03 NOC H BOND

HALOALKANES AND HALOARENES


NATURE OF
CARBON - HALOGEN BOND

NATURE OF C – X BOND
Halogen atoms are more electronegative than carbon, so carbon–
halogen bond of alkyl halide is polar.
+
C X–
There are some more relations,

we will have discussion on them
one by one.
 Bond strength  1
Bond Length
 Bond length  atomic size of halogen.
As we go from F to I , atomic size increases , bond length of C–X
bond increases from C–F to C–I. Hence, bond strength of C-X
bond decreases from C–F to C–I bond.
 Bond strength  Bond Polarity.
 Bond Polarity  Electronegativity difference between

C-atom and X –atom.
 Electronegativity difference  Electronegativity of X – atom.
As we go from F to I , EN value of the halogen decreases.
Hence, bond polarity and bond strength of C–X bond decreases
from C-F to C-I.
 As a consequence of the above two points, reactivity

order of alkyl halides is as follows:
R – Cl < R – Br < R – I
Some comparisons of bond length, bond

enthalpies and dipole moment of
different methyl halides are as follows:
Bond C – X bond Dipole

Bond length enthalpies moment
(pm) (kJ/mol) (Debye)
H3C – F 139 452 1.847

H3C – Cl 178 351 1.860
H3C – Br 193 293 1.830
H3 C – I 214 234 1.636
1) The nature of R-X bond in alkyl halide is _____

MCQS
a) non–polar
b) polar
c) both (a) and (b)
d) none of these
2) As we go from F to I, electronegativity value of halogen____
a) increases
b) decreases
c) remains same
d) all of these
3) As we go from F to I, atomic size_____
a) decreases
b) remains same
c) increases
d) none of these
4) Reactivity order of primary alkyl halides is----
a) R – Br < R – Cl < R – I
b) R – I < R – Cl < R – Br
c) R – Cl < R – I < R – Br
d) R – Cl < R – Br < R – I
METHODS AND PREPARATION

OF HALOALKANES
(PART –I)
Methods of preparation of Haloalkanes

Alcohols react with HX in presence of
1.From Alcohols: with HX anhydrous ZnCl2 to give alkyl halides by
Anhydrous dehydration.
R-OH + H-X R – X + H 2O
ZnCl2
Conc. HCl + Anhydrous ZnCl2 = Lucas reagent

R – OH + Lucas reagent = Groove’s process
(R – Cl is prepared)

From Alcohols: Important points:
Reactivity of hydrohalic acids
HI > HBr > HCl >HF

Reactivity order of alcohols with HX
30 > 2 0 > 10 > CH3OH


From Alcohols: with SOCl2
Reflux
R – OH + SOCl2 R – Cl + HCl + SO2
Pyridine
DARZEN’S
METHOD
Darzen’s method is the best method to prepare R-Cl because the

byproducts are removed in vapour state.
Methods of preparation of Haloalkanes From Alcohols
with NaBr & H2SO4
R – OH + NaBr + H2SO4 R – Br + NaHSO4 + H2O

MCQ
1) Which of the following reagent is used in the Groove’s process?
S
a) HCl
b) Conc. HCl + anhydrous ZnCl2
c) HCl +Zn
d) HCl+Fe
2) The gaseous products liberated in Darzen’s method are
a) HCl
b) HNO3
c) SO2
d) a and c
PREPARATIONS OF
ALKYL HALIDE
(PART-I)
Preparations of RX With PCl3, PCl5 and SOCl2


3R – OH + PCl3 3R – Cl + H3PO3
From alcohols
phosphorous with
acid
 reagents such as
H3 C – CH2 – OH + PCl3 HPCl
3C ,PCl
– CH2and
– ClSOCl
+ H23PO3
3 5
Ethanol Chloroethane


R – OH + PCl5 R – Cl+ HCl + POCl3
phosphoryl chloride

H3C–CH2–CH2–OH + PCl5 H3C–CH2–CH2–Cl + HCl + POCl3
Propan–1– ol
1- Chloropropane

Pyridine
H3C – CH2 – OH + SOCl2 H3C – CH2 – Cl + HCl + SO2
reflux

3H3 C – CH2 – OH + PCl3 3H3C – CH2 – Cl + H3PO3
Reactivity of alcohols
30 > 20 > 10
MCQS
1) Best method for preparation of alkyl chlorides is____
a) Alcohols when refluxed with PCl3.

