Question 10.

1: 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)2CH2I

(iv) (CH3)3CCH2CH(Br)C6H5

(v) CH3CH(CH3)CH(Br)CH3

(vi) CH3C(C2H5)2CH2Br

(vii) CH3C(Cl)(C2H5)CH2CH3

(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-Br-C6H4CH(CH3)CH2CH3

Solution:

(i)

2 − Chloro − 3 – methylbutane

(Secondary alkyl halide)

(ii)
3 − Chloro − 4 – methyhexane

(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)

Question 10.2: Give the IUPAC names of the following compounds:

(i) CH3 CH(Cl) CH(Br) CH3

(ii) CH F2 CBr ClF

(iii) Cl CH2 C ≡ C CH2 Br

(iv) ( CCl 3) 3 CCl

(v) CH3 C (p – Cl C6 H4 )2 CH(Br) CH3

(vi) (CH3 )3 C CH = C Cl C6 H4 I – p

Solution:

(i)

2−Bromo−3−chlorobutane

(ii)
1−Bromo−1−chloro−1, 2, 2−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 − chlorophenyl) butane

(vi)

1−chloro−1−(4−iodophenyl)−3, 3−dimethylbut−1−ene

Question 10.3:

Write the structures of the following organic halogen compounds.

(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

Solution:

(i)
(ii)

(iii)

(iv)
(v)

(vi)

(vii)

(viii)
Question 10.4:

Which one of the following has the highest dipole moment?

(i) CH2Cl2 (ii) CHCl3 (iii) CCl4

Solution:

CCl4 is a symmetrical molecule. Therefore, the dipole moments of all four C− Cl bonds cancel each other. Hence, its resultant dipole moment
is zero.

As shown in the above figure, in CHCl3, the resultant of dipole moments of two C – Cl bonds is opposed by the resultant of dipole moments
of one C−H bond and one C – Cl bond. Since the resultant of one C – H bond and one C−Cl bond dipole moments is smaller than two

C−Cl bonds, the opposition is to a small extent. As a result, CHCl 3 has a small dipole moment of 1.08 D.

On the other hand, in case of CH2Cl2, the resultant of the dipole moments of two C – Cl bonds is strengthened by the resultant of the dipole
moments of two C – H bonds.

Result, CH2Cl2 has a higher dipole moment of 1.60 D than CHCl3 i.e., CH2Cl2 has the highest dipole moment.

Hence, the given compounds can be arranged in the increasing order of their dipole moments as:
CCl4 < CHCl3 < CH2Cl2

Question 10.5: A hydrocarbon C5H10 does not react with chlorine in dark but gives a single monochloro compound C 5H9Cl in bright
sunlight. Identify the hydrocarbon.

Solution:
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, C 5H9Cl 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. Hence, the said compound is cyclopentane.

The reactions involved in the question are:

Question 10.6: Write the isomers of the compound having formula C 4H9Br.

Solution:
There are four isomers of the compound having the formula C 4H9Br. These isomers are given below.

(a) 1−Bromobutane
(b) 2−Bromobutane

(c) 1−Bromo−2−methylpropane

(d) 2−Bromo−2−methylpropane
Question 10.7: Write the equations for the preparation of 1−iodobutane from

(i) 1-butanol

(ii) 1-chlorobutane

(iii) but-1-ene

Solution:

(i)

(ii)

(iii)

Question 10.8: What are ambident nucleophiles? Explain with an example.

Solution:
When there are two nucleophilic sites in a nucleophile, they are called ambident nucleophile. These nucleophilic sites are sites through which
they can attack.

For ex- Nitrite ion

Alkyl nitrites are formed when nitrite ion can attack through oxygen. And, nitroalkanes are formed when it can attack through nitrogen.

Question 10.9:Which compound in each of the following pairs will react faster in SN2 reaction with –OH?

(i) CH3Br or CH3I

(ii) (CH3)3CCl or CH3Cl

Solution:
(i) In SN2 mechanism, the order in which the halides react to some alkyl group is constant. This is because the halide ion becomes a better
leaving group when the size of the ion increases.

R-F << R-Cl << R-Br < R-I

Hence, the reactivity of CH3I is faster as compared to CH3Br in SN2 reactions with OH–.

(ii)

In SN2 mechanism, the nucleophile attacks at the atom bearing the leaving group. The attack of nucleophile in (CH 3)3CCl at the carbon atom
is hindered as the carbon atoms (bearing the leaving group) contains bulky substituents.

However, CH3Cl does not consist of bulky substituents on the carbon atom bearing the leaving group.

Hence, the reactivity of CH3Cl is faster as compared to (CH3)3CCl in SN2 reaction with OH–.

Question 10.10: 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) 2,2,3-Trimethyl-3-bromopentane.

Solution:
(i)

1−bromo−1−methylcyclohexane

All the β-hydrogen are equal in the given compound. Hence, dehydrohalogenation of the given compound gives only one alkene.

(ii)

a and b are different sets of equivalent β-hydrogen atoms. Dehydrohalogenation of this compound gives two alkenes.

The alkene with more number of alkyl groups attached to a doubly bonded carbon atoms is preferablt produces, according to Saytzeff’s rule
in dehydrohalogenation reactions.
Hence, major product in this reaction is 2-methylbut-2-ene.

(iii)

2,2,3-Trimethyl-3-bromopentane

a and b are different sets of equivalent β-hydrogen atoms. Dehydrohalogenation of this compound gives two alkenes.

