Haloalkanes and Haloarenes

Haloalkanes and Haloarenes

Mechanism of Nucleophilic Substitution Reactions
Nucleophilic substitution reactions in halides containing CSP3X bond may take

place through either of the two different mechanisms, SN1 and SN2 .
(A) SN1 Mechanism (Unimolecular Nucleophilic Substitution)

In this type, the rate of reaction is dependent only on the concentration of alkyl
halide.
Rate = 𝐊[𝐑𝐗]
The tertiary alkyl halides react by SN1 mechanism via formation of carbocation as
intermediate as given below:
Step I. In the first step the alkyl halide slowly dissociates into halide ion and
carbocation.
CH3 CH3
……..Slow
H 3C C Br ⇌ H 3C C+ + Br
CH3 CH3
Carbocation
This step is the slowest and reversible. It involves the cleavage of C – Br bond
for which the energy is obtained through solvation of halide ion with the proton of
protic solvent. Since the rate of reaction depends upon the slowest step, the rate of
reaction depends only on the concentration of alkyl halide and not on the
concentration of nucleophile.
Step II. In the second step, carbocation at once combines with the nucleophile to
form the final substituted product.
 The order of reactivity of various alkyl halides through SN1 mechanism is:
3> 2> 1
 Greater the stability of carbocation, greater will be its ease of formation from
alkyl halide and faster will be the rate of reaction.
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The 3 alkyl halides are most reactive because the intermediate carbocation
formed in their case is the most stable. The more stable intermediate is
formed at faster rate.
 Primary allylic and benzylic halides show greater reactivity through SN1
mechanism than primary alkyl halides. This can be explained in terms of
stability of intermediate carbocations. Allylic and benzylic carbocations are
more stable than primary alkyl carbocations due to resonance stabilization
(B) SN2 Mechanism (Bimolecular Nucleophilic Substitution).

In this type the rate of reaction is dependent on the concentration of
alkyl halide as well as nucleophile, i.e.,
Rate = 𝐊[𝐑𝐗][𝐙 − ]
Primary alkyl halides react by SN2 mechanism via formation of a transition state.
H H H
H
- -
Z: + H C X Z C X Z C H + :X
H H H
Transition State
In this mechanism the incoming nucleophile interacts with alkyl halide

causing the carbon-halide bond to break while forming a new carbon nucleophile
bond. These two processes take place simultaneously in a single step and no
intermediate is formed. As the reaction progresses and the bond between the
nucleophile and the carbon atom starts forming and the bond between carbon atom
and leaving group starts breaking. Finally the product is formed and the leaving
group goes away.
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In the transition state, the carbon atom is simultaneously bonded to incoming

nucleophile and the outgoing leaving group and such structures are unstable and
cannot be isolated.
The order of reactivity of various alkyl halides through SN2 mechanism is:
1> 2> 3
This order of reactivity can be explained in terms of stability of the transition
state. Bulky alkyl groups attached to the carbon carrying halogen make the
transition state unstable due to crowding (steric hindrance) and decrease the
reactivity of the alkyl halide through SN2 mechanism. In 3 alkyl halides three alkyl
groups are attached to the carbon carrying halogen. Therefore, transition state in
this case has maximum energy and hence the reactivity is least. The 2 alkyl
halides with two alkyl groups is more reactive whereas 1 alkyl halide with only
one alkyl group is most reactive.
CONVERSIONS
1. Write the equation for the preparation of 1-iodobutane from:-

a) 1-butanol
b) 1-Chlorobutane
c) But-1-ene
2. How will you bring about the following conversions?

a) Ethanol to But-1-yne
b) Ethane to Bromoethane
c) Toluene to Benzyl alcohol
d) Propene to propyne
e) Ethanol to Ethyl fluoride
f) But-1-ene to But-2-ene
g) 1-Chlorobutane to n-Octane
h) Benzene to Biphenyl
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3. Complete the following reactions:-
𝑎𝑐𝑒𝑡𝑜𝑛𝑒
(𝑖)𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝑙 + 𝑁𝑎𝐼
ℎ𝑒𝑎𝑡
𝑒𝑡ℎ𝑎𝑛𝑜𝑙
(𝑖𝑖)(𝐶𝐻3 )3 𝐶𝐵𝑟 + 𝑘𝑂𝐻
ℎ𝑒𝑎𝑡
Water
(𝑖𝑖𝑖)𝐶𝐻3 𝐶(𝐵𝑟)𝐶𝐻2 𝐶𝐻3 + 𝑁𝑎 𝑂𝐻
aq. ethanol
(𝑖𝑣)𝐶𝐻3 𝐶𝐻2 𝐵𝑟 + 𝑘𝐶𝑁
(𝑣)𝐶6 𝐻5 𝑂𝑁𝑎 + 𝐶2 𝐻5 𝐶𝑙
(𝑣𝑖)𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝑂𝐻 + 𝑆𝑂𝐶𝑙2

