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 HALOGEN DERIVATIVES
METHODS OF PREPARATION OF MONO HALOALKANE :
1. From alkanes :
h
CH4  Cl2   CH3Cl  HCl
Note : CH2Cl2, CHCl3 and CCl4 are also formed.
This method is not suitable, because the separation of mixture is difficult and the yield is not sufficient.
2. From alcohols :

(a) ZnCl
2R  X  H O
R  OH  HX  2

(b) ROH  KBr  H 2SO 4 

 RBr  H 2 O  KHSO 4

(c) 
ROH  KI  H3PO4 
 RI  KH 2PO4  H 2O

(d) R  OH  PX5  or PX 3  
R  X

(e) Pyridine
R  OH  SOCl2  R  Cl  SO 2   HCl 
Thionyl
Chloride

Pyridine
CH3CH 2OH  SOCl2  CH3CH 2Cl  SO2   HCl 
Note: Alkyl halide from SOCl2 is pure as SO2 and HCl escape in the gaseous form.

3. Finkelstein reaction (Halogen exchange) :

Acetone
R  Br  NaI  R  I  NaBr


Accetone
CH3  Br  NaI  CH3I  NaBr

Methyliodide

4. Swart’s reaction (Halogen exchange) :

2CH3  Cl  Hg2 F2  2CH3  F  HgCl2


Methyl chloride Methyl fluoride
5. R – Br can also be formed from alkenes :

Br
|
CH3CH  CH 2  HBr 
 CH3  CH  CH3
2  Bromopropane
 Markownikov 's Pr oduct 

Organic Peroxide
CH 3CH  CH 2  HBr 
 CH3CH 2CH 2 Br
 Antimarkownikov 's product 
[1]
6. Borodine - Hunsdiecker Reaction :
R  COOAg  Br2  R  Br  CO 2  AgBr
uv
Note :
(a) Product obtained from this reaction hasone carbon atom less than the fatty acid salt and the
yield of halide is 1° > 2° > 3°.
(b) Iodine forms ester instead of alkyl halide.

2RCOOAg  I2 
 RCOOR  2CO 2  2AgI
 Birnbaun  Simonini reaction 
Properties :
A. Physical
1. Boiling points of haloalkanes are in the order RCl < RBr < RI.
2. Alkyl halides are insoluble in water due to absence of H-bonding.
3. Density : Order of density R–I > R–Br>R–Cl
Alkyl halides are denser than water.
B. Chemical Properties :
1. Nucleophilic Substitution Reaction

gg
R  X  Nu   R  Nu  X 
Order of reactivity. R–I > R–Br > R–Cl > R–F
Aq.KOH or Aq NaOH
(a)  R  OH
R  X 
 Hydrolysis 
(b) Williamson’s ether synthesis

RO N a
R  X   R  O  R  (Ethers)
If alkyl (halide is 1° the major product is ether i.e. SN reaction)

CH3  CH 2 Br  NaOC2 H5   CH3  CH 2  O  C2 H5  NaBr

If alkyl halide is 3° or 2°. The major product is alkene.
 
Na SH
(c)  R  SH (Thio alcohols)
R  X 
NaCN
(d)  R  C  N  Alkyl cyanides   RNC
R  X 
Major Minor

 
(e) N a N3
 R  N 3  Azides 
R  X 


R  C  C N a
(f) R  X 
 R  C  C  R
 Non  terminal alkyne 

AgNO
O
3 R  O  N  O +
R  X  R–N
(g)  Minor  (Major)
Nitroalkane
O
Alkyl nitrite
 
Ag  C  N
(h)  R  N  C  Isocyanides   RCN
R  X 
Major Minor

R MgX
(i)  R  R   Hydrocarbon 
R  X 

Na / dry ether
(j)  R  R  Symmetrical alkane 
R  X 
 Wurtz reaction 
2. Elimination Reaction :
X
|
Base / 
R  CH 2  C H  R   R  CH  CH  R 
 elimination reaction 
Br
|
Alc.KOH / 
CH 3CH 2 CH  CH 3 
 CH 3CH  CHCH3
3. Oxidation :
DMSO
R  CH 2  X 
 R  CHO
Swern oxidation
4. Reduction:
LiAlH
4R  H
R  X 
5. Reaction with Metals :
Mg
R  X 
 RMgX
Grignard reagent

4R X Na  Pb 
 R 4 Pb
Sodium lead alloy  Tetra alkyl lead

2  R  X  Zn 
 R  Zn  R
Dialkyl zinc

R  X  2Li 
 R  Li  LiX
Alkyllithium

TRIHALOALKANES (HALOFORM) : CHX3 :

Preparation :
1. From α, α,α - Trihalocarbonyl Compounds :
O O
|| ||  
NaOH
R  C  CX3 
 R  C O N a  CHX3
O
||
 i  NaOH
 R  C  OH  CHX3
 ii  H 

O O
|| || (i) NaOH
R  C CX3 
 R  C  OH  CHX 3
(ii) H 

2. From primary and secondary alcohol having at least one β - CH group : (Haloform Reaction
 OH O O
| ||  || 

X 2 / OH X2 / O H O H/ H 
R  CH  CH3   R  C CH3   R  C CX3 
 Oxidation


R  COOH  CHX3
3. From carbon tetrachloride (large scale preparation)

2 Fe / H O
CCl4  CHCl3  HCl
Properties :
Physical : It is colourless sweet smelling liquid, insoluble inwater but soluble inorganic solvents, b.p. 61°C.
Chemical :
1. Hydrolysis :