The alkene with more number of alkyl groups attached to a doubly bonded carbon atoms is preferablt produces, according to Saytzeff’s rule
in dehydrohalogenation reactions.

Hence, 3,4,4-trimethylpent-2-ene is the major product.

Question 10.11: 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 fluoride

(vii) Bromomethane to propanone

(viii) But-1-ene to but-2-ene

(ix) 1-Chlorobutane to n-octane

(x) Benzene to biphenyl.

Solution:
(x)

Question 10.12: Explain why

(i) the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride
(ii) alkyl halides, though polar, are immiscible with water
(iii) Grignard reagents should be prepared under anhydrous conditions

Solution:
(i)

The Cl- atom in chlorobenzene is linked to sp2 hybridized carbon atom, whereas in cyclohexyl chloride it is linked to sp 3 hybridized carbon
atom. Now, as sp2 hybridized carbon has more s-character, it is more electronegative than sp 3 hybridized carbon atom. Hence, the density of
electrons of C-Cl bond near the Cl atom is less in chlorobenzene than in cyclohexyl chloride.

Moreover, the electron density is reduced by the –R effect of the benzene ring of chlorobenzene. Hence, chlorobenze has a decreased
polarity of C-Cl bond, also the dipole moment is lower than that of cyclohexyl chloride.
(ii) When the solute water force o attraction is stronger than solute-solute and water-water force of attraction, detmines the miscibility with
water. Dipole – dipole interactions hold the polar molecules of alkyl halides together. Now, the alkyl halide- alkyl halide and water-water
forces of attraction are stronger than the new force of attraction between alkyl halides and water molecules. As a result, alkyl halides (though
polar) are immiscible with water.

(iii) Grignard reagents are very reactive. In the presence of moisture, they react to give alkanes.

Therefore, Grignard reagents should be prepared under anhydrous conditions.

Question 10.13: Give the uses of freon 12, DDT, carbon tetrachloride and iodoform.

Solution:
Uses of Freon -12

Common name given to Freon-12 (dichlorodifluoromethane, CF 2Cl2) is CFC. It is used in aerosol spray propellants such as deodorants, hair
sprays, etc. It is also used in refrigerators and air-conditioners as a refrigerant. It’s manufacturing was banned in United States and many
other countries in 1994 as it was severely damaging the ozone layer.

Uses of DDT

The most commonly used insecticide is DDT (p, p−dichlorodiphenyltrichloroethane). It has various harmful effects due to which it was
banned in United States in 1973, though it is very effective aganst mosquitoes and lice.

Uses of carbontetrachloride (CCl4 )

(i) Refrigerants and propellant for aerosol cans are manufactured using CCl 4.

(ii) Chloroflourocarbons and other chemicals are synthesized.

(iii) Used as a solvent in the manufacture of pharmaceutical products.

(iv) Used as cleaning fluid, a spot reamer in homes and a fire extinguisher during the mid 1960s.

Uses of Iodoform (CHI3)

Iodoform was used earlier as an antiseptic, but now it has been replaced by other formulations-containing iodine-due to its objectionable
smell.

Question 10.14: Write the structure of the major organic product in each of the following reactions:

Solution:
Question 10.15 : What will be the mechanism for the following reaction?

Solution:
The given reaction is

CN– acts as the nuclephile and attacks the carbon atom on which the Br is attached. CN – ion is an ambient nucleophile and can attack
through both C and N positions. It attacks through C atom, in this case.
Question 10.16: 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-2-methylbutane, 3-Bromo-2- methylbutane

(iii) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2-methylbutane, 1Bromo-3- methylbutane.

Solution:

(i)

An SN2 reaction involves the approaching of the nucleophile to the carbon atom to which the leaving group is attached. When the
nucleophile is sterically hindered, then the reactivity towards SN2 displacement decreases. Due to the presence of substituents, hindrance to
the approaching nucleophile increases in the following order.

1-Bromopentane < 2-bromopentane < 2-Bromo-2-methylbutane

Hence, the increasing order of reactivity towards SN2 displacement is:

2-Bromo-2-methylbutane < 2-Bromopentane < 1-Bromopentane

(ii)

Since steric hindrance in alkyl halides increases in the order of 1° < 2° < 3°, the increasing order of reactivity towards SN2 displacement is 3°
< 2° < 1°.

Hence, the given set of compounds can be arranged in the increasing order of their reactivity towards S N2 displacement as:
2-Bromo-2-methylbutane < 2-Bromo-3-methylbutane < 1-Bromo-3-methylbutane

(iii)

The steric hindrance to the nucleophile in the SN2 mechanism increases with a decrease in the distance of the substituents from the atom
containing the leaving group. Further, the steric hindrance increases with an increase in the number of substituents. Therefore, the
increasing order of steric hindrances in the given compounds is as below:

1-Bromobutane < 1-Bromo-3-methylbutane < 1-Bromo-2-methylbutane < 1-Bromo-2, 2-dimethylpropane

Hence, the increasing order of reactivity of the given compounds towards SN2 displacement is:

1-Bromo-2, 2-dimethylpropane < 1-Bromo-2-methylbutane < 1-Bromo-3- methylbutane < 1-Bromobutane

Question 10.17: Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by aqueous KOH?

Solution:

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 1o– carbocation, while C6H5CHClC6H5 forms 2o– carbocation, which is more stable than 1o– carbcation. Hence,
C6H5CHClC6H5 is hydrolyzed more easily than C6H5CH2Cl by aqueous KOH.

Question 10.18: p-Dichlorobenzene has higher m.p. and lower solubility than those of o- and m-isomers. Discuss.

Solution: