Solution

HALOALKANES AND HALOARENES

Class 12 - Chemistry
1. Read the text carefully and answer the questions:
Haloarenes are less reactive than haloalkanes. The low reactivity of haloarenes can be attributed to
- resonance effect
sp2 hybridisation of C-X bond
- polarity of C-X bond
- instability of phenyl cation (formed by self-ionisation of haloarene)
- 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 o/p positions increases the reactivity of haloarenes towards nucleophilc substitution reactions.

(i) (b) resonance stabilisation

Explanation: resonance stabilisation
(ii) (d) (ii) > (i) > (iii) > (iv)

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Explanation: 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

(iii)

(a)
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PhCH2Br (ii) > MeBr (i) > MeCl (iii) > p-MeOC6H4Br (iv)
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Explanation: When in arylhalides the electron withdrawing groups are attached at ortho and para positions to the
chlorine atom then the removal of chlorine atom as Cl- ion becomes easy, therefore, 2,4,6-trinitro chlorobenzene is
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the most reactive among given aryl halides.

(iv)

(b)
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Ga

Explanation: Cl in 2,4,6-trinitrochlorobenzene is activated by three NO2 groups at o, and p-positions and hence
undergoes hydrolysis most readily.
(v)
(a)

Explanation:

2. Read the text carefully and answer the 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

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 different than the compound obtained when n-butyl bromide reacted with sodium metal.
(i) (a) 2,5-dimethylhexane
W urtz reaction

Explanation: C H 3 − C H − C H2 Br + 2N a −−−−−−−−→ C H3 − C H − C H2 − C H2 − C H − C H3
| | |

C H3 C H3 C H3

2,5−Dimethylbexane

(ii) CH
3

(d) C H 3 − C H − C H2 − Br

C H3 C H3 C H3

| alc.KOH | HBr |

Explanation: C H 3 − C − C H3 −−−−−→ C H3 − C = C H2 −−−−−→ C H3 − C H − C H2 − Br

| P eroxide
Br

(C)

(iii) (c) C H3 C H − C H2 Br
|

C H3

Explanation: 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 urtz reaction

2CH3CH2CH2CH2Br + 2Na −−−−−−−−−→ CH3CH2CH2CH2CH2CH2CH2CH3

na
W urtz reaction

2C H3 − C H − C H2 Br + 2N a −−−−−−−−→ C H3 − C H − C H2 − C H2 − C H − C H3
| | |

C H3 C H3 C H3

(A) (D)

(iv) (d) Both positional and functional

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Explanation:
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(v) (a) C H 3 − C = C H2
|
Ga

CH
3

Explanation: C H 3 − C = C H2
|

C H3

3. (a) SOCl2 in presence of pyridine

Explanation: The hydroxyl group of an alcohol is replaced by halogen on reaction with concentrated halogen acids,
phosphorus halides, or thionyl chloride. Thionyl chloride (SOCl2) is preferred because the other two products SO2 and HCl are
escapable gases. Hence, the reaction gives pure alkyl halides.
ROH + SOCl2 → RCl + SO2 (g) + HCl (g)

4.
(c) 2-Bromobutane

Explanation: 2-Bromobutane

It is a chiral molecule since it does not contain plane symmetry and centre of symmetry.

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 5.
(d) Electrophilic substitution reaction
Explanation: This is example of electrophilic aromatic substitution (EAS) reaction. Single Cl ion replaces hydrogen atom and
here FeCl3 acts as halogen carriers.

6.
(d) 2-chloro, 2-methyl propane
Explanation: Longest chain will be of three carbon to which Cl and CH3 will be attached at 2 positions.

7.
(b) passing dry hydrogen chloride gas through a solution of alcohol.
Explanation: The preparation of alkyl chloride is carried out by passing dry hydrogen chloride gas through a solution of
alcohol.
ROH + HCl → RCl + H2O
The reactions of primary and secondary alcohols with HCl require the presence of a catalyst, ZnCl2. With tertiary alcohols, the
reaction is conducted by simply shaking with concentrated HCl at room temperature.
8.
(c) Chloroquine
Explanation: Chloroquine is a synthetic halogen compound. It is used for the treatment of malaria.

