Halo alkane and Halo arens

2 1 Write structures 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-sec. butyl-2-methylbenzene.
3 Thionyl chloride is preferred because the other two products are escapable gases. Hence
the reaction gives pure alkyl halides
4 Why is sulphuric acid not used during the reaction of alcohols with KI?
HI formed will oxidized into I2 by sulphuric acid
5 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
A hydrocarbon C5H10 does not react with chlorine in dark but gives a single monochloro
compound C5H9Cl in bright sunlight. Identify the hydrocarbon.

5 a

g
 h

6 a

7
A B

A B
8 Write the structure of the product formed when chlorobenzene is treated with methyl
chloride in the presence of sodium metal and dry ether

9 Which of the following two reactions is S N2 and why?

10 Write the product formed when p-nitro chlorobenzene is heated with aqueous NaOH at 443
K followed by acidification.
11 Write the structure of the alkene formed by dehydrohalogenation of 1-Bromo-1-
methylcyclohexane with alcoholic KOH.

a) why the boiling points of chlorides, bromides and iodides are considerably higher than
 those of the hydrocarbons of comparable molecular mass?
Due to greater polarity as well as higher molecular mass as compared to the parent
hydrocarbon, the intermolecular forces of attraction (dipole-dipole and van der Waals)
are stronger in the halogen derivatives
b) For the same alkyl group, the boiling points of alkyl halides decrease in the order: RI>
RBr> RCl> RF
This is because with the increase in size and mass of halogen atom, the magnitude of
van der Waal forces increases.
The boiling points of isomeric haloalkanes decrease with increase in branching due to
decrease in surface area and the magnitude of van der Waal forces decreases
c) the para-dichlorobenzene isomers are high melting as compared to their ortho and
meta-isomers.
It is due to symmetry of para-isomers that fits in crystal lattice better as compared to
ortho- and meta-isomers
d) haloalkanes tend to dissolve in organic solvents because the new intermolecular
attractions between haloalkanes and solvent molecules have much the same strength
as the ones being broken in the separate haloalkane and solvent molecule
e) Haloalkanes are insoluble in water
f) Groups like cyanides and nitrites possess two nucleophilic centres and are called
ambident nucleophiles
g) Haloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms
isocyanides as the chief product. Explain.
KCN is predominantly ionic and provides cyanide ions in solution. Although both carbon
and nitrogen atoms are in a position to donate electron pairs, the attack takes place
mainly through carbon atom and not through nitrogen atom since C—C bond is more
stable than C—N bond. However, AgCN is mainly covalent in nature and nitrogen is free
to donate electron pair forming isocyanide as the main product

Arrange each set of compounds in order of increasing boiling points.

(i) Bromomethane, Bromoform, Chloromethane, Dibromomethane.

(ii) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane

Which molecule is chiral ?

Out of  and  which one is optically active and why? (CBSE AI 2019)
Answer:
Although chlorine is an electron withdrawing group, yet it is ortho-, para- directing in
electrophilic aromatic substitution reactions. Why?
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 para- positions. 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

 Alkyl iodides are often prepared by the reaction of alkyl chlorides/ bromides with NaI
in dry acetone. This reaction is known as Finkelstein reaction.

 The synthesis of alkyl fluorides is best accomplished by heating an alkyl

chloride/bromide in the presence of a metallic fluoride such as AgF, Hg2F2 , CoF2 or
SbF3 . The reaction is termed as Swarts reaction

 Wurtz-Fittig reaction
A mixture of an alkyl halide and aryl halide gives an alkylarene when treated with sodium
in dry ether and is called Wurtz-Fittig reaction
 Fittig reaction
Aryl halides also give analogous compounds when treated with sodium in dry ether, in
which two aryl groups are joined together. It is called Fittig reaction

 Wurtz reaction
Alkyl halides react with sodium in dry ether to give hydrocarbons containing double the
number of carbon atoms present in the halide. This reaction is known as Wurtz reaction

