10.haloalkanes & Haloarenes Colour Booklet

Chapter – 1
HALOALKANES &HALOARENES
1 BASIC CONCEPT
[A] Haloalkanes or alkyl halides are the compounds which have the general formula ‘RX’ , where ‘R’ is
an alkyl or substituted alkyl group & ‘X’ is the halogen (F, Cl, Br, I). Likewise, haloarenes or aryl
halides are the compounds containing halogen attached directly to an aromatic ring. They have the
general formula ‘ArX’ (where ‘Ar’ is phenyl or substituted phenyl).
R–X Ar – X
An alkyl halide An aryl halide
(Haloalkane) (Haloarene)
R = Alkyl or substituted alkyl Ar = Phenyl or substituted phenyl
X = F, Cl, Br, I X = F, Cl, Br, I
2 CLASSIFICATION
(a) CLASSIFICATION BASED ON THE NUMBER OF HALOGEN ATOM :
These may be classified as mono, di or poly-halogen compounds depending on whether they contain
one, two or more halogen atoms in their structures.
For example :
CH2X CH2X
C2H5X CH2X CHX
CH2X
(Monohaloalkane) (Dihaloalkane) (Trihalaoalkane)
X X
X X X
X
(Monohaloarene) (Dihaloarene) (Trihalaoarene)
Dihalogen compounds may be further classified as discussed below :
1) GEM-DIHALIDES
The two halogen atoms are attached to the same carbon atom in gem-dihalides.
For example :
H Cl H H H
H–C–C–C–H H – C – C – Cl
H Cl H H H
(Isopropylidene chloride) (Ethylidene chloride)
(2,2-Dichloro propane) (1,1-Dichloro ethane)
2) VIC-DIHALIDES
In these compounds, the two halogen atoms are attached to adjacent carbon atoms.
For example : Cl
Cl – CH2 – CH2 – Cl CH3 – CH – CH2 – Cl
(Ethylene chloride) (Propylene chloride)
(1,2-Dichloride ethane) (1,2-Dichloropropane)
Haloalkanes & Haloarenes
(b) CLASSIFICATION BASED ON HYBRIDISATION OF ‘C’ ATOM
1) Halogen compounds in which halogen is bonded to sp3 hybridized carbon. This class includes :-
I. HALOALKANES OR ARYL HALIDES :-
They are the halogen compounds of saturated hydrocarbon. Their general formula is CnH2n + 1X.
They are further classified as primary haloalkane, secondary haloalkane or tertiary haloalkane
according to whether the halogen atom is bonded to primary, secondary or tertiary carbon atom.
H R2 R2
R1 – C – X R1 – C – X R1 – C – X
H H R3
(Primary haloalkane) (Secondary haloalkane) (Tertiary haloalkane)
If in R – X, R is an alicyclic, i.e., cyclic aliphatic hydrocarbons such as cyclopropane,
cyclobutane, etc. They are known as halocycloalkane or cycloalkylhalide.
For example :
H2C CH2 – CH – X
CH – X
H2C CH2 – CH2
(Halocyclopropane) (Halocyclobutane)
II. ALYLIC HALIDES :
In these compounds, halogen is bonded to allylic carbon, i.e., to the sp3 hybridised carbon next to s
carbon – carbon double bond.
For example :
CH2 = CH – CH2 – X X
(Allyl halide)
(3-Halo-1-propene)
(3-Halocyclohex-1-ene)
III. BENZYLIC HALIDES :
In these halides, the halogen atom is bonded to an sp3 hybridization carbon atom next to an
aromatic ring, i.e., to a benzylic carbon.
For example :
CH2X X R1
C–X
R2
(Benzyl halide)
(1-Halo-1,2,3,4-tetra- (Dialkylbenzyle halide)
hydro naphthalene)
 NOTE :- Benzylic halides may be primary, secondary or tertiary.
2) Halogen compounds in which halogen is bonded to sp2 hybridized carbon.
I. VINYLIC HALIDES :
In these halides, halogen is bonded to one of the carbon atoms of a vinylic carbon, i.e., carbon –
carbon double bond which is sp2 hybridised.
For example :
CH2 = CH – X X
(Vinyl halide) (1-Halocyclohex-1-ene)