peroxide
(𝑣𝑖𝑖)𝐶𝐻3 𝐶𝐻2 𝐶𝐻 = 𝐶𝐻2 + 𝐻𝐵𝑟
(𝑣𝑖𝑖𝑖)𝐶𝐻3 𝐶𝐻 = 𝐶(𝐶𝐻3 )2 + 𝐻𝐵𝑟
4. How the following conversions can be carried out?

a) Propene to Propan-1-ol
b) 1-Bromoporpane to 2-Bromopropane
c) 2-Bromoporpane to 1-Bromopropane
d) Benzene to 4-Bromonitrobenzene
e) Benzene to 3-Bromonitrobenzene
f) Benzyl alcohol to 2-Phenylethanoic acid
g) Ethanol to Propanenitrile
h) Aniline to Chlorobenzene
i) 2-Chlorobutane to 3,4-Dimethylhexane
j) 2-Methyl-1-propene to 2-Chloro-2-methylpropane
k) Ethyl chloride to propanoic acid
l) But-1-ene to n-Butyliodide
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m) 2-chloroporpane to 1-Propanol
n) Chlorobenzene to p-Nitrophenol
o) Chloroethane to Butane
p) Tert-butyl bromide to iso-Butyl bromide
5. What happens when:-

(i) n-butyl chloride is treated with alcoholic NaOH.
(ii) Bromobenzene is treated with Mg is the presence of dry ether.
(iii) Chlorobenzene is subjected to hydrolysis.
(iv) Methyl bromide is treated with sodium in the presence of dry ether.
(v) Methyl chloride is treated with KCN.
1. Account for the following:

Haloalkanes undergo nucleophilic substitutions whereas haloarenes
undergo electrophilic substitutions.
Ans:- Haloalkanes are more polar than haloarenes. Consequently the carbon atom
carrying the halogen in haloalkanes is more electron deficient (more positively
charged) than that in haloarenes. As a result, haloalkanes undergo nucleophilic
substitutions more readily than haloarenes. In contrast, haloarenes contain a
benzene ring, since the typical reactions of benzene are electrophilic substitutions,
therefore, haloarenes undergo electrophilic substitutions while haloalkanes which
do not contain a benzene ring do not undergo the electrophilic substitutions.
2. How will you explain the low reactivity of haloarenes as compared to

haloalkanes towards nuleophilic substitution.
Ans:- Aryl Halides are extremely less reactive towards nucleophilic substitution
reactions due to following reasons:-
a) Resonance effect:- In haloarenes, the electron pairs on halogen atom are in

conjugation with π electrons of the ring and the following resonating structures
are possible.
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Hence, C-Cl bond acquires a partial double bond character due to resonance. As a
result, the bond cleavage in haloarenes is difficult than haloalkanes and therefore,
they are less reactive towards nucleophilic substitution reaction.
b) Hybridization of carbon bearing the halogen atom:- In haloalkanes, the

carbon atom attached to the halogen atom is sp3 hybridized whereas in
haloarenes, the carbon atom attached to the halogen atom is sp2 hybridized.
Now sp2 hybridized orbital of carbon is slightly smaller in size than the sp3
hybrid orbital. Therefore, the carbon-halogen bond is slightly stronger and
shorter in haloarenes than the carbon- halogen bond in haloalkanes.
c) Because of the possible repulsion, it is less likely for the electron rich
nuleophile to approach electron rich arenes.
3. Vinyl chloride is uncreative in nuleophilic substitution reactions?
Ans:- Vinyl chloride, CH2=CH–Cl is unreactive due to resonance effect.