Which one of the following has the highest dipole moment? (i) CH2Cl 2 (ii) CHCl 3 (iii) CCl4

hich compound in each of the following pairs will react faster in SN 2 reaction with –OH?
(i) CH3Br or CH3 I (ii) (CH3 )3CCl or CH3Cl
Explain why
the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride?
Since dipole moment is a product of charge and distance, therefore, chlorobenzene has a
lower dipole moment than cyclohexyl chloride due to the lower magnitude of charge (δ-)
on Cl atom and small C-Cl distance.
C-Cl bond in chlorobenzene acquires some double-bond character due to reasonance -Cl
bond in chlorobenzene is less polar than in cyclohexyl chloride due to Cl atached to sp2-
hybridised carbon
alkyl halides, though polar, are immiscible with water?
Alkyl halides are polar molecules and therefore, their molecules are held together by
dipole-dipole forces. On the other hand, the molecules of H 20 are held together by
hydrogen bonds. When alkyl halides are added to water, 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.
Hence, alkyl halides are immiscible (not soluble) in water.
Grignard reagents should be prepared under anhydrous conditions?
Grignard reagents are very reactive. They react with the moisture present in the
apparatus or the starting materials (RX or Mg).
RMgX + HOH → R-H + Mg(OH)X
Therefore, Grignard reagents must be prepared in anhydrous conditions
SN1 reactions are accompanied by racemisation in optically active alkyl halides.
C – Cl bond length in chlorobenzene is shorter than C — Cl bond length in CH 3 — Cl.
Ethyl iodide undergoes SN2 reaction faster than ethyl bromide.
(±) 2 – Butanol is optically inactive
The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but
in the presence of alcoholic KOH, alkenes are major products. Explain.
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 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
What happens when (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 aqueous KOH, (v) methyl bromide is treated
with sodium in the presence of dry ether, (vi) methyl chloride is treated with KCN?
Arrange the compounds of each set in order of reactivity towards S N2 displacement: (i) 2-
Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane (ii) 1-Bromo-3-methylbutane,
2-Bromo-2-methylbutane, 2-Bromo-3-methylbutane
How the following conversions can be carried out?
Propene to propan-1-ol

Ethanol to but-1-yne

1-Bromopropane to 2-bromopropane

Toluene to benzyl alcohol

Benzene to 4-bromonitrobenzene

Benzyl alcohol to 2-phenylethanoic acid

Ethanol to propanenitrile

Aniline to chlorobenzene

2-Chlorobutane to 3, 4-dimethylhexane

2-Methyl-1-propene to 2-chloro-2-methylpropane

Ethyl chloride to propanoic acid

But-1-ene to n-butyliodide (
Chlorobenzene to p-nitrophenol

2-Bromopropane to 1-bromopropane

Chloroethane to butane
 Benzene to diphenyl

tert-Butyl bromide to isobutyl bromide

Propene to 1-nitropropane

Ethanol to ethyl fluoride

But-1-ene to but-2-ene

Prop-1-ene to 1-fluoropropane

1. Tert-Butylbromide reacts with aq. NaOH by S N1 mechanism while n-butyl bromide reacts by
an SN2 mechanism. Why?
2. Write the main products when
(a) n-butyl chloride is treated with alcoholic KOH.
3. n-butyl chloride is treated with alcoholic KOH.
(ii) 2, 4, 6-trinitrochlorobenzene is subjected to hydrolysis.
(iii) methyl chloride is treated with AgCN.
4. In the following pairs of the halogen compounds, which would undergo S N2 faster?

uestion 10.

(a) Out of  and  which one is more reactive

towards SN2 reaction and why?

stion 8.

Out of   and  which is more reactive

towards SN1 reaction
 5. Which one of the following compounds will undergo a faster hydrolysis reaction by the S N1
mechanism? Justify your answer

6. The following compounds are given to you:

2-Bromopentane, 2-Bromo-2-methyl butane, 1-Bromopentane
(i) Write the compound which is most reactive towards the S N2 reaction.
7. ii) Write the compound which is optically active.
8. Write the compound which is most reactive towards the S N1  reaction

Propose the mechanism of the reaction taking place when

(i) (-) – 2 – Bromooctane reacts with sodium hydroxide to form (+) – octane-2-ol.
Answer: ut of SN1 and SN2 which reaction occurs with
(a) Inversion of configuration
Answer:
SN2
(b) Racemisation

How would you differentiate between SN1 and SN2 mechanisms of substitution reactions? Give one
example of each

A solution of KOH hydrolyses CH3CHClCH2CH3 and CH3CH2CH2CH2Cl. Which one of these is more easily
hydrolysed?