Haloalkanes & Haloarenes

Synopsis:
Compounds in which one or more hydrogen of alkane is replaced by halogen are known as
haloalkanes.

Classification:

b) Based on Hybridisation of
Haloalkanes or haloarenes
carbon to which halogen is a) Based on No.of halogen atoms
attached
i) sp3 C-X bond Monohalogens trihalogens
Ex: CH3Cl, Ex: CHCl3,
Alkyl halides Benzylic halides dihalogens
C2H5Cl, Br
Ex: CH3Cl,
Ex:
C2H5Cl, Allylic halides CH2 Cl Br

Cl Br
Ex: CH2=CH-CH2-I , Vicinal Geminal
dihalides dihalides
Ex: CH2-CH2 Ex: CH2Cl2 ,
Br Cl Cl CH3-CHCl2
CH3-CH-CH2
ii) sp2 C-X bond
Cl Cl
Vinylic halides Aryl halides
Ex: CH2=CH-Br , Cl Br

Cl

iii) sp C-X bond

Ex: HC C Br H3C C C Br
Chloroethyne bromopropyne

Preparation of haloalkanes:
1) From alcohols:
PCl5
R-Cl + POCl3 + HCl
SOCl2 / pyridine
R-Cl + SO2 + HCl (Darzen's reaction)

PX3
R-X + H3PO3 (x = Cl, Br, I)
R-OH

KI + H3PO4
R-I + H2O

HCl + Anhyd.ZnCl2
Lucas reagent R-Cl + H2O (Groove's process)

2) From Alkenes:
anti-Markownikov's rule Markownikov's rule
R CH2 CH2 Br R CH CH2 + HBr R CH CH3
Presence of peroxide
Br
3) From Halide exchange method:
1) Finkelstein reaction:
R-Cl + NaI ⎯⎯⎯
acetone
→ R-I + NaCl.

2) Swart’s reaction:
2CH3Cl + HgF2 ⎯⎯
→ 2CH3F + HgCl2

Note:
1) In Groove’s method the function of ZnCl2 is to weaken the C-OH bond. In case of 30 alcohols ZnCl2 is not
needed.
2) The reactivity of halogen acids towards the reaction with alcohols is HI > HBr > HCl.
3) The reactivity of alcohols, 30 > 20 > 10.
4) Darzen’s process is the best method to prepare alkyl halides. Since all the products formed are gases.

Physical properties:
1) Alkyl halides being polar, insoluble in water as they cannot break H-bonding already existing in water.
2) Greater the molecular mass, stronger is the Vander-Waals force of attraction and hence higher is the MP and
BP. For the same alkyl group, RI > RBr > RCl > RF.
3) On increasing branching, surface area is decreased hence Vander Waals force of attraction is decreased and
BP increased.
4) Thermal stability: R-F > R-Cl > R-Br > R-I
5) Density: RI > RBr > RCl > RF.

Chemical properties:
Because of polar nature of R-X bond, alkyl halides are highly reactive compounds.
They under go
i) Nucleophilic substitution reaction. ii) Elimination reaction.
1) Nucleophilic substitution reaction:
R-X + Nu ⎯⎯
→ R-Nu + X-
Aqueous NaOH
R-OH + NaX
or KOH alcohols
R'-ONa (Sod.alkoxide)
R-O-R' + NaX (Williamson's ether synthesis)
Ethers
KCN (alcoholic)
R-CN + KX
Alkyl cyanides or nitriles
AgCN (alcoholic)
R-NC + AgX
Alkyl isocyanides or isonitriles
AgNO2 (alcoholic)
R-NO2 + AgX
nitroalkanes
KNO2 (alcoholic)
R-O-N=O + KX
alkylnitrites
R'COOAg(alcoholic)
R-X R'COOR + AgX
(silver salt of carboxylic acid)
Esters
+ 2(H) LiAlH4
R-H + HX
Alkanes
R'-Li (Alkyl lithium)
R-R' + LiX
Alkanes R R R
NH3 (Alc) NH3 (Alc) NH3 (Alc) NH3 (Alc) +
- HX R-NH2 R-NH - HX R-N-R R-N-R -
- HX - HX X
10 amine 20 amine 30 amine
R
Dry Ag2O Quaternary ammonium halide
R-O-R + AgX
Ethers
moist Ag2O or AgOH
R-OH + AgX
KSH
RSH + KX
thio alcohol
Na2S
R-S-R + NaX
thio ether
R'-C C Na+-
R'-C C-R + NaX
Sodium alkynide