b) Alcohols when treated with HCl and ZnCl2.
c) Alcohols when refluxed with thionyl chloride (SOCl2).
d) Alcohols when refluxed with PCl5.
2) In case of hydrohalogenation of alcohol, the order of reactivity is____

a) HI  HBr  HCl
b) HBr  HI  HCl
c) HI  HCl  HBr
d) HCl  HBr  HI
3) What is the product, when alcohol is treated with phosphorous

triiodide____
a) alkyl chloride
b) alkane
c) alkyl iodide
d) alkene
4) Tert–butyl alcohol when treated with concentrated HCl, gives _____
a) tert–butyl chloride
b) butane
c) 2–chloro–2–methylpropane
d) both (a) or (c)

PREPARATIONS OF
ALKYL HALIDE (PART-II)
Methods of preparation of Haloalkanes From Hydrocarbons

We will study three reactions for hydrocarbons
1) Halogenation of alkanes
2) Halogenation of alkenes
3) Halogenation of alkynes
Halogenation of alkanes
1) Chlorination (Free radical mechanism) (Substitution of H by
CI)
Diffused
Sunlight /
R H + Cl Cl R Cl + HCl
|
|
|
U.V. light
Alkane alkyl chloride
Chloroalkane
What is this
compound?
Ex:
Diffused
i) H3C – H + Cl Cl sunlight/ H3C – Cl + HCl
|
U.V. light
Methane methyl chloride
(Excess) Chloromethane
(Excess)
Cl2 Cl2 Cl2
Reactivity
H3C – Cl of
CHhalogen
2Cl2
– HCl methylene – HCl is Cl
CHCl
2
>
3 Br > I
– HCl
CCl4
2 carbon
2
chloroform
dichloride tetrachloride
In case of higher alkanes, monohalogenation gives a mixture of all
possible isomeric haloalkanes in which all types of hydrogen atoms
{10 ,20 and 30 } are substituted by halogen atoms.
H3C – CH2 – CH2 – Cl
Cl2 1 – Chloropropane
H3C – CH2 – CH3 (45% )
U.V.
Propane
light H3C – CH – CH3
Cl
2 – Chloropropane
What
What will be the
is this (55% )
product?
compound?
2) Bromination (Free radical substitution)
R – H +Br2 R – Br +HBr
3) Iodination (Reversible reaction)
R – H +I2 R – I+HI
To prevent reversibility, it is carried out with oxidizing agents like
HgO, HIO3 or HNO3 etc.
MCQS
1) The oxidizing agent added to prevent the reversibility
of iodination of alkanes is…
a) HgO
b) HNO3
c) HIO3
d) All these
2) Chlorination of methane gives…
a) CH3Cl
b) CH2Cl2
c) CCl4
d) All these
Thank
you…

03 NOC H BOND

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HALOALKANES AND HALOARENES

HALOALKANES AND HALOARENES

There are some more relations,

 Bond Polarity  Electronegativity difference between

 As a consequence of the above two points, reactivity

Some comparisons of bond length, bond

Bond C – X bond Dipole

H3C – F 139 452 1.847

1) The nature of R-X bond in alkyl halide is _____

2) As we go from F to I, electronegativity value of halogen____

3) As we go from F to I, atomic size_____

4) Reactivity order of primary alkyl halides is----

METHODS AND PREPARATION

Methods of preparation of Haloalkanes

Conc. HCl + Anhydrous ZnCl2 = Lucas reagent

Methods of preparation of Haloalkanes

Reactivity of hydrohalic acids

HI > HBr > HCl >HF

30 > 2 0 > 10 > CH3OH

Methods of preparation of Haloalkanes

Darzen’s method is the best method to prepare R-Cl because the

Methods of preparation of Haloalkanes From Alcohols

with NaBr & H2SO4

R – OH + NaBr + H2SO4 R – Br + NaHSO4 + H2O

b) Conc. HCl + anhydrous ZnCl2

2) The gaseous products liberated in Darzen’s method are

Preparations of RX With PCl3, PCl5 and SOCl2

Preparations of RX With PCl3, PCl5 and SOCl2

Preparations of RX With PCl3, PCl5 and SOCl2

a) Alcohols when refluxed with PCl3.

2) In case of hydrohalogenation of alcohol, the order of reactivity is____

3) What is the product, when alcohol is treated with phosphorous

4) Tert–butyl alcohol when treated with concentrated HCl, gives _____

d) both (a) or (c)

Methods of preparation of Haloalkanes From Hydrocarbons

2) Chlorination of methane gives…

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