Alkyl Halides

JEEMAIN.
GURU
Vidyamandir Classes Organic Halides
Halogen containing Organic Compounds
ALKYL HALIDES : [RX] Section - 1
In ‘Hydrocarbons’ last chapter, you have observed that hydrocarbons react with halogens to form Organic
Halides. These compounds are called halogen derivatives of hydrocarbons. Here, the halogen atom (X)
acts as a functional group and is attached to the carbon atom by a covalent bond. These organic halides are
of two types: Alkyl Halides (aliphatic) and Aryl Halides (aromatic).
The alkyl halides are classified into three categories based on type of carbon atom to which the halogen
atom is attached.
Primary (1°) Halide : RCH2X Secondary (2°) Halides : R2CHX Tertiary (3) Halide : R3CX
(R : alkyl radical, X : F, Cl, Br, I)
The Organic Halides are further classified as monohalides, dihalides and trihalides depending upon number
of halogen atoms.
Tri-haloderivative of CH 4 are known as HALOFORM. Fully halogenated hydrocarbons are also called
perhalohydrocarbons. (C n X 2 n+2 ). For Example : Perfluorethane C2 F6
Preparation of Alkyl Halides :

1. Halogenation :
(a) From Alkanes : Halogenation of alkanes is carried out in the presence of heat or light. Chlorination is
fast, bromination is slow while direct iodination is not possible as the reaction is reversible.
Direct halogenation does not form pure mono-halogen derivatives since a mixture of polyhalogen
derivatives is always obtained. For example, in chlorination of Methane we get a mixture of products.
2 Cl
CH 4  CH3Cl  CH 2 Cl2  CHCl3  CCl4
Methane h or 520  670 K Chloromethane Dichloromethane Trichloromethane Tetrachloromethane
In case of higher alkanes, even mono-halogenation gives a mixture of all the possible isomeric
haloalkanes.
2 Cl , h
CH 3CH 2 CH3  CH3  CH 2  CH 2  Cl  CH 3  CH(Cl)  CH 3
Propane 298K 1-Chloropropane(40%) 2-Chloropropane(55%)
2 Cl , h
CH3 CH 2 CH 2 CH3  CH3CH 2 CH 2 CH 2 Cl  CH3CH 2  CH(Cl)  CH 3
298K 1-Chlorobutane(28%) 2-Chlorobutane(72%)
In general, the ease of substitution of various hydrogens follows the sequence :

Allylic > 3° > 2° > 1° > CH4.
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Organic Halides Vidyamandir Classes
Iodination is reversible, but it may be carried out in the presence of an oxidising agent, such as, HIO3,
HNO3, HgO, etc., which oxidises the HI as it is formed.
hv

CH4 + I2  
 CH3I + HI ; 5HI + HIO3 
 3I2 + 3H2O
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, Hg2F2, CoF3 or SbF3 to give alkyl fluorides.
CH 3 Br  AgF 
 CH 3 F  AgBr
Bromomethane Fluoromethane
2CH3CH 2  Cl  Hg 2 F2 
 2 CH3CH 2  F  Hg 2 Cl2
Chloroethane Fluoroethane
This reaction is called Swarts reaction.

When the organic halide contains two or three halogen atoms at the same carbon, CoF3 or the more easily
available SbF3 is used. For example,
3CH3  CCl2  CH3  2SbF3 

 3CH3  CF2  CH 3  2SbCl3
2,2 - Dichloropropane 2,2 - Difluoropropane
(b) From Alkenes : Alkenes react with halogen acids to form haloalkanes.
The order of reactivity is : HI > HBr > HCl > HF.
RCH  CH 2  HX   R C H  CH3
|
X
The unsymmetrical alkenes follows Markovnikov’s rule during addition forming secondary or tertiary
alkyl halides predominantly.
Note : In presence of peroxides, the addition of HBr only (not HCl or HI) to unsymmetrical alkenes takes place via
Anti Markovnikov’s rule forming primary alkyl bromides. This is known as Peroxide effect or Kharasch
effect.
(c) Allylic halogenation : When alkenes (except Ethylene) are heated with Cl2 or Br2 at a high temperature of
about 773 K, the hydrogen atom at the allylic carbon (i.e., carbon next to the double bond) is substituted
by a halogen atom. For example,
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773K
CH 3  CH  CH 2  Cl2  Cl  CH 2  CH  CH 2
3-Chloroprop-1-ene (Allyl chloride)
However, a more specific reagent for allylic bromination is Nbromosuccinimide (NBS).
Allylic chlorination can also be carried out with sulphuryl chloride.

475, h
CH 3  CH  CH 2  SO2 Cl2 
 Cl  CH 2  CH  CH 2  HCl  SO 2
Traces of peroxide
2. From Alcohols : Generally alkyl halides are prepared from alcohols by replacement of OH group by an
halogen ion. This is usually by using HX or PCl5 .
R – OH + X– 
 R – X + OH
–
(a) By the action of Halogen acids :

Catalyst
R – OH + HX  R – X + H2O
Note :(i) The order of reactivity for halogen acids is : HI > HBr > HCl and for alcohol is : 3 alcohol > 2 alcohol
> 1 alcohol.
(ii) The catalyst used is generally a dehydrating agent such as ZnCl2 or conc. H2SO4.
(i) Using HCl :

anhyd.
CH3CH2OH + HCl(g) 
ZnCl
 CH3CH2Cl + H2O
2
anhyd.
CH3  C H  CH 3  HCl  g   CH3  C H  CH3  H 2 O
ZnCl2
| |
OH Cl
Anhydrous ZnCl2 helps in the cleavage of C – O bond. Being a Lewis acid, it co-ordinates with the
oxygen atom of the alcohol. As a result, C – O bond weakens and ultimately breaks to form carbocations
(C+), which form chlorides.
Room
 CH3 3  C  OH  HCl 
temp
  CH3 3  C  Cl  H 2 O
 conc.
The yield can be improved when the vapours of alcohol and HCl are passed over alumina at 350C.

JEEMAIN.GURU
(ii) Using HBr :

Alkyl bromides are obtained by refluxing the alcohol with constant boiling in HBr (40%) in presence
of a little conc. H2SO4.
H 2SO4
CH3CH2 – OH + HBr 
Reflux
 CH3CH2 – Br + H2O
C2H5OH + KBr + H2SO4 

 C2H5Br + KHSO4 + H2O
Note : The mixture of KBr and H2SO4 is not used in case of secondary and tertiary alcohols as their dehydration
may occur, to give alkenes.
(iii) Using HI :
Re flux
CH3 – CH2 – OH + HI   CH3CH – I + H2O

CH3OH + KI + H3PO4   CH3I + KH2PO4 + H2O
(b) By the action of Phosphorus Halides :

Phosphorus halides react with alcohols to form haloalkanes in excellent yield (80% or above).
ROH + PX5 
 R – X + POX3 + HX
Here X can be either chlorine or bromine or iodine.

3ROH + PCl3 
 3R – Cl + H3PO3
Since PBr3 and PI3 are not very stable compounds, these are generally prepared in situ by the action
of red phosphorus on bromine and iodine respectively.
P  Br
2  R  Br 2 PI
P4  6X 2 
 4 PX 3 ; R  OH  ; R  OH  R I
This method gives good yield of primary alkyl halides but poor yields of secondary and tertiary
alkyl halides.
The method is useful for preparing lower alkyl bromides and iodides in the laboratory.
(c) By the action of Thionyl chloride : (Darzen’s method)

Chloroalkanes are conveniently prepared by refluxing alcohol with thionyl chloride (SOCl2) in
presence of pyridine (C5H5N).
Pyridine
R  OH  SOCl2 
 R  Cl  SO 2   HCl 
Reflux
Thionyl chloride method is preferred over hydrogen chloride or phosphorus chloride method for the
preparation of chloroalkanes since both the by-products (SO2 and HCl) in this reaction being gases
escape, leaving behind chloroalkanes in almost pure state.