O
X HOH/NaOH
OH
H–C—X H – C — OH -H2O
H – C — OH
X OH
O NaOH

O
–+
H – C — ONa
O H
+

O
H – C — OH

2. Nitration :

H  CCl3  Conc.HO  NO2 
 NO2  CCl3  HOH
Chloropricrin used as
(liquid insecticide and as
tear gas or war gas)
3. Reaction with Ketones :
O OH
|| |
OH 
CH 3  C  CH3  HCCl3  CH3  C  CCl3
Acetone Chloroform |
CH3
Chloretone
 hypnotic 

4. α - Elimination reaction

Alc.KOH / 
CHCl3 
 : CCl2  C l  HOH
Dichlorocarbene
 Triplet 
 3 CHCl / alc.KOH /  R – CH – CH – R
(i) R  CH  CH  R 

:CCl2 C

Cl Cl
1,1-Dichloro-2,3-dialkyl cyclopropane

3 CHCl / Alc.KOH / 
(ii) R  NH2  R  N  C  3KCl  3H 2O
 Alkyl isocyanide
:CCl2
 Carbylamine reaction 
(iii) Reimer-Tiemann Reaction
OH OH OH
CHO
(i) CHCl3/alc. KOH/
+
(Major)
CHO
(Minor)
5. Oxidation :
Cl O
O2, hv
CHCl3 H – O – C – Cl Cl – C – Cl + HCl
Phosgene
Cl
Note : To keep chloroform pure, to be used as an anaesthetic and base in cough syrup.
(i) It is stored in brown bottles to cut off light.
(ii) The bottles are filled to the brin to exclude any air (i.e. O2)
(iii) 0.6 to 1% ethyl alcohol is added which acts as negative catalyst for oxidation of chloroform. It converts
harmful phosgene (if formed) to harmless diethylcarbonate
Cl H – O – C2H5 OC2H5
O=C + O=C + 2HCl
Cl H – O – C2H5 OC2H5
Note : Oxidation of chloroform is tested by the formation of HCl which is the by product of oxidation. AgNO3
when added the oxidised chloroform gives white precipitate with HCl.
6. Coupling Reaction
Ag.Powder
2 CHCl3  CH  CH  6AgCl

7. Reaction with benzene

Anly.AlCl3/
CHCl3 + CH
Friedal craft
reaction
(excess) Triphenylmethane

Uses of Chloroform :
(a) As organic solvent (b) As preservation for anatomical specimens
(c) In the preparation of chloretone and chloropicrin (d) In medicines as base

TETRAHALOALKANES (CARBON TETRACHLORIDE)

Preparation :
2Cl / hv Cl / anly.AlCl
1. CH 4  CCl4  4HCl 2 3  CCl  S
2. CS2 
Small  4

3. 2 Cl / hv
CHCl3  CCl4  HCl
Properties :
 OH 
 | 
Aq.NaOH
CCl4    HO  C  OH  
 CO 2  2H 2O
 Hydrolysis  |
 
 OH 
Uses :
1. Acts as fire extinguisher under the name pyrene. Now a days its use is banned because it forms
COCl2 with steam. It is used as antihelmentic (antihevle worm) agent.
2. It is used for the preparation of iron (Refrigerant)

ARYLHALIDES
Preparation :
1. From Benzene diazonium Chloride
X

CuX/HX
X = Cl, Br,
(Sandmeyer reaction)
CN

CuCN + HCN

+ –
N NCl I
KI/

HF / BF3/
(Balz Schiemann reaction)

X
Cu/HX
X = Cl, Br,
(Gatterman reaction)

2. From Benzene :
X
FeX3/
+ X2 (Cl2 or Br2) or
I2/
Properties :
1. Nuclear chain reaction (Electrophilic Substitution) [Halogens are o-p-directors and weakely
deactivators]

(a) Cl Cl Cl
Cl
Cl2/FeCl3
+ (Halogenation)

Cl
Cl Cl
NO2
HNO3/H2SO4
+ (Nitration)

NO2

Cl Cl Cl
SO3H
Fuming H 2SO 4
+ (Sulphonation)

SO3H

Cl Cl
R—X
R
Anhy.AlCl3/ + (Fredal-craft's alkylatron)

O
Cl Cl
R – C – Cl
COR
Anhy.AlCl3/ + (Fredal-craft's acylation)

COR

2. Nucleophilic Substitution Reaction :

Presence of –M showing groups at ortho and para make Nucleophilic substitution easier.

Cl OH
NO2 NO2 O2 N NO2
ag.NaOH
25°C

NO2 NO2
 3. Reduction

Cl

(i) Ni-Al alloy/NaOH/

(ii) Mg/dry ether followed by hydrolysis

4. Coupling Reaction :

Na/dry ether
(i) R – X + C6H5 – X + NaX
Alkyl halide
(Wurtz-Fittig reaction)

Cl Cl

Na/dry ether
(ii) + (Fitting reaction) + NaX
Biphenyl

Cu/200°C
I + I
(iii)
(Ullmann reaction) Biphenyl

5. Reaction with Chloral :

H Cl Cl
Conc.H 2SO4/
CCl3CH O + CCl3 – CH
Chloral H Cl Cl
DDT

2,2-B is (4, chlorophenyl)

1,11-trichloroethane

Uses :
Chlorobenzene is used for the preparation of
(a) Phenol
(b) Nitrochlorbenzene required for the manufacture of azo and sulphur dyes, fungicides,
preservatives, and
(c) DDT
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