NaOH  CH3OH + NaCl
Methyl chloride Sodium hydroxide Methyl alcohol sodium chloride

2. CH3Cl + NaOCH3  CH3OCH3 +NaCl

Methyl chloride Sodium methoxide dimethyl ether sodium chloride

3. CH3Cl + NH3  CH3NH2 + HCl

Methyl chloride Ammonia Methyl amine Hydrogen chloride

4. CH3Cl + KCN  CH3CN + KCl

Methyl chloride Potassium cyanide Methyl cyanide potassium chloride

5. CH3Cl +AgCN  CH3NC + AgCl

Methyl chloride Silver cyanide Methyl isocyanide silver chloride

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 Competitive Corner
 Groups like cyanides and nitrites possess two nucleophilic centres and are called ambident nucleophiles.
 KCN is predominantly ionic and provides cyanide ions in solution. The bonding takes place through C-
atom as the C-C bond is more stable than C-N bond.
 AgCN is mainly covalent in nature and nitrogen is free to donate electron pair forming isocyanide as the
main product.
 Like KCN, KNO2 form R-ONO (alkyl nitrite) while AgNO2 produces R-NO2 (Nitroalkane) as product.
 Vinyl chloride is less reactive towards nucleophilic substitution reactions due to resonance

STEREOCHEMICAL ASPECTS OF NUCLEOPHILIC SUBSTITUTION REACTIONS:

 Plane polarised light: It is a beam of light which has vibration in only one plane

 Optical activity: It is the process of rotating plane of polarized light is called optical activity.
 The compound which exhibits optical activity are called optically active compounds.

 Substance Which rotates plane polarised light to the right side(clockwise) are called dextrorotatory
substance. It is represented by ‘+’ or ‘d’ form.

 Substance Which rotates plane polarised light to the left side (anticlockwise) are called laevorotatory
substance. It is represented by ‘-’ or ‘l’ form.

 Optical isomerism: - When two compounds having the same molecular formula and structural formula
differ in the direction of rotation of the plane polarized light, they are said to be exhibit optical
isomerism.

 Polarimeter: It is an instrument used to find degree of rotation of plane polarised light.

 Asymmetric carbon or stereocentre or Chiral carbon atom: The carbon atom is attached to four
different atoms or group of atoms. It is denoted by asterisk(*) mark.
 The molecule having stereocentre exhibits optical activity.
 Chiral: The objects which are non -superimposable on their mirror images are known as chiral and the
property is known as chirality.
Eg: 2-butanol
 Achiral: The objects which are superimposable on their mirror images are known as achiral.
Eg: 2-propanol
 Enantiomers: are stereoisomers which are non-superimposable mirror images.
Eg: d-lactic acid and l-lactic acid
 Racemic mixture: Equimolar mixture of both dextro and laevo rotatory isomers.
Competitive Corner
 Enantiomers possess identical physical properties namely, melting point, boiling point, solubility,
refractive index, etc. They only differ with respect to the rotation of plane polarised light. If one of the
enantiomer is dextro rotatory, the other will be laevo rotatory.
 Racemic mixture is optically inactive because the rotation of one isomer will be cancelled by the
rotation of other isomer

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 Retention: In this configuration reactant retain its own spatial arrangement of bonds even after the
completion of reaction.

 Inversion of configuration/ Walden Inversion: In this configuration reactant does not retain its own
spatial arrangement of bonds , after the completion of reaction.

 Racemisation:The process of conversion of enantiomer into a racemic mixture is known as

racemisation.

NUCLEOPHILIC REACTION MECHANISMS:

Nucleophilic reaction has been found to proceed by two different Mechanisms which are described below:
1. Substitution nucleophilicunimolecular (SN1): (SN1 mechanism)

MECHANISM :
Step 1:The haloalkane undergoes slow ionization in the presence of protic solvent to form a carbocation
and halide ion.

Step 2: The nucleophile attacks the carbocation to form tertiary butyl alcohol. This attack of OH- can be
from any side (either front or back) as carbocation is planar.