Resonance gives rise to partial double bond character to the carbon halogen bond,
making it stronger and therefore more difficult to cleave.
..
𝐶𝐻2 = 𝐶𝐻 − 𝐶𝑙 ∶ →⊝𝐶𝐻 − 𝐶𝐻 = 𝐶𝑙⊕
2
..
⊝𝐶𝐻 − 𝐶𝐻=𝐶𝑙 ⨁
4. Nucleophilic substitution2 in aryl halides is facilitated by electron
withdrawing group like nitro?
..
Or, why does NO2 group show its effect only at ortho and para positions
and not at meta- position?
Ans:-The presence of nitro group at ortho and para–positions withdraws, the

electron density from the because ring and thus facilitates the attack of the
nucleophile on haloarenes. The carbanion thus formed is stabilized through
resonance. The negative charge appeared at ortho and para-positions with respect
to the halogen substituent is stabilized 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.
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5. Why Chlorobenzene is ortho and para directing in the electrophilic

substitution reaction?
Ans:- In electrophilic substitution reaction, an electrophile will attack on that

carbon that has the higher charge density. Chlorobenzene is the resonating hybrid.
It is clear from the resonating structures that a negative charge is developed either
at 2 and 6 positions (ortho) or the 4 position (para) therefore, an electrophile will
attack and attack on ortho or para- position. Hence, it is ortho and para directing.
6. Although Chlorine is an electron- withdrawing group, yet it is ortho, para

directing in electrophilic aromatic substitution reactions?
Ans:- 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 para-position and
hence makes the deactivation less for ortho and para attack.
7. HX can convert ROH to RX but conversion of phenol to aryl halides is not

possible by HX, why?
Ans:- The method is not applicable for the preparation of the aryl halides because
the carbon- oxygen bond in phenols has a partial double bond character and is
difficult to break being stronger than a single bond.
8. Nucleophilic substitution in aryl halides is facilitated by electron

withdrawing group while electrophilic substitution is facilitated by electron
releasing group why?
Ans:- Nucleophilic substitutions in aryl halides takes place via carboanions as

intermediates, which are stabilized by electron withdrawing group whereas
electrophilic substitutions takes place through carbocations as intermediate, which
are stabilized by electron releasing groups. The rate of the reaction increases if the
intermediate is stabilised.
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9. Differentiate between retention and inversion.
Ans:- If the relative configuration of the atoms/ groups around a chiral centre in an
optically active molecule remains the same before and after the reaction, the
reaction is said to proceed with retention of configuration. On the other bond, if the
relative configuration of the atoms/ groups around a steriocentre in the product is
opposite to that in the reactant, the reaction is said to proceed with inversion of
configuration. For example
C2𝐻5 C2𝐻5
C2𝐻5
H +Y H
H +Y C C
C -X
-X X CH3 Y
CH3 Y CH3
Inversion Reactant Retention
10. Primary allylic and benzylic halides show greater reactivity through
SN1mechanism than primary alkyl halides. Explain it?
Ans:- This can be explained in terms of stability of intermediate carbocations.

Allylic and benzylic carbocations are more stable than primary alkyl carbocations
due to resonance stabilization.
+ +
𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻2 𝐶𝐻2 − 𝐶𝐻 = 𝐶𝐻2
Resonance in Benzyl Carbocation

Allyl and benzyl carbocations being more stable are formed at faster rate than
primary alkyl halides and this accounts for the greater reactivity of allylic and
benzylic halides through SN1 mechanism
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11.Identify chiral and achiral molecules in each of the following pair of

compounds.
H H
a)
CH3 C CH3 C
Br OH Br Br
OH
b)
H
C CH3
C CH3
CH3 OH H
CH3
c) CH3 CH CH2 CH3 CH3 CH2 CH2 CH2 Br
Br
12.Predict the order of reactivity of the followings compounds in SN1 and SN2
reactions:-
a) The four isomeric bromobutanes
b) C6 H5 CH2 Br, C6 H5CH(C6 H5)Br, C6 H5 CH (CH3) Br, C6 H5CBr(CH3)(C6 H5)
13.Which alkyl halide from the following pairs would you expect to react
more rapidly by SN2 mechanism?
a) CH2 CH2 CH2 CH2 Br Or CH3 CH2 – CH − CH3
Br
𝐶𝐻3
a)b) 𝐶𝐻3 𝐶𝐻2 – 𝐶𝐻 − 𝐶𝐻3 𝑂𝑟 𝐶𝐻3 – 𝐶 − 𝐵𝑟

14. 𝐵𝑟 𝐶𝐻3
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c) CH3 − CH − CH2 CH2 Br Or CH3 CH2 – CH − CH2 Br