Note: The cyanides further react to give different compounds.

partial hydrolysis
i) R-CN + H2O ⎯⎯⎯⎯⎯⎯⎯⎯→ R-CONH2
Acid amide.
complete hydrolysis
ii) R-CN + H2O ⎯⎯⎯⎯⎯⎯⎯⎯⎯→ R-COOH (acids)
H / Pt or LiAlH
2
iii) R-CN + 2H2 ⎯⎯⎯⎯⎯⎯⎯⎯→ 4 R CH2NH2 (Mendius reaction)
or Na/C H OH
2 5
The isocyanides on reduction give 20 amine.
Na/C H OH
iv) R-NC ⎯⎯⎯⎯⎯⎯⎯ 2 5 → R-NH-CH3 (2o amine)
Reduction

2) Elimination reaction:
Alkyl halides undergo β elimination reaction in presence of Alcoholic KOH to yield Alkenes.
CH3-CH2-CH2Br ⎯⎯⎯⎯
→ CH3-CH=CH2 + HBr.
alc.KOH

In case of unsymmetrical alkyl halides, elimination follows Saytzeff’s rule, according to which,
hydrogen is eliminated preferentially from the carbon atom which has less number of hydrogen atoms
and thus highly substituted alkene is the major product.

CH3 – CH – CH2 – CH3 ⎯⎯⎯⎯⎯⎯

alcoholic KOH
heat → CH3 – CH = CH – CH3 + CH3 – CH2 –
CH=CH2
|
Br 2-butene(80%) 1–butene(20%)
more substituted alkene less substituted alkene
The order of reactivity of alkyl halides towards dehydrohalogenation is 30 > 20 >10

3) Reduction:
CH3-CH2-Cl ⎯⎯⎯⎯⎯⎯ → CH3-CH3 + HCl
2 5 Zn-Cu in C H OH or
Zn/HCl or LiAlH 4

CH3CH2I +HI ⎯⎯⎯ → CH3-CH3+I2

Red P
150 0 C

4) With metals:
i) With Sodium (Wurtz reaction)
R-X + 2Na + X-R ⎯⎯⎯→ R-R + 2NaX
dry ether

ii) With magnesium:

R-X + 2Mg ⎯⎯⎯Ether
→ R-Mg-X
Alkyl magnesium halide (Grignard reagent)
iii) With Lithium:
R-X + 2Li ⎯⎯ → R-Li + LiBr
iv) Wurtz fitting reaction:
CH3-Cl +2Na + C2H5Cl ⎯⎯⎯→ C6H5CH3 + 2NaCl
dry ether

Toluene

Reaction Mechanisms:
1) SN1-mechanism –Substitution nucleophilic, first order.
This type of reactions proceeds in the following two steps:
CH3 CH3
1. Slow step +
H3C C X H3C C + X-
CH3 CH3
2. CH3 CH3
+ - fast
H3C C + Z H3C C Z
Nucleophile
CH3 CH3
The first step is slow and is rate determining.
Rate: K [(CH3)3C-X]
➢ The order of reactivity of alkylhalide depends on stability of carbocation formed in the first step
∴ 3  2 1
0 0 0
➢ It may be noted that in case of optically avtive alkylhalides SN1 reactions, results unto racemic
mixture.

2) SN2 [Substitution nucleophilic, second order]

This type of reaction occurs in one step.

CH3 H CH3 CH3

Z- X- Z C H
H C X Z C X
H H
H
Here nucleophile attacks from the opposiste side to that contianing the halogen atom, In this
process,the rate of reaction is directly proportional to the concentration of both nucleophile and the
substrate. R = K [CH3CH2X] [Z]
The orde of reactivity is 1  2  3
0 0 0

➢ It is noted that in case of optically active alkyl halides, SN2 reactions are accompained by
inversion of configuration.
➢
Optical rotation:
Substances which rotate the path of plane polarised light to either left or right are known as
optically active and the rotation is known as optical rottaion.
If the substance rotates the plane polarised light in clockwise direction (right ) it is called
dextroratatory or d-form
If the substrate rotates the plane polarised light in anticlockwise direction (left) , is called
laevorotatory or l-form.
The compounds which differ only in the behaviour towards polarised light are called optical
isomers and the phenomenon is called optical isomerism.
The conditions for the presence of optical isomerism, is.
1) The compounds must have a chiral or asymmetric carbon atom i.e. carbon atom should be linked to
four different groups.
2) Mirror image must be non-superimposable. Non-superimposable mirror images are said to be
enantioners.
Chiral carbon: The carbon attached to four different groups or atoms is called chiral carbon.
H H
H3C C X X C CH3
C2H5 C2H5

A B
mirror
‘A’ and ‘B’ are mirro images of each other or enantiomers. They rotate the plane of polarised
light upto the same extent but in opposite dierection.