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 Competitive Corner
Kinetics of reaction: In this type of reaction the rate of the reaction depends only on the concentration of
haloalkanes and it is independent of the concentration of the nucleophile.
Rate = [Alkyl halide]
 SN1 reactions gives racemisation configuration. Actually the carbocation formed in the slow step(step
2) being sp2 hybridised is planar. The attack of the nucleophile may takes place from either side
resulting in a mixture of products, one having the same configuration(retention) as that of alkyl halide
and the other having opposite configuration(inversion)

2. Substitution nucleophilic bimolecular (SN2):

CH3Cl + KOH → CH3OH + KCl

MECHANISM:This mechanism involves only one step, when the nucleophile attacks the carbon of methyl
chloride from opposite direction it form transition state, As transition state is unstable there will be
cleavage of carbon- chlorine bond to form methyl alcohol.

Competitive Corner
Kinetics of reaction: This is a one step reaction hence the rate determining step involves two reactants
i.e. a molecule of alkyl halides & the nucleophile therefore the reaction is called bimolecular reaction
Rate  [Alkyl halide] [Nucleophile]
 SN2 mechanism has the inverted configuration as compared to the reactant. This is because
the nucleophile attaches itself on the side opposite to the one where the halogen atom is
present.
Order of reactivity of various alkyl halides SN1 and SN2 reactions :
 In case of alkyl halides, 30 alkyl halides undergo SN1 reaction very fast because of the high stability
of 30 carbocations.
 Methyl halides react most rapidly in SN2 reactions because there are only three small hydrogen atoms.
Tertiary halides are the least reactive because bulky groups hinder the approaching nucleophiles. Thus
the order of reactivity followed is: Primary halide > Secondary halide > Tertiary halide.
 The order of reactivity of alkyl halides towards SN1 and SN2 reactions as follows:

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 Note:Allylic and benzylic halides show high reactivity towards the SN1 reaction. The carbocation
thus formed gets stabilised through resonance as shown below.

 Difference between SN1 and SN2 reactions:

SN1 SN2
Rate depends only on the concentration of alkyl Rate depends on the concentration of both
halide. alkyl halide and nucleophile
It occurs in two steps It occurs in only one step
Racemisation configuration Inversion configuration
It does not involve transition state It involves transition state
Order of reactivity is 30>20>10 Order of reactivity is 10>20>30
It follows first order kinetics It follows second order kinetics

ii.ELIMINATION REACTIONS/ Dehydrohalogenation/ Saytzeff’s:

When a haloalkaneheated 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.

 If more than one β-hydrogen is present then a highly substituted alkene formed as a major product.
such reactions takes place according to Saytzeff’s rule

Saytzeff’s 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.”

iii.REACTION WITH METALS:

When an alkyl halide is treated with Magnesium in dry ether medium, alkyl magnesium halide called
Grignard reagent in obtained.
R – X + Mg  R – Mg – X

 In the Grignard reagent, the carbon-magnesium bond is covalentbut highly polar, with carbon pulling
electrons from electropositivemagnesium; the magnesium halogen bond is essentially ionic

 Grignard reagents are highly reactive and react with any source of proton to give hydrocarbons. It is
therefore necessary to avoid even traces of moisture

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 Competitive Corner
 Grignard reagents are highly reactive and react with any source of proton to give hydrocarbons. Even
water, alcohols, amines are sufficiently acidic to convert them to corresponding hydrocarbons.

 It is therefore necessary to avoid even traces of moisture from a Grignard reagent. That is why reaction
is carried out in dry ether. On the other hand, this could be considered as one of the methods for
converting halides to hydrocarbons..

2.Wurtz Reaction:
Alkyl halides heat with metallic sodium in dry ether medium to give alkanes.
ether
2R – X + 2Na R – R + 2Na X
ether
Eg: C2H5 Br + 2Na + Br- C2H5 C2H5 – C2H5 + 2NaBr
Ethyl bromide Butane
REACTIONS OF HALOARENES:
i.REACTION WITH METALS:
1. Fittig reaction: when aryl halides are heated with sodium in dry ether, two aryl groups join together
forming biphenyl.

2. Wurtz- Fittigreaction:When a mixture of alkyl halide and aryl halide is heated with sodium in dry ether
medium, alkyl benzene (alkylarene) is formed .

ii.Nucleophilic substitution:
Aryl halides are extremely less reactive towards nucleophilic substitution reactions due to the following
reasons:
1) Resonance effect: In haloarenes C—Cl bond acquires a partial double bond character due to resonance.
As a result, the bond cleavage in haloarene is difficult than haloalkane and therefore, they are less
reactive towards nucleophilic substitution reaction.

