Haloalkanes and Arenes Q and Ans

08/12/2022, 12:46 Preview Question Paper
Kovai Vidhyashram
Haloalkanes and haloarenes Q & A
Date : 08-Dec-22
12th Standard
Reg.No. :
Chemistry
Time : 03:00:00 Hrs
Total Marks : 150
153 x 2 = 306
1)What are ambident nucleophiles? Explain with an example.
Answer : Ambident Nucleophile- An anionic nucleophile, which has two nucleophilic centers, or two negative
sites is known as an ambident nucleophile. This negative charge is delocalized due to resonance.
Example – Cyanide and Thiocyanate are examples of ambident nucleophiles.
-C≡N ↔ :C=N-
S=C=N- ↔ -S - C≡ N
2)Which compound in each of the following pairs will react faste in SN2 reaction with OH-?
(a) CH3Br or CH3I
(b) (CH3)3CCl or CH3Cl
Answer : In the SN2 mechanism, the reactivity of halides for same halides group increase down the group.
Because increase in size increase, the halide becomes a better leaving group. Therefore, CH3I will react faster
than CH3Br in SN2 reactions with OH-.
3) In the following pairs of halogen compounds, which compound undergoes faster SN1 reaction?
Answer : (i)
It is primary halide and therefore undergoes SN2 reaction faster.

(ii)

As iodine is a better leaving group because of its large size, it will be released at a faster rate in the presence of
incoming nucleophile.
4)The treatment of alkyl chlorides with aqueous KOH lead to the formation of alcohols but in presence of alcoholic
KOH alkenes are major products. Explain.
Answer : In an aqueous solution, KOH almost completely ionises to give OH– ions. OH– ions is a strong
nucleophile, which leads the alkyl chloride to undergo a substitution reaction to form alcohol.
On the other hand, an alcoholic soln 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.
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 β - carbon.
5)Identify all the possible monochloro structural isomers that would be expected to form on free radical chlorination
of (CH3)2CHCH2CH3
Answer : In the given molecule, there are four different types of hydrogen atoms. Replacement of these hydrogen
atoms will give the following four monochloro derivatives.
(i) (CH3)2CHCH2CH2Cl
(ii) (CH3)2CHCH(Cl)CH3
(iii) (CH3)2C(Cl)CH2CH3
(iv) CH3CH(CH2Cl)CH2CH3
6)Haloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms isocyanides as the
chief product. Explain
Answer : This is nucleophilic substitution reaction. KCN is an ionic compound, it breaks into K+ and CN- in
aqueous solution. It attacks 'C' of alkyl halide through carbon since C-C bond is more stable than C-N bond
due to lack of polarity. However, AgCN is covalent compound, therefore, bond can form only throu9'h 'N' which
has lone pair to donate for forming coordinate bond in isocyanide.
7) Write the isomers of the compound having formula C4H9Br.
https://cbse.qb365.in/5a50ff6949242e940854f70f4a117d80/32678/36a213dec58f9ae20b81cd14d3358981#pattern_32678qakey 1/66
Answer : (i)
(ii)
(iii)
(iv)
8)Write the equations for the preparation of 1-iodobutane from

(1)1-butanol
(2) 1-Chlorobutane
(3) but-1-ene
Answer : (i)
(ii)
(iii)
9)Predict all the alkenes that would be formed by dehydrohalogenation of the following halides with sodium ethoxide
in ethanol and identify the major alkene.
(i) 1-Bromo-1-methylcyclohexane
(ii) 2-chloro-2-methylbutane
(iii) 3-Bromo-2, 2,3-trimethylpentane.
Answer : (i) In l-bromo-l-rnethylcyclohexane, the β -hydrogens on either side of the Br atom are equivalent,
therefore, only 1- alkene is formed.
ii) 2-CWoro-2-methylbutane has two different sets of equivalent β-hydrogens and hence, in principle, can give
two alkenes (I and II). But according to SaytzetT rule, more highly substituted alkene (II), being mor~ stable, is
the major product.
(iii) 3-Bromo-2, 2, 3-trimethylpentane has two different sets of β-hydrogens and hence, in principle, can give
two alkenes (I and II). But according to SaytzetT rule, more highly substituted alkene (II), being more stable, is
the major product.
10) Out of C6H5CH2Cl and C6H5CHClC6H5 which is more easily hydrolysed by aqueous KOH?
Cl
Answer : |
C 6 H 5 − C H − C 6 H 5 will
get hydrolysed easily because carbocation formed will be stabilized by
resonance effect of two phenyl groups, whereas in C6 H 5 C H2 C l , he carbocation is stabilized by resonance
effect of one phenyl group.
11) p-Dichlorobenzene has higher m.p. than those of o- and m-isomers. Discuss.
Answer : The p-isomer being more symmetrical fits closely in the crystal lattice and thus has stronger
intermolecular forces of attraction than those of o- and m-isomers. Since during melting or dissolution, the
crystal lattice breaks, therefore, a larger amount of energy is needed to melt or dissolve the p-isomer than the
corresponding o- and m- isomers. In other words, the melting point of the p-isomer is higher and its solubility
lower than the corresponding o- and m- isomers.
12)Primary alkyl halide C4H9Br (A) reacted with alcholicKOH to give compound (B). Compound (B) is reacted will NBr
to give (C) which is an isomer of (A). When (A) is reacted with Na metal , if gives a compound (D), C8H18 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.
C H3 C H3 C H3
| | |
H Br
Answer : C H3 − C H − C H2 Br + K OH (a/c) ⟶ C H3 − C H = C H2 ⟶ C H3 − C − C H3
|
Br
'A' 'B' 'C'

'C' is the isomer of 'A'.
C H3 C H3 C H3
| | |
Dry
2C H3 − C H − C H2 Br + 2N a ⟶ C H3 − C H − C H2 − C H2 − C H − C H3 + 2N aBr
ether
′ ′
D (C8 H 18 )
Dry
2C H3 C H2 C H2 C H2 Br + 2N a ⟶ C H3 − C H2 − C H2 − C H2 − C H2 − C H2 − C H2 − C H3
ether n−Octane(C8 H 18 )
'D' and n-octane are different.

13) Write the mechanism of the following reaction:
EtOH −H 2 O
nBuBr + K C N ⟶ nBuC N
Answer : KCN gives CN- ion as a nucleophile in aqueous medium. Resonating forms of KCN are
+
¯¯
¯¯
¨ ¯¯
¯ +
K [∗C ≡ N :] ⟷ [tC = N3 ]K
Thus, cyanide ion is an ambident nucleophile. Therefore, it can attack the C-atom of C-Br bond in n-BuBr
either through C-atom or through N-atom. Thus, two possible products are cyanides and isocyanides,
respectively. But C-C bond is more stable than C-N bond, so attack occurs through C-atom and hence, cyanide
is predominantly formed.
14) P-Dichlorobenzene has higher m.pt. and solubility than those of o- and m-isomers. Discuss.
15) Which of the following compounds will have the highest melting point and why?
II will have highest melting point due to symmetry of para position, it fits into crystal lattice readily.
16) Answer the following questions:
(i) What is meant by chirality of a compound? Give an example.
(ii) Which one of the following compounds is more easily hydrolyzed by KOH and why?
C H 3 C H C lC H 2 C H 3 or C H 3 C H 2 C H 2 C l
Answer : (i) Chirality: It is a geometrical property of a rigid object ( or molecules ) by which it gets such spatial
arrangement of points or atoms that, the molecule becomes non-super imposable of its mirror image.
The chiral molecule of the object does not have any element of symmetry like, a mirror image, centre of
inversion (i) etc.
3-bromopent-1-ene is represented as
(ii) Due to +I effect of alkyl groups the 2° carbonium ion CH3—CH+ —CH2—CH3 derived from sec. butyl chloride
is more stable than the 1° carbonium ion CH3—CH2—C H2+ derived from n-propyl chloride. Therefore sec. butyl
chloride gets hydrolyzed more easily than n-propyl chloride under SN1 conditions.
This is because; iodine is a better leaving group due to its large size. So, it will be released at a faster rate in the
presence of an incoming nucleophile
17) Suggest a possible mechanism for the following reaction:
EtOH 2 , H 2 O
n − BuBr + K C N −−−−−−−→ n − BuC N
Answer : The given reaction is

The reaction is an SN2 reaction. In this reaction, CN- acts as the nucleophile and attacks the carbon atom to
which Br is attacked. CN- is an ambident nucleophile and can attack through both C and N. In this case, it
attacks through the C-atom.
18) Which one in the following pairs of substances undergoes SN2 substitution reaction faster and why
Answer :
It is primary halide therefore undergoes SN2 reaction faster.
As iodine is a better leaving group because of its large size, it will be released at a faster rate in the presence of
incoming nucleophile.
19) Which one in the following pairs undergoes SN1 substitution reaction faster and why?
Answer : (i)
3° halide reacts faster than 2° halide because of the greater stability of tertiary carbocation.
(ii)
(ii) 2° halide reacts faster than 1° halide because of the greater stability of secondary carbocation than primary.
20) Complete the following reaction equations:
Answer :
21) (i) Why is it that haloalkanes are more reactive than haloarenes towards nucleophiles?
Answer : (i) As C-X bond in aryl halide acquires a partial double bond character due to resonance while the C-X
bond in alkyl halide is a pure single bond. Hence, Bond Strength of Haloarenes is more than that
of Haloalkanes. So, Haloarenes are less reactive than Haloalkanes towards nucleophilic substitution.
22) Identify the compounds A, B, C and D in the following sequence of reaction:
Answer :
23) Write the structural formulae of the organic compounds 'A', 'B', 'C' and 'D' in the following sequence of reaction
Answer :
24)Why are haloarenes more stable than haloalkanes and undergo electrophilic substitution reaction at ortho and
para positions?
Answer : Haloarenes are resonance stabilized. Due to resonance, C-X bond in haloarenes acquire a double bond
character which makes them more stable than haloalkanes.
25) Convert:
(i) Benzene to p-nitrochlorobenzene
(ii) Benzene to aniline
(iii) Benzene to m-nitrochlorobenzene
(iv) Benzene to diphenyl
(v) Benzene to p-chlorotoluene
(vi) Chlorobenzene to DDT
(vii) Chlorobenzene to phenyl cyanide
(viii) Benzene diazonium chloride to aniline.
Answer :
26) Arrange the following compounds according to reactivity towards nucleophilic substitution reaction with reagents
mentioned:
(i) 4-nitrochlorobenzene; 2, 4-dinitrochloro-benzene and 2, 4, 6-trinitrochlobenzene with CH3ONa
(ii) Chlorobenzene, 4-chloro-1-methyl-benzene, 4-nitrochlorobenzene and 2, 4, 6-trinitro-chlorobenzene with caustic
alkali.
Answer : (i) 2,4,6, trinitrochlorobenzene > 2,4 dinitrochlorobemzene > 4- nitrochlorobenzene
(ii) 2, 4, 6-trinitro-chlorobenzene > 4-nitrochlorobenzene > Chlorobenzene > 4-chloro-1-methyl-benzene >
27)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) Cyclohexylmethyl bromide
(b) 3-Bromopent-1-ene
Answer :
28)How will you bring about the following conversions?

(a) Bromoethane to cis-hex-3-ene
(b) Benzyl alcohol to phenylethanenitrile
(c) Cyclopentene to cyclopenta-1, 3-diene
(d) Aniline to phenyl isocyanide.
Answer :
29) Write the structure of the major organic product in each of the following reactions
Answer :
30)Draw the structures of optically active unsaturated compound having molecular formula C5H9Br, that after
addition of H2 becomes either optically inactive or shows optical activity.
Answer :
31)Write the structure of the following organic halogen compounds:

(a) 2-Chloro-3-methylpentane
(b) p-Bromochlorobenzene
(c) 1- Chlore-4-ethylcyclohexane
(d) 2-(2-Chlorophenyl)-1-iodooctane
Answer :
32)Write the structure of the following organic halogen compounds:

(a) 2-Bromobutane
(b) 4-tert-Butyl-3-iodoheptane
(c) 1-Bromo-4-sec-buty1-2-methyl benzene
(d) 1, 4-Dibromobut-2-ene.
Answer :
33) Give the uses of Freon-12, DDT.

Answer : (i) Freon-12 is used as refrigerant in fridge and air-conditioners. (ii) DDT is used as insecticide.
34)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. But why does preparation of aryl iodides requires
presence of an oxidising agent?
Answer : It is because iodination is reversible as HI formed is good reducing agent which needs to be removed
with the help of oxidising agent.
35) Out of o-and p-dibromobenzene which one has higher melting point and why?
Answer : p-dibromobenzene has higher melting point because it is symmetrical and fits into crystal lattice more
readily.
36) Haloarenes are less reactive than haloalkanes and haloalkenes. Explain.
Answer : In haloarenes the bond between the halogen and the benzene ring is not a single It has a partial
double bond character due to resonance.Thus the attack of the nucleophile becomes more difficult in a
haloarene than a haloakane.
37) Discuss the role of Lewis acids in the preparation of aryl bromides and chlorides in the dark.
Answer : It helps in generation of electrophile.
38) Which of the following compounds(a) and (b) will not react with a mixture of NaBr and H2SO4. Explain why?
Answer : (b) will not react due to presence of double bond character in C---- O bond due to resonance.
39) Which of the products will be major product in the reaction given below? Explain.
C H3 C H = C H2 + H I → C H3 C H2 C H2 I + C H3 C H I C H3
′ ′ ′ ′
A B
Answer : ‘B’ is major product of the reaction.
40) Draw other resonance structures
related to the following structure and find out whether the functional group present in the molecule is ortho, para
directing or meta directing.
Answer :
The functional group is ortho and para directing because electron density is maximum at ortho and partho
para-positions.
A hydrocarbon of molecular mass 72 g mol-1 gives a single monochloro derivative and two dichloro derivatives on
41)
photo chlorination. Give the structure of the hydrocarbon.
Answer :
42)Name the alkene which will yield 1-chloro-1-methylcyclohexane by its reaction with HCl. Write the reactions
involved.
Answer :
43) Which of the following haloalkanes reacts with aqueous KOH most easily? Explain giving reason.
(i) 1-Bromobutane
(ii) 2-Bromobutane
(iii) 2-Bromo-2-methylpropane
(iv) 2-Chlorobutane
Answer : (iii) 2-Bromo-2 methylpropane will react with aq KOH most easily because it will form 3o carbocation
which is most stable.
44) Which of the following compounds would undergo SN1 reaction faster and why?
Answer : (B) Undergoes SN1 reaction faster than (A) because in case of (B), the carbocation formed after the loss
of Cl – is stabilised by resonance, whereas, no such stabilisation is possible in the carbocation obtained from
(A).
45) Diphenyls are potential threat to the environment. How are these produced from arylhalides?
Answer : In an environment, diphenyl is formed during the incomplete combustion of mineral oil and coal. It is
present in the exhaust gases of vehicles and in exhaust air from residential and industrial heating devices.
Acute exposure to high levels of biphenyl has been observed to cause eye and skin irritation and toxic effect on
the liver, kidneys and central/peripheral nervous system. Kidneys of animals are also affected due to the
ingestion of biphenyls.
Aryl halides, when treated with sodium in the presence of dry ether gives diphenyl. This reaction is called
Fitting reaction.
46) What are the IUPAC names of the insecticide DDT and banned in India and other countries?
Answer : The IUPAC name of DDT is 2,2-bis(4-chlorophenyl)-1,1,1-trichloroethane. The IUPAC name of
bezenehexachloride is 1,2,3,4,5,6-hexachlorocyclohexane. Their use is banned in India and other
countries because DDT is not metabolised very rapidly or solubilized effectively by animals.
47)Elimination reactions (especially β-elimination) are as common as the nucleophilic substitution reaction in case of
alkyl halides. Specify the reagents used in both cases.
Answer : Aq. KOH is used in case of nucleophilic substitution; whereas alcoholic KOH is used in elimination
reaction.
48)Aryl halides are extremely less reactive towards nucleophilic substitution. Predict and explain the order of
reactivity of the following compounds towards nucleophilic substitution:
Answer : The order of reactivity III > II > I
49)tert-Butylbromides reacts with aq. NaOH by SN1 mechanism while n-butylbromide reacts by SN2 mechanism.
Why?
Answer : It is because tert-butyl carbocation is more stable than n-butyl carbocation, therefore, tertiary butyl
chloride follows SN1 mechanism; whereas n-butyl bromide is primary halide, undergoes SN2 mechanism.
50) Discuss the nature of C-X bond in the haloarenes.
Answer : In haloarenes, there is double bond character between C----X Bond due to resonance, therefore, it is
less reactive and difficult to break.
51)How can you obtain iodoethane from ethanol when no other iodine containing reagent except NaI is available in
the laboratory?
Answer :
Cyanide ion acts as an ambident nucleophile From which end it acts as a stronger nucleophile in aqueous
52)
medium? Give reason for your answer.
Answer : It acts as a stronger nucleophile from carbon end because it will lead to the formation of C-C bond
which is more stable than C-N bond.
53)Some alkyl halides undergo substitution whereas some undergo elimination reaction on treatment with bases.
Discuss the structural features of alkyl halides with the help of examples which are responsible for this difference.
Answer : Primary alkyl halides prefer to undergo substituation reaction by SN2 mechanism; whereas tertiary
halides undergo elemination reaction due to formation of stable carbocation.
54)Some halogen containing compounds are useful in daily life. Some compounds of this class are responsible for
exposure of flora and fauna to more and more of UV light which causes destruction to a great extent. Name the
class of these halocompounds. In your opinion, what should be done to minimise harmful effects of these
compounds.
Answer : CFC (Chlorofluoro carbons) are responsible for the destruction of ozone layer and UV light can reach
earth which may cause skin cancer and affect flora and fauna.
These compounds should be banned and their use should be made to minimum extent.
55) Suggest a possible reason for the following observations:
(i) The order of reactivity of haloalkanes is RI > RCI > RBr.
(ii) Neopentyl chloride (CH3)3CCH2CI does not follow SN2 mechanism.
(iii) Ethers have low boiling points.
Answer : (i) It is because of lower bond dissociation energy in the case of R
___
I than R
___ ___
C l . R C l is more
___
polar than R Br , therefore, more reactive.
(ii) It is because it forms stable carbocation, therefore , follows SN 1 mechanism.
(iii) Ethers are not associated with H-bonding and have weak van der Waal's forces of attraction, hence they
have low boiling point.
56) Complete the following reaction.
H Br N al
C H3 − C H = C H2 ⟶ X ⟶ Y
peroxide Acetone
Answer :
H Br.peroxide H Br.peroxide
C H3 − CH = C H2 ⟶ C H3 C H2 C H2 − Br ⟶ C H3 C H2 C H2 − I
P ropene (anti−M ark addition) 1−Bromopropane(X) (F inkestein reaction) I −I odopropane(Y )
57) CHF3 is less acidic than CHCl3. Explain

Answer : Due to stronger -I-effect of F than CI, CHF3 should be more acidic than CHCI3. But actually reverse is
true. This is due to the reason that: CCI3- left after the removal of a proton from CHCI3 is stabilized by
resonance due to the presence of d-orbitals on CI but: CF3- left after the removal of a proton from CHF3 is not
stabilized by resonance due to the absence of d-orbitals on F.
58) What will the major organic product of the following reaction?
(i)Br2 ,hv
C2 H 5 C2 H 5 ⟶
(ii)N aC N
Answer : When ethylbenzene is treated with Br2 in presence of light, the bromine free radical formed during the
reaction, abstracts the IX (but not ) hydrogen from the ethyl group to form a resonance stabilized benzylic
radical (I) which then reacts with Br2 to form I-bromo-I-phenylethane (II). This on treatment with NaCN
undergoes nucleophilic substitution to form 2-phenylpropanenitrile (III).
Arrange the following halides in order of increasing SN2 reactivity:

59)
CH3Cl, CH3Br, CH3CH2Cl, (CH3)2CHCl
Answer : As the size of the alkyl group increases, S N2 reactivity decreases. Further, C-Br bond being weaker is
easier to break than C-Cl bond. Therefore, the overaU increasing S N2 reactivity follows the order:
(C H 3 ) C H l < C H 3 C H 2 C l < C H 3 C l < C H 3 Br.
2
An alkyl halide (A), on reaction with magnesium in dry ether followed by treatment with ethonal gave 2-
60)
methylbutane. Write all the possible structures of A.
Answer : The structures of all the possible alkyl halides that can be obtained by monohalogenation of 2-
methylbutane are:
3 1 3 2
C H3 − C − C H 2 C H 2 Br C H3 − C − C H − C H3
| | |
C H3 C H3 Br
1−Bromo−3−methylbutane 2−Bromo−3−methylbutane
The Grignard reagents of all these four alkyl halides will give 2-methylbutane on treatment with ethanol.
61)An alkyl chloride (X)reacts with magnesium metal in presence of dry ether followed by treatment of ethanol gives
propane. Write the structure of the alkyl halide (X).
Answer : The alkyl halide (X) on treatment with Mg metal in dry ether gives a Grignard reagent which on
treatment with ethanol gives propane. Therefore, the Grignard reagent may be either n-propylmagnesium halide
or isopropylmagnesium halide and the corresponding alkyl halide (X) may be ether n-propyl halide or isopropyl
halide.
M g/dry ether
C H3 C H2 C H2 − X or (C H3 ) C H − X ⟶
2
n−P ropyhalide(X) I sopropyl halide(X)
C H3 C H2 OH
C H3 C H2 C H2 − M gX or (C H3 ) C H − M gX ⟶ C H3 C H2 OM gX
2
n−P ropyhalide(X) I sopropyl mag. halide
62) Difference between chiral and achiral molecules.