Racemic mixture: It is an equimolar mixture of two enantiomers. The process is called racemisation.
Ex; When equal amounts of (+) lactic acid and (-) lactic acid are mixed together, we get (±) lactic acid.
The Racemic mixture is always optically inactive because rotation caused by one enantiomers is
exactly cancelled by an equal and opposite rotation caused by the other enantiomer.
Haloarenes or Arylhalides:
In these compounds the halogen is linked directly to the carbon of the benzene.

1) Namenclature:
Common name is aryl halide IUPAC name is haloarene.
Ex:
Cl Br

Chlorobenzene Bromobenzene

2) Methods of preparation:
1) By electrophilic substitution:

Note: 1) Iodo derivatives cannot be obtained by direct reaction with iodine as the reaction is
reversible. C6H6 +I2 ⇄ C6H5I + HI

Iodo derivative can be prepared by reaction which is carried out in presence of a oxidising
agent. The oxidising agent oxidises HI to iodine.
2HI + 2HNO3 ⎯⎯
→ 2NO2 + 2H2O + I2

(O)
+ I2 + H2O
HNO3

2) Aryl fluorides, cannot be prepared by direct fluorination because of the high affinity of
fluorine for hydrogen and the reaction is very violent

2) From diazinium salts:

NaNO2
C6H5NH2 C6H5N2+Cl-
HCl, 5 0C

CuCl CuBr KI H + BF4- Cu powder + HBr

1. C6H5Cl 2. C6H5Br 3. C6H5I 4. C6H5F 5. C6H5Br

1 and 2 → Sandmeyer’s reaction

4 → Balz-Sciemann reaction
5 → Gattermann reaction
Note: in Sandmeyer’s reaction, Cl of CuCl attached to benzene ring

4) From phenol:
C6H5-OH + PCl5 ⎯⎯
→ C6H5Cl + HCl + POCl3.

5) By Raschig reaction (manufacture of chlorobenzene)

2C6H6 + 2HCl + O2 ⎯⎯⎯
Cu Cl
→ 2C6H5Cl + 2H2O
2 2

Chemical properties:
Aryl halides are less reactive compared to alkyl halides as the halogen atom in these
compounds is firmly attached to benzene.
Reason for inertness or low reactivity:
i) Delocalisaiton of electron by resonance.
ii) Bond energies due to difference in hybridisation
iii) Polority of C-X bond.

1)Nucleophilic substitution:
NaOH (aq); 623 K, 300 atm
C6H5OH + NaCl

C6H5Cl
NH3, Cu2O; 475 K, 60 atm
C6H5NH2

2) Wurtz-Fittig reaction:
C6H5Br +2Na +CH3Br ⎯⎯⎯→ C6H5-CH3 + 2NaBr
dry ether

Toluene
3) Fittig reaction:
C6H5Cl +2Na + C6H5Br ⎯⎯⎯→ C6H5- C6H5
dry ether

Biphenyl

4) Electrophilic substitution:
Cl Cl
NO2

+ (Nitration reaction)

O 4
NO H 2S
3
NO2 1-chloro-2-notrobenzene
( Sulphonation reaction) H
c . 1-chloro-4-notrobenzene
Cl on
Cl Cl C Cl Cl
SO 3H
Cl
Conc. H2SO4 + Cl2
+
 +
Anhydrous FeCl3
SO 3H 2-chlorobenzene (Halogenation reaction) Cl 1, 2-dichlorobenzene
4-chlorobenzene sulphonic acid
sulphonic acid 1, 4-dichlorobenzene

Cl Cl CH3COCl CH3Cl Cl Cl
COCH3 Anhyd. AlCl3 Anhyd. AlCl3
CH3

+ +

COCH3 CH3 1-chloro-2-methyl

2-Chloroacetophenone
1-chloro-4-methyl benzene
4-Chloroacetophenone benzene
( Friedel-Crafts Acylation reaction) ( Friedel-Crafts alkylation reaction)

Important points:
Preparation of Haloalkanes from Groove’s process:
When Neopentyl alcohol reacts with Lucas Reagent, ir forms 2-chloro-3-methylbutane.
CH3 H+ CH3
+
H3C C CH2 OH H3C C CH2
-H2O
CH3 CH3