2) Difference in hybridisation of carbon atom in C—X bond: In haloarene C—X bond is less polar as C
is sp2 hybridised. However in haloalkane C—X bond is more polar as C is sp3 hybridized. As a result
C—X bond is shorter in haloarene and is difficult to break.

iii) Instability of phenyl cation :Phenyl cation is not resonance stablised.

iv) High electron density on benzene: Because of the possible repulsion, it is less likely for the electron
rich nucleophile to approach electron rich arenes.

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NUCLEOPHILIC SUBSTITUTION REACTION :
1. Replacement by hydroxyl group :Chlorobenzene can be converted into phenol by heating in aqueous
sodium hydroxide solution at a temperature of 623K and a pressure of 300 atmospheres.

Competitive Corner
 The presence of an electron withdrawing group (-NO2) at ortho- and para-positions increases
the reactivity of haloarenes towards nucleophilicreaction .
 As the number of electron withdrawing group increases, Nucleophilic reaction also increases

iii.ELECTROPHILIC SUBSTITUTION REACTIONS:

1. Halogenation: when chlorobenzene is heated with chlorine in the presence of anhydrous AlCl3 a mixture
of ortho and para dichlorobenzene is obtained.

2. Nitration: when chlorobenzene is heated with a mixture of concentrated HNO3 and concentrated H2SO4a
mixture of ortho and parachloronitrobenzene is formed.

3. Sulphonation: when chlorobenzene is heated with concentrated H2SO4 a mixture of ortho and
parachlorobenzenesulphonic acid is formed.

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4. Friedel- Crafts Reaction:
a) Friedel- Crafts alkylation: when chlorobenzene is heated with methyl chloride in the presence of
anhydrous AlCl3 catalyst a mixture of ortho and parachlorotoluene is formed.

b) Friedel- Crafts Acylation: when chlorobenzene is heated with acetyl chloride in the presence of
anhydrous AlCl3 catalyst a mixture of ortho and parachloroacetophenone is formed.

 USES OF POLYHALOGEN COMPOUNDS:

1. Dichloromethane (DCM) :It is used as a solvent for
 Paint remover.
 Manufacture of drugs.
 Metal cleansing and finishing.
 Propellant in aerosol
Effects:
 Affects central nervous system.
 Slightly impaired hearing and vision, dizziness, nausea , numbness and redness of skin.
2. Trichloromethane( Chloroform ):
 As a solvent for fats, alkaloids and iodine.
 In production of freons( Chloroflouro compounds of ethane and methane )
 Anaesthetic in surgery.
Effects:
 It depress the CNS.
 Cause dizziness,fatigue and headache.
 It damages liver , kidney and develop sores in skin.
 It gets oxidised by air in presence of light to form COCl2( Phosgene– a poisionous gas ), hence it is
stored in dark bottels in absence of air.
2CHCl3 + O22COCl2 + 2HCl (presence of sunlight).
3. Iodoform( CHI3 ) :
It is used as an antiseptic. But due to its objectional smell, it has been replaced by other suitable antiseptic
containing iodine.
4. Carbon tetrachloride ( CCl4) :
 Used in the manufacture of refrigerant and propellants.
 As cleansing agent and degreasing agent in industries.
 Spot remover and fire extinguisher at home.
Effects:
 It causes liver cancer, dizziness , vomiting and damages the nerve cells.
 It causes eye irritation and depletes the ozone layer.
5. Dichlorodiphenyltrichloroethane (DDT):
 It was used because of its effectiveness against mosquito , that spreads malaria and lice that carries
typhus.
 Being as an insecticide and very highly toxic , it has got high chemical stability hence is restricted the
use in many countries.

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SRI ADICHUNCHANAGIRI INDEPENDENT PU COLLEGE, SHIMOGA
II PUC - Online Classes
SUBJECT : CHEMISTRY
Topic : Haloalkanes and Haloarenes (1 Mark Questions)

Introduction:
1. What are haloalkanes?
These are the compounds formed by the replacement of hydrogen atom(s) by halogen atom(s) in
an aliphatic hydrocarbon.

2. What are haloarenes?

These are the compounds formed by the replacement of hydrogen atom(s) by halogen atom(s) in
an aromatic hydrocarbons.

3. Write the general formula of haloalkane /haloarenes.

CnH2n+1 or R-X

4. Name the hybridized state of carbon to which halogen attached in haloalkane.

sp3

5. Name the hybridized state of carbon to which halogen attached in haloarenes.

sp2

6. What is the use of the drug Chloramphenicol?

Chloramphenicol is chlorine containing antibiotic which is effective for the treatement of
typhoid.