Answer : A chiral molecule is one that is not superimposable on its mirror image. These molecules contain one
asymmetric or chiral carbon atom. For example, butan-2-oI,
An achiral molecule, on the other hand, is one which is superimposable on its mirror image. For example,
propan-2-ol.
63) Identify and indicate the presence of centre of chirality, if any, in the following molecules? How many stereoisomers
are possible for each.
(i) 2-Aminobutane
(ii) 3-Bromopent-1-ene
(iii) 1,2-Dichloropropene
(iv) 3-Methyl-1-pentene
Answer :
64) What is meant by chirality of a compound. Give one example.

Answer : A compound is said to be chiral if it exists in two stereoisomeric forms which are non-superimposable
mirror images of each other. This property of non-superposability is called chirality and the two compounds
which are nonsuperimposable mirror images of each other are called enantiomers.
For example, butan-2-ol is a chiral compound because it exists in two stereoisomers which are non-
superimposable mirror images of each other.
65) What are enantiomers? Draw the structure o the possible enantiomers of 3-methylpent-1-ene.
Answer : Stereoisomers which are non-superirnposable mirror images of each other are called enantiomers. The
enantiomers of 3-methylpent -l-ene are:
66) Distinguish between enantiomers and diastereomers.
Answer : Stereoisomers which are non-superimposable mirror images of each other are called enantiomers
while stereoisomers which are not mirror images of each other are called diastereomers. For example, tartaric
acid exists in three stereoisomeric forms I, II and III
Structures 1 and II are non-superimposable mirror images of each other and hence are enantiomers. But
structures 1and III (or II and III) are not mirror images and hence are diastereomers.
67) Difference between retention and inversion.
Answer : 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 hand, if the relative configuration of the atoms/groups around a chiral centre in the product is
opposite to that in the reactant, the reaction is said to proceed with inversion of configuration. For example,
68) (± )-2-Butanol is optically inactive. Give reasons.

Answer : (±)-2-Butanol contains equal amounts of the two enantiomers, i.e., (+)-2-butanol and (-)-2~butanol.
Since (+)-2-butanol rotates the plane of polarized toward right, (-)-2-butanol rotates the plane of polarized
towards left but to the same extent. The overall rotation is zero and hence (±)-2-butanol is optically inactive.
69)Optically active 2-iodobutane on treatment with Nal in acetone gives a product which does not show optical
activity. Explain.
Answer : Optically active 2-iodobutane on treatment with Nal in acetone undergoes racemization and hence the
product does not show optical activity as explained below: When optically active 2-iodobutane (I) is treated with
1- ion, it undergoes Walden inversion (SN2 reaction) to give 2-iodobutane (II) which is the enantiomer of (1). Now
2- iodobutane (II) undergoes Walden inversion to give enantiomer (I). As a result of repetition of these two
Walden inversions, ultimately a 50 : 50 mixture of the two enantiomers is obtained. In other words, optically
active 2- iodobutane undergoes racemization.
70)Out of Various possible isomers of C7H7Cl containing a benzene ring. suggest the structure with the weakest C-Cl
bond.
Answer : Four isomers are possible; their structures are:
Just as in chlorobenzene, the C-Cl bond in 0-, m- and p-chlorotol~enes, has some double bond character due
to resonance. In contrast, in benzyl chloride, the C-Cl bond is a pure single bond. Hence, out of the four
isomers, the C-Cl bond is the weakest in benzyl chloride. Alternatively, the cleavage of C-Cl bond in benzyl
chloride gives benzyl cation which is stabilized by resonance.
On the other hand, cleavage of C-Cl bond in 0-, m- or p-chlorotoluenes gives tolyl cation which is.highly
unstable. As a result, the energy of activation for the cleavage of C-l bond in benzyl chloride is much smaller
than that of C-CI bond in O-, m- or p-chlorotoluenes. Consequently, the C-l bond is the weakest in benzyl
chloride.
71)p-Chloronitrobenzene undergoes nucleophilic substitution faster than chlorobenzene. Explain giving the
resonating structures as well.
Answer : Attack of nucleophile on p-chloronitrobenzene gives carbanion (I) which is stabilized by x-electrons of
the benzene ring as well as by the -R-effect and the -I-effect of the - NO2 group as shown below:
on the other hand attackp of the nucleophile on chlorobenzene gives carbanion (II) which is stablized only by
the electrons of the beneze ring as shown below
Due to greater stability of the carbanion (I)over carbanion (Il), p-cWoronitrobenzene undergoes nucleophilic
substitution faster than chlorobenzene.
72) Name the following halides according to IUPAC system and classify them as alkyl, allyl, benzyl(primary,
secondary,tertiary), vinyl or aryl halides.
(i) (CH3)2CHCH(Cl)CH3
(ii) CH3CH2CH(CH3)CH(C2H5)Cl
(iii) CH3CH2C(CH3)2CH2l
(iv) (CH3)3CCH2CH(Br)C6H5
Answer : (i) 2-Chloro- 3-methylbutane 2° (secondry) halide
(ii) 3-Chloro-4-methylhexane 2° (secondry) halide
(iii) 1-Iodo-2, 2-dimethylbutane 1° (Primary) halide
(iv) 1-Bromo-3, 3-dimethyl-1-phenylbutane Benzylic halide (2°)
(i) CH3CH(CH3)CH(Br)CH3
(ii) CH3C(C2H5)2CH2Br
(iii) CH3C(Cl)(C2H5)CH2CH3
(iv) CH3CH=C(Cl)CH2CH(CH3)2
Answer : (i) 2-Bromo-3-methylbutane 2° (secondry) halide
(ii) 1- Bromo- 2-ethyl- 2-methyl butane 1° halide
(iii) 3-Chloro-3-methylpentane 3° (Tert.) halide I
(iv) 3-Chloro-S-methylhex-2-ene Vinylic halide
(i) CH3CH=CHC(Br)(CH3)2
(ii) p-ClC6H4CH2CH(CH3)2
(iii) m-ClCH2C6H4CH2C(CH3)3
(iv) o-Br-C6H4CH(CH3)CH2CH3
Answer : (i) 4-Bromo-4-methylpent-2-ene 3° and Allylic halide
(ii) 1-Chloro-4-(2-methylpropyl) benzene Aryl halide
(iii) 1-Chloromethyl-3-(2,2-dimethylpropyl) Benzene Benzylic halide (1°)
(iv) 1-Bromo-2-(1-methylpropyl)benzene Aryl halide
75) Which of the following has highest dipole moment?
(i) CH2Cl2
(ii) CHCl3
(iii) CCl4
Answer : The three dimensional structures of the three compounds along with the direction of dipole moment in
each of their bonds are given below:
CCl4 being symmetrical has zero dipole moment. In CHCI3, the resultant of two C--C1 dipoles is opposed by the
resultant of C-H and C-CI bonds. Since the latter resultant is expected to be smaller than the former, therefore,
CHCI3 has a finite dipole (1·03 D) moment. In CHCI2 the resultant of two C-Cl dipole moments is reinforced by
resultant of two C-H dipoles, therefore, CH2CI2 (1·62 D) has a dipole moment higher than that of CHC3.Thus,
CH2CI2 has the highest dipole moment.
76) EtOH −H 2 O
Explain the following reaction : n-BuBr+KCN −−−−−−−→n-BuCN
Answer : KCN has nucleophile CN- ion which is ambident nucleophile because of the following two contributing
structures:
Therefore, it can attack the carbon atom of C-Br bond in n-BuBr either through C or N. Since C-C bond is
stronger than C-N bond, therefore, the attack occurs through C to form n-butyl cyanide as given below:
77)Which of the compounds will react faster in SN1 reaction with the -OH ion?
CH3-CH2-Cl or C6H5-CH2-Cl
Answer : SN1 reactions occur through carbocation intermediates. C6H5 -CH2CI readily undergoes ionization to
give C6HsCH+2 which is stabilized by resonance.
In constant, CH3CH2CI does not undergo ionization to give CH3CH 2+.As a result, C6H5CH2CI reacts faster than
CH3CH2CI with OH- ion.
78) Why iodoform has appreciable antiseptic property?
Answer : The antiseptic property of iodoform is due to liberation of 12 when it comes in contact with skin and
not due to iodoform itself.
contact with skinow
C H I3 ⟶ I2 (has antiseptic property)
I odo f orm I odine
79) Discuss the role of Lewis acid in the preparation of aryl bromides and chlorides in the dark.
Answer : The role of Lewis acids in the preparation of aryl chlorides and bromides is to generate the
electrophiles, i.e., CI+and Br+ from the corresponding halogens
These electrophiles then react with arenes to form the corresponding aryl halides by electrophilic substitution
mechanism.
80) Why is the solubility of haloalkanes in water very low?
Answer : It is because haloalkanes are less polar and cannot form H-bonds with water.
81) Compound 'A' with molecular formula C4H9Br is treated with aq.KOH solution. The rate of this reaction depends
upon the concentration of the compound 'A' only. When another optically active isomer 'B' of this compound was
treated with aq.KOH solution, the rate of reaction was found to be dependent on concentration of compound and
KOH both.
(i) Write down the structural formula o both compounds 'A' and 'B'
(ii) Out of these compounds which one will be converted to the product with inverted configuration.
Answer : (i) Since the rate of reaction depends upon the concentration of 'A' only, therefore, 'A' -should be
3o halide which will follow SN1 mechanism.
82) Write down the structure and IUPAC name for neopentyl bromide.
C H3
|
Answer : C H3 − C − C H2 Br
|
C H3
1-Bromo-2,2-dimethyl propane (Neopentyl bromide)

83)A hydrocarbon of molecular mass 72g mol-1 gives a single monochloro derivative and two dichloro derivatives on
photochlorination. Give the structure of the hydrocarbon.
Answer : The hydrocarbon having molecular mass of 72g mol-1 must be C 5 H12 . Since on photochlorination, it gives a
derivative, therefore, all the twelve hydrogens in this hydrocarbon are equivalent. Thus, the hydrocarbon must be neope
dimethylpropane.1t forms only one monochloro derivative and two dichloro derivatives as shown below:
C H3 C H3 C H3 C I CH
| | |
C H3 − C C H3 − C − C H2 C I C H3 − C − C H2 C I C H3 − C
| | |
C H3 C H3 C H3 C
2,2−Dimethylpropane 1−Chlro−2,2−dimethylpropane 1−Dichlro−2,2−dimethylpropane 1,1−Dichlro−2,2
(All the 12 H ′ sare (M onochloro derivative) (Dichloro derivative) (Dichloro der
equivalent)

84)Write the structures and names of the compounds formed when compound 'A' with molecular formula, C7H8 is
treated with Cl2 in the presence of FeCl3
Answer : Compound with MF C7H8 is toluene. Since CH3 group is 0, p-directing, therefore, chlorination of
toluene with Cl2 in presence of FeCl3 gives a mixture of o-chlorotoluene and p-chlorotoluene, in which the p-
isomer predominates.
85) Why can aryl halides not be prepared by reaction of phenol with HCl in the presence of ZnCl2?
Answer : It is due to double bond character in phenol due to resonace, hence, breaking of this bond is
difficult to replace it by CI.
Identify the products A and B formed in the following reaction:
86)
CH3-CH2-CH=CH-CH3+HCl ⟶ A+B
Answer :
C H3 − C H2 = C H = C H − C H3 + H C I ⟶ C H3 − C H2 − C H − C H2 − C H3 + C H3 − C H2 − C H2 −
|
Cl
′ ′ ′ ′
A B
87) Write down the structure and IUPAC name for neopentyl bromide.
C H3
|
Answer : C H3 − C − C H2 Br
|
C H3
1-Bromo-2,2-dimethyl propane (Neopentyl bromide)

88) Allyl chloride is hydrolysed more readily than n-propyl chloride. Why?
Answer : In SN1 reactions, carbocations are the intermediates. Obviously more stable the carbocation, more
reactive is the alkyl halide. Since allyl chloride upon ionization gives allyl cation which is stabilized by
resonance but the carbocation obtained from n-propyl chloride is not, therefore, allyl chloride It undergoes
hydrolysis much faster than n-propyl chloride.
A hydrocarbon of molecular mass 72g mol-1 gives a single monochloro derivative and two dichloro derivatives on
89)
photochlorination. Give the structure of the hydrocarbon.
Answer : The hydrocarbon having molecular mass of 72g mol-1 must be C5 H 12 .Since on photochlorination, it gives a sin
derivative, therefore, all the twelve hydrogens in this hydrocarbon are equivalent. Thus, the hydrocarbon must be neope
dimethylpropane.1t forms only one monochloro derivative and two dichloro derivatives as shown below:
C H3 C H3 C H3 C I C
| | |
C H3 − C C H3 − C − C H2 C I C H3 − C − C H2 C I C H3 −
| | |
C H3 C H3 C H3 C
2,2−Dimethylpropane 1−Chlro−2,2−dimethylpropane 1−Dichlro−2,2−dimethylpropane 1,1−Dichlro−2,2
(All the 12 ′ s are (M onochloro derivative) (Dichloro derivative) (Di

H
equivalent)
90) Why it is necessary to avoid even traces of moisture during the use of a Grignard reagent?
Answer : Grignard reagents react with water to give the corresponding hydrocarbons.
RM gX + H OH ⟶ RH + M g(OH )X
H ydrocarbon
Grignard reagent
91) How do polar solvents help in the first step in SN1 mechanism?
Answer : The first step in SN 1 SN1reactions involves the formation of carbocations. Polar solvents stabilize the
carbocations thus formed by solvation and hence favour the SN 1 mechanism.
92) Write a test to detect the presence of double bond in a molecule.
Answer : Add bromine water. If it decolourises, then the presence of double bond in a compound is confirmed.
93) Why can aryl halides not be prepared by reaction of phenol with HCl in the presence of ZnCl2?
Answer : It is due to double bond character in phenol due to resonace, hence, breaking of this bond is
difficult to replace it by CI.
94)What are the IUPAC names of the insecticide DDT and benzene hexachloride? Why is their use banned in india
and other countries?
Answer : The IUPAC name of DDT is 2, 2-bis (4-chlorophenyl)-I, I, l-trichloroethane and that of benzene
hexachloride is I, 2, 3, 4, 5, 6-hexachlorocyclohexane. Their use in India and other countries has been banned
because they are not biodegradable. As a result, these insecticides enter the food chain of animals and get
deposited in their fatty tissues over a period of time and affect their reproductive systems.
95) Allyl chloride is hydrolysed more readily than n-propyl chloride. Why?
Answer : In S N1 reactions, carbocations are the intermediates. Obviously more stable the carbocation, more
reactive is the alkyl halide. Since allyl chloride upon ionization gives allyl cation which is stabilized by
resonance but the carbocation obtained from n-propyl chloride is not, therefore, allyl chloride It undergoes
hydrolysis much faster than n-propyl chloride.
96) Why it is necessary to avoid even traces of moisture during the use of a Grignard reagent?
Answer : Grignard reagents react with water to give the corresponding hydrocarbons.
RM gX + H OH ⟶ RH + M g(OH )X
H ydrocarbon
Grignard reagent
97) Write the structure of 3-bromo-2-methylpropene
Answer :
98)Name two alkenes that will yield 1-chloro-1methylcyclohexane by its reaction with HCI. Write the reactions
involved.
Answer : Two alkenes are possible. These are :
99) How will you bring about the conversion : methyl bromide to methyl iodide ?
Dry acetone
Answer : C H3 − Br + N aI ⟶ C H3 − I
(F ilkenstein reaction) M ethyl iodile
100) Write down the product formed when HBr adds to 3-methyl-1-butene.
Answer : (i) Addition of H+ to 3-methyl-1-butene first gives 2° carbocation (I) which being less stable rearranges
to the more stable 3° carbocation (II). Nucleophilic attack by Be ion on this carbocation gives 2- bromo-2-
methylbutane as the major product,
(ii) Electrophilic addition reaction occurs. In the first step, H+ adds to that carbon atom of the double bond
which carries the CH3 group since it produces carbocation (I) which is stabilized by +R-effect of the Ph group
and +l-effect of the CH2CH3 group. Subsequent nucleophilic attack by Br- on carbocation (I) gives l-bromo-l-
phenylpropane (II) as the final product.
(iii) In presence of peroxides, addition of HBr to alkenes occurs anti to Markovnikov's rule. Thus,
A hydrocarbon of molecular mass 72 g mol-1 gives a single monochloro derivate and two dichloro derivatives on
101)
photochlorination.Give the structure of the hydrocarbon.mono-and dichloroderivatives
Answer : The hydrocarbon having molecular mass of 72 g mol-1 must be C 5H12. Since on photochlorination, it gives a si
monochloro derivative, therefore, all the twelve hydrogens in this hydrocarbon are equivalent. Thus, the hydrocarbon m
neopentane or 2, 2-dimethylpropane.1t forms only one monochloro derivative and two dichloro derivatives as shown bel
C H3 C H3 C H3 C H3
| | | |
C H3 − C − C H3 C H3 − C − C H3 C I C H3 − C − C H3 C I C H3 − C
| | | |
C H3 C H3 C H3 C H3
2.2−Dimethylpropane l−Chloro−2.2− 1.3−Dichloro− L ′l−Dichloro−
′ dimethylpropane 2.2−dimethylpropane 2,2−dimethylpropane

(Allthe12H sare
(M onochloroderivative) (Dichloroderivative) tDichloroderivative)

equivalent)
102) How will you prepare bromobenzene from aniline ?
Answer :
103) Which of the following has highest dipole moment ?

(i) CH2CI2
(ii) CHCI3
(iii) CCI4
Answer : The three dimensional structures of the three compounds along with the direction of dipole moment in
each of their bonds are given below:
CCl4 being symmetrical has zero dipole moment. In CHCI3 , the resultant of two C-C1 dipoles is opposed by the
resultant of C-H and C-CI bonds. Since the latter resultant is expected to be smaller than the former, therefore,
CHCI3 has a finite dipole (1·03 D) moment. In CH2CI2, the resultant of two C-Cl dipole moments is reinforced by
resultant of two C-H dipoles, therefore, CH 2CI2 (1·62 D) has a dipole moment higher than that of CHCI3. Thus,
CH2CI2 has the highest dipole moment.
104) What happens when chlorine is passed through boilingtoluene in the presence of sunlight ?
Answer : Free radical substitution occurs at the methyl group giving first benzyl chloride, then benzyl dichloride
and finally benzotrichloride.
383K, hv 383,hv 383,hv
C 6 H 5 C H3 + C l2 ⟶ C 6 H 5 C H2 C I ⟶ C 6 H 5 C H C l2 ⟶ C 6 H 5 C C l3
T olune −H C I Benzyl chloride −H C I Benzyl dichloride −H C I Benzylchloride
105)Arrange each of the following compounds in order of increasing boiling points : Bromomethane
bromoform,chloromethane,dibromomethane.
Answer : (i) For the same alkyl group, boiling point increases with the size of the halogen atom. Therefore,
boiling point of bromomethane is higher than that of chloromethane. Further, the boiling points increase as the
number of halogen atoms increases. Therefore, the boiling point of bromoform with three Br atoms is the
highest, followed by dibromomethane with two Br atoms while bromomethane with one Br atom is the lowest.
Combining all the arguments presented above, the boiling points of the four compounds discussed above
increase in the order: chloromethane < bromomethane < dibromomethane < bromoform.
(ii) For the same halogen, boiling point increases as the size of the alkyl group increases. Therefore, the boiling
point of l-chlorobutane is higher than those of l-chloropropane and isopropyl chloride. Further, the boiling point
decreases as the branching increases, therefore, the boiling point of 1- chloropropane is higher than that of
isopropyl chloride. Combining these two arguments, the boiling points of the three compounds discussed above
increase in the order: Isopropyl chloride < 1-chloropropane < 1-chlorobutane.
106) Which is a better nucleophile, a bromide ion or an iodide ion ?
Answer : Because of bigger size and lower electronegativity, iodide ion can donate a pair of electrons more easily
than bromide ion and hence iodide ion is a better nucleophile than bromide ion
107) Difference between
(i) retention and inversion
(ii) enatiomers and diasteromers
Answer : (i) 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 hand, if the relative configuration of the atoms/groups around a chiral centre in the
product is opposite to that in the reactant, the reaction is said to proceed with inversion of configuration. For
example,
Stereoisomers which are non-superimposable mirror images of each other are called enantiomers while
stereoisomers which are not mirror images of each other are called diastereomers. For example, tartaric acid
exists in three stereoisomeric forms I, II and III
108)Optically active 2-iodobutane on treatment with Nal in acetone gives a product which of these are optical
activity.Explain
Answer : Optically active 2-iodobutane on treatment with Nal in acetone undergoes racemization and hence the
product does not show optical activity as explained below:
When optically active 2-iodobutane (I) is treated with 1- ion, it undergoes Walden inversion (SN2 reaction) to give
2 iodobutane (II) which is the enantiomer of (1). Now 2- iodobutane (II) undergoes Walden inversion to give
enantiomer (I). As a result of repetition of these two Walden inversions, ultimately a 50 : 50 mixture of the two
enantiomers is obtained. In other words, optically active 2- iodobutane undergoes reacemization.
Write all the streoisomers possible for the compound with M.F.C4H10O2.Which of these are are optically active
109)
and which are not ? Give reasons.
Answer :
Structure (II) has a centre of symmetry and hence is achiral. It also has a plane of symmetry as shown below.
Therefore, structure (II) represents a meso-compound.
Finally, structures (I and (II) and (II and III) are not mirror images and hence are diastereomers .
110)Wurtz reaction fails in case of tert-alkyl halides. Explain.
Answer : tert-Alkyl halides prefer to undergo dehydrohalogenation in presence of a strong base such as Na
metal instead of undergoing Wurtz reaction as explained below:
Thus, only 1o and 2° alkyl halides undergo Wurtz reaction while 3° alkyl halides prefer to undergo
dehydrohalogenation to form alkenes.
111) Explain the following :
(i) In nucleophilic aromatic substitution reactions,flurides are more reactive than chlorides while in aliphatic
nucleophilic substitution reactions reverse is true.
(ii) Chlorobenzene forms Grignard reagent in THF but not in ether.
Answer : (i) The greater reactivity of fluorides as compared to chlorides in nucleophilic aromatic substitution is
due to the strong -I-effect of the F atom which favours the initial nucleophilic attack on the aromatic ring.
However, in nucleophilic aliphatic substitution, the greater reactivity of chlorides as compared to fluorides is
due to greater leaving ability of Cl- ion over F- ion.
(ii) Due to + R-effect of CI, the C-Cl bond has some double bond character and hence little more difficult to
break. In other words, energy of activation for cleavage of C-Cl bond is little higher which cannot be supplied by
the low boiling point (b.p. 308 K) of ether but can be easily supplied by the little higher b.p. (340 K) of THF.
112) Give at least one test which can distinguish between C2H5Br and C2H5CI.
Answer : Make the Lassaigne's extract of C2H5Br and C2H5CI separately. Acidify them with dil. HNO3 and add
AgNO3 solution. C2H5Br gives pale yellow ppt. of AgBr partially soluble in ammonia while C2H5CI gives white
ppt. of AgCl soluble in ammonia.
113)Elimination reactions (especially β-elimination) are as common as the nucleophilic substitution reaction in case
of alkyl halides. Specify the reagents used in both cases.
Answer : Both elimination reactions (particularly β - elimination reactions) and nucleophilic substitution
reactions occur simultaneously. However, by a proper choice of reagents and reaction conditions, we can make
one reaction to predominate over the other. Usually strong and bulkier bases and high temperature favour
elimination reactions whereas weaker and smaller bases and lower temperature favour substitution reactions.
For example, ethyl bromide on heating with alcoholic KOH (which contains the stronger base C2 H 5 O− ion) at
bout 473-523 K undergoes elimination to give ethene while with aqueous KOH at about )73 K it gives ethanol.
KOH (aq) KOH (alc
C H 3 C H2 OH ⟵ C H 3 C H2 Br ⟶ C H2 = C H2
Ethanol 373 K Ethyl bromide 473−523 K Ethene
(Subsititution) (Elimination)
For further details refer to 'Supplement your knowledge for competitions.

114) How will you obtain monobromobenzene from aniline?
Answer :
tert-Butyl bromide reacts with aq.NaOH by SN1 mechanism while n-butyl bromide reacts by SN2 mechanism.
115)
Why?
Answer : tert-Butyl bromide readily loses Be ion to form stable tert-butyl carbocation. Therefore, it undergoes
reaction by SNI mechanism which occurs in two steps. In the first step, tert-butyl carbocation is formed. This
step is slow and hence is the rate determining step of the reaction. In the second step, the tert-butyl
carbocation is readily attacked by OH- ion to form tert-butyl alcohol.
On the other hand, n-butyl bromide does not undergo ionization to produce n-butyl carbocation because it is
not stable. Therefore, it prefers to undergo reaction by SN2 mechanism which occurs in one step through a
transition state involving nucleophilic attack of the OH- ion. from the back side with simultaneous expulsion of
Br- ion from the front side.
116) Predict the major product formed when HCl is added to isobutylene. Explain the mechanism involved.
Answer :
Mechanism. This reaction is an example of electrophilic addition reaction and occurs in two steps: Step I. In the
first step, a proton adds to form two possible carbocations (I and II). Since carbocation (I) is 3°, therefore, it is
much more stable than carbocation (II) which is 1°,
Step II. In the second step, the Cl- ion readily attacks the 3° carboation (I) forming 2-chloro-2-methylpropane as
the major product.
117)How can you obtain iodoethane from ethanol when no other iodine containing reagent except NaI is available in
the laboratory?
Answer : First convert ethanol to chloroethane on treatment with HCI (g) and anhyd. Z nC l2 (or bromoethane
on treatment with P + Br2 ) and then to iodoethane on treatment with NaI in acetone by Finkelstein reaction.
AnhydZnC l2
C H 3 C H 2 OH + H C I ⟶ C H 3 C H 2 C I + H 2 O
Ethanol C hloroethane
P +Br2
C H 3 C H 2 OH ⟶ C H 3 C H 2 Br
Ethanol Bromoethane
Acetone
C H 3 C H 2 C I or C H 3 C H 2 Br + N aI ⟶ C H 3 C H 2 I + N aC I or N aBr
C hloroethane Bromoethane (F inkelstein reaction) I odeothane
Cyanide ion acts as an ambident nucleophile. From which end it acts as a stronger nucleophile in aqueous
118)
medium? Give reason for your answer.
Answer : It acts as a stronger nucleophile from carbon end because it will lead to the formation of C-C bond
which is more stable than C-N bond.
119) How will you carry out the following conversions in not more than two steps:
(i) Toluene to benzyl alcohol
(ii) Benzyl alcohol to phenyl ethanenitrile
Answer :
120) Write the structure of the major organic product in each of the following:
H eat
(a) (C H3 ) C Br + H 2 O ⟶
3
Water
(ii)CH3 CH(Br)CH2 CH3 + NaOH ⟶

aq.ethanol
(c) C H3 C H2 Br + K C N ⟶
(iv) C6 H5 ONa + C2 H5 Cl ⟶
Answer :
121) Explain the following:

(i) Although haloalkanes are polar in character yet they are insoluble in water.
(ii) Chloroform is a chlorine compound, but it fails to react with AgN O3 solution.
Answer : (i) Although haloalkanes are polar compounds, yet these are practically insoluble in water.This is
because these are not able to form hydrogen bonds with water.However, these are soluble in organic solvents
like alcohol, benzene, ether, etc.
(ii) Chloroform is a chlorine compound but it is covalent in nature.Therefore, it does not ionize in water to give
−
C l ions.Hence it does not react with AgN O3 solution.
122) Convert the following in not more than two steps:

(a) Propene to propyne
(b) Ethanol to but-1-yne
Br2 2 alc.KOH
Answer : (a) C H3 CH = C H2 ⟶ C H3 C H − C H2 ⟶ C H3 C ≡ C H
P ropene |
| P ropyne
Br Br
+
SOC I2 H C ≡C N a
(b) C H3 C H2 OH ⟶ C H3 C H2 C I ⟶ C H3 C H2 C ≡ CH
Ethanol But−1−yne
123)Explain as to why haloarenes are much less reactive than haloalkanes towards nucleophilic substitution
reactions.
Answer : Haloarenes are much less reactive than haloalkanes towards nucleophilic substitution reactions _
because of the following reasons:
1. Resonance effect: In haloarenes, there is delocalisation of electrons due to resonance. For example,
chlorobenzene is considered to be a resonance hybrid of the following structures:
It is evident tht, the contribution of structures III, IV and V imparts a partial double bond character to the
carbon-chlorine bond. This is confirmed by X-ray analysis which shows that the C - CI bond length in
chlorobenzene is 1.69A while the C-CI bond length in ethyl chloride molecule is 1.82A. The shortening of bond
length imparts stability to aryl halides and the bond cleavage becomes rather difficult. The aryl halides
are therefore, less reactive than alkyl halides.
2. Different hybridisation states of carbon atom: In haloalkanes the carbon atom of the C - X bond is sp3
hybridised while in haloarene halides, the carbon atom is sp2 hybridised. The Sp2 hybridised carbon atom with
a greater s-character is more electronegative. It can hold the electron pair of the bond more tightly than the Sp3
hybridised carbon atom in alkyl halides. Therefore, it has less tendency to release electrons to the halogen. As a
result, the bond cleavage in aryl halides is some what more difficult than in alkyl halides.
Thus, haloarenes are less reactive towards the substitution reactions than haloalkanes.
124) How would you convert the following:
(i) Prop-1-ene to 1-fluoropropane
(ii) Chlorobenzene to 2-chlorotoluene
(iii) Ethanol to propane nitrile
H Br AgF
(i) C H3 C H = C H2 ⟶ C H3 C H2 C H2 ⟶ C H3 C H C H2 C H2
Answer : P rop−1−ene P eroxide 1−F luoropropane
′
(S wart s reaction)
AgC N
(iii) C H3 C l ⟶ C H3 N C
¥ethyl isocyanide
125) Give reasons:

(i) C − C l bond length in chlorobenzene is shorter than C − C l bond length in C H3 − Cl
(ii) The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride.
(iii) SN 1 reactions are accompanied by racemization in optically active alkyl halides.
Answer : (i) In chlorobenzene, there is a delocalisation of electrons due to resonance.

It is considered to be resonance hybrid of the following structures:
The contribution of structure III, N and V imparts a partial double bond character to C-CI bond.This is
confirmed by X-ray analysis which shows that C-CI bond length in chlorobenzene is 1.69 whereas C-CI bond
∘
length in ethyl chloride is 1.82A. There is no resonance in CH3CI and hence no partial double bond character.
(ii) In chlorobenzene, the C of C-CI bond is sp2-hybridised while the C of C - CI bond in cyclohexyl chloride is
sp3-hybridised.
Therefore, the sp2-hybridised C of chlorobenzene has more s-character and hence more electronegative than the
sp3-hybrid C of cyclohexyl chloride. As a result, the Sp2 hybrid of C-CI bond in chlorobenzene has less
tendency to release electrons to CI than the sp3 hybrid carbon of cyclohexyl chloride. As a result, the C-CI bond
in chlorobenzene is less polar than in cyclohexyl chloride.
(iii) The SN1 reactions proceed through the formation of carbocations. In case of optically active alkyl halides the
product formed is a racemic mixture.This is because the intermediate carbocation is planar species, therefore,
the attack of the nucleophile, OH- ion can take place from both the faces (front and rear) with equal ease. As a
result, 50 : 50 mixture 0 the two enantiomers (laevo and dextro) is formed. Thus, the product formed is a
racemic mixture (±)which is optically inactive.
For example, hydrolysis of optically active 2-bromobutane results in the formation of racemic mixture (±)-butan-
2-oL.
126) 2
(i) Which alkyl halide from the following pair is chiral and undergoes faster SN reaction?

1 2
(ii) Out of SN and SN , which reaction occurs with
(a) Inversion of configuration
(b) Racemisation
Answer : is chiral.
undergoes faster towards SN2 reaction as it is a primary halide.

(a) SN2 reaction occurs with inversion of configuration.
(b) SN1 reaction proceeds with racernisation.
127) What happpens when :
(i) CH3 -CI is treated with aqueous KOH?
(ii) CH3 -CI is treated with KCN?
(iii) CH3 -Br is treated with Mg in the presence of dry ether ?
Answer : (i) CH3 - CI + KOH→CH3OH + KCI
(aq) Methanol
(ii) CH3 - CI + KCM → CH3 CN + KCI
Methyl cyanide
Dry ether
(iii) CH3 Br + Mg ⟶ CH3MgBr

Methyl magnesium bromide
128) Give chemical tests to distinguish between the following pairs of compounds :
(i) Benzyl chloride and chlorobenzene
(ii) Chloroform and carbon tetrachloride
Answer : (i) On adding sodium hydroxide and silver nitrate to both the compounds, benzyl chloride forms white
precipitate but chlorobenzene does not form white precipitate.
C6H5CH2CI + NaOH→C6H5CH2OH +NaCI
NaCI + AgNO3→AgCI(s) + NaNO3
(white ppt.)
(ii) On heating chloroform and carbon tetrachloride with aniline and ethanolic potassium hydroxide separately
chloroform forms pungent smelling isocyanide but carbon tetrachloride does not form this compound.
Δ
C6H5NH2 + CHCI3 + 3KOH →C6H5NC + 3KCI + 3H2O

Phenyl isocyanide
129) Haloalkanes undergo nucleophilic substitution whereas haloarenes undergo electrophilic substitution. Explain.
Answer : In haloalkanes, the halogen atom is attached to carbon atom. As the halogen atom is
more electronegative than carbon, the bond between carbon and halogen is polar in character.
δ+ δ−
C − X
Due to presence of partial positive charge on carbon atom, the nucleophiles can attack on electron deficient
carbon thereby resulting in the displacement of weaker nucleophile, thus typical reactions of alkyl halides are
nucleophilic substitution reactions:
R : X + : Z-→R : Z + X-
Nucleophile Halide ion
Whereas in haloarenes, as the halogen atom attached to benzene ring, releases electron towards benzene ring (
+m effect) thereby the ortho and para positions become site of attack for electrophiles more than nucleophiles.
130) Draw the structures of major monohalo products in each of the following reactions :
Answer :
131) Bring out the following conversions.

(ii) Chlorobenzene to 2-chloroacetophenone
(iii) Chloroethane to butane
Answer :
132) Draw the structures of the following organic halogen compounds

(i) p-bromochlorobenzene
(ii)1-chloro-4-ethylcyclohexane
Answer :
133) Write chemical equations when

(i) ethyl chloride is treated with aqueous KOH
(ii) chlorobenzene is treated with CH3COCl in the presence of anhydrous AIC13
Answer : C H 3 Br + CH − C I + K OH (aq) → C H 3 C H 2 OH + K C I
Ethylchloride Ethanol
134) Write the chemical equations when,

(i) methyl chloride is treated with AgN02.
(ii) bromo benzene is treated with CH3CI in the presence of anhydrous AICl3
C H 3 C I + AgN O2 + AgC I
Answer : M ethyl
C hloride
135) Discuss the mechanism of SN1reaction of haloalkanes.

Answer : SN1reactions are generally carried out in polar protic solvents (like water, alcohol, acetic acid, etc). The
reaction between tert-butyl bromide.and hydroxide ion yields ter/-butyl alcohol and follows the first order
kinetics.
− −
(C H 3 ) C Br + OH → (C H 3 ) C OH + Br
3 3
The steps involved are

(i) Formation of carbocation intermediate
+ −
(C H 3 ) C − BrS low(C H 3 )3 C + Br
3
−−− → (C arbocation)
(ii) Attack of nucleophile on carbocation formed leading to formation of substituted product.

+ −
(C H 3 ) C + OH F ast(C H 3 ) C OH
3 3
(N ucleophile)−
− −→
Write the IUPAC name of the compound shown alongside and mention the hybridisation of each carbon-halogen
136)
bond.
Answer : IUPAC Name: 3-bromo-1-chlorocyclohex-1-ene

Hybridisation C-Cl (Sp2), C-Br (sp3)
137) Draw the structure of the following compounds.
(i) 2,2-dimethyl-1-bromobutane
(ii) 2,2,4,4-tetramethylhexane
Answer :
138) Write the structures of the following organic halogen compounds.

(i)1-bromo-4-sec-butyl-2-methylbenzene
(ii) 1,4-dibromobut-2-ene
Answer :
139) Write the IUPAC name of the following compounds.
Answer : (i) 3-chloro-5-tluoro-3,5-dimethylheptalle

(ii) 2-chloro-3,3-dimethylbutane (halogen is preferred over alkyl group while naming).
140) Why aryl halides cannot be prepared by the reaction of phenol with HCI in the presence of ZnCI2?
Answer : Due to resonance in phenol, C-O bond of phenol has some partial double bond character, which
strengthens the bond. So, it is difficult to break this C-O bond of phenol while the C-O bond of alcohol is purely
single bond and comparatively weaker bond. So, alkyl halides can be prepared by the reaction of alcohols with
HCI in the presence of ZnCl2 while aryl halides cannot be prepared by the reaction of phenol with HCI in the
presence of ZnCI2.
141) Write the structure of the major organic products in each of the following reactions:
Acetone
(i)CH3 CH2 CH2 Cl + NaI ⟶
Heat
Pyridine
(ii)CH3 CH2 CH2 OH + SOCl2 ⟶

Peroxide
(iii)CH3 CH2 CH = CH2 + HBr ⟶
(iv) C H 3 C H = C (C H 3 ) + H Br
|
C H3
Answer :
142) (i) Give the reaction for the formation of phosgene gas.
(ii) What happens when phosgene gas reacts with ethanol? (Give chemical reaction only).
Air or
Answer : (i)2CHCl3 + O 2 2COCl2 + 2HCl
Light
(ii)COCl2 + 2C2 H5 OH ⟶ (C2 H5 ) CO 3 + 2HCl

2
Phosgene Ethanol Diethyl carbonate

143) Why is iodination of benzene difficult?
Answer : Iodination of benzene is difficult bcoz they require presence of oxidizing agents such as HNO3,HIO4 to
oxidize HI. Aryl chlorides( halogens bonded with sp3 hybridised)and bromides can be easily prepared by
electrophilic substitution with cl,br at dark ordinary temperature in presence of Lewis acid as catalyst to
generate electrophile but in case of iodine the reactions are reversible.
144) Complete the following reactions.
Answer :
145) Write the reaction for the formation of each of the following.
(i) Dichloromethane
(ii) Phosgene
hv
Answer :
(i)CH4 + 2Cl2 ⟶ CH2 Cl2 + 2HCl
hv
(ii)2CHCl3 + O 2 ⟶ 2COCl2 + 2HCl
146) Give the IUPACnames of the following compounds.
Answer : (i) 1-chloro-2,2-dimethylpropane

(ii) 4-bromo-3-methylpent-2-ene
(iii) 1-chloro- 3, 3-dimethylbutane
(iv) 3, 5-dichloro-3, 5-dimethylheptane
147) P, Q, R and S undergoes SN2 reaction with KI in acetone. What is the order of the rate of reaction?
Answer : S > P > R > Q

Relative reactivity for SN2 reaction in the given structurest is
(a) Which alkyl halide from the following pairs would you expect to react more rapidly by an SN2 mechanism and
148)
why?
(b) Racemisation occurs in SN1 reactions. Why?

