Haloalkanes & Haloarenes

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CLASS – 12TH

CBSE 2024

Haloalkanes &
Haloarenes
APNI KAKSHA NOTES

APNI KAKSHA 1
Haloalkanes
Haloalkanes are the halogen deivatives of hydrocarbons.
Classification of Haloalkanes
Monohalides (R-X): Monohalides are monohalogen
derivatives of alkanes which have a general formula
CnH2n+1X and are known as alkyl halides.
R-X may be of three types:
1 Primary R − CH X
2 Secondary R CHX
3 Tertiary R CX
Dihalides (𝐂 𝐇 𝐗 ) : Dihalides are the di-halogen derivatives of alkanes and are of geminal and
vicinal types.

Example
(a) CH CHBr (Ethylidine dibromide),
(b) BrCH CH Br (Ethylene dibromide)
(a) Mono Halogen Derivatives Examples
Example
(i) Chlorobenzene (ii) p-Bromotoluene

(iii) Bromobenzene (iv) m-Bromotoluene

(b) Side chain Halogen Derivatives


Example
(i) Benzyl chloride (ii) -Phenylethyl bromide

Allylic, Vinylic and Benzylic Halides


(a) Allylic Halides

APNI KAKSHA 2
Example
(i) 3-Haloprop-1-ene(1º) (ii) 3-Halo-3-methylcyclohex-1-ene(3)

(b) Vinylic Halides


(i) Chloroethene (ii) 1-Chloroprop-1-ene

Which of the following belongs to the class of Vinyl halides? CBSE 2023
(A) CH2 = CHCH2CH2Cl (B) CH2  C  CH3
|
Br
(C) CH2 = CH – CH2 – Br (D) CH  C — Br

(c) Benzylic Halides


(i) Benzyl halide (1º) (ii) A benzylic halide (3º)

Named Reaction
(a) Sandmeyer Reaction:

(b) Finkelstein Reaction:


R  X  NaI 
dry acetone
R  I  NaX  X  Cl,Br 
(C) Swartz Reaction:
CH3 – Br + AgF  CH3 – F + AgBr
Instead of Ag – F, other metallic fluoride like Hg2F2, CoF2 or SbF3 can also be used.
(d) Wurtz Reaction:
2R  X  2Na  
dry ether
 R  R  2NaX
(e) Wurtz – Fitting Reaction:

+ 2Na+R– X +2Nax

APNI KAKSHA 3
(f) Fitting Reaction:

Methods of preparation
Halogenation of alkanes
R  H  X 2 
hv
 R  X  HX

For example
CH4  Cl2  hv
or520650K
CH3Cl  CH2Cl2  CHCl3  CCl4
Cl2 ,hv
CH3  CH2  CH3 
298K
CH3  CH2  CH2  Cl  CH3  CHCl  CH3
Propane 1Chloropropane(45%) 2Chloropropane55%

Cl2 ,hv
CH3CH2CH2CH3 
298K
CH3CH2CH2CH2Cl  CH3CH2  CHCl  CH3
Butane 1Chlorobutane 28% 2Chlorobutane72%

In general, the ease of subsitution of various hydrogens follows the sequence:


Allylic > 3º > 2º > 1º > CH4
Reactivity order in halogens: F > Cl > Br > I lodination is reversible, but it may be
carried out in presence of an oxidising agent, such as, HIO , HNO , HgO , etc., which
oxidises the HI as it is formed.

5𝐻𝐼 + 𝐻𝐼𝑂 ⎯ 3𝐼 + 3𝐻 𝑂

Flourination: The best way to prepare alkyl


fluorides is by halogen exchange. An alkyl
chloride or bromide is heated in the presence
of a metallic fluoride, such as AgF,
Hg F , CoF or SbF to give alkyl fluorides.
CH3Br  AgF 
CH3F  AgBr
Bromomethane Fluoromethane

2CH3CH2Cl+Hg2F2 2CH3CH2F + Hg2 Cl2

APNI KAKSHA 4
MIND MAPS

Physical properties of monohalides


 Lower members of monohalides
(CH X, C H X) are colourless gases while
higher members are colourless liquid up to
C , members are colourless solids.
 Boiling point and density increase with
increase in molecular weight.
C H Cl > C H Cl > C H Cl > CH Cl
RI > RBr > RCl > RF
Likewise it happens in alkanes, branching also decrease B.P

Boiling Point ⟶ 375 K 364K 346K


 Dipole moment: RCl > RF > RBr > RI
CH Cl > CH Br > CH Br > CH I
→ . . . .
 Stability : RF > RBr > RCl > RI
 Solubility 𝛼 Mol.wt.

APNI KAKSHA 5
In general: CH X > C H X > C H X > C H X
Q. Haloalkanes are less soluble in water, why?
Ans. Haloalkanes are polar molecules, neither they form H-bond with water nor can they break
the H-bonds already existing between water molecules. As a result, the solubility of
haloalkanes in water in very low.
CHEMICAL REACTIONS

SN1 indicates the unimolecular nucleophilic substitution reaction in organic chemistry.


Their rate determining step of the mechanism depends on the decomposition of a single
molecular species. So that, the rate of S N1 reaction can be expressed as rate = K[R – LG].
Furthermore, SN1 is a multi-step reaction, which forms an intermediate and several
transition states during the reaction. This intermediate is a more stable carbocation and
the reactivity of the molecule depends on the alkyl group.

Fast

Slow

Fast

In the following pairs of halogen compounds, which would undergo S N2 reaction faster?

CH2Cl and Cl ; and Cl

CH2Cl It is primary halide and therefore undergoes S N2 reaction faster.

APNI KAKSHA 6
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.
Predict the order of reactivity of the following
Compound in SN1 and SN2 reaction.
(i) The four isomeric bromobutanes
(ii) C6H5CH2Br, C6H5CH(C6H5)Br, C6H5CH(CH3)Br, C6H5C(CH3)(C6H5)Br

SN2 indicates the bimolecular nucleophilic substitution reaction in organic chemistry. In


this mechanism, separation of leaving group and formation of new bond happen
synchronously. Therefore, two molecular species are involved in the rate determining
step and this leads to the term bimolecular nucleophilic substitution reaction or S N2. The
rate of the SN2 reaction can be expressed as rate = K[R – LG][Nu–]. In inorganic chemistry,
this reaction is also called associative substitution or interchange mechanism.

Fast

Slow

Here, nucleophile attacks from the opposite direction of the leaving group. Thus, SN2
reaction always leads to an inversion of stereochemistry. This reaction works best with
methyl and primary halides because bulky alkyl groups block the backside attack of the
nucleophile. In addition, the stability of the leaving group as an anion and the strength of
its bond to the carbon atom both affect the rate of reaction.

APNI KAKSHA 7
Electrophilic Substitution Reaction of Haloarenes:

APNI KAKSHA 8
Previous year Questions
Q.1 (a) Write equation for preparation of 1-iodobutane from 1-chlorobutane. [CBSE 2022]
(b) Out of 2-bromopentane, 2-bromo-2-methylbutane and 1 -bromopentane, which
compound is most reactive towards elimination reaction and why?
(c) Give IUPAC name of

Ans. (a) CH3CH2CH2CH2 –Cl NaI


acetone
CH3CH2CH2CH2  I
(b) 2-bromopentane
(c) 4-bromo-4-Methylpent-2-ene
Q.2 Racemisation occurs in [CBSE 2022]
(A) 𝑆 2 reaction (B) 𝑆 1 reaction
(C) Neither S 2 nor S 1 reactions (D) S 2 reaction as well as S 1 reaction
Ans. (B)
3. Identify the chiral molecule in the following pair: [CBSE 2020]

(b) Write the structure of the product when chlorobenzene 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-bromo-1
methylcyclohexane with alcoholic KOH.
Ans. (A) (i)

(B) + CH3Cl 


Na/dry ether
(C) + alc. KOH 

4. Out of Chlorobenzene and Cyclohexyl chloride, which one is more reactive towards
nucleophilic substitution reaction and why? [CBSE 2019]
Ans. Cyclohexyl chloride
5. Among all the isomers of molecular formula C HBr, identify [CBSE 2019]
(a) The one isomer which is optically active.
(b) The one isomer which is highly reactive towards SN2.
(c) The two isomers which give same product on dehydrohalogenation with alcoholic
KOH.
Ans. (a) (b) CH3CH2CH2CH2Br

(c) (i) 2-Bromo-2-methylpropane

APNI KAKSHA 9
(ii) 1-bromo-2-methylpropane

APNI KAKSHA 10

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