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9.
(b) Chloramphenicol

10.
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Explanation: Chlorine containing antibiotics, chloramphenicol, produced by soil microorganisms is very effective for the
treatment of typhoid fever. Chloramphenicol is an antityphoid drug.
(a) SN1 reaction
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Explanation: Racemisation occurs in SN1 reaction not in SN2 reaction because in case of SN1 a group (base/nucleophile)
attack from (in front and back side) both sides.
11.
(b) (a), (b), (c)
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Explanation: Asymmetric/chiral carbon atom is that in which all of its four valencies with four different groups or atoms (can
not be superimpose). In molecules (i), (ii), and (ii), all have asymmetric carbon as each carbon has satisfied all four valencies
with four different groups of atoms.
12.
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(d) Neopentane
Ga

Explanation: Neopentane has all same type of hydrogen and has molecular weight 72u.
water

13. C H 3 C H(Br)C H2 C H3 + N aOH −−−→ C H3 − C H − C H2 C H3 + N aBr

2-Bromobutane |

OH

Butane - 2 - ol

14. Propene (CH3 - CH = CH2) on treatment with HBr in presence of peroxide gives anti-markownikov's product 1-bromopropane
C H3 − C H2 − C H2 Br which on treatment with AgNO2 gives 1-nitropropane (CH3-CH2-CH2NO2) and AgBr.

P eroxide AgN O2

C H3 − C H = C H2 + HBr −−−−−→ C H3 − C H2 − C H2 Br −−−−→ AgBr + C H3 − C H2 − C H2 N O2

Pr opene 1−Bromopropane 1−N itropropane

15. Step 1 Treat but-1-ene with HBr, in presence of peroxide to bring about anti-markownikov addition
Step 2 Treat the resulting 1-bromobutane with aq KOH to bring about substitution to give an alcohol
Step 3 Treat the resulting butan-1-ol with SOCl2 in presence of pyridine to give 1-chlorobutane
peroxide

C H3 − C H2 − C H = C H2 + HBr −−−−−→ C H3 − C H2 − C H2 − C H2 Br
aq.KOH SOC l2 ,pyridine

−−−−−→ C H3 − C H2 − C H2 − C H2 OH −−−−−−−−−→ C H3 C H2 C H2 C H2 C l

16.

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17. i. 2C HC l3 + O2 → 2C OC l2 + 2HC l
Chlorof orm P hosgene

ii. C HC l3 + C l2 → C C l4 + HC l
Chlorof orm Carbon tetrachloride

18. a.

is more reactive towards SN2 because it is a primary halide.

b.

is more reactive towards nucleophilic substitution reaction because it is more reactive due to the presence of electron with
drawing - NO2 group.

c. It is optically active due to chiral carbon.

a
tan
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19.
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20.
Ga

Hydrolysis by aqueous KOH proceeds through the formation of carbocation. If carbocation is stable, then the compound is easily
hydrolyzed by aqueous KOH.
Now C6H5CH2Cl forms 1 − carbocation, while C6H5CHClC6H5 forms 2 − carbocation, which is more stable than 1 −
∘ ∘ ∘

carbocation. Hence, C6H5CHClC6H5 is hydrolyzed more easily than C6H5CH2Cl by aqueous KOH.
21. Aryl bromides and chlorides can be prepared from arenes by electrophilic substitution reaction by Chlorine and Bromine
respectively. This reaction is carried out by treating the arene with chlorine or bromine in the presence of iron (III) chloride in the
absence of light. Iron (III) chloride, that is, FeCl3 is a Lewis acid, which generates the electrophile required to take the reaction

forward. FeCl3 forms a coordination compound with Cl2, making the complex Cl+[FeCl4-]. The chloride ion gains a partial
positive charge, acting as an electrophile, and attacking the ϖ bonds. The final products are o-aryl halide and p-aryl halide isomers
which can be separated easily.

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22. Structure of the following organic halogen compound:
i. 2-(2-Chlorophenyl)-1-iodooctane

ii. 2-Bromobutane
C H3 − C H2 − C H − C H3
|

Br

iii. 4-tert-Butyl-3-iodoheptane
CH3 - CH2 - C H - C H - CH2 CH2 CH3
| |

I C(CH )
3 3

23. Diphenyl such as p, p-dichlorodiphenyltrichloroethane (DDT) first chlorinated organic insecticides, which have been used as

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organic pesticides, are a potential threat to the environment because, in the early years(after world war II) of its extensive usage, it
was shown to have high toxicity towards fish and many insects also developed resistance towards it. The chemical stability of
DDT and its fat solubility compounded the problem. In the chemical aspect, DDT is not metabolized very rapidly or solubilized

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effectively by animals. It is deposited and stored in the fatty tissues. If ingestion continues at a steady rate, DDT builds up within
the animal over time, damaging the environment, therefore DDT was banned in the united states in 1973. Diphehyls are produced
from aryl halides from two methods, Fitting reaction, and Ullman biaryl synthesis.
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In Fittig reaction, the aryl halides are treated with sodium metal in the presence of dry ether to produce substituted aryl
compounds, in this case, the biphenyl compound.
In Ullmann synthesis, which is a coupling reaction, aryl halides are heated in the presence of Cu to form biphenyl/diphenyl
compounds.
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Ga

24. i. Both alkyl halides and water are polar molecules. The intermolecular force of attractions between two alkyl halide molecules
is dipole-dipole attraction. While The intermolecular force of attractions between two water molecules is by hydrogen
bonding. When alkyl halides are mixed with water a new force of attraction between the alkyl halides and water comes into
play, this new force of attraction is much weaker than the forces of attractions already existing between two alkyl halides and
two water molecules respectively. This is the reason that alkyl halides, though polar, are immiscible with water.
ii. In Grignard reagent, the carbon-magnesium bond is highly polar, with carbon pulling electrons from electropositive
magnesium. The magnesium halogen bond is essentially ionic in nature. Thus, a Grignard reagent is a very versatile or very
reactive reagent which can react with any source of a proton to give hydrocarbons. If even traces water is present in the
reaction, then they will react with the reagent producing the corresponding hydrocarbon thus making the reagent ineffective.

Therefore, Grignard's reagents should be prepared under anhydrous conditions.

25. Aryl halides are less reactive towards nucleophilic substitution reactions than alkyl halides due to following reasons:
i. The electrons on the halogen atom are in conjugation with the electrons of the aryl ring, giving the C—X bond a partial double
bond character. The entire molecule is then resonance stabilized and the following structures are possible. Due to this bond
formation, C—X bond cleavage in haloarenes(due to partial double bond character) is more difficult than haloalkanes(as due

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 to the presence of a single bond).

ii. In haloalkanes, the carbon attached to halogen is sp3 hybridized while in haloarene, the carbon attached to the halogen is
sp2 hybridized. The sp2 hybridized carbon holds the halogen atom tightly and tighter than a bond between sp3 carbon atom
and halogen atom in haloalkanes. The C—X bond length in haloarenes(177pm) is shorter than haloalkanes(169pm) and thus
more difficult to break. Hence it is difficult to break a shorter bond than the longer bond, therefore less reactive than
haloalkanes towards nucleophilic substitution reaction.
iii. The phenyl cation does not get resonance stabilized and hence cannot follow the SN1 mechanism of nucleophilic substitution.
iv. Aryl halides are less reactive than alkyl halides because of possible repulsion between electron-rich arenes and approaching
electron-rich nucleophiles.
Reactivity of aryl halides can be increased with the presence of an electron-withdrawing group at the ortho- and para- positions.
No effect is observed at the meta- position. Presence of the nitro group, an example of an electron-withdrawing group, at the
ortho- and para- positions withdraws the electron density from the benzene ring and thus facilitates the attack of the nucleophile
on haloarene. The carbanion thus formed is stabilised through resonance. The negative charge present at the ortho- and para-
positions with respect to the halogen substituent is stabilized by –NO2 group while in case of meta-nitrobenzene, none of the

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resonating structures bear the negative charge on carbon atom bearing the –NO2 group. Hence no effect on the reactivity of aryl

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halide is observed on the presence of the meta-position electron-withdrawing group.

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vk
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Ga

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