Answer : (a) CH3CH2CH2CH2Br will react faster towards SN2 mechanism because it has less stearic hindrance
due to which nucleophile can readily attack as compared to
(b) In SN1 mechanism, inte~ediate carbocation is sp2 hybridised and has planar structure, therefore, there is
equal probability of attacking nucleophile from either of the side leading to formation of equal amount of dextro
and laevo rotatory products leading to racemisation.
tert-Butylbromide reacts with aq. NaOH by SN1 mechanism while n-butylbromide reacts by SN2 mechanism.
149)
Why?
Answer : It is because tert-butyl carbocation is more stable than n-butyl carbocation, therefore, tertiary butyl
chloride follows SN1 mechanism; whereas n-butyl bromide is primary halide, undergoes SN2 mechanism due to
less stearic hindrance.
150) Some alkyl halides undergo substitution whereas some undergo elimination reaction on treatment with bases.
Discuss the structural features of alkyl halides with the help of examples which are responsible for this difference.
Answer : Primary alkyl halides prefer to undergo substitution reaction by SN2 mechanism; whereas tertiary
halides undergo elemination reaction due to formation of stable carbocation.
151) (i) CH3Cl + KCN ⟶ ?
(ii)
Answer : (i) CH3Cl + KCN ⟶ CH3CN + KCl

(ii)
152) Write a chemical reaction involved in the formation of Freon-12. What is the name of this reaction?
Answer : This is Swarts reaction.
Δ
3CCl4 + 2SbF3 → 3CCl2 F2 + 2SbCl 3
SbCl5
Freon-12
153) Complete the following chemical equation:
(i) CH3CI + KNO2 ⟶
Acetone
(ii) C2 H5 Cl + NaI ⟶
Answer : (i) CH3 Cl + KNO2 ⟶ CH3 − O − N = O + KCl

Acetone
(ii) C2 H5 Cl + NaI ⟶ C2 H5 I + NaCl
71 x 3 = 213
154)A hydrocarbon C5H10 does not react with chlorine in dark but gives a single monochloro compound C5H9Cl in
bright sunlight. Identify the hydrocarbon.
Answer : A hydrocarbon with the molecular formula, C5H10 belongs to the group with a general molecular
formula CnH2n. Therefore, it may either be an alkene or a cycloalkane. Since hydrocarbon does not react with
chlorine in the dark, it cannot be an alkene. Thus, it should be a cycloalkane. Further, the hydrocarbon gives a
single monochloro compound, C5H9Cl by reacting with chlorine in bright sunlight. Since a single monochloro
compound is formed, the hydrocarbon must contain H−atoms that are all equivalent. Also, as all H−atoms of a
cycloalkane are equivalent, the hydrocarbon must be a cycloalkane.
155) Give the IUPAC names of the following compounds:

(i) CH3CH(Cl)CH(Br)CH3
(ii) CHF2CBrClF
(iii) ClCH2C ≡ CCH2Br
(iv) (CCl3)3CCl
(v) CH3C(p-ClC6H4)2CH(Br)CH3
(vi) (CH3)3CCH= C(Cl)C6H4I-p
Answer : The IUPAC names of various compounds are given below in order:
(i) 2-Bromo-3-chlorobutane
(ii) 1-Bromo-1-chloro-1,22-trifluoroethane
(iii) 1-Bromo-4-chlorobut-2-yne
(iv) 2-(Trichloromethyl)-1,1,1,2,3,3,3-heptachloropropane
(v) 2-Bromo-3,3-bis (4-chlororphenyl) butane
(vi) 1-Chloro-1-(4-iodophenyl)-3,3-dimethylbut-1-ene
156) Write IUPAC names of the following:
Answer : (i) 4-Bromopent-2-ene

(ii) 3-Bromo-2-methylbut-1-ene
(iii) 4-Bromo-3-methylpent-2-ene
(iv) 1-Bromo-2-methylbut-2-ene
(v) 1-Bromobut-2-ene
(vi) 3-Bromo-2-methylprop-1-ene
157) Write the products of the following reactions:
Answer :
158) Identify chiral and achiral molecules in each of the following pair of compounds. (Wedge and Dash
representations)
(i)
(ii)
(iii)
Answer :
159) Arrange the compounds of each set in order of reactivity towards SN2 displacement:
(i)2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(ii)1-Bromo-3-methylbutane, 2-Bromo-2methylbutane, 2-Bromo-3-methylbutane
(iii)1-Bromobutane, 1-Bromo-2, 2-dimethylpropane, 1-Bromo-2-methylbutane, 1-Bromo-3-methylbutane
Answer : The reactivity in SN2 reactions depends upon steric hindrance; more the steric hindrance slower
the reaction.
Since due to steric reasons, the order of reactivity in SN2 reactions follows the order: 1° > 2° > 3 D.therefore,
order of reactivity of the given alkyl bromides is:
J-Bromopentane > 2-Bromopentane > 2-Bromo-2- methylbutane.
Since due to steric reasons, the order of reactivity of alkyl halides in SN2 reactions follows the order: 1° > 2° >
3°, therefore, the order of reactivity of the given alkyl bromides is:
1-Bromo-3-methylbutane (1o) > 2-Bromo-3-methyLbutane'(2°) > 2-Bromo-2-methylbutane(30)
Since in case of 1° alkyl halides, steric hindrance increases in the order: n-alkyl halides, alkyl halide with a
substituent at any position other than the β-position, one substituent at the β-position, two substituents at the
β -position, therefore, the reactivity decreases in the same order. Thus, the reactivity of the given alkyl bromides
decreases in the order:

1-Bromobutane > 1-Bromo-3 - methyLbutane > 1-B romo-2 - methyLbutane > 1-Bromo-2, 2 dimethylpropane.
160) Give the uses of freon 12, DDT, carbon tetrachloride and iodoform
Answer : Uses of Freon-12
(i) Freons are used as refrigerants in refrigerators and air conditioners.
(ii) These have also been used extensively as propellants for aerosols and foams to spray out deodorants,
cleaners, shaving creams, hair sprays and insecticides.
However, the use of freon restricted or banned in many countries because they are responsible for ozone
depletion.
Uses of CC14
(i) It is used as a solvent for oils, fats, waxes, etc.
(ii) It is used as a fire extinguisher under the name pyrene.
(iii) It is used in dry cleaning.
(iv) It is used for the manufacture of freon.
Uses of Iodoform
(i) It is used as an antiseptic and this nature is due to iodinethat it liberates. However, because ofits very un-
pleasant smell, it has now been replaced by better antiseptics.
(ii) It is used in the manufacture of pharmaceuticals.
161) Explain the following :
(i) The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride.
(ii) Alkyl halides, through polar, are immiscible with water.
(iii) Grignard's reagents should be prepared under anhydrous conditions.
Answer : (i) In chlorobenzene, the C atom of the C-Cl bond is sp2 hybridized and has more s character and
electronegativity. In cyclohexyl chloride, the C atom of the C-Cl bond is sp3 hybridized, has less s character and
less electronegative. Hence, the C-Cl bond in chlorobenzene is less polar than the C-Cl bond in cyclohexyl
chloride.
Also, in chlorobenzene, the lone pair of electron on the Cl atom is in resonance with a benzene ring. This gives
partial double bond
character to C-Cl bond and there is a decrease in the magnitude of partial negative charge on Cl atom.
However, in cyclohexyl chloride,
there is a C-Cl single bond. The dipole moment is a product of charge and distance. Also C-Cl bond with partial
double bond character
has lower bond length than with C-Cl single bond. Hence, chlorobenzene has lower dipole moment than
cyclohexyl chloride.
(ii) Inter-molecular attractive forces present in alkyl halides are dipole dipole interactions and in case of water
molecules, intermolecular
hydrogen bonds are present. When alkyl halides are added to water, the intermolecular attractive force present
between an alkyl halide
and water molecules are weaker than the forces that are already present between two alkyl halide molecules
and two water molecules.
Hence, alkyl halides are water-immiscible.
(iii) Grignard reagents are highly reactive with moisture that is present in apparatus or starting materials.
Hence, we should prepare Grignard reagents in the anhydrous condition.
RMgX + HOH → RH + MgOHX
162) Write the structures of different dihalogen derivatives of propane.

Answer : The structures of different dihalogen derivatives of propane are :
163) In the following pairs of halogen compounds, which compound undergoes faster SN1 reaction?
(i)
(ii)
Answer : (i)
SN1 reaction proceeds via the formation of carbocation. The alkyl halide (I) is 3° while (II) is 2°. Therefore, (I)
forms 3° carbocation while (II) forms 2° carbocation. Greater the stability of the carbocation, faster is the rate of
SN1 reaction. Since 3° carbocation is more stable than 2° carbocation. (I), i.e. 2-chloro-2-methylpropane,
undergoes faster SN1 reaction than (II) i.e., 3 chloropentane.
(ii)
The alkyl halide (I) is 2° while (II) is 1°. 2° carbocation is more stable than 1° carbocation. Therefore, (I), 2-
chloroheptane, undergoes faster SN1 reaction than (II), 1-chlorohexane.
164) Why is sulphuric acid not used during the reaction of alcohols with KI?
Answer : In the presence of sulphuric acid (H2SO4), KI produces HI
2KI + H2 SO4 → 2KHSO4 + 2HI
Since H2SO4 is an oxidizing agent, it oxidizes HI (produced in the reaction to I2).

2HI + H2 SO4 → I2 + SO2 + H2 O
As a result, the reaction between alcohol and HI to produce alkyl iodide cannot occur. Therefore, sulphuric acid
is not used during the reaction of alcohols with KI. Instead, a non-oxidizing acid such as H3PO4 is used.
(i) 2-Chloro-3-methylpentane
(ii) p-Bromochlorobenzene
(iii) 1-Chloro-4-ethylcyclohexane
(iv) 2-(2-Chlorophenyl)-1-iodooctane
(v) 2-Bromobutane
(vi) 4-tert-Butyl-3-iodoheptane
(vii) 1-Bromo-4-sec-butyl-2-methylbenzene
(viii) 1,4-Dibromobut-2-ene
Answer : (i) 2-Chloro-3-methylpentane
(ii) p-Bromochlorobenzene
(iii) 1-Chloro-4-ethylcyclohexane
(iv) 2-(2-Chlorophenyl)-1-iodooctane
(v) 2-Bromobutane
(vi) 4-tert-Butyl-3-iodoheptane
(vii) 1-Bromo-4-sec-butyl-2-methylbenzene
(viii) 1,4-Dibromobut-2-ene
166) Which one of the following has the highest dipole moment?
(i) CH2Cl2
(ii) CHCl3
(iii) CCl4
Answer : Dichloromethane has highest dipole moment among CH2Cl2, CHCl3 and CCl4. The decreasing order of
dipole moments is CH2Cl2> CHCl3> CCl4. These molecules have tetrahedral geometry due to sp3 hybridization
of carbon atom.In CCl4, the individual C−Cl bond dipoles cancel each other which results in zero dipole
moment.
Hence, CCl4 is non polar.
167) Answer the following:
(i) Haloalkanes easily dissolve in organic solvents, why?
(ii) What is known as a racemic mixture? Give an example.
(iii) Of the two bromoderivatives, C6H5CHI(CH3)Br and C6H5CH(CH5)Br which one is more reactive in SN1
substitution reaction and why?
Answer : i) Haloalkanes can easily dissolve in organic solvents of low polarity because the new forces of
attraction set up between haloalkanes and the solvent molecules are of same strength as the forces of attraction
being broken.
(ii) A mixture of equal amounts of two enantiomers is known as racemic mixture. For example: When a 3°
halide undergoes substitution with KOH, the reaction proceeds through SN 1 mechanism forming the racemic
mixture in which one of the products has the same configuration as a reactant, while the other product has an
inverted configuration.
More stable the carbocation, more reactive will be substrate .the carbocation formed by two compounds are as
follows:
Compound (C6H5)2CHBr = carbocation (C6H5)2CH+
Compound C6H5CH(CH3)Br=carbocation C6H5(CH3)CH+
Out of these two carbocations (C6H5)2CH+ is more stable than C6H5(CH3)CH+ because the
carbocation(C6H5)2CH+ is resonance stabilised by two benzene rings .therefore (C6H5)2CHBr is more reactive
than C6H5CH(CH3)Br. Resonance stabilisation of carbocation with one benzene ring is shown :
168) Complete the following chemical equations:
Answer :
169) (a) write a chemical test to distinguish between:

(i) Chlorobenzene and Benzyl chloride.
(ii) Chloroform and Carbon tetrachloride.
(b) Why is methyl chloride hydrolysed more easily than chlorobenzene?
Answer : (a) (i) Chlorobenzene and Benzyl chloride Take both the compounds in a test tube. Add 1 - 2 ml of
aqueous KOH to each of the test tubes. Acidify with dilute HNO3 and add AgNO3. Benzyl chloride gives white
precipitate while chlorobenzene does not.
(ii) Chloroform and Carbon tetrachloride Chloroform on warming with alcoholic KOH and aniline will give foul
smell of isocyanide; whereas, Carbon tetrachloride will not show any change.
(b)Methyl chloride hydrolysed more easily than chlorobenzene. It is due to double bond character in
chlorobenzene due to resonance which is difficult to break as compared to single bond (C—Cl) in CH3Cl.
170) (i) State one use each of DDT and iodoform.
(ii) Which compound in the following couples will react fastert in SN2 displacement and why?
(a) 1-Bromopentane or 2-bromopentane
(b) 1-Bromo-2-methylbutane or 2-bromo- 2-methylbutane.
Answer : (i) DDT: It is used as insecticide to control flies, mosquitoes, etc. Iodoform: Iodoform is used as an
antiseptic.
(ii) 1-Bromopentane, as it is a primary alkyl halide. and
(b) 1-Bromo-2-methyl butane, as it is a primary alkylhalide.
171)How would you differentiate between SN1 and SN2 mechanisms of substitution reactions? Give one example of
each.
Answer : SN1 Reactions: They are substitution nucleophilic unimolecular reactions in which the rate of the
reaction depends on the concentration of only one reactant. Product formation takes place by the formation of
carbo cation as reaction intermediate. For example:
SN2 reactions they are substitution nucleophilic bimolecular reactions in which rate of the reaction depends on
the concentration of two reactants. For example:
The product formation takes place by formation of transition state.

Complete the following reactions:
172)
′ ′
SOC I2 KC N
(i) C H 3 C H 2 OH −−−−→ A
′
−−−→
′
B
′ ′
P C l5 AgC N
(ii) C H 3 − C H − C H3 −
− −→
′
A −−−→ B
′
|
OH
AgN O 2
(iii) C H 3 C H 2 −−−−→ ′ A′
(iv) (CH3)2CHCI + CH ≡ CNa → 'A'
(v) C H 3 C H 2 C H 2 C l + C H 3 C OOAg → A
′ ′ ′
+ B
′
dry ether
(vi) 2(C H 2 )2 C H Br + 2N a −−−−−→
Answer :
173)An organic compound 'A' having molecular formula C4H8 on treatment with dil. H2SO4 gives 'B'. 'B' on treatment
with conc. HCl and anhydrous ZnCl2 gives 'C' and on treatment with sodium ethoxide gives back 'A'. Identify the
compounds 'A', 'B' and 'C' and write the equations involved.
Answer :
An alkyl chloride (A), on reaction with magnesium in dry ether followed by treatment with ethanol gave 2-
174)
methylbutane. Write all the possible structures of (A).
Answer : The structures of all the possible alkyl halides that can be obtained by monohalogenation of 2-
methylbutane are :
The Grignard reagents of all these four alkyl halides will give 2-methylbutane on treatment with ethanol.
175) Explain why
(a) vinyl chloride is unreactive in nucleophilic substitution reactions?
(b) neo-pentyl bromide undergoes nucleophilic substitution reaction very slowly?
(c) 3-bromocyclohexene is more reactive than 4-bromocyclohexene in hydrolysis with aqueous NaOH?
(d) tert-butyl chloride reacts with aqueous sodium hydroxide by SN1 mechanism while n-butyl chloride reacts by SN2
mechanism?
Answer : (a) Vinyl chloride is unreactive in nucleophilic substitution reactions because of double bond character
between bond which is difficult to break.
(b) neo - Pentyl bromide is 1∘ halide, forms 1∘ carbocation which is less stable, changes 3∘ to
carbocation which requires energy, therefore, undergoes nucleophilic substitution reaction slowly.
(c) 3-Bromocyclohexene forms allyi carbocation which is more stable than carbocation formed by 4-
bromocyclohexene, therefore, it can undergo hydrolysis faster.
176) Write the equations for the preparation of 1-iodobutane from:
(a) 1-iodobutane from:
(b) 1-butanol
(c) but-1-ene.
Answer : (i) 1-butanol
177) Indentify A, B, C, D, E, R and R1 in the following:
Answer :
178)Primary alkyl halide C4H9Br (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) C8H18 that
was n-butyl bromide is reacted with sodium. Give the structural formula of (A) and write the equations for all the
reactions.
Answer :
179) Compound 'A' with molecular formula C4H9Br is treated with aq. KOH solution. The rate of this reaction depends
upon the concentration of the compound 'A' only. When another optically active isomer 'B' of this compound was
treated with aq. KOH solution, the rate of reaction was found to be dependent on concentration of compound and
KOH both.
(i) Write down the structural formula of both compounds 'A' and 'B'.
(ii) Out of these two compounds, which one will be converted to the product with inverted configuration.
Answer : (i) Since the rate of reaction depends upon the concentration of 'A' only, therefore, 'A' should be
∘
3 halide which will follow SN 1 mechanism.
(ii) 'B' will be converted into inverted configuration due to back side attack of nucleophile,
i.e. dextro will change to laevo and laevo will change into dextro.
180) Explain why

(i) the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride?
(ii) why alkyl halides, though polar, are immiscible with water?
Answer : (i) Due to greater s-character, a sp2-hybrid carbon is more electronegative than a sp3-hybrid
carbon.Therefore, the sp2-hybrid carbon of C-Cl bond in chlorobenzene has less tendency to release electrons to
CI than a sp3-hybrid carbon of cyclohexyl chloride.
As a result, the C-CI bond in chlorobenzene is less polar than in cyclohexyl chloride. In other words, the
−
magnitude of negative charge, i.e., δ is less on CI atom of chlorobenzene than in cyclohexyl chloride.
Further, due to delocalization of lone pairs of electrons of the CI atom over the benzene ring, C-C1 bond in
chlorobenzene acquires some double character while the C-CI bond in cyclohexyl chloride is a pure single bond.
In other words, C-CI bond in chlorobenzene is shorter than in cyclohexyl chloride. Since dipole moment is a
product of charge and distance, therefore, chlorobenzene has lower dipole moment than cyclohexyl chloride due
to lower magnitude of -ve charge on the Cl atom and shorter C-Cl distance.
(ii) Alkyl halides are polar molecules, therefore, their molecules are held together by dipole-dipole attraction.
The molecules of H2O are held together by H-bonds. Since the new forces of attraction between water and alkyl
halide molecules are weaker than the forces of attraction already existing between alkyl halide-alkyl halide
molecules and water- water molecules, therefore. alkyl halides are immiscible (not soluble) with water.
181) Classify the following compounds as primary, secondary and tertiary halides.
(i) 1-Bromobut-2-ene
(ii) 4-Bromopent-2-ene
(iii) 2-Bromo-2-methylpropane
Answer :
C H3
∘ ∘
|
1 2 ∘
3
(i) C H3 C H = C H − C H 2 Br (ii)C H3 − C H Br − C H = C H − C H3 (iii)C H3 − C − Br
|
CI
1-Bromobut-2-enc 4-Bromopent-2-ene 2-Bromo-2-

methylpropane
(1o Alkyl halide) (2o Alkyl halide) (3o Alkyl
halide)
182) Chlorobenzene is extremely less reactive towards a nucleophilic substitution reaction. Give two reasons for the
same.
Answer : Haloarenes are much less reactive than haloalkanes towards nucleophilic substitution reactions
It is evident that, the contribution of structures III, IV and V imparts a partial double bond character to the
length imparts stability to aryl halides and the bond cleavage becomes rather difficult. The aryl halides are,
therefore, less reactive than alkyl halides.
Thus haloarenes are less reactive towards the substitution reactions than haloalkanes.
183)An alkyl halide X, of formula C6 H 13 C l on treatment with potassium tertiary butoxide, gives the isomeric alkenes
Y and Z (C6 H 12 ).Both alkenes on hydrogenation give 2,3-dimethylbutane.Predict the structures of X, Y and Z.
Answer : It is given that
C H3 C H3
| |
(C H 3 ) C OK H2
3
C6 C3 C I ⟶ T woisomeric ⟶ C H3 − C H − C H − C H3
(X) 2,3−Dimethylbutance
alkenes of
f ormula C 6 H 12
(Y ) and (Z)
The two alkenes forming 2, 3-dimethyl butane are:

C H3 C H3 C H3 C H3
| | | |
C H3 − C = C − C H3 and C H2 = C − C H − C H3
(Y ) (Z)
184)An organic compound C8 H 18 on monochlorination gives a single monochloride.Write the structure of the
hydrocarbon.
Answer : Since the hydrocarbon gives a single monochloride all the I8H atoms are equivalent. This means it has
six C H3 groups attached to the interlinked C atoms
Therefore, its structure is
C H3 C H3
| |
C H3 − C − C − C H3
| |
C H3 C H3
185) Hydrolysis of 2-bromo-3-methylbutane (2°) gives only 2-methyl1-2-butanol (3°).Explain.
Answer : During SNIreaction, the ionization gives 2° carbocation which rearranges by a hydride shift to a more
stable 3"-carbocation to form 3°-alcohol as:
186) Trichloromethane or chloroform is a colorless oily liquid with a peculiar smell.It is sparingly soluble in water.The
vapor when enhaled cause unconsciousness and therefore, it is used as an anesthetic.
Answer the following questions:
(i) What happens when chloroform is not protected from oxygen during its storage?
(ii) Why is the use of chloroform as an anesthetic has been reduced?
Answer : (i) In the presence of air and light, chloroform is oxidized to poisonous gas phosgene.
Air or light
1
C H C l3 + O2 ⟶ C OC l2 + H C l
2
P hosgene
(ii) Continuous chloroform exposure may damage liver and kidneys because chloroform is metabolised to
poisonous phosgene.Some people develop sores when the skin comes in contact with chloroform for a long
time.Therefore, use of chloroform as an anesthetic has been replaced by less toxic and safer anesthetic such as
ether.
187) D.D.T is one of the most powerful insecticides which is effective against the mosquitoes that spread
malaria.Mukesh's mother wanted to buy D.D.T from the market to use at night to protect her family from
mosquitoes.But Mukesh stopped his mother from purchasing D.D.T.
(a) How did Mukesh convince her mother for not using D.D.T at night?
(b) What values are attached to suggestion of Mukesh?
Answer : (a) Though D.D.T is a very powerful insecticide for mosquitoes, yet the excessive use of D.D.T has
many problems.The use of D.D.T has the following disadvantages:
(i) Many species of insects develop resistance to D.D.T.
(ii) It has a high toxicity towards fish.
(iii) The chemical stability of D.D.T and its fat solubility has problems.
(iv) It is not biodegradable and its residues accumulate in environment and its long term effects could be
dangerous.
(v) D.D.T is not metabolized very rapidly by animals rather it gets deposited and stored in fatty tissues.Because
of its dangerous effects, its use has been banned in U.S.A in 1973.However, in spite of its dangerous effects,
D.D.T is still being used in India because of non-availability of other cheaper insecticides.
(b) Mukesh's suggestion is very important to protect our environment.Because of long-term dangerous side
effects of D.D.T., it should not be used to save our environment.
188)How would you distinguish between SN 1 and SN 2 mechanisms of substitution reactions?Give one example of
each.
Answer : (I) Unimolecular nucleophilic substitution reaction (SN1): Those substitution reactions in which rate of
reaction depends upon the concentration of only one of the reactants, i.e. alkyl halides are called SN1 reactions,
e.g. hydrolysis of tertiary butyl chloride follows SN1 reaction. This reaction takes place in two steps. The first
step involves formation of carbocation.
The slowest step is rate determining step which involves one species only. Therefore, the rate of reaction
depends only on the concentration of tertiary butyl chloride. Tertiary halides follow SN1 mechanism. Polar
protic solvents like 'fater and alcohol favour SN1 because they stabilize carbocation by solvation.
(ii) Bimolecular nucleophilic substitution reaction (SN2): The reaction whose rate depends on the concentration
of two species, alkyl halide and nucleophile. They involve one step mechanism. Back side attack of nucleophile
and departing of leaving group take place simultaneously.
Non-polar solvents favour SN2 mechanism. Primary halides follow SN2 mechanism.

189) Account for the following :
(i) The C-CI bond length in chlorobenzene is shorter than that in CH3-CI.
Answer : (i) Iodide is a better leaving group because of its larger size than bromide, therefore, ethyl iodide
undergoes SN 2 reaction faster than ethyl bromide.
(ii) (±) 2-butanol is a racemic mixture. It is a mixture which contains two enantiomers in equal proportion and
thus, have zero optical rotation due to internal compensation. Therefore, it is optically inactive.
(iii) In halobenzenes (like chlorobenzene), the lone pair of electrons on halogen atom is delocalised on the
benzene ring. As a result, C - Xbond (C - Cl bond in case of chlorobenzene) acquires some double bond
character while in CH3-X, C-X bond is a pure single bond. Therefore, C-X bond in halobenzene is shorter than
in CH3 -X.
190) Give reasons:
(a) n-Butyl bromide has higher boiling point than t-butyl bromide.
(b) Racemic mixture is optically active.
(c) The presence of nitro group (-N02)at O/P positions increases the reactivity of
haloarenes towards nucleophilic substitution reactions.
Answer : (a) n-Butyl bromide is a straight chain molecule with strong intermolecular forces whereas t-butyl
bromide is a branched chain molecule with weak intermolecular forces due to smaller surface area. Hence, n-
Butyl bromide has higher boiling point than t-butyl bromide.
(b) Racemic mixture contains d and l enantiomers in equal proportions. As the rotation due to one enantiomer
is cancelled by equal and opposite rotation of another enantiomer, therefore, it is optically inactive.
(c) In haloarenes, N02 group is present at O/P position results in the stabilisation of resulting carbanion by-R
and - I effects and therefore increases the reactivity of haloarenes towards nucleophilic substitution reactions.
191) How do you convert:
(i) Chlorobenzene to biphenyl,
(ii) Propene to I-iodopropane,
(iii) 2-bromobutane to but-2-ene.
Answer : (i) Chlorobenzene to biphenyl: When two chlorobenzene combine with sodium metal in the presence of
dry ether it forms biphenyl.
(ii) Propene to 1-iodopropane :
P eroxide
CH3CH = CH2 + HI ⟶ CH3CH2I + CH3CHICH3
′
Anti−M arkovnokov s rule
(Major) (Minor)
H Br/P eroxide N aI /acetone
CH3CH = CH2 ⟶ CH3CH2CH2Br ⟶ CH3CH2CH2I

(iii) 2 - bromobutance to but-2-ene
Alc.KO
H 3 C − C H2 − C H − C H3 ⟶ H3 C − CH = C H − C H3 + C H3 − C H2 − C H = C H2
| But−2−ene But−1−ene
Br (80 (20
192) What happens when

(i) Chlorobenzene is treated with CI2/FeCI3,
(ii) Ethyl chloride is treated with AgNO2,
(iii) 2-bromopentane is treated with alcoholic KOH?
Write the chemical equations in support of your answer.
Answer : (i)
(ii) CH3CH2CI + AgNO2→CH3CH2NO2+AgCI

(iii) CH3CH2CH2CH(Br)CH3 + KOH(alc.)→CH3CH2CH=CH CH3
193) Write the mechanism of the following reaction:
C H 3 C H 3 OH H BrC H 3 C H 3 Br + H 2 O
−−−→
Answer : The mechanism of the given reaction is as follows:

Step 1 : H Br → H + + Br−
Step 2 Protonation of alcohol
194) Complete the following reactions
C H 3 C H 2 C H = C H 2 + H Br →
Answer : In case of non-symmetric unsaturated 1 compounds, addition of HI and HBr takes place according to
Markownikoff's rule
195) Following compounds are given to you:

2-bromopentane, 2-bromo-2-methylbutane, I-bromoperltane
(a) Write the compound which is most reactive towards SN2 reaction.
(b) Write the compound which is optically active.
(c) Write the compound which is most reactive towards β elimination reaction.
Answer : SN2reactions involve the formation of transition state. Higher the steric hindrance, lesser the stability
of transition state and lower is ·their reactivity towards SN2.
b) Among the given compounds, 2-bromopentane is optically active due to presence of chiral carbon (*)
A chiral carbon have four different groups or atoms attached separately to its four valencies
c) 2-bromo-2-methylbutane is most reactive towards β -eiimination reaction because in this case more
substituted alkene is the major product.
196) Write the major product(s) in the following:
Dry ether
2C H 3 − C H − C H 3 −−−−−−−→
|
Na
CI
C H 3 − C H 3 − BrAgC N
−−−−→
Answer :
197) (i) Why are alkyl halides insoluble in water?

(ii) Why is butan-1-ol optically inactive but butan-2-ol is optically active?
Answer : Butan-1-ol is optically inactive compound due to the absence of asymmetric C-atom (or chiral C-atom)
whereas butan-2-o1 is optically active compound due to the presence of asymmetric C-atom (or chiral C-atom).
198) Give reasons for the following:

(i) Ethyl iodide undergoes SN2 reaction faster than ethyl bromide.
(ii) (±) 2-butanol is optically inactive.
(iii) C-X bond length in halobenzene is smaller than C-X bond length in CH3 -X.
Answer : (i) Iodide ion is a better leaving group because of its larger size than bromide ion, therefore ethyl iodide
undergoes SN2 reaction faster than ethyl bromide.
ii) (±) 2-butanol is a racemic mixture. It is a mixture which contains two enantiomers in equal proportion and
thus, have zero optical rotation. Therefore, it is optically inactive
(iii) Due to delocalization of lone pairs of electrons of the X atom over the benzene ring, C-X bond in
halobenzene acquires some double bond character while in CH3-X, C-X bond is a pure single bond. Therefore,
C-X bond in halobenzene is shorter than in CH3-X.
(i) Ethyl iodide undergoes SN2 reaction faster than ethyl bromide.
(ii) (±) 2-butanol is optically inactive.
(iii) C-X bond length in halobenzene is smaller than C-X bond length in CH3 -X.
Answer : (i) Iodide ion is a better leaving group because of its larger size than bromide ion, therefore ethyl iodide
undergoes SN2 reaction faster than ethyl bromide.
ii) (±) 2-butanol is a racemic mixture. It is a mixture which contains two enantiomers in equal proportion and
thus, have zero optical rotation. Therefore, it is optically inactive
(iii) Due to delocalization of lone pairs of electrons of the X atom over the benzene ring, C-X bond in
halobenzene acquires some double bond character while in CH3-X, C-X bond is a pure single bond. Therefore,
C-X bond in halobenzene is shorter than in CH3-X.
200) Give reasons for the following observations:
(i) p-dichlorobenzene has higher melting point than those of 0 and m-isomers
(ii) Haloarenes are less reactive than halo alkanes towards nucleophilic substitution reaction.
(iii) The treatment of alkyl chloride with aqueous KOH leads to the formation of alcohol but in the presence of
alcoholic KOH, alkene is the major product.
Answer : symmetry of the m~lecule is related to its c.rystallattice structure and hence, to its melting point and
solubility. A highly symmetrical structure has a higher melting point
The melting point of p-isomer of dichlorobenzene is higher than that of o- and m-isomers. This is because p-
isomer has symmetrical structure due to which its molecules can easily pack closely in crystal lattice. Thus, it
has stronger intermolecular forces of attraction than o- and m-isomers
Difference lies in the mode and extent of dissociation of KOH in the presence of different solvents OH- is a good
nucleophile while C2H3O- is a strong base
In aqueous solution, KOH is almost completely ionised to give OH- ions which being a strong nucleophile gives
a substitution reaction on alkyl halide to form alcohol.
But an alcoholic solution of KOH contains alkoxide ions RO- which being much stronger base than OHions
preferentially eliminates a molecule of HCI from an alkyl chloride to form alkenes.
(i) p-bromochlorobenzene
(ii) 2-(2-chlorophenyl)-I-iodooctane
(iii) 2-bromobutane
Answer :
202)Among the following alcohols, which will yield the corresponding alkyl chloride on reaction with concentrated HCI
at room temperature?
C H 3 − C H 2 −C H −C H2 OH
|
C H3
C H3
|
C H 3 C H 2 − C −OH
|
C H3
C H 3 − C H 2 − C H 2 −C H −OH
|
C H3
Answer : 30 alcohols are very reactive and hence, their reactions with conc. HCI takes place even at room
temperature.
Why is the solubility of haloalkanes in water very low? why Grignard reagents should be prepared under
203)
anhydrous conditions?
Answer : Grognard reagents are very reactive. They react with moisture present in the apparatus or the starting
materials, i.e., R-X, Mg and the solvent (ether or THF)
− + −
δ δ δ
R − M g X + H − OH ⟶ R − H + M g(OH )X
Therefore,Grignard reagents must be prepared under anhydrous conditions.

204) (i) Account for the following
(a) Electrophilic substitution reactions in haloarenes occur slowly.
(b) Haloalkanes, though polar, are insoluble in water.
(ii) Arrange the following compounds in increasing order of reactivity towards SN2 displacement: 2-bromo-2-
methylbutane,1-bromopentane, 2-bromopentane.
Answer : (a) Halogen atoms of haloarenes has -I effect which has some tendency to withdraw electrons from
benzene ring. As a result, the ring gets somewhat deactivated as compared to benzene and hence electrophilic
substituation reactions in haloarenes occur slowly.
(b) Haloalkanes, though polar, are insoluble in water because less energy is released when new attractins are
set up between the haloalkanes and water molecules because these are not as strong as the hydrogen bonds
already existing between H2O molecules. As a result, holoalkanes are insoluble in water.
(ii) The correct increasing order of reactivity towards SN2 displacement is 2-bromo-2-methylbutane < 2-
bromopentane < 1-bromopentane.
205) Write the structural formula of A, B, C and D in following sequence of reaction:
(ii) Illustrate Sandmeyer's reaction with the help of a suitable example.
Answer :
Mixing the solution of freshly prepared diazonium salt with cuprous chloride or cuprous bromide, results in the
replacement of the diazonium group by -CI or -Br.
206) (a) Identify the chiral molecule in the following pair:
(b) Write the structure of the product when chi oro benzene is treated with methyl chloride in the presence of sodium
metal and dry ether.
(c) Write the structure of the alkene formed by dehydrohalogenation of 1-bromol-methylcydohexane with alcoholic
KOH.
Answer : (a) A molecule which completely lacks symmetry is called chiral. The mirror images of such molecules
are non-superimposable. Molecule (i) is chiral in given structures as the mirror images are non-superimposable.
(b) It is Wurtz-Fittig reaction.
β - hydrogen on each side of Br atom are equivalent, because of which only one alkene will be formed.
Which one of the following pair undergo SN1 reaction faster and why?
207)
H2C= CHCHCICH3or CH3 - CH2CHCICH3
Answer : CH2 = CHCHClCH3, due to the delocalisation.
208) How will you obtain mono bromo benzene from aniline? Give reaction.
Answer : React the aniline with a mixture of NaNO2 and HBr at 273-278 k . It will give benzene diazonium
bromide . Again react the benzene diazonium bromide with Cu2O2 . This will give mono bromo benzene.
209) Give reasons for the following observations.
(i) p-dibromobenzene has higher melting point than those of o- and m-Isomers.
(ii) Out of chlorobenzene and chloromethane, which is more reactive towards nucleophilic substitution reaction?
(iii) Racemisation occurs in SN1reaction.
Answer : (i)In case of dichlorobenzenes, para isomer is more symmetrical than ortho and meta isomers. Hence,
in the crystal lattice, para isomer fits more closely than ortho and meta isomers. Due to this, more energy is
required to break the crystal lattice of para isomer. Hence, p-Dichlorobenzene has higher melting point than
those of o- and m-isomers.
(ii)Out of chlorobenzene and chloromethane, chloromethane is more reactive towards nucleophilic substitution
reactions since it is an alkyl halide. Chlorobenzene is less reactive towards nucleophilic substitution reaction
because of the resonance effect and polarity of C−Cl bond.
(iii) Racemisation occurs in SN1reaction. both inversion and retention of the configuration.
210) How will you bring about the following conversions?
(i)1-bromobutane to 2-bromobutane
(ii) Aniline to chlorobenzene
Answer : (i) Dehydrohalogenation followed by Markovnikov's addition.
(ii)
211) Explain the formation of the two products in the following reaction:
CH3 CH = CHCH2 Cl + H2 O ⟶
CH3 CH = CHCH2 OH + CH3 CH(OH)CH = CH2
Answer : 1-chloro but-2-ene undergoes hydrolysis in warm water to give a mixture of these allylic alcohols.
The two products can be explained by an SN1mechanism that produces an allylic cation that can react with
water at either 1 or 3 position.
212) Name the polyhalogen which is used to prepare chloropicrin?

Answer : Chloroform (CHCl3)
213) (i) Why are haloalkanes more reactive towards nucleophilic substitution reaction than haloarenes?
214) Which of the following two substances undergo SN1reaction faster and why?
Answer : In SN1 reaction, reactivity depends upon the stability of intermediate carbocation. A secondary
carbocation is more stable than primary carbocation.
Former carbocation being secondary, is more stable than the latter being primary. Hence, it undergoes
SN1reaction faster.
215) What will be the major organic product of the following reactions?
Answer :
216) Why aryl halides are less reactive towards nucleophilic substitution reactions than alkyl halides?
Write the IUPAC name of the following compounds:
217)
Answer : (i) 2-Chloro-3,3-dimethylbutane

(ii) 4-Chloropent-l-ene
(iii) 4-Bromo-4-methyl pent-2-ene
218) Write the IUPAC name of
(i) (CH3)2CHCH(CI)CH3.
(ii)
Answer :
(iii) 2-Bromo-4-chloropentane
219) Give reasons:
(a) n-Butyl bromide has higher boiling point than r-butyl bromide.
(b) Racemic mixture is optically inactive.
(c) The presence of nitro group (-NO2) at olp positions increases the reactivity of haloarenes towards nucleophilic
substitution reactions.
Answer : (a) It is because n-butyl bromide has more surface area than t-butyl chloride, therefore, more van der
Waals' forces of attraction, hence higher boiling point.
(b) Racemic mixture contains equal amount of dextro and laevo rotatory compounds. Half of molecules rotate
plane polarised light towards left, remaining half towards right such that net optical rotation is zero. Therefore,
Racemic mixture is optically inactive.
(c) -NO2 stabilises the -ve charged ion formed during nucleophilic substitution reactions ofhaloarenes,
therefore, increases reactivity towards nucleophilic substitution reaction.
220) (a) Why are alkyl halides insoluble in water?
(b) Why is Butan-l-ol optically inactive but Butan-2-ol is optically active?
(c) Although chlorine is an electron withdrawing group, yet it is ortho-, para- directing in electrophilic aromatic
substitution reaction. Why?
Answer : (a) Alkyl halides are insoluble in water because they can neither form H-bonds with water nor they can
break H-bonds between water molecules.
(b) Butan-l-ol is achiral, i.e. does not have chiral 'C' atom which is attached to four different groups, therefore, it
is optically inactive.
Butan-2-ol is chiral, i.e. has chiral 'C' atom, attached to four different groups.
(c)
221) Write the main product when

(i) 2, 4, 6- Trinitro chlorobenzene is subjected to hydrolysis
(ii) n-Butyl chloride is treated with alcoholic KOH
(iii) methyl chloride is treated with AgCN.
Answer :
(ii) CH3CH2CH2CH2Cl. + KOH (ale) ⟶ CH3 --CH2 --CH=CH2 + KCl + H2O

n-Butyl chloride 1-Butene
(iii) CH3 Cl + AgCN ⟶ CH3 N ≡ C + AgCl
Methyl chloride Methyl isocyanide
222) (a) Draw the structures of major monohalo products in each of the following reactions:
(b) Which compound in each of the following pairs will react faster in SN2 reaction

(i) CH3Br or CH3I
(ii) (CH3 )3C-CI or CH3 -Cl
Answer : (a)
(b) (i) CH3I will react faster.