JEEMAIN.GURU
Note : Bromides and iodides are not prepared by this method, because thionyl bromide is unstable and thionyl
iodide does not exist.
3. From Silver salt of fatty acids :

4 CCl , Reflux
CH3CH2COOAg + Br2  CH3CH2 – Br + CO2 + AgBr

This reaction is called as Borodine Hundsdiecker reaction and is a free radical reaction. This reaction
gives the product with one carbon atom less than the fatty acid. The yield of the alkyl halide formation with
this reactions is :
primary > secondary > tertiary.
Chloroalkanes can also be prepared by this method by using Cl2 instead of Br2 but the yields are poor.
With I2, silver salts give esters instead of iodoalkanes.
2RCO2Ag + I2 
 RCOOR + CO2 + 2AgI
Note : This method is very popular in the formation of aromatic bromides as they yield is very high.
4. Halogen exchange reaction :

Iodoalkanes can be easily prepared from the corresponding chloroalkanes or bromoalkanes by heating
with sodium iodide in acetone or methanal.
Acetone
RCl + NaI  RI + NaCl X = Cl or Br

This reaction is called Frinkelstein Reaction.

Its a halide exchange reaction which involves a substitution of Cl/Br by I. The reaction was specially de
signed to prepare iodo-alkanes which were not easily prepared using simple halogenation method. (Due to
the reversibility of Iodination)
Acetone X = Cl or Br
R  X+ NaI  R  I+ NaX 
Reaction is believed to be based on the principle of greater solubility of NaI in acetone as compared to
NaCl or NaBr because of greater covalent character in NaI. That is why despite of being a weaker reagent
than Cl / Br  , I  still substitues them and the NaCl/NaBr formed precipitates out driving the equilibrium in
forward direction.
Note : Fluoro alkanes are difficult to prepare as all the hydrogen atoms are replaced by fluorine. The monofluoro
alkanes are prepared by heating alkyl halides with KF in diethyl glycol.
KF
RX  RF  KX
(CH 2 OH) 2

JEEMAIN.GURU
Physical Properties :
1. Physical state, colour, odour, etc : Alkyl halides are colourless when pure, but bromides and particularly
iodides develop colour when exposed to light. Methyl chloride, Methyl bromide, Ethyl chloride and some
Chlorofluoromethanes and Chlorofuloroethanes are gases at ambient temperatures. Other chloro, bromo,
iodo compounds are either liquids or solids. Many volatile halogen compounds have sweet smell.
2. Melting points and boiling points : The melting points and boiling points of haloalkanes are several
degrees higher than those of parent alkanes mainly due to greater magnitude of van der Waals forces of
attraction.
For the same alkyl group, the boiling points of haloalkanes decrease in the order : RI > RBr > RCl > RF. This
is because with the increase in the size and mass of the halogen, the magnitude of the van der Waal’s forces of
attraction increases.
For isomeric alkyl halides, the boiling points decrease with branching, because with branching the surface area
of the alkyl halide decreases and hence the magnitude of the van der Waal’s forces of attraction decreases.
The boiling points of chloro, bromo and iodo compounds increase as the number of halogen atoms increases.
3. Solubility : Even though haloalkanes (dipole moment, 2.05 – 2.15 D) are polar molecules still they are
insoluble in water. This is due to the reason that haloalkanes can neither form hydrogen bonds with water nor
can they break the hydrogen bonds already existing between water molecules. However, they are quite
soluble in organic solvents of low polarity such as petroleum ether, benzene, ether chloroform, carbon tetra-
chloride etc.
4. Density : Alkyl fluorides and chlorides are generally lighter than water whereas alkyl bromides and iodides
are heavier. Their relative densities follow the order : RI > RBr > RCl.
5. Stability : Since the strength of the C – X bond decreases in the order : C – F > C – Cl > C – Br > C  I,
therefore stability of the haloalkanes having same alkyl group is in the order :
R – F > R – Cl > R – Br > R  I.
That is why alkyl iodides, on standing become violet or brown because of their decomposition in presence of
light to give iodine.
Light
2R – I  R – R + I2
6. Dipole moment : CH3  Cl > CH3  F > CH3  Br > CH3  I
Reactions of Alkyl halides :

The alkyl halides are highly reactive compounds due to the polarity of C – X. The order of reactivity is :
With respect to halogen atom : RI > RBr >R Cl ; With respect to alkyl groups : 3° > 2° > 1°

JEEMAIN.GURU
1. Nucleophillic Substitution Reactions :

 
In alkyl halides, C  X bond is highly polar, so nucleophile (Nu–) attacks electrophillic carbon atom easily..
Hence alkyl halides give Nucleophillic Substitution Reactions readily. The halogen atom is replaced by a wide
range of nucleophiles to give almost all important organic families.
RX  Nu  
 R  Nu  X
Nucleophile Leaving group
Note : Nucleophile is a species which is seeking to attack electrophilic region i.e., carbon with a +ve charge or
  charge. It is able to share its rich electron cloud with electrophilic species. Some important electron
rich nucleophiles are OH  , CN  , RO  , RCOO  and RS ions.
The mechanism of nucleophile substitution reaction will be discussed in next chapter ‘Organic
Conepts’.
(i) Substitution by aq. KOH :
H O
2  RCH RCH OH + KX
RCH2X + KOH  2 2

(ii) Substitution by moist Silver oxide (AgOH) :
2  AgOH H O
Ag2O 
RCH2X + AgOH 
 RCH2OH + AgX
(iii) Substitution by Sodium alkoxides (RONa) :

Na
RCH2OH  RCH2O–Na+
RCH2O– acts as strong nucleophile and attacks on alkyl halides to produce ethers..
– 
CH3Br + RCH2O Na+ 
 CH3 – O – CH2R + NaBr
The above reaction is called as Williamson’s synthesis of ethers.
Note : (i) 2° and 3° alkyl halides, however prefer to give alkenes as elimination products.
(ii) The ethers are also prepared by use of Ag2O.

2RI  Ag 2 O 
 ROR  2AgI
(dry)
(iv) Substitution by Hydro sulphide group : (Formation of Thioalcohols).

2 5 2 C H OH / H O
RX  NaSH  R  SH  NaX
 Thioalcohol

JEEMAIN.GURU
(v) Substitution by Mercaptide group : (Formation of Thioethers).

(a) By heating an alkyl halide with Sodium or Potassium mercaptide : (Na–S–R)
2 5 C H OH / H O
2 R  S  R   Na  X 
RX  NaSR  
 Thioether
(b) By heating an alkyl halide with Sodium or Potassium sulphide :
2 R  X+ Na 2S 
 R  S R + 2 NaX
Thioether
(vi) Substitution by Amino group : (Formation of Amines)

Haloalkanes when heated with an ethanolic solution of ammonia in a sealed tube at 373 K, form a
mixture of 1, 2 and 3 amines along with quaternary ammonium salts.
2 5 C H OH
RX+ NH 3  RNH 2 + HX
 1° Amine
Note : If alkyl halide is in excess, then 2 and 3 amines and even quaternary salts are also formed.
NH RX RX RX

RX  3  RNH 
2  R 2 NH 
 R 3 N 
 R 4 N X
alcohol
1°Amine 2°Amine 3°Amine (Quaternay salt)
This reaction is called Hoffmann ammonolysis of alkyl halides.
(vii) Substitution by Cyanides :
2 5 C H OH / H O
2  R CN  KX
(a) RX  KCN 

(KCN is an ionic compound giving – CN as nucleophile)
Note : In this reaction, if alkyl halide, RX is tertiary (3), instead of substitution, elimination occurs to give an alkene.
(CN– acting as a base against 3° halides).
H O
2  RCOOH  NH 
Note : R  C   4
H
2 5 C H OH / H O
2  RNC
(b) RX  AgCN   AgX

Isocyanides

(AgCN is covalent compound giving  N  C , an amident nucleophile)