7. Name the disease which causes the deficiency of Thyroxine.

Goiter

8. Name the synthetic drug which is used in the treatement of malaria

Chloroquine

Classification:
9. Give an example for monohaloalkane.
CH3Cl / C2H5Cl / CH3-CH(Cl)-CH3 etc

10. Give an example for dihaloalkane.

Cl-CH2-CH2-Cl / CH3-CH(Cl)2 etc.

11. Give an example for trihaloalkane.

(Cl)CH2-CH (Cl)-CH2 (Cl) / (Br) CH2-CH(Br)-CH2(Br) etc

12. Give an example for primary haloalkane.

CH3Cl /C2H5Br/CH3CH2CH2I etc

13. Give an example for secondary haloalkane.

CH3-CH (Cl)-CH3

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14. Give an example for tertiary haloalkane.

15. What are Allylic halides?

The compounds in which the halogen atom is bonded to an sp3 hybridised carbon atom next to
carbon-carbon double bond (i.e allylic carbon)
16. Give an example for Allylic halides.
Cl

CH2=CH-CH2-Cl /CH2=CH-CH2-Br /

17. What are Benzylic halide?

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

18. Give an example for Benzylic halide.

CH2Cl

19. What are Vinylic halides?

The compounds in which the halogen atom is bonded to an sp2 hybridised carbon atom of a
carbon – carbon double bond.

20. Give an example for Vinylic halide.

Cl

(OR) CH2=CH-Cl etc

21. What are Aryl halides?

The compounds in which the halogen atom is bonded to the sp2 hybridised carbon atom of an
aromatic ring.

22. Give an example for Aryl halide.

Cl

Nomenclature:
23. Write the IUPAC name for CH2=CH-CH2-CH2-Br
4-Bromobut-1-ene or 4-Bromobutene

24. Write the IUPAC name of the following compound CH3-CH-(CH3)-CH2Cl

1-Chloro-2-methyl propane

25. Write the structure of p-Bromochlorobenzene

Br

Cl

26. Give the IUPAC name of (CH3)3CBr

2-bromo-2-methylpropane

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27. Give the IUPAC name of Allyl bromide
3-bromopropane

Nature of C-X bond:

28. Give reason: Carbon – halogen bond in haloalkane is polar in nature.
Because, Halogen atom is more electronegative than carbon in haloalkane.

29. Write the increasing order of bond length of CH3F, CH3Cl, CH3Br and CH3I
CH3F < CH3Cl < CH3Br < CH3I

30. Write the decreasing order of Bond enthalpies of CH3F, CH3Cl, CH3Br and CH3I
CH3F>CH3Cl>CH3Br>CH3I

31. Write the increasing order of dipole moment of CH3F, CH3Cl, CH3Br and CH3I
CH3I < CH3Br < CH3F < CH3Cl

Preparation:
32. Write the general equation for the preparation of alkyl chlorides from alcohol using SOCl2
𝑝𝑦𝑟𝑖𝑑𝑖𝑛𝑒
R-OH + SOCl2 R-Cl + SO2+HCl

33. Preparation of haloalkane using thionyl chloride is preferable method. Why?

Because here the other two products formed are SO2 and HCl which are escapable gases. So the
reaction gives pure alkyl halide.

34. Write the general reaction for the preparation of haloalkane using phosphorous trihalides.

35. What is the role of red phosphorous in the preparation of haloalkane using alcohol.
Phosphorous tribromide and triiodides are prepared in situ by the reaction of red phosphous
with bromide and iodine respectively.

36. What is the role of ZnCl2 during the formation of haloalkane

It acts as a catalyst in the reaction of primary and secondary alcohol with halogen acid

37. Catalyst is not required during the preparation of haloalkane by using tertiary alcohol and
halogen acid. Why?
Tertiary alcohols react rapidly with halogen acid due the more stability of tertiary carbocation
than secondary and primary carbocation.

38. Aryl halides are not prepared by using the mixture of phenol and halogen acid. But alkyl
halides are prepared by mixing of alcohol with halogen acid. Why?
Because in phenol carbon-oxygen bond has a partial double bond character and is difficult to
break being stronger than a single bond.