(ii) CH3CI will react faster.
223) Write the IUPAC name of the following compounds:
Answer :

(a) The presence of -NO2 group at ortho or para position increases the reactivity of haloarenes towards nucleophilic
(b) p-dicholorobenzene has higher melting point than that of ortho or meta isomer.
(c) Thionyl chloride method is preferred for preparing alkyl chloride from alcohols.
Answer : (a) -NO2 group stabilises intermediate having -ve charge, therefore, increases rate of nucleophilic
(b) It is because p-isomer is symmetrical and fits into crystal lattice readily.
(iii) It is because side products formed are SO2 and HCl gases, can be easily removed to get pure alkyl halide.
14 x 4 = 56
225) Read the passage given below and answer the following questions:
A primary alkyl halide (A) C4H9Br reacted with alcoholic KOH to give compound (B). Compound (B) is reacted with
HBr to give compound (C) which is an isomer of (A). When (A) reacted with sodium metal, it gave a compound (D)
C8H18 that is different than the compound obtained when n-butyl bromide reacted with sodium metal
The following questions are multiple choice questions. Choose the most ap appropriate answer:
(i) Compound (A) is
(a) CH3 CH2 CH2 CH2 Br (b)
(c) (d) CH3 CH2 CH2 Br
(ii) Which type of isomerism is present in compound (A) and (C)?

(a) Positional (b) Functional (c) Chain (d) Both (a) and (c)
(iii) IUPAC name of compound (D) is
(a) n-octane (b) 2,5-dimethylhexane (c) 2-methylheptane (d) 3,4-dimethyl hexane.
(iv) When compoound (C) is treated with alc. KOH and then treated with HBr in presence of peroxide, the compound
obtained is
a) (b)
(c) CH3 CH2 CH2 CH2 Br (d)
Answer : (i) (b): When compound (A) reacted with Na-metal, it gave a compound D(C8H18) which is different
from the compound obtained when n-butyl bromide reacted with Na metal and hence the
compound (A) must be isobutyl bromide.
W urtzreaction
2CH3 CH2 CH2 CH2 Br + 2Na → CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH3
Nucleophilic substitution reactions are of two types; substitution nucleophilic bimolecular (SN2) and substitution
nucleophilic unimolecular (SN1) depending on molecules taking part in determining the rate of reaction. Reactivity of
alkyl halide towards SN1 and SN2 reactions depends on various factors such as steric hindrance, stability of
intermediate or transition state and polarity of solvent. SN2 reaction mechanism is favoured mostly by primary alkyl
halide then secondary and then tertiary. This order is reversed in case of SN1 reactions.
The following questions are multiple choice questions. Choose the most appropriate answer:
(i) Which of the following is most reactive towards nucleophilic substitution reaction?
(a) C6 H5 Cl (b) CH2 = CHCl (c) ClCH2 CH = CH2 (d) CH3 CH = CHCl
(ii) Isopropyl chloride undergoes hydrolysis by

(c) SN1 and (d) neither SN1 and
(a) SN1mechanism(b) SN2mechanism
SN2mechanism SN2mechanism
(iii) The most reactive nucleophile among the following is
(a) CH3O- (b) C6H5O- (c) (CH3)2CHO- (d) (CH3)3CO-
(iv) Tertiary alkyl halides are practically inert to substitution by SN2mechanism because of
(a) insolubility (b) instability (c) inductive effect (d) stearic hindrance.
Answer : (i) (c) : Allylic chlorides are most reactive.

(ii) (c): 20 - alkyl halides undergo hydrolysis by SN1 or SN2 mechanism.
(iii) (a): Smaller the size of the nucleophile (i.e., CH3O-), more reactive it is.
(iv) (d): Stearic hindrance due to bulky alkyl groups prevents the attack of the nucleophile in SN2 mechanism.
227) Read the passage given below and a.9swer the following questions:
A chlorocompound (A) on reduction with Zn-Cu and ethanol gives the hydrocarbon (B) with five carbon atoms. When
(A) is dissolved in dry ether and treated with sodium metal it gave 2,2,5,5 tetramethylhexane. The treatment of (A)
with alcoholic KCN gives compound (C).
(i) The compound (A) is
(a) 1-chloro- 2, 2-dimethylpropane (b) 1-chloro- 2, 2-dimethyl butane
(c) 1-chloro-2-methyl butane (d) 2-chloro-2-methyl butane.
(ii) The reaction of (C) with Na, C2H5OH gives
(a) (CH3)3C CH2CONH2 (b) (CH3)3C NH2
(c) (CH)3C CH2CH2NH2 (d) (CH3)2CHCH2NH2
(iii) The reaction of (C) with Na, C2H5OH is called
(a) Gilman reaction (b) Mendius reaction
(c) Grooves process (d) Swart's reaction.
(iv) Compound (B) is
(a) n-pentane (b) 2, 2-dimethylpropane
(c) 2-methylbutane (d) none of these.
Answer :
(iii) (b)
When haloalkanes with β-hydrogen atom are boiled with alcoholic solution of KOH, they undergo elimination of
hydrogen halide resulting in the formation of alkenes. These reactions are called β-elimination reactions or
dehydrohalogenation reactions. These reactions follow Saytzeff's rule. Substitution and elimination reactions often
compete with each other. Mostly bases behave as nucleophiles and therefore can engage in substitution or
elimination reactions depending upon the alkyl halide and the reaction conditions.
(i) Among the following the most reactive towards alcoholic KOH is
(a) CH2 = CHBr (b) CH3 COCH2 CH2 Br (c) CH3 CH2 Br (d) CH3 CH2 CH2 Br
−
aq. OH
(ii) The general reaction, R − X ⟶ ROH + X

−
is expected to follow decreasing order of reactivity as in (t- Bu
= tertiary Butyl group)
(a) t-BuI > t-BuBr > t-BuCI > t-BuF (b) t-BuF > t-BuCI > t-BuBr > t-BuI
(c) t-Bu'Br > t-BuCI > t-BuI > t-BuF (d) t-BuF > t-BuCI > t-BuI > t-BuBr
(iii) Reaction of t-butyl bromide with sodium methoxide produces
(a) sodium t-butoxide (b) t-butyl methyl ether
(c) iso-butane (d) iso-butylene.
(iv) In the elimination reactions, the reactivity of alkyl halides follows the sequence
(a) R - F > R - Cl > R - Br > R - I (b) R - I > R - Br > R - Cl > R - F
(c) R - I > R - F > R - Br > R - Cl (d) R - F > R-I > R-Br > R-CI
Answer : (i) (d): In alkyl halides, polarity of C - Br bond increases with increase in chain length.
(ii) (a): The order of reactivity of alkyl halides: iodide > bromide > chloride (nature of the halogen atom)
tertiary > secondary > primary (type of halogen atom).
(iii) (d) : Iso-butylene is obtained.
(iv) (b): The order of bond dissociation energy: R - F > R - CI > R - Br > R - I. During dehydrohalogenation C - I
bond breaks more easily than C - F bond. So reactivity order of halides R - I > R - Br > R - CI > R - F
Consider the given sequence of reactions:
(i) Identify w.
(ii) When X reacts with CH3COCI in presence of anhy. AICI3, the reaction is known as
(a) Fittig (b) Ullmann (c) Wurtz-Fittig (d) Friedel-Crafts acylation
reaction reaction reaction reaction.
(iii) When X is treated Ni-Al / NaOH the product obtained is
(a) benzene (b) phenol (c) p-chlorophenol (d) triphenyl.
(iv) Compound Z is
(a) phenol (b) p-chlorophenol (c) p-nitrophenol (d) nitrobenzene
Answer :
Haloarenes are less reactive than haloalkanes. The low reactivity of haloarenes can be attributed to
(i) resonance effect
(ii) Sp2 hybridisation of C - X bond
(iii) polarity of C - X bond
(iv) instability of phenyl cation (formed by self-ionisation ofhaloarene)
(v) repulsion between the electron rich attacking nucleophiles and electron rich arenes.
Reactivity of haloarenes can be increased or decreased by the presence of certain groups at certain positions for
example, nitro (-NO2) group at olp positions increases the reactivity of haloarenes towards nucleophilc substitution
reactions.
(i) Aryl halides are less reactive towards nucleophilic substitution reaction as compared to alkyl halides due to
(a) the formation ofless stable carbonium ion (b) resonance stabilisation
(c) larger carbon-halogen bond (d) inductive effect.
(ii) Which of the following aryl halides is the most reactive towards nucleophilic substitution?
(iii) Which one of the following will react fastest with aqueous NaOH?
The reactivity of the compounds (i) MeBr, (ii) PhCH2Br, (iii) MeCI, (iv) p- MeOC6H4Br decreases as
(a) (i) > (ii) > (iii) > (iv) (b) (iv) > (ii) > (i) > (iii)
(c) (iv) > (iii) > (i) > (ii) (d) (ii) > (i) > (iii) > (iv)
Answer : (i) (b)
(ii) (d): When in aryl halides the electron withdrawing groups are attached at ortho and para positions to the
chlorine atom then the removal of chlorine atom as CI- ion becomes easy, therefore, 2,4,6- trinitro
chlorobenzene is the most reactive among given aryl halides.
(d) : The order of reactivity follows the sequence: benzyl halides > alkyl halides > aryl halides. Out of chlorides
and bromides, bromides are more reactive. Therefore, the correct order of reactivity is PhCH2Br(ii) > MeBr(i) >
MeCI(iii) > p-MeOC6H4Br (iv).
231)Read the passage given below and answer the following questions:
In haloalkanes, when a nucleophile stronger than the halide ion approaches the positively charged carbon atom of
an alkyl halide, the halogen atom along with its bonding electron pair gets displaced and a new bond with the carbon
and the nucleophile is formed. These reactions are called nucleophilic substitution reactions.
In these reactions the atom or group of atoms which loses its bond from carbon and takes on an additional pair of
electrons is called leaving group. Halide ions are good leaving groups. Some important nucleophilic substitution
reactions of haloalkanes with common nucleophiles are given in the table below.
Substitution
Nudeophile Class of main
Reagent product
(Nu-) product
R-Nu
NaOH or KOH -
1. OH ROH Alcohol
or moist Ag2O
2.H2O H 2O ROH Alcohol
3.NaI I- R-I Alkyl iodide
4.R'NH 2 ′ ¨ RNHR' Sec. amine
R NH2
¯¯
¯¯
5.KCN C ≡ N : RCN Nitrile (cyanide)
6.KNO2 O=N-O- R-O-N=O Alkyl nitrite
In these questions (i-iv), a statement of assertion followed by a statement of reason is given. Choose the
correct answer out of the following choices.
(a) Assertion and reason both are correct statements and reason is correct explanation for assertion.
(b) Assertion and reason both are correct statements but reason is not correct explanation for assertion.
(c) Assertion is correct statement but reason' is wrong statement.
(d) Assertion is wrong statement but reason is correct statement.
(i) Assertion: Alkyl halides are hydrolysed to alcohols by moist silver oxide.
Reason: RCI is hydrolysed to ROH easily but reactions slow down on addition of KI.
(ii) Assertion : Alkyl halides form alkenes when heated above 300°C.
Reason: CH3CH2I reacts slowly with strong base as compared to CD3CH2I.
(iii) Assertion : RBr reacts with AgNO2 to give nitro alkane.
Reason: Silver nitrite (AgNO2) is an ionic compound, therefore the negative charge on nitrogen is the attacking site.
(iv) Assertion: The nucleophilic substitution of vinyl chloride is difficult than ethyl chloride.
Reason: Vinyl group is electron donating group.
Answer : (i) (c) : KI reacts with RCI to form RI. This RI molecule now hydrolysed easily to give ROH because
alkyl iodide are more reactive than alkyl chloride. Thus, reaction becomes faster on addition of KI.
(ii) (c): CH3CH2I reacts more rapidly with strong base in comparison to CD3CH2I. The elimination of HI (or DI)
in presence of strong base shows E2 elimination. The rate determining step involves the breaking up of C - H (or
C - D) bond. The C - D bond being stronger than C - H bond is difficult to break.
(iii) (c) : Silver nitrite is a covalent compound and the bond between Ag - O is covalent. Therefore, it does not
have a negative charge on the oxygen atom. Hence, the nucleophillic attack occurs through the lone pair on
nitrogen forming nitro alkanes (R - NO2).
(iv) (c): The carbon-halogen bond in vinyl halides has some double bond character and hence little difficult to
break.
When a chemical reaction involves bond cleavage or bond formation at an asymmetric carbon atom, three different
products may be formed. For example, during the substitution of a group X by Y in the following reaction, the three
possible products may be shown below:
(i) If B is the only product, the process is called retention of configuration because B has the same configuration as
the starting reactant (A).
(ii) If C is the only product, the process is called inversion of configuration because C has the configuration opposite
to the starting reactant (A).
(iii) If an equimolar mixture of B and C (i.e., a 50 : 50 mixture) is formed, then the process is called racemisation and
the product is optically inactive because one isomer will rotate the light in the direction opposite to another.
In these questions ( i-iv), a statement of assertion followed by a statement of reason is given. Choose the
(b) Assertion and reason both are correctstatements but reason is not correct explanation for assertion.
(c) Assertion is correct statement but reason is wrong statement.
(i) Assertion: A reaction is said to be stereospecific if a particular stereoisomer of the reactant produces a specific
stereoisomer of the product.
Reason: Bromination of cis-2-butene gives meso-2, 3-dibromobutane which is stereospecific
(ii) Assertion: Addition of Br2 to cis-but-2-ene is stereoselective.
Reason: SN2 reactions are stereospecific as well as stereoselective.
(iii) Assertion: Optically active 2-iodobutane on treatment with NaI in acetone undergoes recemization.
Reason: Repeated Walden inversions on the reactant and its product eventually gives a racemic mixture.
(iv) Assertion: SN2reaction of an optically active alkyl halide with an aqueous solution of KOH always gives an
alcohol with opposite sign of rotation.
Reason: SN2reactions always proceed with inversion of configuration.
Answer : (i) (c): Bromination of cis-2-butene give (±) 2,3-dibromobutane.
(ii) (b)
(iii) (a)
(iv) (a)
The order of reactivity towards SN1 reaction depends upon the stability of carbocation in the first step. Greater the
stability of the carbocation, greater will be its ease of formation from alkyl halide and hence faster will be the rate of
the reaction. As we know, 3° carbocation is most stable, therefore, the tert-alkyl that halides will undergo SN1
reaction very fast. For example, it has been observed that the reaction (CH3)3CBr with OH- ion to give 2-methyl-2-
propanol is about 1 million times as fast as the corresponding reaction of the methyl bromide to give methanol.
The primary alkyl halides always react predominantly by SN2 mechanism. On the other hand, the tertiary alkyl
halides react predominantly by SN1 mechanism. Secondary alkyl halides may react by either mechanism or by both
the mechanisms without much preference depending upon the nature of the nucleophile and solvent.
(i) Assertion: Low concentration of nucleophile favours SN1mechanism.
Reason: 2° alkyl halides are less reactive than 1° towards SN1 reactions.
(ii) Assertion: Polar solvent slows down SN2reactions.
Reason: CH3-Br is less reactive than CH3Cl.
(iii) Assertion: Benzyl bromide when kept in acetone- water it produces benzyl alcohol.
Reason: The reaction follows SN2 mechanism.
(iv) Assertion: Rate of hydrolysis of methyl chloride to methanol is higher in DMF than in water.
Reason: Hydrolysis of methyl chloride follows second order kinetics.
Answer : (i) (c) : Ability to accommodate a positive charge determines the ease of heterolysis leading to SN1
mechanism. This ability to accommodate positive charge is more in the 20 alkyl halide since it has two alkyl
groups as compared to one in 10 alkyl halide .
(ii) (c): CH3 - Br is more reactive than CH3 - Cl. The C - Br has bond dissociation energy of 293 kJ mol-1 while C
- CI bond has its dissociation energy of 351 kJ mol-1. As the bond dissociation energy increases, the ease of
breaking of C - X bond decreases and hence the reactivity of haloalkanes decreases.
(iv) (a)
The aryl halides are relatively less reactive towards nucleophilic substitution reactions as compared to alkyl halides.
This low reactivity can be attributed to the following factors:
1. The C - X bond in halobenzene has a partial double bond character due to involvement of halogen electrons in
resonance with benzene ring.
2. The C - X bond in aryl halides is less polar as compared to that in alkyl halides as sp2 hyridised carbon is more
electronegative than sp3 hybridised carbon.
(i) Assertion: Primary benzylic halides are more reactive than primary alkyl halides towards SN1 reactions.
Reason: Reactivity depends upon the nature of the nucleophile and the solvent.
(ii) Assertion : is more reactive than towards nucleophilic substitution reactions.
Reason: Tertiary alkyl halides react predominantly by SN1 mechanism.

(iii) Assertion: Chlorobenzene is more reactive than p-chloroanisole to nucleophilic substitution reactions.
Reason: Greater the stability of'carbanion, greater is its ease of formation and hence, more reactive is the aryl
halide.
(iv) Assertion: Chlorobenzene is less reactive than benzene towards the electrophilic substitution reaction.
Reason: Resonance destabilises the carbo cation.
Answer : (i) (b): Primary benzylic halides show higher reactivity in SN1reactions than primary alkyl halides. This
is due to the greater stabilisation of the benzylic carbocation intermediates by resonance.
(ii) (a)
(iii) (a) : On comparing the relative stabilities of carbanion of chlorobenzene and p-chloroanisole.
the electron donating group (OCH3) in anisole tends to intensify the negative charge relative to carbanion in
chlorobenzene. Thus, p-chloroanisole is less reactive than chlorobenzene.
(iv) (c): Chlorobenzene is less reactive than benzene towards the electrophilic substitution reactions due to -I
effect.
235) Haloalkanes are colourless (when pure), sweet smelling liquids. CH3Cl, CH3Br and C2H5CI and freons are gases.
Boiling' point increases with increase in molecular weight and increase in carbon chain and decreases with
branching. They are insoluble in water due to inability to form H-bonds with water. Dipole moment increases with
polarity, density increases with increase in molar mass. They are non-inflammable, therefore, CCl4 is used as fire
extinguisher under the name pyrene. p-dichloro benzene has zero dipole moment, higher melting point than o-
dichloro benzene due to symmetry, fits into crystal lattice readily. Haloalkanes undergo nucleophilic substitution
reaction by SN2 mechanism, 1° > 2° > 3°, SN1 if carbocation formed is stable. They also undergo nucleophilic
elimination reactions with alcoholic KOH. Haloarenes are less reactive than haloalkanes towards nucleophilic
substitution due to resonance. Haloarenes undergo electrophilic substitution reaction like nitration, sulphonation,
Friedel Crafts alkylation, acylation. Chloroform is used as solvent, Freon is used as refrigerant, dichloromethane is
used as paint remover. Iodoform is used as antiseptic. DDT is insecticide but nonbiodegradable.
(a) Arrange R-F, R-Br, R-I, R-CI in increasing order of boiling point.
(b) A hydrocarbon' A' (C5H10) gives only one monochloro product on photo chlorination. Identity 'A'.
(c) Out of CH2 = CH-CH2CI and CH3CH2CH2Cl which one undergoes SN1 mechanism faster?
(d) Complete the following:
(e) Why is chloroform stored in dark coloured bottles?

(f) What is use of fully fluorinated organic compounds?
(g) Name the chlorine containing drug used in treatment of coronavirus and malaria.
Answer : (a) R-F < R-Cl < R-Br < R-I
(b)
⊕
(c) CH2 =CH-CH2Cl because CH2 − CH − CH
2
is more stable due to resonance.
(d)
(e) It is done so as to prevent formation of COCl2 which is poisonous.

Sunlight
1
CHCl3 + O2 ⟶ COCl2 + HCl
2
(f) They are used as blood substitute in surgery.

(g) Hydroxychloroquine
236) The substitution reaction of alkyl halides occurs in SN1 or SN2 mechanism whatever mechanism alkyl halide
follow for substitution reaction to occur, the polarity of the carbon-halogen bond is responsible for the substitution
reaction. The rate of SN1 reactions are governed by the stability of carbocation where as for SN2 reactions steric
factor is the deciding factor. If the starting material is a chiral compound, we may end up with an inverted product
or racemic mixture depending upon the type of mechanism followed by alkyl halide. Cleavage of ethers with HI is
also .governed by steric factor and stability of carbocation which indicates that in organic chemistry, these two major
factors help us in deciding the kind of product formed.
(a) Predict the stereochemistry of the product formed if optically active alkyl halide undergoes substitution reaction
by SN1 mechanism.
(b) Name the instrument used for measuring the angle bl which the plane polarised light is rotated.
(c) Predict the major product formed when 2-bromopentane reacts with alcoholic KOH.
(d) Write the structure of the products formed when anisole is treated with ID.
(e) Write the structure of product formed when ethoxy benzene is treated with HI.
Answer : (a) Racemic mixture will be formed.

(b) Polarimeter
(c) Pent-2-ene will be major product.
(d) Phenol and CH3I are formed
(e)
237)Observe the histogram related by comparison of boiling points of some alkyl halides and answer the questions
that follow
(a) Name the alkyl halides in gaseous state.

(b) Why do alkyl iodides have highest boiling points among alkyl halides?
(c) How does boiling point vary with increase in carbon chain?
(d) What is effect of branching on boiling point? Why?
(e) What happens to inflammability with increase in halogen atoms? Illustrate with example.
Answer : (a) CH3Cl (chloromethane), CH3Br (bromomethane), CH3CH2Cl (chloroethane)
(b) It is due to higher molar mass, bigger size, more van der Waals' forces of attraction.
(c) As the carbon chain increases, surface area increases, van der Waals' forces of attraction increases, hence
boiling point increases.
(d) Boiling point decreases with branching because surface area decreases, van der Waals' forces of attraction
decreases.
(e) Inflammability decrease with increase in number of halogen atoms e.g. CCl4 is used as fire extinguisher
under the name pyrene.
238)Observe the table in which physical data of Halo methane, polyhalogen derivative and haloarenes is given. Answer
the questions based on them.
Table: Some Physical Data of Halomethanes (CH3-X)
Bond C-X lengthBond enthalpyDipole moment
1 CH3F 139 452 1.847D
2 CH3Cl 178 351 1.860D
3 CH3Br 193 293 1.83D
4 CH3I 214 234 1.636D
5 CH2Cl2 - - 1.62D
6 CHCl3 - - 1.03D
7 CCl 4 - - Zero
Dipole momentMelting point
8 p-dichloro benzene Zero 325K
9 o-dichloro benzene 2.54D 216K
10m-dichloro benzene 1.72D 249K
Boiling point
11 C 6H 5F 1.60D 358K
12 C6H5CI 1.69D 405K
13 C6H5Br 1.70D 429K
14 C 6H 5I 1.70D 462K
(a) Why is dipole moment of CH3F less than CH3CI?
(b) Why is CH3I more reactive than CH3Cl?
(c) Why is melting point of p-dichlorobenzene higher than o-dichlorobenzene but boiling point of o-isomer is higher
than p-isomer?
(d) Why does o-dichlorobenzene has higher dipole moment than m-dichlorobenzene?
(e) Why does C6H5I has higher dipole moment than C6H5F?
Answer : (a) It is because μ = e x d, C-F bond distance is less than C-Cl, therefore, product of charge and
distance is slightly lower in CH3F than CH3Cl.
(b) t is due to lower bond dissociation enthalpy of C-I bond than C-Cl bond.
(c) p-dichlorobenzene fits into crystal lattice more readily than o-isomer, therefore, has higher melting point. o-
isomer has higher boiling point due to higher dipole moment, more polarity than p-isomer.
−−−−−−−−−−−−−−−−−
(d) μ = √μ
2
1
+ μ
2
2
+ 2μ1 μ2 cos θ , μ1 and μ 2 2 are dipole moments of C-X bond μ1 = μ2 and cos 60 = 0.5 in
o-isomer cos 120 0 = -0.5 in m-isomer.
(e) It is due to C-I bond is longer than C-F bond and μ= e x d.
37 x 5 = 185
239) Name the following halides according to IUPAC system and classify them as alkyl, allyl, bezyl (primary, secondary,
tertiary), vinyl or aryl halides:
(i) (CH3)2 CHCH(CI)CH3
(ii) CH3CH2CH(CH3)CH(C2H5)Cl
(iii) CH3CH2C(CH3)2CH2I
(iv) (CH3)3CCH2CH(Br)C6H5
(v) CH3CH(CH3)CH(Br)CH3
(vi) CH3C(C2H5)2CH2Br
(vii) CH3C(Cl)C2H5CH2CH3
(viii) CH3CH = C(Cl)CH2CH(CH3)2
(ix) CH3CH = CHC(Br)(CH3)2
(x) p-ClC6H4CH2CH(CH3)2
(xi) m-ClCH2C6H4CH2C(CH3)3
(xii) o-BrC6H4CH(CH3) CH2CH3.
Answer : The IUPAC names of various compounds are given below in order:
(i) 2-Chloro-3-methylbutane (secondary alkyl halide)
(ii) 3-Chloro-4-methylhexane (secondary alkyl halide)
(iii) 1-Iodo-2,2-dimethylbutane (primary alkyl halide)
(iv) 1-Bromo-3,3-dimethyl-1-phenylbutane (secondary benzyl halide)
(v) 2-Bromo-3-methylbutane (secondary alkyl halide)
(vi) 1-Bromo-2-ethyl-2-methylbutane (primary alkyl halide)
(vii) 3-Chloro-3-methylpentane (tertiary alkyl halide)
(viii) 3-Chloro-5-methylhex-2-ene (vinyl halide)
(ix) 4-Bromo-4-methylpent-2-ene (allyl halide)
(x) 1-Chloro-4-(2-methylpropyl) benzene (aryl halide)
(xi) 1-Chloromethyl-3-(2,2-dimethylpropyl) benzene (primary benzyl halide)
(xii) 1-Bromo-2-(1-methylpropyl) benzene (aryl halide)
240) Draw the structure of major monohalo products in each of the following reactions:
Answer :
241) Which alkyl halide from the following pairs would you expect to react more rapidly by an SN2 mechanism?
Explain your answer.
(i)
(ii)
(iii)
Answer : (i)
2-bromobutane is a 2° alkylhalide whereas 1-bromobutane is a 1° alkyl halide. The approaching of nucleophile

is more hindered in 2-bromobutane than in 1-bromobutane. Therefore, 1-bromobutane reacts more rapidly
than 2-bromobutane by an SN2 mechanism.
(ii)
2-Bromobutane is 2° alkylhalide whereas 2-bromo-2-methylpropane is 3° alkyl halide. Therefore, greater

numbers of substituents are present in 3° alkyl halide than in 2° alkyl halide to hinder the approaching
nucleophile. Hence, 2-bromobutane reacts more rapidly than 2 bromo-2-methylpropane by an SN2 mechanism.
(iii)
Both the alkyl halides are primary. However, the substituent -CH3 is at a greater distance to the carbon atom
linked to Br in 1-bromo-3 methylbutane than in 1-bromo-2-methylbutane. Therefore, the approaching
nucleophile is less hindered in case of the former than in case of the latter. Hence, the former reacts faster than
the latter by SN2 mechanism.
(i) n-butyl chloride is treated with alcoholic KOH,
(ii) bromobenzene is treated with Mg in the presence of dry ether,
(iii) chlorobenzene is subjected to hydrolysis,
(iv) ethyl chloride is treated with (aq.) KOH,
(v) methyl bromide is treated with sodium in the presence of dry ether,
(vi) methyl chloride is treated with KCN?
Answer : (i) When n - butyl chloride is treated with alcoholic KOH, the formation of but - l - ene takes place.
This reaction is a dehydrohalogenation reaction.
(ii) When bromobenzene is treated with Mg in the presence of dry ether, phenylmagnesium bromide is formed.
(iii) Chlorobenzene does not undergo hydrolysis under normal conditions. However, it undergoes hydrolysis
when heated in an aqueous sodium hydroxide solution at a temperature of 623 K and a pressure of 300 atm to
form phenol.
(iv) When ethyl chloride is treated with aqueous KOH, it undergoes hydrolysis to form ethanol.
(v) When methyl bromide is treated with sodium in the presence of dry ether, ethane is formed. This reaction is
known as the Wurtz reaction.
(vi) When methyl chloride is treated with KCN, it undergoes a substitution reaction to give methyl cyanide.
243)Draw the structure of all eight structural isomers that have the molecular formula C5H11Br. Name each isomer
according to IUPAC system and classify them as primary, secondary or tertiary bromide.
Answer :
CH3CH2CH2CH2CH2Br 1-Bromopentane
(1o)
2-
CH3CH2CH2CH(Br)CH3
Bromopentane(2o)
3-Bromopentane
CH3CH2CH(Br)CH2CH3 o
(2 )
1-Bromo-3-
(CH3)2CHCH2CH2Br
methylbutane (1o)
2-Bromo-3-
(CH3)2CHCHBrCH3
methylbutane(2o)
2-Bromo-2-
(CH3)2CBrCH2CH3
methylbutane (3o)
1-Bromo-2-
CH3CH2CH(CH3)CH2Br
methylbutane(1o)
1-Bromo-2,2-
(CH3)3CCH2Br dimethylpropane
(1o)
244) Predict the order of reactivity of the following compounds in SN1 and SN2 reactions:
(i) The four isomeric bromobutanes
(ii) C6H5CH2Br, C6H5CH(C6H5)Br, C6H5C(CH3)(C6H5)Br.
Answer : (i) CH3CH2CH2CH2Br < (CH3)2CHCH2Br < CH3CH2CH(Br)CH3 < (CH3)3CBr (SN1) CH3CH2CH2CH2Br >
(CH3)2CHCH2Br > CH3CH2CH(Br)CH3 > (CH3)3CBr (SN2) Of the two primary bromides, the carbocation
intermediate derived from (CH3)2CHCH2Br is more stable than derived from CH3CH2CH2CH2Br because of
greater electron donating inductive effect of (CH3)2CH- group. Therefore, (CH3)2CHCH2Br is more reactive than
CH3CH2CH2CH2Br in SN1 reactions. CH3CH2CH(Br)CH3 is a secondary bromide and (CH3)3CBr is a tertiary
bromide. Hence the above order is followed in SN1. The reactivity in SN2 reactions follows the reverse order as
the steric hinderance around the electrophilic carbon increases in that order.
(ii) C6H5C(CH3)(C6H5)Br > C6H5CH(C6H5)Br > C6H5CH(CH3)Br > C6H5CH2Br (SN1) C6H5C(CH3)(C6H5)Br <
C6H5CH(C6H5)Br < C6H5CH(CH3)Br < C6H5CH2Br (SN2) Of the two secondary bromides, the carbocation
intermediate obtained from C6H5CH(C6H5)Br is more stable than obtained from C6H5CH(CH3)Br because it is
stabilised by two phenyl groups due to resonance. Therefore, the former bromide is more reactive than the
latter in SN1 reactions. A phenyl group is bulkier than a methyl group. Therefore, C6H5CH(C6H5)Br is less
reactive than C6H5CH(CH3)Br in SN2 reactions.
245) Write the structure of the following compounds:
(i) 2-Chloro-3-methylpentane
(ii)1-Chloro-4-ethylcyclohexane
(iii) 4-tert-Butyl-3-iodoheptane
(iv)1,4-Dibromobut-2-ene
(v)1-Bromo-4-butyl-2-methylbenzene.
Answer : (i) 2-Chloro-3-methylpentane
(ii)1-Chloro-4-ethylcyclohexane
(iii) 4-tert-Butyl-3-iodoheptane
(iv) 1,4-Dibromobut-2-ene
(v)1-Bromo-4-butyl-2-methylbenzene.
246) Among the isomeric alkanes of molecular formula C5H12, identify the one that on photochemical chlorination
yields.
(i) A single monochloride
(ii)Three isomeric monochlorides
(iii) Four isomeric monochlorides.
C H3
|
Answer : (i) C H3 − C − C H3
|
C H3
All the H atoms are equivalent.

a b c b a
(ii) C H3 − C H2 − C H2 − C H2 − C H3
n−P entane
Replacement of a, b atom gives different products.

a b c d
(iii) C H3 − C H2 − C H2 − C H3
|
C H3
Replacement of a, b, c and d H atoms give different products.

247) Arrange each set of compounds in order of increasing boiling points.
(i) Bromomethane, bromoform, chloromethane, dibromomethane.
(ii)1-Chloropropane, isopropyl chloride, 1-chlorobutane.
Answer : (i) For the same alkyl group, boiling point increases with the size of the halogen atom. Therefore,
boiling point of bromomethane is higher than that of chloromethane. Further, the boiling points increase as the
number of halogen atoms increases. Therefore, the boiling point of bromoform with three Br atoms is the
highest, followed by dibromomethane with two Br atoms while bromomethane with one Br atom is the lowest.
Combining all the arguments presented above, the boiling points of the four compounds discussed above
increase in the order:chloromethane < bromomethane < dibromomethane.
(ii) For the same halogen, boiling point increases as the size of the alkyl group increases. Therefore, the boiling
point of 1-chlorobutane is higher than those of 1-chloropropane and isopropyl chloride. Further, the boiling
point decreases as the branching increases, therefore, the boiling point of 1- chloropropane is higher than that
of isopropyl chloride. Combining these two arguments, the boiling points of the three compounds discussed
above increase in the order: Isopropyl chloride < 1-chloropropane < 1-chlorobutane.
248) How will you bring about the following conversions?
(i) Ethanol to but-1-yne
(ii) Ethane to bromoethene
(iii) Propene to 1-nitropropane
(iv)Toluene to benzyl alcohol
(v) Propene to propyne
(vi) Ethanol to ethyl fluride
(vii) Bromomethane to propanone
(viii) But-1-ene to but-2-ene
(ix) 1-Chlorobutane to n-octane
(x) Benzene to biphenyl
Answer : (i) Ethanol to but-1-yne

Pyridine
CH3 − CH2 − OH + SOCl2 ⟶ CHethyl chloride CH2 − Cl + SO 2 ↑ +HCl ↑

ethanol
liq. NH3
− +
HC ≡ CH + NaNH 2 ⟶ HC ≡ C N
acetylene sodium acetylide
− +
CH3 − CH2 − Cl + HC ≡ C Na → CH3 − CH2 − C ≡ CH + NaCl
but −1− yne
(ii) Ethane to bromoethene

UV light Br 2
CH3 − CH3 + Br2 ⟶ CH3 − CH2 Br

alc.KOH
CH2 = CH2 ⟶ Br − CH2 − CH2 − Br
−HBr
(iii) Propene to 1-nitropropane

Peroxide AgNO
2
CH3 −CH = CH2 + HBr ⟶ CH3 − CH2 − CH2 Br ⟶ CH3 − −CH2 − CH2 NO2 + AgBr
propene
1− nitropropane
(iv) Toluene to benzyl alcohol

UV light NaOH
C 6 H 5 − CH 3 + Cl2 ⟶ C 6 H 5 − CH2 Cl ⟶ C 6 H 5 − CH 2 OH + NaC

toluene benzyl alcohol
(v) Propene to Propyne
CCl4 NaNH 2
CH3 −CH = CH2 + Br2 ⟶ CH3 − CH(Br) − CH2 (Br) CH3 C ≡ CH
propene liq N H 3 propyne
(vi) Ethanol to ethyl fluoride

ZnCl2
CH 3 − CH2 OH + HCl ⟶ CHethyl chloride CH2 − Cl + H 2 O
ethyl alcohol
(vii) Bromomthane to propanone
KCN
CH3 −Mg−Br
CH3 − Br ⟶ CH3 − CN
⟶
CH3 − CCH3 = NMgBr hydrolysis CH3 − CO − CH3
bromomethane
(viii) But-1-ene to but-2-ene

HBr alc.KOH
CH3 − CH2 − CH = CH2
Markownikoff's rule
CH3 − CH2 − CH(Br) − CH3
−HBr
CH3 − CH = CH − CH3
but-2 −CHe
(ix) 1-chlorobutane to n-octane
ary ener
2CH3 − CH1− chlorobutane − CH2 − Cl + 2Na ⟶ CH3 − (CH2 ) − CH3 + 2NaCl

6
n-octane
x) Benzene to biphenyl
dark,Fe
C 6 H 6 + Br2 ⟶ C 6 H 5 − Br
benzene bromobenzene
Wurtz-Fittig reaction
dry ether
2C6 H5 − Br + 2 Na ⟶ C6 H5 − C6 H5 + 2NaBr

biphenyl
249) Write the structure of the major organic product in each of the following reactions:
acetone,heat
(i) CH3CH2CH2Cl+Nal −−−−−−−→
ethanol,heat
(ii) (CH3)3CBr+KOH −−−−−−−→
water
(iii) CH3CH(Br)CH2CH+NaOH −−−→
aq.ethanol
(iv) CH3CH2Br+KCN−−−−−−→
(v) C6H5ONa+C2H5Cl →
(vi) CH3CH2CH2OH+SOCl2→
peroxide
(vii) CH3CH2CH=CH2+HBr−−−−−→
(viii) CH3CH=C(CH3)2+HBr→
Answer : The major organic products are shown below:
acetone
(i) CH3 CH2 CH2 Cl + NaI CH3 CH2 CH2 I(1 − iodopropane ) + NaCl
heat
(ii) (ii) (CH3 )3 CBr + KOH ethanol CH3 C (CH3 ) = CH2 (2 − methylpropene ) + KBr + H2 O

heat
water
(iii) CH3 CH(Br)CH2 CH3 + NaOH ⟶ CH3 − CHOHCH2 CH3 (2 − butanol )
(iv)
(v) C6 H5 ONa + C2 H5 Cl ⟶ C6 H5 OCH2 H3 + NaCl

(vi) CH3 CH2 CH2 OH + SOCl2 ⟶ CH3 CH2 CH2 − Cl(1 − chloropropane ) + HCl + SO2
peroxide
(vii) CH3 CH2 CH = CH2 + HBr ⟶ CH3 CH2 CH2 CH2 − Br(1 − bromobutane)
(viii) CH3 CH = C(CH3 )2 + HBr ⟶ CH3 CH2 C(Br) (CH3 ) CH3 (2 − bromo − 2− methylbutane)
250) How the following conversions can be carried out?

(i) Propene to propan-1-ol
(ii) Ethanol to but-2-yne
(iii) 1-Bromopropane to 2-bromopropane
(iv)Toluene to benzyl alcohol
(v) Benzene to 4-bromonitrobenzene
(vi) Benzyl alcohol to 2-phenylethanoic acid
(vii) Ethanol to propaneitrile
(viii)Aniline to chlorobenzene
(ix) Ethyl chloride to propanoic acid
(x) 2-Methyl-1-propene to 2-chloro-2-methylpropane
(xi) Ethyl Chloride to propanoic acid
(xii) But-1-ene to n-butyl iodide
(xiii) 2-Chloropropane to 1-propanol
(xiv) Isopropyl alcohol to iodoform
(xv) Chlorobenzene to p-nitrophenol
(xvi) 2-Bromopropane to 1-bromopropane
(xvii) Chloroethane to butane
(xviii) Benzene to diphenyl
(xix) tert-Butyl bromide to isobutyl bromide
(xx) Aniline to phenyl isocyanide.
Answer :
Although chlorine is an electron-withdrawing group, yet it is ortho-para-directing in electrophilic aromatic

251)
substitution reactions. why ?
Answer : 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 stabilise the carbocation and the effect is more pronounced at ortho- and
parapositions. The inductive effect is stronger than resonance and causes net electron withdrawal and thus
causes net deactivation. The resonance effect tends to oppose the inductive effect for the attack at ortho- and
parapositions and hence makes the deactivation less for ortho- and paraattack. Reactivity is thus controlled by
the stronger inductive effect and orientation is controlled by resonance effect.
252) Identify A, B, C, D, E, R and R' in the following:
(i)

(ii)
(iii)
Answer : (i) Haloalkanes react with Mg in dry ether to form Grignard reagents (RMgX), which react with water to
form hydrocarbons.
(iii) Haloalkanes react with Na in dry ether to give hydrocarbons containing double number of C-atoms.
253) Predict all the alkeness that would be formed by dehydrohalogenation of the following halides with sodium
ethoxide in ethanol and identify the major alkene
(a) 1-Bromo-1-methylcyclohexane
(b) 2-Chloro-2-methylbutane
(c) 2, 2, 3-Trimethyl-3-bromopentane.
Answer : The reactions are given above:

(i) 1-methylcyclohexene is the major product.
Only one alkene is formed at beta H atoms on either side of Br atoms are equivalent.
(ii) 2-methyl-2-butene is the major product.