JEEMAIN.GURU
(viii) Substitution by salts of Carboxylic acids :

O
||
Ethanol
RCH 2 Br  R COOAg  RCH 2 O  C  R   AgBr
 Esters
(ix) Substitution by Acetylides : (Formation of higher alkynes)
RX  R   C  C  Na 
 R C  C  R  NaX
Sodium Alkynide Higher alkynes
Note : In this reaction also, if alkyl halide, RX is tertiary (3), instead of substitution, elimination occurs to give an
alkene.
Sodium alkynides are themselves prepared by the action of sodamide (or Na in liq. NH3 at 196 K) on
terminal alkynes.
Liq. NH  
R  C  CH  NaNH 2  3 R  C  C  N a  NH3
196 K
(x) Substitution by AgNO2 and KNO2 :

 C H OH /H O
RX  K   O  N  O 
2 5 2  R  O  N  O  KX

 Alkyl nitrite
O
C2 H5 OH /H 2 O
||
RX  Ag  O  N  O   R  N  O  AgX

Nitroalkane
–
(xi) Substitution by N3 (Azide ion) :
RX+ N 3 
 RN3 + X
Alkyl azides
2. Elimination reaction with alc. KOH/NaOH : (Dehydrohalogenation)

alc.
RCH 2CH 2 X 
 RCH = CH 2 + KX+ H 2O
KOH,  Alkenes
If the structure of the alkyl halide is such that it can undergo elimination in two different ways, due to availability
of different types of -hydrogen, then the more highly substituted alkene is the major product of
dehydrohalogenation. This is known as Saytzeff ’s rule.
  
alc.
R C H 2  C H 2  C H 3  RCH  CHCH3  RCH 2 CH  CH 2  KX  H 2 O
| KOH Major Minor
X

JEEMAIN.GURU
The reaction is also referred to as -elimination (1, 2-elimination), as -H is lost.

In general the ease of dehydrohalogenation for a given alkyl group decreases in the order : 3 > 2 > 1 and
for a given halogen, the order decreases as : R – I > R – Br > R – Cl.
Note : The above elimination is also achieved using alkoxide ( RO  / ROH ), as discussed in “Organic Concepts”.
3. Action of Heat :
Alkyl halides when heated above 300C, tend to lose a molecule of hydrogen halide forming alkenes.
300C
RCH2CH2X   RCH = CH + HX
2
The decomposition follows the order :

With respect to alkyl group : 3 > 2 > 1 and With respect to halogens : R – I > R – Br > R – Cl
4. Wurtz Reaction :
dry
2 RI + 2 Na 
 R  R+ 2 NaI
ether
Reaction usually gives
mixture of products.
This is referred to as “intramolecular wurtz reaction”.
5. Formation of Grignard Reagent :
ether
RX  Mg 
 R  Mg  X
Alkyl magnesium halides
The alkyl magnesium halides are known as Grignard Reagent. The chemistry Grignard Reagent is dis-
cussed is section 5.
6. Reaction with other active metals :
Dry
CH3 CH 2 Br  2 Li   CH 3CH 2 Li  LiBr
ether
Ethyl bromide Ethyllithium
Alkyl lithiums are similar in properties with Grignard reagents. These are highly reactive reagents.
Dry
4CH3CH 2 Br  4 Pb / Na 

ether
 CH3CH 2 4 Pb  4 NaBr  3Pb
Ethyl bromide Sod. lead alloy Tetraethyllead  TEL 

JEEMAIN.GURU
Tetraethyl lead (TEL) is used as an anti-knocking agent in gasoline used for running automobiles.
2 C 2 H5 Br  Na  Hg 
  C2 H5 2 Hg  NaBr
Sodium amalgam Diethylmercury
Ether
2C 2 H5 Br  2 Zn   C2 H5  2 Zn  ZnBr2

Dialkyl zinc compounds are called Frankland reagents.
7. Reduction : (Formation of alkanes).

(i) Hydrogen in the presence of a metal catalyst such as Ni or Pd or Pt :
Ni
RX  H 2  RH  HX

(ii) Hydro-iodic acid in the presence of red phosphorus :
Re d P
CH 3CH 2  I  HI  CH3  CH3  I2
420 K
(iii) Nascent hydrogen produced by the action of zinc or tin or hydrochloric acid or by the action of zinc-
copper couple on alcohol.
Zn  HCl
CH 3CH 2 Cl  CH3  CH3  HCl
or Zn  Cu  alcohol
(iv) Substitution by hydride ion : H  from LIAlH 4 as a Nucleophile.
dry ether
LiAlH 4  4 RX  4R  H  AlX3  LiX
(R  3 alkyl group as 3 RX prefer elimination)
Tertiary alkyl halides, however, undergo dehydrohalogenation to give alkenes. On the other hand sodium
borohydride (NaBH4) reduces secondary and tertiary alkyl halides but not primary whereas tri-phenyl tin
hydride (Ph3SnH) reduces all the three types of alkyl halides.
8. Isomerisation : When a haloalkane is heated to 573 K or at a lower temperature in presence of anhy

drous AlCl3 (Lewis acid) it undergoes isomerisation.
Cl
|
573K
CH 3  CH 2  CH 2  Cl 
 CH3  C H  CH3
Anhyd. AlCl3

JEEMAIN.GURU
Illustration - 1 Identify the compounds A, B, . . . . . . . in the following reaction setup.
NBS HBr / Peroxide Na / ether

C3 H 6 
 A 
 B  C
1. H O
+
KCN 3
A  D 
E
2. [ O ]
SOLUTION :
NBS
C3H 6  A (Visualize allylic substitution in alkenes)
CCl 4
Hence C3H6 is an alkene (Note that C3H6 also represents cyclopropane).
Note : Heating effect on Di-carboxylic acids and   Keto acid,
Oxalic Acid : 
(COOH) 2 
 H2O+ CO+ CO2

Malonic Acid : CH 2 (COOH)2   CO2 + CH3COOH
Succinic Acid :
  Keto acid:

JEEMAIN.GURU
Illustration - 2 Identify (A) to (G) in the following series of reactions. Also identify the major product
among F and G.
SOLUTION :
Note : (i) Diene (i.e., elimination product) will be major here, since conjugated diene is highly stable.
(ii) Usually cycloalky bromide (2) prefer elimination over substitution will RO .
(iii) OH  (aq) acts as a nucleophile whereas OH  (alcoholic) acts as a base.
Illustration - 3 Identify P, Q, R, .... in the following reaction set up.
SOLUTION :

JEEMAIN.GURU
IN-CHAPTER EXERCISE - A
1. Identify A, B, C, . . . . .
1. HBr / Peroxide 1. A
(a) C2 H 4 
 C2 H5 I (b) C6 H 5CH 2 Br  C6 H 5CH 2COOH
2. A 2. B
2. Identify (A), (B), (C), . . . . . in each of the following.

PBr
3  A  B  Alc.KOH HBr AgCN
(a) CH 3CH 2CH 2OH        C    D 
+
Alc .KOH H /H O
2   B   SOCl
2   C    D  H
(b)  CH 3 2 CHCl   A  
LiAlH 4
NBS Alc .KOH HBr

(c) CH 3CH 2CH = CH 2   A    B  
 C 
CCl4
CH OH
3  A  2 Br EtONa
(d) CH 3  CH 2 3 MgBr      B  
 C  +  D 
127C EtOH / NaOH
NOW ATTEMPT IN-CHAPTER EXERCISE-A REMAINING QUESTIONS IN THIS EBOOK

JEEMAIN.GURU
ARYL HALIDES : [Ar - X ; Ar - Aryl group) Section - 2

The halogen derivatives in which the halogen atom is directly attached to the carbon atom of benzene ring
are known as aryl halides. Chloro, Bromo and Iodo benzenes, Chlorotoluenes, Chlorophenols are some of
important aryl halides.
Preparation of Aryl halides :
1. Direct halogenation :
Note : (i) Here FeCl3 is acting as a halogen carrier.

(ii) Iodides are not formed this way, as HI is strong reducing agent. By using ICl, one can get iodo
benzene.
C6H6 + ICl   C6H5  I + HCl
2. From Benzene Diazonium Chloride :
The formation of benzene diazonium chloride is known as Diazotisation.

(a) Sandemeyer Reaction :
Note that Iodides are not formed in the given manner.
(b) For iodides :
Note that it is not Sandemeyer reaction.

JEEMAIN.GURU
(c) For fluorides :
Note : Haloarenes particularly chloro and bromo arenes can also be prepared by Gattermann reaction. It is a
modification of the Sandmeyer reaction. In this reaction, a mixture of freshly prepared copper powder in
the presence of corresponding halogen acid (HCl or HBr) is used instead of cuprous halide as used in
Sandmeyer reaction. The yield of this reaction is around 40%.
3. From Silver salt of carboxylic acids : (For bromides only).

CCl
4  C H  Br  CO  AgBr
C6 H5 COOAg  Br2  6 5 2
70 C
The above reaction is known as “Hundsdicker Reaction”. By this method mainly aromatic bromides are
formed as the yield in case of aliphatic bromides is poor.
4 CCl
RCOOAg + Br2 

RBr + CO2 + AgBr
70 C
4. Commercial preparation of chlorobenzene :

CuCl
2  2 C H Cl  2 H O
2 C6 H 6  2 HCl  O2  6 5 2

Physical Properties : Physical properties of aryl halide is similar to alkyl halide.

The boiling points of isomeric dihalobenzenes are very nearly the same but the melting points of the para
isomers are higher than the ortho and meta isomers. Being more symmetrical, the para isomer fits better in
the crystal lattice of the soid form than the ortho or meta isomers.
Boiling point o > p > m Melting point p > o > m
Reactions of Aryl Halides :

Aryl halides are relatively un-reactive towards nucleophillic substitution under conditions which are used for
alkyl halides since the lone pair of electrons over halogen atom is involved in resonance with benzene ring.

JEEMAIN.GURU
As a result of resonance, -C of ring loses its electrophillic character, so Nu fails to attack -C in aryl
halides. C - Cl bond acquires a partial double bond character (C - Cl), which is difficulat to break by Nu  .
For example, Chlorobenzene does not react with aq. NaOH. It does not give a precipitate of AgCl with
alcoholic AgNO3.
However, Aryl halides show nucleophilic substitution reaction under drastic conditions of high temperature
and pressure along with use of copper salts.
1. Nucleophillic substitution reactions :

350 , 200 atm
C6 H5  Cl  NaOH 
 C6 H5  OH  NaCl
Cu salt
This reaction is referred to as Dow’s process for the manufacture of phenol.

200 C, 50 atm
C6 H5  Cl  2 NH3 
 C6 H5  NH 2  NH 4 Cl
Cu salt
This reaction is known as Dow’s reaction.
250 C
C6 H5  Cl  CuCN 
 C6 H5  CN
pyridine
Note : (i) The presence of a deactivating group (strong electron withdrawing group) such as nitro, cyano in ‘o’ or ‘p’
position makes nucleophillic substitution possible. This results in an increase in electrophillic character of -
Carbon atom (which otherwise to lost due to resonance).
(ii) With strong bases like NaNH2 or KNH2, aryl halides reacts easily to form aniline.

JEEMAIN.GURU
(iii) Chlorobenzene reacts with methyl cyanide in presence of NaNH2 at room temperature to
give benzyl cyanide.
2 NaNH
C6H5Cl + CH3CN  C6H5CH2CN + HCl
base
2. (a) Wurtz - Fittig reaction :

ether
C6H5 – Br + 2Na + CH3Br   C6H5 – CH3 + 2NaBr
heat
Toluene
(b) Fittig reaction :
3. Ullmann reaction :
4. Reduction :
5. Reaction with Metals :

ether
C6 H5  I  Mg 
 C6 H 5  MgI (Grignard Reagent)
ether
C6 H5  I  2 Li 
 C6 H5 Li  LiI (Aryl Lithium)

JEEMAIN.GURU
6. Formation of DDT :
Two moles of Chlorobenzene reacts with chloral in H2SO4 to give 1,1,1-Trichloro-2,2-(p-chlorophenyl)
ethane, an insecticide commonly known as DDT.
7. Electrophillic substitution reaction (involving benzene ring) :

Halogen are weakly deactivating group because of their strong electron withdrawing tendency, but due to
+M effect, they are weakly ‘o’ and ‘p’ directing.

JEEMAIN.GURU
Illustration - 4 How will you convert.

(a) Bromobenzene to styrene (in 4 steps) (b) Bromobenzene to Benzyl alcohol (in 3 steps)
SOLUTION :
Illustration - 5 Anisole can be prepared by either of following methods. Which of the two methods is the
correct ?
Method : I Method : II
SOLUTION :
Aryl halides do not give nucleophilic substitution reaction under normal conditions (whereas alkyl halides give
this reaction). It is due to resonance in these compounds. C – X bond is not polar as in alkyl halides and due
to partial double bond character (Resonance), it is not easily broken.
Hence Method - II is not correct.
 Clearly Method - I is the correct choice for the formation of anisole as it is a simple nucleophillic substitu
-tion of CH3Cl by Phenoxide, as nucleophile. Hence for preparing aromatic ethers, we should always
prefer Method - I in general.

JEEMAIN.GURU
Illustration - 6 Identify A, B, C ...... in the following reaction set up.
SOLUTION :
IN-CHAPTER EXERCISE - B
1. Identify A, B, C, . . . . .
1. A 1. A
(i) C6 H 5 NH 2  C6 H 5 I (ii) C6 H 5Cl  C6 H 5COOH
2. B 2. B
A aq.
(iii) C6 H 5Cl 
 B ( DDT ) (iv) o-Bromobenzyl bromide  A
KOH
1. Mg / ether ( excess )
(v) o-Bromobenzyl bromide  B
2. H 2 O
3 HNO ( conc.) 3 CH ONa

(vi) C6 H 5 Br 
 ( A  B )  (C  D )
H 2 SO4 ( conc.)

JEEMAIN.GURU
POLYHALOGEN DERIVATIVES Section - 3
Di-Halides
These compounds are divided into two categories : Geminal dihalides and Vicinal-(1, 2)-dihalides.
Geminal dihalides (or Gem-dihalides) Vicinal - (1, 2) - dihalides
[or, alkylidene dihalides] [or alkylene dihalides]
RCHX2 (Terminal) ;
Preparation of Di-halogen derivatives :

1. From Alkenes and Alkynes :
 CH2X  CH2X
CH2 = CH2 + X2  Viccinal dihalide
CH  CH + 2 HX 
 CH3 CHX2 Geminal dihalide
CH3 – C  CH + 2 HX 
 CH3 – C(X)2 – CH3 Geminal dihalide
2. By the action of Phosphorus pentachloride (PCl5) :
CH3CHO + PCl5 
 CH3CHCl2 + POCl3
Aldehyde Gem dihalide
CH 3COCH3 + PCl5 
 CH3  CCl2  CH 3 + POCl3
Gem dihalide
Reactions of Di-halogen derivatives :

1. Action of alcoholic KOH : (Dehydrohalogenation)
alc.
XCH 2 CH 2 X  CH  CH
Viccinal KOH
alc.
CH3 CH X 2  CH  CH
Gem KOH

JEEMAIN.GURU
2. Action Zinc dust : (Dehalogenation)

Zn
XCH2CH2X  CH2 = CH2 (alc. alcoholic medium)
alc.
3. Action of aq. KOH : (Alkaline hydrolysis)
XCH 2CH 2X + 2 KOH(aq) 

 CH 2  CH 2
(vicinal) | |
OH OH Ethylene glycol
CH 3CHXCH 2X + 2 KOH(aq) 
 CH3  CH 2  CH 2
(vicinal) | |
(Propan-1, 2-diol)
OH OH
CH 3CHX 2 + 2 KOH(aq) 
 CH3CH(OH)2   CH3CHO
H O 2
(gem) Acetaldehyde
CH3CX 2CH3 + 2 KOH(aq) 

 CH3  C(OH)2  CH3 
 CH3  CO CH3
 H2O
(gem) (Unstable) Acetone
Note : The above reaction is used to distinguish between gem and viccinal dihalides.
Gen diols are unstable and loses H 2O to form carbonyl compounds.
4. Reactions of alc. KCN :

alc. 2  ( CH COOH ) H O
X  CH 2  CH 2  X  2KCN  NC  CH 2  CH 2  CN  2 2
 H
(succinicacid)
alc. H O  
CH3 CHX 2  2KCN  2  CH C H  COOH   CH CH COOH
 CH3CH (CN) 2  3 2 3 2
H H O 2
(  -methylmalonicacid)
Note : Malonic acid and its  - alkyl derivatives loses CO2 on heating to give corresponding monocarboxylic
acid.
Tri-Halogen Derivatives :
Trihaloderivative of methane is called as haloform.
CHCl3 CHBr3 CHI3

Chloroform Bromoform Iodoform
(Liquid) (Liquid) (Yellow solid)

JEEMAIN.GURU
Haloforms are prepared by haloform reaction. Any organic compound having

CH3  CH  R or CH3  CH R type of
| ||
OH O
structure undergoes haloform reaction on treatment with halogen and alkali or with hypohalite salt (NaOX).
X2
CH 3  CH  R or CH3  C R   CHX3  RCOO
| || 
OH
OH O
R = H, alkyl phenyl
CH3  CH(OH)  R+ 4 X 2 + 6 NaOH 

 CHX3 + RCOONa + 5 NaX + 5H2O
CH3COR + 3X 2 + 4 NaOH 
 CHX3 + RCOONa + 3 NaX + 3H 2O
Mechanism of Haloform Reaction :

X2
(i) Oxidation : CH 3  C H  R   CH 3  C  R  2 HX
| Oxidation ||
OH O
(ii)   Halogenation :
Similarly remaining   H atomos undergoes halogenation to form tri-haloketone.
(iii)
Chloroform : [ CHCl3 ]
It is a sickly sweet smelling liquid with b.p. as 61C. It is sparingly soluble in H2O but readily soluble in
ethanol and ether. It is used in surgery as an anaesthetic. It is non-inflammable but its vapours may burn with
green flame.

JEEMAIN.GURU
Preparation of Chloroform :
1. By distilling ethanol with a suspension of bleaching powder in water : (Laboratory method)
CaOCl2 + H2O 
 Cl2 + Ca(OH)2
(Bleaching powder)
Here chlorine acts both as an oxidising as well as a chlorinating agent.
Oxidation : CH3CH2OH + Cl2 
 CH3CHO + 2HCl
Chlorination : CH 3CHO  3Cl2 

 CCl3CHO
Trichloro acetaldehyde
 Chloral 
H2 O
Ca(OH)2 + 2CCl3CHO   2CHCl
3
+ (HCOO)2Ca
Chloroform cal. formate
Note : (i) In place or CaOCl2, we can use NaOH/Cl2.

NaOH + Cl2 
 NaOCl + HCl
NaOCl 
 [O] + NaCl
(ii) Pure Chloroform can be prepared by the action of sodium hydroxide solution on chloral hydrate.
CCl3CH(OH)2 or CCl3CHO.H 2 O  NaOH 

 CHCl3  HCOONa  H2 O
Chloralhydrate Chloroform Sod.formate
CCl3CH(OH)2 is stable due to H-bonding as :
2. From Acetone :
CH3 COCH3  3Cl2 

 CCl3 COCH3
Trichloroacetone
2CCl3COCH3 + Ca(OH)2 
 CHCl3 + (CH3COO)2Ca
Note : Acetone is preferred to Ethyl alcohol, as the yield is better.
3. From Carbon tetrachloride :

Fe + H O
2 CHCl + HCl
CCl4 + 2[H]  3
HCl

JEEMAIN.GURU
4. From chlorination of Methane at 370°C :

370°C
CH 4 + 3Cl2 
 CHCl3 +3HCl
diffuse sunlight
Reactions of Chloroform :
1. Oxidation : Chloroform in presence of sun light and air (O2) undergoes slow oxidation to form a highly
poisonous gas, Phosgene, COCl2.
light
2CHCl3 + O2 
 2COCl3 + 2 HCl
Phosgene
Note : Chloroform is stored in brown bottles to cut off light and filled upto brim to stop the above decomposition.
1% ethanol is also added which destroys the trace of phosgene that may be formed on storage.
2 C 2 H5 OH  COCl2 
 (C 2 H5 ) 2 CO3  2 HCl
Diethyl carbonate
(Non - toxic)
2. Reduction :
Zn  HCl
CHCl3  2  H   CH 2 Cl2  HCl
Zn + H O
2  CH + 3HCl
CHCl3 + 6[H]  4
3. Heating with Silver powder : (Dehalogenation)

High temp.
2 CHCl3  6 Ag 
 CH  CH  6 AgCl
4. Nitration : CHCl3  HNO3 

 CCl3 NO 2  H 2 O
Chloropicrin
Chloropicrin is a poisonous liquid and used as insecticide and in chemical warfare.

5. Condensation with Ketones :
OH
|
KOH
 CH3 2  C  O  H  CCl3   CH3 2  C  CCl3
Acetone Chloretone
Chloretone is a colourless crystalline solid and is used as a hypnotic (sleep inducing drug).

JEEMAIN.GURU
6. Carbylamine reaction :
alc.
RNH2 + CHCl3 + 3KOH 
 RNC + 3 H2O + 3 KCl
(aliphatic 1° amine) Alkyl Isocyanide
alc.
C6H5NH2 + CHCl3 + 3KOH 
 C6H5NC + 3 H2O + 3 KCl
(aromatic 1° amine) Phenyl Isocyanide
Isocyanides (carbylamines) have a very disagreeable smell, so the above reaction is used as a test (under the
name Carbylamine Test) of chloroform and test of both aliphatic and aromatic primary amines.
7. Reimer - Tiemann reaction :
Note : You will study the details of Reimer-Tiemann reaction later in Chapter on Phenols.
8. Hydrolysis :
Iodoform : [CHI3 ]
Iodoform resembles chloroform in the methods of preparation.
Preparation of Iodoform :
1. With Ethyl alcohol :
C2 H5 OH  4I2  6 NaOH 
 CHI3   HCOONa  5 NaI  5H 2 O
Iodoform
(Yellow solid)
 CHI3 + 5NaI + HCOONa + 3CO2 + 2H2O

C2H5OH + 4I2 + 3Na2CO3 

JEEMAIN.GURU
2. With Acetone :
 CHI3 + 3NaI + CH3COONa + 3H2O
CH3COCH3 + 3I2 + 4NaOH 
Note : This reaction is known as Iodoform reaction or Iodoform test. Since the iodoform is a yellow coloured
solid, so the iodoform reaction is used to test ethyl alcohol, acetaldehyde, secondary alcohols of type
R(CH3)CHOH (methyl alkyl carbinol) and methyl ketones (RCOCH3), because all these form iodoform.
The side product of the iodoform reaction, sodium carboxylate is acidified to produce carboxylic acid
(RCOOH).
Iodoform is a pale yellow solid, with m.p. 392 K, having characteristic odour. It is insoluble in water but
dissolves readily in ethyl alcohol and ether.
It is used as an antiseptic for dressing wounds.
Reactions of Iodoform :
Tetra - Halogen Derivatives :

Carbon Tetrachloride : CCl4
Preparation of Carbon tetrachloride :
1. From Methane :
hv
CH 4 + 4 Cl2  CCl4 + 4 HCl
CuCl 2 (Impure)
Methane used here is obtained from natural gas.