39. Why Aryl fluoride is not formed during electrophilic substitution of arenes?
Because of high reactivity of fluorine.

40. How would you separate ortho and para isomers of aryl halides?
They can be separated by large difference in their melting points.

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41. Name the catalyst used in an electrophilic substitution of arenes.
Iron or Iron (III) chloride
42. Write the general equation for Sandmeyer’s reaction

43. Write the general equation for the preparation of iodobenzene from benzene diazonium
halide.

44. Write the reagent used for the replacement of diazonium group by chlorine.
Cuprous chloride (Cu2Cl2)

45. Write the major product when propene reacts with Hydrogen iodide.
CH3CHICH3

46. How would you identify the addition of double bond in a molecule?
An addition of bromine in carbon tetrachloride to an alkene results in the discharge of reddish
brown colour of bromine.

47. Write the equation for the preparation of vic- dibromide.

48. Name the reagent used in the reaction of alkyl halide in Finkelstein reaction.
Sodium iodide in dry acetone

49. Write the reagent used in the reaction of alkyl halide in Swartz reaction.
AgF/Hg2F2/CoF2/SbF3

50. Name the halogen exchange method for the preparation of halo alkanes.
Swartz reaction and Finkelstein reaction

51. H5C6- N2Cl + CuBr → H5C6 –Br + N2 Name the reaction

Sandmeyer’s reaction

52. H3C-Br + AgF → H3C-F + AgBr. Name the reaction.

Swartz reaction

53. What is the role of dry acetone in Finkelstein reaction?

It facilitates the forward reaction because formed NaCl and NaBr is precipitated in dry acetone.

Physical properties:
54. The intermolecular attractions are stronger in alkyl halide compared to the parent
hydrocarbon. Why?
Due to the high polarity and high molecular mass of alkyl halides than the parent hydrocarbon.

55. Write the decreasing order of boiling point of alkyl halides for the same alkyl group.
RI > RBr > RCl > RF

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56. Give reason: The boiling point of Methyl iodide is more than that of methyl chloride.
In methyl iodide, due the large size and mass of iodine, the magnitude of vanderwaal’s force
increases. so it has high boiling point.

57. Among bromobutane and 2-bromo-2-methyl propane, which one has high boiling point?
Bromobutane (b.p- 375K)

58. How the variation of boiling point takes place in isomeric alkyl halides?
The boiling point decreases with increase in branching.
59. para-isomers have high melting point than their ortho and meta–isomers. Why?
Because, para-isomers are symmetric in nature and hence they fits in crystal lattice.

60. How density varies with increase in molecular mass of alkyl halides?
Increases

61. Why haloalkanes are less soluble in water?

For the dissolution of haloalkane in water, energy is required to break the attractions between
haloalkane molecule and to break the hydrogen bonds present in water.
New inter molecular attractions formed between haloalkane and water is not strong as compared
to the original hydrogen bond of water.

62. Why haloalkanes readily soluble in organic solvents?

Because the new intermolecular attractions formed between haloalkane and organic solvents
have much strength as the once being broken in the separate haloalkane and solvent molecules.

63. Among isobutylbromide and tertiary butyl bromide which has higher boiling point?
Isobutyl bromide

64. Why is boiling point of C2H5Br higher than that of C2H5Cl?

Because, in C2H5Br the size of bromine is larger than chlorine.

Chemical properties:
65. What is the final product formed when iodomethane is treated with excess of alcoholic
ammonia?
CH3NH2 (Methanamine)

66. Name the major product when Butene reacts with HBr in presence of peroxide.
1-Bromobutane or Bromobutane

67. Give an example for ambident nucleophile.

Cyanide ion (CN-) / nitrite (NO2-) ion

68. Name the product formed when haloalkane reacts with KCN.
Alkyl cyanide

69. Haloalkane reacts with AgCN gives isocyanides. Why?

AgCN is covalent in nature, nitrogen is free to donate electron pair so isocyanides are formed.

70. Haloalkanes react with KCN gives alkyl cyanides and not isocyanides why?
KCN is ionic in nature and gives CN- ions in solution. Here the attacking of haloalkane through
carbon takes place and not through nitrogen because C-C bond is more stable than C-N bond. So
Cyanides are formed.

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71. Identify ‘A’ in the following reaction in CH3CH2Br+ AgCN → A + AgBr
H3C –CH2-NC (Ethyl isocyanide)

72. R-X + AgCN → ---- + AgX. Complete the reaction.

R-NC (ioscyanide)

73. Write the order of reactivity of different alkyl halide towards SN2 mechanism.
Primary > Secondary > Tertiary

74. Tertiary alkyl halides are least reactive towards SN2 mechanism. Why?
Tertiary alkyl halide contains bulky groups and they hinder the approaching nucleophiles (stearic
effect).

75. Name the reaction intermediate formed in SN1 mechanism.

Carbocation

76. SN1 reactions are generally carried out in polar protic solvent. Why?
SN1 reaction involves the breaking of C-Br bond, for which the energy is obtained through
salvation of halide ion with the proton of protic solvent.

77. During the conversion of tertiary butyl bromide to tertiary butyl alcohol, the rate of a
reaction depends on which factor?
Depends only on the concentration of tertiary butyl bromide.

78. Tertiary alkyl halides undergo SN1 reaction very fast. Give reason.
Because of high stability of 30 carbocations

79. Allylic and benzylic halides show high reactivity towards the SN1 reaction. Why?
The carbocations formed from those compounds get stabilized through resonance.

80. Write the decreasing order of reactivity of halides for a given alkyl group.
R-I > R-Br > R-Cl > R-F

Stereochemical aspects of nucleophilic substitution reaction:

81. What are optically active compounds or optical isomers?
Compounds when passed through solution, they have the capacity to rotate the plane polarized
light are known as optically active compounds.

82. What type of isomerism is shown by lactic acid?

Optical isomerism

83. What is polarimeter?

It is an instrument which is used to measure the angle of rotation of plane polarized light.

84. What are dextrorotatory substances?

These are the compounds which rotate the plane polarized light to the right or clock wise
direction.

85. What are laevorotatory substances?

These are the compounds which rotate the plane polarized light to left or anticlockwise
direction.

86. What is an asymmetric carbon or stereocentre(or)chiral carbon?

The carbon to which four different atoms or group of atoms get attached.

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87. What is the criteria for optical activity?
Asymmetry of the molecule

88. What is Chirality?

The property due to which the compounds are non-super imposable on their mirror images.

89. What are chiral compounds?

The compounds which are non-super imposable on their mirror image.

90. What are achiral compounds?

The compounds which are super-imposable on their mirror images.

91. Give an example for chiral molecule.

Butan-2-ol / 2-chlorobutane / 2,3-dihydroxypropanal / Bromo chloro iodo methane / 2-
bromopropanoic acid

92. Give an example for achiral molecule.

Propane -2-ol

93. What are Enantiomers?

The compounds which are non-super imposable mirror images of each other.

94. Equal mixtures of Enantiomers are optically inactive. Give reason.

Because optical rotation by d-isomer is cancelled by the optical rotation by l-isomer.

95. What are Racemic mixtures?

An equimolar mixtures of d and l isomers is known as racemic mixture.

96. A racemic mixture is opically inactive why?

Bacause optical rotation by d-isomer is cancelled by the optical rotation due to l-isomer.

97. What is Retention of configuration?

It is the preservation of integrity of the spatial arrangement of bonds to an asymmetric centre
during a reaction.

98. What is inversion of configuration?

The process of inversion of configuration of carbon of haloalkane under the attack of nucleophile
is known as inversion of configuration.

99. Why the product of SN2 is inversion configuration?

Because, the nucleophile attacks the stereo centre from the side opposite to the halogen.

100. Why Dehydrohalogenation is also known as β-elimination reaction?

There is an elimination of hydrogen from β-carbon and elimination of halogen from α-carbon
takes place, so it is known as dehydrohalogenation reaction.

101. Name the reagent used in β-elimination reaction?

Alcoholic KOH

102. Name the major product during the dehydrohalogenation of 2-Bromopentane .

Pent -2-ene

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103. Which rule is applicable during the dehydrohalogenation reaction.
Saytzeff rule

104. Predict the major product CH3 –CH(CH3)-CH2 – Br + KOHalc →

H3C - C = CH2
CH3
(2-methyl propene)

105. What are Organometallic compounds?

The compounds containing carbon-metal bonds.

106. What is Grignard reagent?

Alkyl magnesium halide is known as Grignard reagent.

107. Write the general formula of Grignard reagent.

R-Mg-X

108. What is the nature of carbon-magnesium bond in Grignard reagent?

Covalent in nature

109. What is the nature of Magnesium –halogen bond in Grignard reagent?

Ionic in nature

110. It is necessary to remove moisture from Grignard reagent. Why?

Because Grignard reagents are highly reactive and they react with any source of proton (like
water, alcohol etc) to give hydrocarbon.

111. Which organic product formed when ethyl bromide is treated with Magnesium metal in
dry ether?
C2H5MgBr

112. Write the general reaction for the conversion of Grignard reagent to hydrocarbons.
RMgX + H2O →R-H + Mg(OH)X

113. Give the general Wurtz reaction.

𝑑𝑟𝑦 𝑒𝑡 ℎ𝑒𝑟
2R-X + 2Na R-R + 2NaX

𝒅𝒓𝒚 𝒆𝒕𝒉𝒆𝒓
114. Complete the following reaction. 2CH3Cl + 2Na …..
CH3 –CH3 + 2NaCl

115. Aryl halides are extremely less reactive towards nucleophilic substitution reaction than
alkyl halide. Give reason.
Due to resonance effect/ due to more electronegativity of sp2 hybridized carbon of aryl halide
/Due to instability of phenyl cation.

116. What is the nature of NO2 group?

Electron withdrawing group.

117. The introduction of NO2 group at ortho – and para positions but not at meta –position
during the conversion of chlorobenzene into phenol. Give reason.
The presence of nitro group at ortho- and para – position increases the stability of carbanion
formed but it is impossible at meta – position.
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118. Electrophilic substitution reaction occur slowly and it requires more drastic conditions in
arylhalide when compared to that of benzene,Why?
Because in aryl halide, -I effect of halogen has tendency to withdraw electrons from the benzene
ring.

119. Name the major product when chlorobenzene reacts with chlorine in the presence of
anhyd.FeCl3
1, 4 –Dichlorobenzene
120. Write the composition of Nitrating mixture.
Conc.HNO3 and conc.H2SO4

121. What are the products obtained when chlorobenzene reacts with nitrating mixture?
1-Chloro-2-nitrobenzene and 1-Chloro-4-nitrobenzene

122. Write the major product formed when chlorobenzene reacts with conc.H2SO4
4-Chlorobenzenesulphonic acid

123. Complete the following equation:

Cl Cl
CH3

+
CH3
1-chloro-2-methylvbenzene
1-Chloro-4-methyl benzene
(Minor) ( Mojor)

𝒆𝒕𝒉𝒆𝒓
124. Name the following: 2RX + 2Na R-R + 2NaX reaction
Wurtz reaction

125. Write the general Wurtz –Fittig reaction

𝑑𝑟𝑦 𝑒𝑡 ℎ𝑒𝑟
R-X + 2Na + Ar-X R-Ar + 2NaX

Polyhalogen compounds:
126. What are polyhalogen compounds?
Compounds containing more than one halogen atom are known as polyhalogen compounds.

127. Give an example for polyhalogen compounds.

Dichloromethane (Methylene chloride ) / Trichloromethane (Chloroform)/Triiodo methane
(Iodoform)/Carbon tetrachloride/ Freons/ DDT

128. Name the polyhalogen used in the production of Freon refrigerant R-22.
Chloroform ( Trichloromethane )

129. Which poisonous gas is formed when chloroform oxidizes in air and light?
COCl2 (Phosgene/Carbonyl chloride)

130. What is Phosgene?

It is a poisonous gas which is formed by the oxidation of chloroform by air.
131. Why Chloroform is stored in closed dark coloured bottle?
Because when it exposed to air, easily undergo oxidation and forms a poisonous gas Phosgene.

132. Write the equation for the Oxidation of Chloroform.

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133. Give the reason for the antiseptic property of Iodoform .
Due to the liberation of free iodine it shows antiseptic property and not from iodoform itself.

134. Which polyhalocompound show antiseptic property?

Iodoform (CHI3)

135. What are Freons?

Chlorofluoro carbon compounds of methane and ethane.

136. What is use of Freon?

It is used for Refrigeration/Air propellants/ Air conditioning purpose etc.

137. What is the disadvantage of Freon?

It causes the depletion of Ozone layer.

138. Name the first chlorinated organic insecticide (or) Expand DDT.
Dichlorodiphenyltrichloroethane (DDT)

139. What is the disadvantage of DDT

It is not metabolized very rapidly by animals, instead it is deposited and stored in fatty tissues.

140. Write the structure of DDT

………………………………………………………….

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