CH3 CH3
𝟏4. In the following pairs of halogen compounds which compound undergoes

faster SN1 reaction?
i) Cl Cl
C and C
Cl
ii)
and
Cl
15.Arrange the compounds of each set in order of reactivity towards SN2

displacement.
a) 2-Bromo-2-methylbutane, 1-Bromo pentane , 2-Bromopentane
b) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 2-Bromo-3-methyl
butane
c) 1-Bromopentane, 1-Bromo-2,2-Dimethylpropane, 1-Bromo-2-methyl
butane,1-Bromo-3-methylbutane.
16.Out of C6H5CH2Cl and C6H5CHClC6H5 Which is easily hydrolysed by

aqueous KOH.
17.Predict all the alkenes that would be formed by dehydrohalogenation of the

following halides with sodium ethoxide in ethanol and identify the major
alkene.
a) 1-Bromo-1-methyl cyclohexane
b) 2-Chloro-2-methyl butane
c) 2, 2, 3-Trimethyl-3-bromo pentane
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18. Neopentyl bromide undergoes nucleophilic substitution reactions very

slowly. Why?
Ans:- Nepentyl bromide undergoes SN2 reaction slowly due to :-
a) Bulkyl neopentyl group, difficult for a nucleophile to attack from backside at C
of C-Br bond.
b) Cleavage of C-Br bond gives 1 carbocation which is less stable.
19.The treatment of alkyl chlorides with aqueous KOH leads to the formation
of alcohols but in presence of alcoholic KOH alkenes are major products.
Explain.
Ans:- When an alkyl halide is treated with some nucleophile/ base, there is always
competition between substitution and elimination to take place. In the recent case,
substitution would result in alcohol as product whereas elimination would result in
alkene as product. In the presence of solvent of low polarity such as alcohol
elimination reaction is favoured whereas in the presence of solvent of high polarity
(such as water) substitution will be favoured.
20. Haloalkones react with KCN to form alkyl cyanide as main product while
Ag CN forms isocyanide as the chief product. Explain.
Ans:- KCN is predominantly ionic and provide cyanide ions in solution. Although
both carbon and nitrogen atoms are in a position to donate electron pair. The attack
takes place mainly through carbon atom and not through nitrogen atom since C–C
bond is more stable than C–N bond. However, AgCN is mainly covalent in nature
and nitrogen is free to donate electron pair forming isocyanides as the main
product.
21. Explain giving reason, “Although haloalkanes are polar in nature yet they
are slightly soluble in water but soluble in organic solvent.
Ans:- The haloalkanes are only very slightly soluble in water. In order for a
haloalkane to dissolve in water, energy is required to overcome the attractions
between the haloalkanes molecule and break the hydrogen bonds between water
molecule.
Less energy is released when new attractions are set up between the
haloalkane and the water molecules as these are not so strong as the original
hydrogen bonds in water. As a result, the solubility of haloalkanes in water is low.
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However, haloalkanes tend to dissolve in organic solvents because the new

intermolecular attractions between haloalkanes and solvent molecules have much
the same strength as the ones being broken in the separate haloalkanes and solvent
molecules.
22.Explain the following in one or two sentences.

a) Allyl chloride is hydrolysed more readily than n- propyl chloride.
b) Vinyl Chloride is hydrolysed more slowly than Ethyl chloride.
Ans:- Allyl chloride readily undergoes ionization to produce resonance stabilized
allyl carbocation. Since carbocations are reactive species. Therefore, allyl cation
readily combines with OH – ions to form allyl alcohol.
𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻2 − 𝐶𝑙 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻2 ⊕ + 𝐶𝑙 ⊝ → 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻2 − 𝑂𝐻

slow
23.Anhydrous ZnCl2 is used in the preparation of alkyl chloride from alcohols

and conc. HCl. Explain.
Ans:- Cl – ion is a poor nucleophile and anhydrous ZnCl2 is a lewis acid. ZnCl2
attaches to the oxygen of hydroxyl group, and helps in the removal of OH group.
Thus alkyl chloride is formed easily.
24. Explain why:-

a) The dipole moment of chlorobenzene is lower than of cyclohexyl chloride.
b) Grignard reagents should be prepared under anhydrous conditions.
Ans:- (a) In chlorobenzene the electron withdrawing inductive effect of Cl atom is
opposed by electron releasing resonance effect. Therefore, it has relatively lower
dipole moment. On the other hand in cyclohexyl chloride there is only electron
withdrawing inductive effect of Cl atom due to which it has higher dipole moment.
(b) Grignard reagents react with water and get decomposed

RMgX + H2O  R – H + Mg(OH)X
25. Why cannot benzene be iodinated with I2 directly?

Ans:- Iodination with I2 is slow (F2> Cl2> Br2> I2) and somewhat reversible.
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26. Why are Enantiomers also called optical isomers?

Ans:- Enantiomers rotate the plane of polarized light either towards right or
towards left.
27.What is racemic mixture?

Ans:- A mixture containing equimolar amount of enantiomers.
28. What is the difference between d and l?
29.Can the C+ of a carbocation be a chiral centre.
30. Ethyl chloride is a gas, whereas Ethyl iodide is a liquid at room

temperature. Explain.
Ans:- Because Ethyl iodide has greater molecular mass so greater Van der wall’s
attractions, hence ethyl iodide is liquid at room temperature.
31. The boiling points of Haloalkanes are in the order RF < RCl < RBr < RI .
Explain this order.
32. Among isomeric alkyl halides the boiling point decreases with increasing
in branching in the alkyl group. Explain.
33. What is sequence of dipole moment for CH3-X for different halogens?
Ans:- CH3-Cl >CH3-F > CH3-Br > CH3-I
34.What is the role of acetone in Finkelstein reaction?

dry acetone
Ans:- R-X + Na I R-I + NaX , X = Cl, Br.
NaCl or NaBr thus formed is precipitated in dry acetone. It facilitates the forward
reaction according to le- chatelier’s principle.
35. C-F bond has higher electronegativity difference than C-Cl bond yet
dipole moment of CH3F is less than CH3-Cl. Why?
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36. Haloalkanes have boiling point higher as compared to those of

corresponding alkanes . explain.
37.Out of PCl5 and SOCl2 which is preferred for preparing chloroalkanes

from alcohols. Why.
Ans:- C2 H5OH + SOCl2 C2H5 Cl + SO2 + H Cl 
Thionyl chloride is preferred for the preparation of chloro compounds
because both the byproducts [SO2 and HCl] are gaseous which escape from
the reaction mixture. This makes the purification of the chloro compounds
easy.
38.A hydrocarbon 𝐂𝟓 𝐇𝟏𝟎 does not react with chlorine in dark but gives a
single monochloro compound 𝐂𝟓 𝐇𝟗 Cl in bright sunlight. Identify the
hydrocarbon.
39.What are ambident nucleophiles? Explain with an example.
40.Which compound in each of the following pairs will react faster in SN2
reaction with –OH?
(i) C𝐇𝟑 Br or C𝐇𝟑 I (ii) (𝐂𝐇𝟑 )𝟑 CCl or C𝐇𝟑 Cl
42.p-Dichlorobenzene has higher melting point and solubility than those of o-

and m-isomers. Discuss.
43. Primary alkyl halide 𝐂𝟒 𝐇𝟗 Br (a) reacted with alcoholic KOH to give
compound (b). Compound (b) is reacted with HBr to give (c) which is an
isomer of (a). When (a) is reacted with sodium metal it gives compound (d),
𝐂𝟖 𝐇𝟏𝟖 which is different from the compound formed when n-butyl bromide is
reacted with sodium. Give the structural formula of (a) and write the
equations for all the reactions.
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Some Commercially Important Compounds

Dichloromethane (Methylene chloride): Dichloromethane is widely used as a
solvent, as a paint remover, as a propellant in aerosols, and as a process solvent in
the manufacture of drugs. It is also used as a metal cleaning and finishing solvent.
Methylene chloride harms the human central nervous system. Exposure to lower
levels of methylene chloride in air can lead to slightly impaired hearing and vision.
Trichloromethane (Chloroform): Chemically, chloroform is employed as a
solvent for fats, alkaloids, iodine and other substances. The major use of
chloroform today is in the production of the Freon refrigerant R – 22. It was once
used as a general anaesthetic in surgery but has been replaced by less toxic, safer
anaesthetics, such as ether.
Chloroform is slowly oxidized by air in the presence of light to an extremely
poisonous gas, carbonyl chloride, also known as phosgene.
light
2CHCl3 + O2 → 2 COCl2 + 2HCI
Phosgene
Triiodomethane (Iodoform): It was used earlier as an antiseptic but the
antiseptic properties are due to the liberation of free iodine and not due to iodoform
itself. Due to its objectionable smell, it has been replaced by other formulations
containing iodine.
Tetrachloromethane (Carbon tetrachloride): It is produced in large quantities of
use in the manufacture of refrigerants and propellants for aerosol cans. It is also
used as feedstock in the synthesis of chlorofluorocarbons and other chemicals
pharmaceutical manufacturing, and general solvent use.
There is some evidence that exposure to carbon tetrachloride causes liver
cancer in humans. The most common effect are dizziness, light headedness, nausea
and vomiting.
Freons: The chlorofluorocarbon compounds of methane and ethane are
collectively known as freons. They are extremely stable, unreactive, non – toxic,
non – corrosive and easily liquefiable gases. Freon 12(CCl2 F2 ) is one of the most
common freons in industrial use. It is manufactured from tetrachloromethane by
Swarts reaction. These are usually produced for aerosol propellants, refrigeration
and air conditioning purposes.
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p,p-Dichlorodiphenyl-trichloroethane (DDT): DDT, the first chlorinated organic

insecticides, was originally prepared in 1873. The use of DDT increased
enormously on a worldwide basis after World War II, primarily because of its
effectiveness against the mosquito that spreads malaria and lice that carry typhus.
Cl
Cl
Cl Cl
Cl H
DDT
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CBSE EXAMINATION QUESTIONS

1. How would you differentiate between SN1 and SN2 mechanism of
substitution reactions? Give one example of each of them.
2. Answer the following:
a) Haloalkanes easily dissolve in organic solvent. Why?
b) What is known as a racemic mixture? Give an example of the racemic
mixture.
c) Of the two bromoderivatives, C6 H5 CH (CH3) Br and C6 H5 CH (C6 H5)
Br, which one is more reactive in SN1 substitution reaction and why?
3. Rearrange the compounds of each of the following sets in order of
reactivity towards SN2 displacement.
a) 2-Bromo-2-methyl butane, 1-Bromo pentane, 2-Bromo pentane
b) 1-Bromo-3-methyl butane, 2-Bromo-2-methyl butane, 2-Bromo-3-methyl
butane
c) 1-Bromopentane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2-methyl
butane, 1-Bromo-3-methyl butane.
4. Chlorobenzene is extremely less reactive towards a nucleophilic
substitution reaction. Give two reasons for the same.
5. (i) Which alkyl halide from the following air is chiral and undergoes faster
SN2 reaction?
(ii) Out of SN1 and SN2, which reaction occurs with?
(a) Inversion of configuration
(b) Racemisation
Br
Br
(a)
(b)
6. Draw the structure of major monohalo product in each of the following

reactions:
(a) 𝑆𝑂 𝐶𝑙2
OH →
(b) 𝑃𝑒𝑟𝑜𝑥𝑖𝑑𝑒
𝐶𝐻2 − 𝐶𝐻 = 𝐶𝐻2 + 𝐻𝐵𝑟 →
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7. Give reasons:
(a) n – Butyl bromide has higher boiling point than t – butyl bromide.
(b) Racemic mixture is optically inactive.
(c) The presence of nitro group (- NO2) at o/p positions increases the
reactivity of haloarenes towards nucleophilic substitution reactions.
8. Out of 𝐂𝐇𝟑 ―𝐂𝐇―𝐂𝐇𝟐 ―𝐂𝐥 𝐚𝐧𝐝 𝐂𝐇𝟑 ―𝐂𝐇𝟐 ―𝐂𝐇―𝐂𝐥 which is more reactive
towards SN1
│ │
𝐂𝐇𝟑 𝐂𝐇𝟑
𝐫𝐞𝐚𝐜𝐭𝐢𝐨𝐧 𝐚𝐧𝐝 𝐰𝐡𝐲?
9. Give reasons:
(i) C―Cl bond length in chlorobenzene is shorter than C―Cl bond
length in 𝐂𝐇𝟑 ―𝐂𝐥.
(ii) The dipole moment of chloro benzene is lower than that of cyclohexyl
chloride.
(iii) SN1 reactions are accompanied by recemization in optically active
alkyl halides.
10.Following compounds are given to you:

2-Bromopentane, 2-Bromo-2-methyl butane, 1-Bromopentane
(i) Write the compound which is most reactive towards SN2 reaction.
(ii) Write the compound which is optically active.
(iii) Write the compound which is most reactive towards β – elimination
reaction.
111

Haloalkanes and Haloarenes

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Haloalkanes and Haloarenes

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Haloalkanes and Haloarenes

Haloalkanes and Haloarenes

Nucleophilic substitution reactions in halides containing CSP3X bond may take

(A) SN1 Mechanism (Unimolecular Nucleophilic Substitution)

(B) SN2 Mechanism (Bimolecular Nucleophilic Substitution).