2. From Carbon disulphide :
AlCl
3 CCl + S Cl
CS2 + 3Cl2  4 2 2
Fe/Cl2
S2Cl2 is separated by fractional distillation. It is then treated with more CS2 to give CCl4. CCl4 is washed with
NaOH and distilled to obtain pure CCl4.
2S2 Cl2  CS2 

 CCl4  6S
(Pure)

JEEMAIN.GURU
3. From Propane :
400°C
CH3CH 2CH3 + 9 Cl2 
 CCl4 + C2Cl6 + 8HCl
70-100 atm (Liquid) (Solid)
Note : CCl4 is a colourless and poisonous liquid which is insoluble in H2O. It is a good solvent for grease and oils.
CCl4 is used in fire extinguisher (esp. electric fires) as Pyrene. It is also an insecticide for hookworms.
Organic halogen compounds are less inflammable than the hydrocarbons. The inflammability decreases with
increasing halogen content. Because they are good solvents for fats and oils and do not catch fire easily,
polychloro compounds (tri and tetrachloro ethylenes) are widely used as solvents for dry cleaning, carbon
tetra-chloride is used in fire extinguishers and called as pyrene. 1, 1, 2-Trichloroethylene called westrosol.
Reactions of Carbon tetrachloride :

500°C
1. Oxidation : CCl4 + H 2O   COCl2 + 2 HCl
(steam) Phosgene
Fe/H 2 O
2. Reduction : CCl4 + 2[H]   CHCl3 + HCl
 2 KOH
3. Hydrolysis : CCl4 + 4 KOH(aq)   C(OH)4   CO2   K 2CO3 + H 2O
2 H O
4 KCl (Unstable) 2
SbF
6  CCl F + 2 HCl
4. Action of HF : CCl4 + 4 HF  2 2
Freon-12
5 SbCl
5. Action of SbF3 : 2CCl4  2SbF3  3CCl2 F2  SbCl3
Note : Freon is widely used as a refrigerant cooling agent in refrigerators and air conditioners. It is also used as a
propellant in aerosols and foams. Recently, it is discovered that Freon depletes ozone layer. So, its uses
have been banned in many countries.
6. Reimer – Tiemann reaction :
Some other Important Halides :

Vinyl Chloride : [CH2 = CHCl ; vinyl group CH2 = CH– ]

JEEMAIN.GURU
Preparation of Vinyl chloride :

HgCl2
1. From Acetylene : CH  CH  HCl   CH 2  CHCl
70 C
2. From Ethylene Chloride : (Viccinal dihalides)

NaNH
2  CH  CHCl
C H 2  C H 2  2
| | 1.0 eqv.
Cl Cl

ClCH2 – CH2Cl   CH2 = CHCl + HCl
600  650 C
600 C
3. From Ethylene : CH 2  CH 2  Cl2  CH 2  CHCl  HCl
Properties of Vinyl chloride :

Vinyl chloride is a colourless gas at room temperature, with b.p. as –13C. The halogen atom in vinyl chloride is
not reactive as in other alkyl halides. However, –C = C– bond of vinyl chloride gives the usual addition reactions.
The non-reactivity of of vinyl chloride innucleophillic substitution reactions is due to resonance in it.
Reactions of Vinyl chloride :

It gives same reactions as given by alkenes.

JEEMAIN.GURU
Allyl Chloride : [CH2 = CHCH2Cl]

Preparation of Allyl chloride :
1. From Propene :
500-600°C
CH 2 = CHCH 3 + Cl2  CH 2 = CHCH 2Cl + HCl
Propene Allyl chloride
2. By the action of Phosphorus halide on allyl alcohol :


CH 2 = CHCH 2OH + PCl5 
 CH 2 = CHCH 2Cl + POCl3 + HCl
Allyl alcohol

3CH 2 = CH  CH 2OH + PCl3 
 3CH 2 = CH  CH 2Cl + H3PO3
3. Allyl bromide is prepared using NBS :
NBS
CH3CH = CH 2  CH 2 - CH = CH 2 (NBS : N - Bromosuccinimide)
CCl4 |
Br
Reactions of Allyl chloride :

1. Addition Reactions :
CH2 = CH  CH2Cl + Br2 
 Br – CH2 – CH(Br)  CH2Cl
CH2 = CH  CH2Cl + HBr 

 CH3CH(Br) – CH2Cl
2-Bromo-1-Chloropropane
Note : The addition follows Markonikov’s rule. However in presence of peroxides, 1,3-Dibromopropane is formed.
HBr
CH 2  CH  CH 2Br  C H 2  CH  CH 2Br
Peroxide |
Br

Since in allyl chloride, there is no resonance (unlike in vinyl chloride), nucleophillic substitution reactions take
place with ease. For example :
CH2 = CH – CH2Cl + KOH(aq) 
 CH2 = CHCH2OH + KCl
CH2 = CH – CH2Cl + NH3 
 CH2 = CH-CH2NH2 + HCl
CH2 = CHCH2Cl + KCN 
 CH2 = CH-CH2CN + KCl
dry ether
CH2 = CHCH2Cl + Mg   CH2 = CHCH2 MgCl
(Allylic Grignard Reagent)
CH2 = CH – CH2Cl + CH3ONa 
 CH2 = CH – CH2 – O – CH3 (Allyl methyl ether)

JEEMAIN.GURU
Benzyl Chloride : [ C6H5CH2Cl ]

Preparation of Benzyl chloride :
1. From Toluene :
2. By heating benzene with formaldehyde :
3. By the action of PCl5 on benzene alcohol :
Note : Benzyl bromide is prepared by action of NBS/CCl4 on toluene (Allylic bromination).
Reactions and Properties of Benzyl Chloride :

It is a colourless bad smelling liquid, with b.p. at 179C. Its vapours bring tears from eyes and are irritating.
It is insoluble in water but soluble in organic solvent.
The main reactions of benzyl chloride and bromide are like those of Alkyl halides. Nucleophillic substitution
reactions occur with ease unlike in case of aryl halides (due to resonance in aryl halides).

JEEMAIN.GURU
2. Wurtz Reaction :
3. Wurtz - Fitting reaction :
4. Oxidation :
5. Reduction :
Zn  Cu
C6H 5CH 2Cl + 2[H] 
 C6H 5CH 3 + HCl
couple Toluene
Illustration - 7 Identify A, B, C, . . . . .
PCl
5  A  aq.KOH NaOH
(a) CH 3CHO   C     D  aq.
 B 
Cl2
aq.KOH NaOH / I
2 C   D aq.
(b) C3 H 6Cl2 ( A) 
 B   
SOLUTION :
(a)
aq.KOH NaOH
(b) C3H6Cl2 
 B  C (s)  D (aq)
(A) I2
Since (B) gives iodoform test, so (B) is either a 2º alcohol of type CH3 — C H — R or a methyl ketone
|
OH

JEEMAIN.GURU
of type CH3 — C — R .
||
O
Now (B) is obtained by hydrolysis of a dihalide (A). A must be gem-dihalide, as viccinal dihalide gives glycols
on hydrolysis. Now (A) can be terminal gem-dihalide or a non-terminal one. (A) cannot be terminal gem-
dihalide as it will give CH3CH2CHO on hydrolysis which will not respond to iodoform test. Hence (A) is
Cl
|
CH3 — C— CH3 .
|
Cl
Cl
|
aq.KOH NaOH
CH3 — C — Cl   CH3COCH3  CHI3 (s)  CH3COONa (aq)
| I2
Cl Yellow solid
Iodoform
Illustration - 8 An organic compound (A) ; C4H8Cl2 on hydrolysis forms another compound (B) ; C4H8O.
(a) If the compound (B) responds positively to iodo form test, then identify (A) and (B).
(b) If (B) does not responds to iodo form test, then identify possible structures of (A) and (B).
(c) If all possible structures of (B) visualised above in (a) and (b) are treated with Zn–Hg/HCl, what are the
products ?
SOLUTION :
(a) KOH(aq) NaOH

A 
 B 
 CHI3
I2
C4 H8Cl2 C 4 H8 O
 (B) is a methyl ketone since it responds positively to iodoform test.