CH3 Cl
-
+ + Cl
H3C C CH2 H3C C CH2 CH3 H3C C CH2 CH3
CH3 CH3 CH3
HALOALKANES AND HALOARENES
Previous Year Questions

1. 1-Bromocyclohexane reacts with Mg in presence of ether gives A, which is on acid catalyzed

hydrolysis leads to B ? KCET-2015
OH MgBr OH

a) b) c) d)

2. The hydrolysis of optically active 2-bromobutane with aqueous NaOH result in the formation
of KCET-2015
a. (+) butan-2-ol b. (–)butan-2-ol c. (+/-) butan-1-ol d. (+/-) butan-2-ol

3. Identify the product, Z in the belowreaction

Ethanol ⎯PCl
⎯→ 5
X ⎯Alc.KOH
⎯⎯→ Y ⎯H⎯ ⎯⎯⎯⎯⎯→Z
2SO4 , room temp, H2O, Δ
KCET-2016
a. Ethane b. Diethylether c. CH3CH2OSO3H d. ethanol
4. Reactivity of order of halides for dehydrohalogenation is. KCET-2016
a. R–F>R–Cl>R–Br> R–I b. R–I>R–Br >R–Cl>R–F
c. R–I>R–Cl>R–Br>R–F d. R–F>R–l>R–Br>R–Cl

5. Toluene reacts with halogen in presence of Iron (III) chloride giving ortho and para halo
compounds. The reaction is KCET-2017
a. Electrophilic elimination reaction b. Free radical addition reaction
c. Electrophilic substitution reaction d. Nucleophilic substitution reaction

6. Identify the product ‘C’ in the below reaction

, KCET-2017
a. Acetone b. Acetaldehyde c. Methane d. Ethyl Alcohol

7.
8. Which of the following halide undergoes hydrolysis on warming with water/aqueous NaOH?
KCET-2019
Cl Cl Cl
Cl
NO 2 O 2N NO 2
a) b) c) d)

NO 2 NO 2 NO 2

9. The compound having longest C–Cl bond is. KCET-

2019
Cl
Cl
Cl

a) b) c) H2C CHCl d)

NO 2

10. The alkyl halides required to prepare 2-methylpentane by Wurtz reaction KCET-2019
Cl Cl
a) and b) and Cl

c) Cl and Cl d) Cl
and
Cl

11.

12. Identify ‘X’ in the following reaction: KCET-2020

Anhyd.AlCl3
+ 6Cl2 X + 6HCl
(excess)
dark, cold
Cl Cl Cl Cl
Cl Cl Cl Cl Cl
a) b) c) d)
Cl Cl Cl Cl
Cl Cl
13. The correct IUPAC name of KCET-2021
NO 2
F

a) 4-Ethyl-1-Fluoro-2-nitrobenzene
b) 1-Ethyl-4-Fluoro-3-nitrobenzene
c) 3-Ethyl-6-Fluoronitrobenzene
d) 5-Ethyl-2-Fluoronitrobenzene
14. The order of reactivity of the compounds C6H5CH2Br, C6H5CH(C6H5)Br, C6H5CH(CH3)Br and
C6H5C(CH3)(C6H5)Br in SN2 reaction. KCET-2021

CH3 H H H
a) H5C6 C Br < H5C6 C Br < H5C6 C Br < H5C6 C Br
C6H5 C6H5 CH3 H
H H H CH3
b) H5C6 C Br < H5C6 C Br < H5C6 C Br < H5C6 C Br
H CH3 C6 H5 C6H5

H H H CH3
c) H5C6 C Br < H5C6 C Br < H5C6 C Br < H5C6 C Br
CH3 H C6H5 C6H5

H H H CH3
d) H5C6 C Br < H5C6 C Br < H5C6 C Br < H5C6 C Br
C6H5 H CH3 C6H5

15. Which of the following Chlorohydrocarbon readily undergoes solvolysis? KCET-2022

CH2CH2Cl Cl
CH2Cl

a) b) c) H2C CHCl d)
16. In the following pairs of halogen compounds, which compound undergoes faster SN1 reaction?
KCET-2022
Cl Cl

i) and i) and Cl

Cl Cl Cl

a) and
Cl b) and Cl

Cl Cl

c) d) and
and
Cl
Cl

17. Identify the products A and B in the reactions: KCET-2022

R – X + AgCN → A + Ag X
R – X + KCN → B + K X
a) A = RNC; B = RCN b) A = RNC; B = RNC
c) A = R - CN; B = RCN d) A = RCN; B = RNC