Two different alkenes are formed. More substituted alkene is the major product as it is more stable. This is in
accordance with Saytzeff's rule.
(iii) 3,4,4-Trimethylpent-2-ene is the major product.

Two different alkenes are formed. More substituted alkene is the major product as it is more stable. This is in
accordance with Saytzeff's rule.
254) The following reaction gives two products.
Explain the formation of the products and write their structures.
Answer :
255) Explain why alkyl halides are generally not prepared in the laboratory by free radical halogenation of alkanes.
Answer : Free radical halogenation is not a suitable method for laboratory synthesis of alkyl halides because of
the following two reasons :
(i) It gives a mixture of isomeric monohalogenated products whose boiling points are so close that they cannot
be easily separated in the laboratory.
(ii) Polyhalogenation may also occur to some extent thereby making the mixture more complex and hence more
difficult to separate.
256)Explain why chorination of n-butane in presence of light at 298 K gives a mixture of 72% of 2-chlorobutane and
28 % of 1-chlorobutane.
Answer : According to the question,
The relative ratios of these two isomeric chlorobutanes can be easily calculated by knowing: (i) the number and
type of hydrogens (i.e. 1°, 2° or 3°) to be substituted and (ii) their relative rates of substitution (i.e. I : 3·8 : 5·0
for CI2 at 298 K). Thus
0 0
N o. of 1 H Reactivity o 1 H 28./.
1−C hlorobutane 6 1 6
= × = × = =
0 0 3.8 15.2
2−C hlorobutane N o. of 2 H Reaativity of 2 H 4 72./.
257) Wurtz reaction falils in case of tert-alkyl halides. Explain.

Answer : tert-Alkyl halides prefer to undergo dehydrohalogenation in presence of a strong base such as Na
metal instead of undergoing Wurtz reaction as explained below:
+ + −
(C H 3 )3 C − Br + 2N a ⟶ (C H 3 )3 N a + Na Br
tert−Butyl bromide tert−Butylsodium
Thus, only rand 2° alkyl halides undergo Wurtz reaction while 3° alkyl halides prefer to
undergo dehydrohalogenation to form alkenes.
258) Explain the following in one or two sentences
(i) Displacement of cyanic and amide ion is never observed in nucleophilic substitution reactions.
(ii) RCI is hydrolysed to ROH slowly but the reaction is rapid if a catalytic amount of KI is added to the reaction
mixture.
Answer : (i) HCN (PKa 10) and NH3 (PKa 11·25) are very weak: acids. Therefore, their conjugate bases, i.e., CN-
ion and NH2 - are very strong bases. Since strong bases are bad leaving groups, their displacement
in nucleophilic substitution reactions is never observed,
(ii) Iodide ion is a powerful nucleophile and hence reacts rapidly with RCI to form RI,
Further because 1- ion is a better leaving group than Cl- ion, therefore, RI is more rapidly hydrolysed than RCI
to form ROH,
The I- ion thus regenerated recycles in the above reaction thereby explaining its catalytic effect.
259)(R)-2- Bromooctane reacts with NaSH to form (S)-2- octanethiol with inversion of configuration at the
stereocentre.How can we obtain (R)-2 octanethiol from (R)-2-bromoctane?
Answer : We know that SN2 reactions proceed with inversion of configuration at the stereocentre. If, however,
two SN2 reactions are carried out at the same stereocentre of a compound, retention of configuration will occur.
Thus, (R)-2-octanethiol can be obtained from (R)-2-bromooctane by first reacting it with Nal in acetone and then
with NaSH in ethanol
260) Benzene on reaction with HOCI in presence of an acid produces organic compound (A), (A) on treatment with
NaNH2/liq. NH3 furnishes another organic compound (B). (B) on treatment with HBF4 affords an organic compound
(C) wich on heating with NaNO2 gives organic compound (D). Identify (A), (B), (C) and (D).
Answer : (i) HOCI in presence of an acid generates the reactive electrophile, chloronium ion «r, which
attacks benzene to give chlorobenzene (A).
(ii) Chlorobenzene (A) on treatment with NaNH2/liq. NH3 undergaes-dehydrohalogenation via benzyne to afford
aniline (B).
(iii) Aniline (B) on treatment with HBF4 forms the corresponding salt anilinium tetrafluoroborate (C) which on
heating with NaN02 undergoes Balz-Schiemann reaction through the intermedium formation of
benzenediazonium tetrafluoroborate to afford fluorobenzene (D).
(i)n-butyl chloride is treated with alcoholic KOH.
(ii)bromobenzene is treated with Mg in the presence o dry ether.
(iii)Chlorobenzene is subjected to hydrolysis.
(iv)methyl bromide is treated with sodium in presence of dry ether.
(v)methyl chloride is treated with KCN?
△
Answer : C H3 C H2 C H2 C H2 C I + K OH (alc. ) ⟶ C H3 C H2 C H = C H2 + K C I + H 2 O
n−Butylchloride But−l−ene
Dry ether
(iv) 2C H3 Br + 2N a ⟶ C H3 C H3 + 2N aBr
W urt Ethane
reaction
(vi) C H3 C I + K C N ⟶ C H3 C N + K C I
M ethyl M ethyl
chloride chloride
262) Some halogen containing compounds are useful in daily life. Some compounds of this class are responsible for
exposure of flora and fauna to more and more of UV light which causes destruction to a great extent. Name the class
of these halo compounds. In your opinion, what should be done to minimise harmful effects of these compounds.
Answer : CFC (chlorofluoro carbons) are responsible for the destruction of ozone layer and UV light can reach
earth which may cause skin cancer and affect flora and fauna.
These compounds should be banned and their use should be made to minimum extent.
263) Haloalkanes contain halogen atoms (s) attached to the sp3-hybridised carbon atom of an alkyl group. Many
halogen containing organic compounds occur in nature and some of them are clinically useful.
(i) Prove the importance of halogen containing organic compounds with the help of three examples.
(ii) Mention the values associated with your reply.
Answer : (i) Halogen containing organic compounds are useful in industry as well as in day to day life.
For example:
(a) Chloramphenicol: It is a chlorine containing antibiotic produced by soil microbes. It is very effective for the
treatment of typhoid fever.
(b) Thyroxine: It is an iodine containing hormone secreted by the thyroid gland in our body. This hormone
regulates the metabolic rate of the body and maintains basal metabolic rate. Deficiency of this hormone causes
goitre. This disease can be prevented by taking iodised salt and sea foods.
(c) Chloroquine: It is a drug used for the treatment of malaria.
(ii) Awareness about the halogen containing organic compounds which are used for the treatment of diseases
like typhoid and malaria and importance of iodine in our diet.
264) Ramesh was reading about a haloalkane in his book. He found that this compound is used as a solvent for fats,
alkaloids, iodine and other substances. It is a colourless oily liquid with a peculiar sickly smell. It was once used as
a general anaesthetic in surgery.
Ramesh wanted to test the effect of this halo alkane on himself.
(i) Name the haloalkane discussed in the above paragraph.
(ii) Why is it used as a general anaesthetic in surgery?
(iii) The test that Ramesh wanted to conduct on himself was correct or not? Give reasons to support your answer.
Answer : (i)The haloalkane discussed in the above paragraph is trichloromethane (CHCI3 ,chloroform).
(ii) It is used as a general anaesthetic in surgery because inhaling chloroform depresses the central
nervous system.
(iii) The test that Ramesh wanted to conduct on himself was not fair since chloroform forms poisonous carbonyl
chloride with air.
265)Carbon compounds containing more than one halogen atom are usually called polyhalogen compounds.
Polyhalogen compounds are useful in industry and agriculture. One of the important polyhalogen compound is used
as an insecticide.
(i) Name the polyhalogen compound for which Paul Muller won the Nobel Prize in medicine and physiology. Draw its
structure also.
(ii) Why is the use of DDT banned in some countries?
(iii) What values do you derive from the answer of above question?
Answer : (i) The polyhalogen compound for which Paul Muller was awarded the Nobel Prize is
DDT. (Dichlorodiphenyltrichloroethane). The structure of DOT is given below:
(ii) The use of DOT is banned in some countries because:
(a) it is toxic to aquatic life.
(b) it is not degraded rapidly by soil microorganisms due to its complex structure.
(c) it is not metabolized rapidly by animals and deposited in the fatty tissues.
(d) Because of its stability, it accumulates in food chain leading to biomagnification.
(iii) Environmental protection and sensitivity towards life.
266) Rakesh, Chemistry teacher of class XII asked Rahul to store tricholoromethane in dark coloured bottle to protect
if from sunlight. But Rahul did not take it seriously and stored it in normal transparent glass bottle.
(i) Why Rakesh instructed Rahul to store chloroform in dark coloured bottle only ? What other precaution should be
taken while its storage?
(ii) Write the chemical reaction involved in the formation of carbonyl chloride.
(iii) Is the act done by Rahul in above para correct? Give reson?
(iv) What values Rahullacks in ?
Answer : (i) Rakesh instructed Rahul to store chloroform in dark coloured bottle only because chloroform is
slowly oxidised by air in the presence of light to an extremely poisonous gas called carbonyl chloride or
phosgene. The other precaution which should
be taken while storing chloroform is that the bottle of chloroform should be filled completely up to the brim to
keep air out. Also, it should be sealed
properly.
Light
(ii) 2CHCI3 + O2 ⟶ 2COCI2 + 2HCI

Chloroform Phosgene
(iii) The act done by Rahul is not correct because the resultant compound obtained by the oxidation of
chloroform is a poisonous gas which may be dangerous for the life of pupils.
(iv) Rahullacks in discipline. We should always follow the instructions given by the teachers.
267) How can the following conversions be carried out?
(i) Ethyl chloride to propanoic acid
(ii) Ethanol to propane nitrile
(iii) l-bromopropane to 2-bromopropane
(iv) 2-chlorobutane to 3,4-dimethylhexane
(v) 2-methyl-I-propene to 2-chloro-2-methylpropane
Answer :
268) How can the following conversions be carried out?

(i) 2-bromopropane to 1-brornopropane
(ii) But-1-ene to n-butyl iodide
(iii) 2-chloropropane to 1-propanol
(iv) iso-propyl alcohol to iodoform
(v) Chlorobenzene to p-nitrophenol
Answer :
269) Name the following polyhalogen compounds.

(i) Compound that act as a propellant in aerosols.
(ii) Compound that is used in the preparation of chloropicrin.
(iii) Compound that act as fire extinguisher.
(iv) Compound that is a cheap insecticide.
(v) Compound that is used in hair sprays.
Answer : (i) Carbon tetrachloride (CCI4)
(ii) Chloroform (CHCI3)
(iii) Carbon tetrachloride (CCI4)
(iv) DDT
(v) Freons
270) (i) What are enantiomers? Draw the structures of the possible enantiomers of 3-methylpent-1-ene.
(ii) Optically active 2-bromobutane, on treatment with NaI in acetone gives a product, which does not show optical
activity. Give reason.
(iii) An optically active compound with molecular formula of C7H15 Br,reacts with aqueous KOH to give a racemic
mixture of products. Write the mechanism involved for this reaction.
Answer : (i) Stereoisomers which are non- superimposable mirror images of each other are called enantiomers.
(ii) The product obtained after the reaction contain equal amount of both d and 1-isomers of 2-iodobutane and
this racemic mixture does not show optical activity due to external compensation.
(iii) A racemic mixture as we know, can be formed if the alkyl halide takes part in SN1 reaction. The order of
reactivity of alkyl halides is : 3∘< 2∘< 1∘ The given molecular formula C7H15Br suggests that the alkyl halide is
tertiary and is also optically active in nature. the possible structural formula for the compound.
(iii) On reacting with aqueous KOH, it will form an alcohol in which the attacking nuclephile is OH- ion.
The product is a mixture of the two enantiomers formed in equal proportions. It is therefore, a racemix (±)
(±) mixture and optically inactive.
271) i) Account for the following:
(a) Allyl chloride is more reactive than the n-propyl chloride towards nucleophilic substitution reaction. Explain why?
(ii) What happens, when
(a) ethyl chloride is treated with aqueous KCN?
(b) chlorobenzene is subjected to hydrolysis?
Answer : a) Allyl chloride posses resonance structure therefore prefers to show nucleophilic substitution
reaction as compared to n-propyl chloride as shown in figure below for allyl.
(ii) (a)(i) Methyl chloride is treated with alcoholic KCN.
(ii) Ethyl chloride is treated with alcoholic KOH.
(iii) Chloroform is heated with Ag powder.
(b) Phenol is formed. No reaction occurs under normal conditions. However. Hydrolysis takes place under
specific conditions and phenol is formed as the product.
272) (a) Consider the three types of replacement of group X by group Y as shown here.
This can result in giving compound (A) or (B) or both. What is the process called if
(i) (A) is the only compound obtained?
(ii) (B) is the only compound obtained?
(iii) (A) and (B) are formed in equal proportions?
(b) Complete the equations for the following reactions:
Answer : (a) (i) Retention of configuration, i.e. dextro rotatory substance remains dextro rotatory.
(ii) Inversion of configuration (Walden Inversion), i.e. dextro rotatory substance changes to laevo rotatory and
vice versa. It takes place in SN2 mechanism
(iii) Racemisation takes place, i.e. equal amount of dextro and laevo rotatory substances will be formed. It takes
place in SN1 mechanism.
273) (a) How would you convert the following.

(i) Prop-1-ene to 1-fluoropropane
(ii) Chlorobenzene to 2-Chloro toluene
(iii) Ethanol to Propane nitrile
(b) Although chlorine is an electron withdrawing group, yet it is ortho-, para-directing in electrophilic aromatic
substitution reactions. Explain why it is so?
Peroxide
Answer : (a) (i) CH − CH = CH2 + HBr ⟶ CH3 CH2 CH2 Br
AgF
CH3 CH2 CH2 F
3
Swartz reaction
Prop-1-ene 1-Bromopropane 1-Fluoropropane

PCl5 KCN
CH3 CH2 OH ⟶ CH3 CH2 Cl ⟶ CH3 CH2 CN
Ethanol Chloroethane Propane nitrile

(b) Chlorobenzene is resonance hybrid of following structures:
Since, electron density is maximum at o-and p-positions due to +R effect, therefore, electrophilic substitution
will take place at o and p-positions.
274) (a) An alkyl chloride (A), on reaction with magnesium in dry ether followed by treatment with ethanol gave 2-
methylbutane. Write all the possible structures of (A).
(b) Write IUPAC name of
Answer :
There are four possible structures of 'A' as shown above.

(b) 4-Bromo-3-methylpent-2-ene
275) (a) Out of (CH3)3C-Br and (CH3)3C-I, which one is more reactive towards SN1and why?
(b) Why dextro and laevo - rotatory isomers of Butan-2-ol are difficult to separate by fractional distillation?
(c) Out of which one is more reactive towards SN2 reaction and why?
(d) Out of which one is more reactive towards SN2 reaction and why?
(e) Out of which one is optically active and why?
Answer : (a) (CH3 ) C-I will be more reactive because C-I has lower bond dissociation enthalpy than C-Br bond,
due to longer bond length.
(b) It is because they do not differ appreciably in their boiling points (physical properties), differ in optical
rotation and biological properties.
(c) because it is primary halide and has less stearic hinderance.
(d) is more reactive because -NO2 being electron withdrawing stabilizes intermediate negatively
charged ions.
(e) is optically active because it has chiral 'C' atom (asymmetric carbon).

Haloalkanes and Arenes Q and Ans

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Haloalkanes and Arenes Q and Ans

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08/12/2022, 12:46 Preview Question Paper

Time : 03:00:00 Hrs

Total Marks : 150

It is primary halide and therefore undergoes SN2 reaction faster.

8)Write the equations for the preparation of 1-iodobutane from

'A' 'B' 'C'

'D' and n-octane are different.

n − BuBr + K C N −−−−−−−→ n − BuC N

Answer : The given reaction is

It is primary halide therefore undergoes SN2 reaction faster.

28)How will you bring about the following conversions?

31)Write the structure of the following organic halogen compounds:

32)Write the structure of the following organic halogen compounds:

33) Give the uses of Freon-12, DDT.

Answer : ‘B’ is major product of the reaction.

40) Draw other resonance structures

Answer : The order of reactivity III > II > I

57) CHF3 is less acidic than CHCl3. Explain

Arrange the following halides in order of increasing SN2 reactivity:

62) Difference between chiral and achiral molecules.

64) What is meant by chirality of a compound. Give one example.

68) (± )-2-Butanol is optically inactive. Give reasons.

Explain the following reaction : n-BuBr+KCN −−−−−−−→n-BuCN

1-Bromo-2,2-dimethyl propane (Neopentyl bromide)

(All the 12 H ′ sare (M onochloro derivative) (Dichloro derivative) (Dichloro der

1-Bromo-2,2-dimethyl propane (Neopentyl bromide)

(All the 12 ′ s are (M onochloro derivative) (Dichloro derivative) (Di

97) Write the structure of 3-bromo-2-methylpropene

′ dimethylpropane 2.2−dimethylpropane 2,2−dimethylpropane

(M onochloroderivative) (Dichloroderivative) tDichloroderivative)

102) How will you prepare bromobenzene from aniline ?

103) Which of the following has highest dipole moment ?

For further details refer to 'Supplement your knowledge for competitions.

(ii)CH3 CH(Br)CH2 CH3 + NaOH ⟶

121) Explain the following:

122) Convert the following in not more than two steps:

125) Give reasons:

Answer : (i) In chlorobenzene, there is a delocalisation of electrons due to resonance.

undergoes faster towards SN2 reaction as it is a primary halide.

(iii) CH3 Br + Mg ⟶ CH3MgBr

C6H5NH2 + CHCI3 + 3KOH →C6H5NC + 3KCI + 3H2O

131) Bring out the following conversions.

132) Draw the structures of the following organic halogen compounds

133) Write chemical equations when

134) Write the chemical equations when,

135) Discuss the mechanism of SN1reaction of haloalkanes.

The steps involved are

(ii) Attack of nucleophile on carbocation formed leading to formation of substituted product.

Answer : IUPAC Name: 3-bromo-1-chlorocyclohex-1-ene

138) Write the structures of the following organic halogen compounds.

139) Write the IUPAC name of the following compounds.

Answer : (i) 3-chloro-5-tluoro-3,5-dimethylheptalle

(ii)CH3 CH2 CH2 OH + SOCl2 ⟶

(iii)CH3 CH2 CH = CH2 + HBr ⟶

(ii)COCl2 + 2C2 H5 OH ⟶ (C2 H5 ) CO 3 + 2HCl

Phosgene Ethanol Diethyl carbonate

(ii)2CHCl3 + O 2 ⟶ 2COCl2 + 2HCl

146) Give the IUPACnames of the following compounds.

Answer : (i) 1-chloro-2,2-dimethylpropane

Answer : S > P > R > Q

(b) Racemisation occurs in SN1 reactions. Why?

due to which nucleophile can readily attack as compared to

Answer : (i) CH3Cl + KCN ⟶ CH3CN + KCl

Answer : (i) CH3 Cl + KNO2 ⟶ CH3 − O − N = O + KCl