O
||
Hence (B) is CH3 — C — CH 2 CH3
Cl
|
Clearly (A) will be CH3 — C— CH 2 — CH3
|
Cl

JEEMAIN.GURU
(b) If (B) does not give iodoform test, it can be an aldehyde.

Hence (B) may be : CH3CH2CH2CHO or CH3 — C H — CHO
|
CH3
aq.
Accordingly (A) will be : CH3CH 2CH 2 C H  Cl   CH3CH 2CH 2CHO
| KOH
Cl
aq.
or  CH3 2 CH  C H  Cl 
KOH
 CH3 2 CH  CHO
|
Cl
(c) The possible structures of B and their reduction products with Zn – Hg/HCl (Clemmenson’s reduction) are:
Illustration - 9 An organic compound (A), C H Br reacts with aq.KOH solution to give another com-
8 9
pound (B), C8H10O. The compound (B) upon treatment of alkaline solution of iodine gives a yellow precipi-
tate. The filtrate on acidification gives a white solid (C), C7H6O2. Give structures of A, B, C and explain the
reactions involved.
aq.KOH NaOH
SOLUTION : C8 H9Br 
 C8H10O  CHI3 
I 2
(A) (B) Yellow ppt
Since (A) is hydrolysed, Br is not attached to ring i.e., it is attached to the side chain. (A) could be :
Since (B) responds positively to iodoform test, (A) is certainly

JEEMAIN.GURU
The filtrate contains sodium benzoate : which is acidified to give a white solid benzoic
acid (C7H6O2).
Illustration - 10 An alkene (A) C16H16 on ozonolysis gives only one product (B) C8H8O. Compound (B) on
reaction with NaOH/I2 yields sodium benzoate. Compound (B) reacts with Zn-Hg/HCl yielding a hydrocarbon
(C) C8H10. Write the structures of compounds (B) and (C). Based on this information two isometric structures
can be proposed for alkene (A). Write their structures and identify the isomer which on catalytic hydrogena-
tion (H2/Pd – C) gives a racemic mixture.
SOLUTION :
(s) Clearly the compound (C) is iodoform ; CHI3
O
—
—
Hence the structure of B is : C — CH3 (C8H8O) Acetophenone

JEEMAIN.GURU
(A) must be a symmetric alkene as it gives only one compound, C8H8O.
(A) is : C = C
—
Me Me
A shows Geometrical isomers : A1 and A2
Me
C=C C=C
Me Me Me
cis - form trans - form
2 H ,Pd /C
A1 or A2  Racemic mixture
Recall that hydrogenation is a ‘syn’ addition.

JEEMAIN.GURU
IN-CHAPTER EXERCISE - C
1. What is the final product in each reaction ?

HNO CHCl
3 ?
(a) 3 ?
CHCl3  (b) C6 H 5 NH 2 
KOH
2. What happens when ? Give equations only :

(a) Chlorine reacts with CS2 in presence of anhydrous aluminium chloride
(b) Chlorine is passed through ethyl alcohol
(c) Chloral is treated with aqueous sodium hydroxide
(d) Chloroform is boiled with aqueous potassium hydroxide
3. Identify the products (A), (B) and (C).

HBr Hydrolysis2 3 C Na CO
  A  
C2 H 4    B    
I2
4. Explain the following :

(a) Carbon tetrachloride is used as fire extinguisher
(b) Iodoform gives precipitate with AgNO3 on heating while chloroform does not.
(c) Alkyl iodides become darken on standing in presence of light.
(d) While preparing alkyl halides form alkanes, dry gaseous halogen acids are used instead of their
aqueous solutions.
5. Match the following :

(A) Carbon tetrachloride I. Antiseptic
(B) Chloretone II. Refrigerant
(C) Westrosol III. Chloroform
(D) Freon IV. Polymer
(E) Iodoform V. Hypnotic
(F) Teflon VI. Pyrene
(G) Carbylamine reaction VII. Solvent
NOW ATTEMPT IN-CHAPTER EXERCISE-C REMAINING QUESTIONS IN THIS EBOOK

JEEMAIN.GURU
THE CHEMISTRY OF GRIGNARD REAGENT Section - 4
Introduction :
Organo-magnesium halides popularly known as Grignard reagents were discovered by French chemist
Victor Grignard. The organic part may be derived from various types of hydrocarbons. The most important
type is alkyl magnesium halide. It is represented as RMgX (X : Cl, Br or I).
Generally Grignard Reagent is prepared by treating an organic halide with magnesium metal in ether as
solvent.
reflux in
RX + Mg RMgX Alkyl magnesium halide
ether
Reflux is a technique, allowing one to boil the contents of a vessel over an extended period.
‘R’ may be primary (1), secondary (2) or tertiary (3) alkyl, may be replaced by cycloalkyl, alkenyl, aryl
or alkynyl group.
The halide ions are Cl, Br or I. Fluorides are least reactive, so they are not considered. The reactivity of
halides follows the order : I > Br > Cl > F. Alkyl halides are more reactive than aryl and vinyl halides.
Aryl and vinyl halides are best prepared by using THF (Tetrahydrofuran) instead of ether as solvent.
THF
CH 2 = CHCl + Mg 
 CH 2 = CHMgCl
60° C
Note : In the preparation of Grignard reagents, ether as a solvent is must. The Grignard reagent are unstable in
aqueous medium so avoid aqueous medium.
( O  H), 1° and 2°alcohols (  O H), primary amines
Properties :
 
Grignard Reagent, RMgX is a very strong base because of polarisation of RMg bond  R  MgX. It
abstracts a proton from species containing acidic hydrogen such as water (– O  H), 12 and 3
alcohols (– OH), 1 and 2 amines (– N  H), terminal alkynes (– C  C – H). In the reactions with these
species, a proton is transferred to the negatively polarised carbon atom of the Grignard Reagent to give a
hydrocarbon.
Grignard Reagent, RMgX is not only a strong base, but also a strong nucleophile i.e., it shows a strong
tendency to donate the electron cloud to the species seeking electrons (Electrophiles).
Reactions As Base :
Grignard reagent as a base reacts with compounds such as acids, water, primary alcohols, primary amines
and terminal alkynes, all containing active Hydrogen atom (H) to give alkanes. “This reaction is also used to
determine active hydrogen atoms in the organic compoud”.

JEEMAIN.GURU

  
R  M gI  HO  H 
 RH  Mg(OH)I
δ  δ+
R  MgI + R   O  H  RH + Mg  OR   I
 
 RH  Mg  NHR   I
R  MgI  R  NH  H 
 
R  MgI  R   C  C  H 
 RH  R   C  C  MgI
Reactions As Nucleophile :
Grignard reagent acts as a strong nucleophile and shows nucleophillic addition reactions to give various
products. Alkyl group being electron rich (carbanian) acts as a nucleophile in Grignard reagent and reacts
with carbonyl compounds, esters, acid halides, cyanides etc.
   
R  Mg X  R  Mg X
1. With carbonyl group :
(a) With aldehydes :
(i)
(ii)

JEEMAIN.GURU
(b) With ketones :
2. With acid chloride :
Note : Ketones (e.g., acetone) formed above further reacts with Grignard reagent to form 3 alcohols if one uses
excess of Grignard reagent. However with 1 : 1 mole ratio of acid halides and Grignard reagent, one can
prepare only ketones.
3. With Esters :
(a) With formates :
Note : The aldehydes react further with CH3MgBr to give 2 alcohol, if it is present in excess. But with 1 : 1 mole
ratio of reactants will certainly give aldehydes only.