In this mechanism the incoming nucleophile interacts with alkyl halide

In the transition state, the carbon atom is simultaneously bonded to incoming

1. Write the equation for the preparation of 1-iodobutane from:-

2. How will you bring about the following conversions?

3. Complete the following reactions:-

(𝑣𝑖)𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝑂𝐻 + 𝑆𝑂𝐶𝑙2

(𝑣𝑖𝑖𝑖)𝐶𝐻3 𝐶𝐻 = 𝐶(𝐶𝐻3 )2 + 𝐻𝐵𝑟

4. How the following conversions can be carried out?

5. What happens when:-

1. Account for the following:

2. How will you explain the low reactivity of haloarenes as compared to

a) Resonance effect:- In haloarenes, the electron pairs on halogen atom are in

b) Hybridization of carbon bearing the halogen atom:- In haloalkanes, the

3. Vinyl chloride is uncreative in nuleophilic substitution reactions?

Ans:- Vinyl chloride, CH2=CH–Cl is unreactive due to resonance effect.

Ans:-The presence of nitro group at ortho and para–positions withdraws, the

5. Why Chlorobenzene is ortho and para directing in the electrophilic

Ans:- In electrophilic substitution reaction, an electrophile will attack on that

6. Although Chlorine is an electron- withdrawing group, yet it is ortho, para

7. HX can convert ROH to RX but conversion of phenol to aryl halides is not

8. Nucleophilic substitution in aryl halides is facilitated by electron

Ans:- Nucleophilic substitutions in aryl halides takes place via carboanions as

9. Differentiate between retention and inversion.

Ans:- This can be explained in terms of stability of intermediate carbocations.

Resonance in Benzyl Carbocation

11.Identify chiral and achiral molecules in each of the following pair of

c) CH3 CH CH2 CH3 CH3 CH2 CH2 CH2 Br

a)b) 𝐶𝐻3 𝐶𝐻2 – 𝐶𝐻 − 𝐶𝐻3 𝑂𝑟 𝐶𝐻3 – 𝐶 − 𝐵𝑟

c) CH3 − CH − CH2 CH2 Br Or CH3 CH2 – CH − CH2 Br

𝟏4. In the following pairs of halogen compounds which compound undergoes

15.Arrange the compounds of each set in order of reactivity towards SN2

16.Out of C6H5CH2Cl and C6H5CHClC6H5 Which is easily hydrolysed by

17.Predict all the alkenes that would be formed by dehydrohalogenation of the

18. Neopentyl bromide undergoes nucleophilic substitution reactions very

However, haloalkanes tend to dissolve in organic solvents because the new

22.Explain the following in one or two sentences.

𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻2 − 𝐶𝑙 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻2 ⊕ + 𝐶𝑙 ⊝ → 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻2 − 𝑂𝐻

23.Anhydrous ZnCl2 is used in the preparation of alkyl chloride from alcohols

24. Explain why:-

(b) Grignard reagents react with water and get decomposed

25. Why cannot benzene be iodinated with I2 directly?

26. Why are Enantiomers also called optical isomers?

27.What is racemic mixture?

28. What is the difference between d and l?

29.Can the C+ of a carbocation be a chiral centre.

30. Ethyl chloride is a gas, whereas Ethyl iodide is a liquid at room

34.What is the role of acetone in Finkelstein reaction?

36. Haloalkanes have boiling point higher as compared to those of

37.Out of PCl5 and SOCl2 which is preferred for preparing chloroalkanes

39.What are ambident nucleophiles? Explain with an example.

42.p-Dichlorobenzene has higher melting point and solubility than those of o-

Some Commercially Important Compounds

p,p-Dichlorodiphenyl-trichloroethane (DDT): DDT, the first chlorinated organic

CBSE EXAMINATION QUESTIONS

6. Draw the structure of major monohalo product in each of the following

10.Following compounds are given to you:

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