JEEMAIN.GURU
(b) With carboxylates
Note : The ketones react further with CH3MgI to give 3 alcohol, if it is present in excess. But 1 : 1 mole ratio of
reactants will certainly give ketones only.
(c) With Lactones (cyclic esters)
Note : If an organic compound has both ester and keto group, the Grignard regent prefers to attack keto group
(keto group has higher electrophillic character than ester group).
4. With cyanides :
5. With CO2 :
O O O
|| || H2O
||
R MgI  C  O 
 R  C  OMgI 

 R  C  OH  Mg (OH)I
dryice H
Carboxylic acid

JEEMAIN.GURU
6. With Oxygen :
1 H 2O
RMgI  O 2  ROMgI   ROH  MgI(OH)
2 H
7. With ethylene oxide (oxiranes) :
Note : All the above reactions can also be visualised by taking phenyl group (ph : C6H5 –) instead of R (Alkyl) to
get corresponding aromatic compounds.
8. With inorganic halides :

(Formation of Organometallics)
4C2 H5MgBr  2PbCl2 

 (C2 H5 ) 4 Pb  Pb  4MgBr(Cl)
Tetraethyl lead
 
TEL
2RMgBr  CdCl2 
 (R)2 Cd  2MgBr(Cl)
Dialkylcadmium
Illustration - 11 Identify compounds A, B, C ............ in the following reaction setup.
SOLUTION :

JEEMAIN.GURU
The formation major and minor products during the dehydration of alcohols will be discussed more exten-
sively in upcoming modules.
Illustration - 12 Identify componds A, B, C, .............. in the following reaction setup.
SOLUTION :

JEEMAIN.GURU
Illustration - 13 Identify the final product in the given sequence of reactions.
SOLUTION :
Formation of (C) from (B) is referred to as “intramolecular nucleophilic addition”.
Illustration - 14 Identify all the possible products in the given reaction. One or more options may be cor-
rect.
2 ? NaNH
CH 3  C  CH  Me3C  Br 
(A) Me3 – C – C  C – Me (B) Me2C = CH2
(C) Me3C – CH2 – C  CH (D) CH3C  CH
SOLUTION :

NaNH
CH3  C  CH  
2  CH  C  C  Na 
3
Terminal alkyne Propynide anion
Acidic Hydrogen
 Propynide anion can act as nucleophile and also as a base.
 Me3 – C – Br (tert. butyl bromide) is a tertiary (3) halide, which prefers elimination over substitution.
Hence the correct options are (A), (B) and (D).

JEEMAIN.GURU
IN-CHAPTER EXERCISE - D
1. Identity A, B, C, - - - - - - - - - in the following.
PCl
5  A  Mg 1. cylohexamone
(a) EtOH  B 
C
Et 2O 2 H 3O +
(b)
(c) MeMgBr 1. cyclopentanone

HC  CH  A   B ; B C
2.H3O+
(d)
NH
3  A 
2  B  Br Na
(e) CH 3CH 2CH 2 MgBr  C
127°C ether
NOW ATTEMPT IN-CHAPTER EXERCISE-D REMAINING QUESTIONS IN THIS EBOOK
NOW ATTEMPT OBJECTIVE WORKSHEET BEFORE PROCEEDING AHEAD IN THIS EBOOK

JEEMAIN.GURU
SOLUTIONS - IN-CHAPTER EXERCISE-A

HBr NaI
1. (a) CH 2  CH 2  CH3CH 2 Br  C2 H5I
Peroxide Acetone
NaI in acetone : I– becomes a strong Nu– and substitutes Br– ion.
(b)
 KCN H3 O
 
A : KCN  RBr   RCN   RCOOH 

 
B : H3O+ * alkyl, allyl and benzyl halides give above substitution.
2. (a)
(b)
(c)
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JEEMAIN.GURU
(d)
SOLUTIONS - IN-CHAPTER EXERCISE-B
1. (i)
(ii)
(iii)
(iv)
(v)
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JEEMAIN.GURU
(vi)
Note : No reaction (No substitution for aryl bromide)

* If NO2 (a deactivating group) is at ‘o’ or ‘p’ position, then substitution is possible.
SOLUTIONS - IN-CHAPTER EXERCISE-C

HNO3
1. (a) CHCl3   CCl3  NO2
3 CHCl
(b) C6H5 NH 2  C6 H5 NC
KOH
AlCl3
2. (a) CS2  3Cl2   CCl4  S2Cl2
[O] Cl2
(b) C2 H5OH  Cl2  CH3CHO   CCl3CHO (Chloral)
(c) CCl3CHO  NaOH 

 CHCl3  HCOONa
(d) CHCl3  4KOH (aq.) 

 HCOOK  3KCl  2 H2 O
HBr Hydrolysis
2 3 CHI Na CO
3. C2 H4  C2 H5 Br 
 C2 H5OH  3
I 2
4. (a) Dense vapours of CCl4 form a protective layer on the burning objects and present the oxygen or air to come
in contact with the burning objects.
(b) C – I bond being less stable than C – Cl bond and thus undergoes fission on heating giving I– ions which
combines with Ag+ ions to form a yellow ppt.
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JEEMAIN.GURU
(c) Alkyl iodides are less stable and lose free iodine. This iodine makes the remaining iodides darken.
(d) Dry hydrohalogen acids are stronger acids and better electrophiles than H3O+ formed in aqueous solutions.
Furthermore, H2O is a nucleophile and can easily react with R – X to form alcohol.
5. [A-VI], [B-V], [C-VII], [D-II], [E-I], [F-IV], [G-III]
SOLUTIONS - IN-CHAPTER EXERCISE-D
1. (a)
(b)
(c)
(d)
(e)
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Vidyamandir Classes
My Chapter Notes
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Vidyamandir Classes
Illustration - 1

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Vidyamandir Classes

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Vidyamandir Classes

Alkyl Halides

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JEEMAIN.

Vidyamandir Classes Organic Halides

Halogen containing Organic Compounds

ALKYL HALIDES : [RX] Section - 1

Preparation of Alkyl Halides :

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

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This reaction is called Swarts reaction.

3CH3  CCl2  CH3  2SbF3 

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However, a more specific reagent for allylic bromination is Nbromosuccinimide (NBS).

Allylic chlorination can also be carried out with sulphuryl chloride.

(a) By the action of Halogen acids :

(i) Using HCl :

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(ii) Using HBr :

C2H5OH + KBr + H2SO4 

(b) By the action of Phosphorus Halides :

Here X can be either chlorine or bromine or iodine.

(c) By the action of Thionyl chloride : (Darzen’s method)

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3. From Silver salt of fatty acids :

4. Halogen exchange reaction :

This reaction is called Frinkelstein Reaction.

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Organic Halides Vidyamandir Classes

Reactions of Alkyl halides :

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Vidyamandir Classes Organic Halides

1. Nucleophillic Substitution Reactions :

(ii) Substitution by moist Silver oxide (AgOH) :

(iii) Substitution by Sodium alkoxides (RONa) :

(iv) Substitution by Hydro sulphide group : (Formation of Thioalcohols).

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(v) Substitution by Mercaptide group : (Formation of Thioethers).

(b) By heating an alkyl halide with Sodium or Potassium sulphide :

(vi) Substitution by Amino group : (Formation of Amines)

This reaction is called Hoffmann ammonolysis of alkyl halides.

(vii) Substitution by Cyanides :

(KCN is an ionic compound giving – CN as nucleophile)

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(viii) Substitution by salts of Carboxylic acids :

(x) Substitution by AgNO2 and KNO2 :

2. Elimination reaction with alc. KOH/NaOH : (Dehydrohalogenation)

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The reaction is also referred to as -elimination (1, 2-elimination), as -H is lost.

The decomposition follows the order :

Reaction usually gives

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Dialkyl zinc compounds are called Frankland reagents.

7. Reduction : (Formation of alkanes).

(iv) Substitution by hydride ion : H  from LIAlH 4 as a Nucleophile.

8. Isomerisation : When a haloalkane is heated to 573 K or at a lower temperature in presence of anhy

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