II. ARYL HALIDES :
In these halides, the halogen atom is directly bonded to carbon atom of aromatic ring. These
are called haloarene or aryl halides, e.g., halobenzene.
X
(Halobenzene)
3 COMMON & IUPAC NAMES OF SOME HALIDES
COMMON NAME STRUCTURE IUPAC NAME

Methyl chloride CH3 – Cl Chloromethane
n-propyl fluoride CH3 – CH2 – CH2 – F 1-Fluoropropane
Iso-propyl chloride CH3 – CH – Cl 2-chloropropane
CH3
n-Butyl chloride CH3 – CH2 – CH2 – CH2 – Cl 1-chlorobutne
Sec-butyl chloride CH3 – CH2 – CH – CH3 2-chlorobutane
Cl
Iso-butyl chloride CH3 – CH – CH2 – Cl 1-chloro-2-methyl propane
CH3
Tert-butyl chloride CH3
CH3 – C – CH3 2-Bromo-2-methyl propane
Br
Neo-pentyl bromide CH3
CH3 – C – CH2 – Br 1-Bromo-2,2-dimethyl propane
CH3
Iso-pentyl chloride CH3 – CH – CH2 – CH2 – Cl 1-Chloro-3-methyl butane
Vinyl chloride CH2 = CH – Cl Chloro ethane
Allyl bromide CH2 = CH – CH2 – Br 3-Bromoprop-1-ene
Methylene chloride CH2 – Cl2 Dichloromethane
Chloroform CHCl3 Trichloromethane
Carbon tertrachloride CCl4 Tetrachloromethane
O-chloro toluene CH3
Cl 2-chlorotoluene or,
1-chloro-2-methyl benzene
Benzyl chloride CH2 – Cl Chlorophenyl methane
Alkyl halides: CH3CH2CH2Br Benzylic halides:

(Propyl bromide) CH2Br
DO YOU
Memories
Cycloalkyl halides:
KNOW Br
Allylic halides: CH2 = CH – CH2 – Cl
Aryl halides:
Cl
Cyclohexyl bromide
Vinylic halides: CH2 = CH – Cl
4 METHODS OF PREPARATION OF HALOALKANES

Anhydrous ZnCl2
C2H5OH + HCl C2H5Cl + H2O
Ethanol Chloroethane
3C2H5OH + PCl3 3C2H5Cl + H3PO3

Ethanol Phosphorus acid
From ALCOHOLS
C2H5OH + PCl5 C2H5Cl + POCl3 + HCl
Phosphorus oxychloride
Pyridine
C2H5OH + SOCl2 C2H5Cl + SO2↑ + HCl↑
Thionyl chloride
U.V. Light
CH4 + Cl2 CH3Cl + HCl
500 – 6000C
CH2 = CHCH3 + Cl2 CH2 = CH – CHCl + HCl
Propene Allyl chloride
From HYDROCARBONS
CH2 = CH2 + HI CH3CH2I
Ethene Iodoethane
Benzoyl peroxide
CH3CH = CH2 + HBr CH3CH2CH2Br
1-Bromopropane
Acetone
C2H5Br + NaI C2H5I + NaBr Finkelstein reaction
From 2C2H5Cl + Hg2F2 2C2H5F + Hg2Cl2

HALIDE EXCHANGE Mercurous Fluroethane
Fluoride
Cl F
3CH3 – C – CH3 + 2SbF3 3CH3 – C – CH3 + 2SbCl3
Cl F
CCl4 / Reflux
C2H5COOAg + Br2 C2H5Br + CO2 + AgBr
Silver propionate
From SILVER SALTS OF Borodine Hunsdiecker reaction
HALIDE EXCHANGE
O O
2R – C – OAg + I2 R – C – OR + CO2 + 2AgI
Simonini reaction
Illustration: 1. 2-Bromo-3-methylbutane on heating with alcoholic KOH yields 2-methyl-2-butene as the

major product why?
Solution: CH3
H3C H CH3 – CH – CH = CH2 (Minor)
CH3 – C – C – CH3 Alc. KOH / Δ
H Br CH3
CH3 – C = CH – CH3 (Major)
This could be explained through the formation of more stable carbonium ion as intermediate.
H3C H CH3
CH3 – C – C – CH3 Alc. KOH / Δ CH3 – C – C – CH3 (Less stable)
H Br Rearranged H
H3C CH3
CH3 – C – CH2 – CH3 −𝐻 ⨁ CH3 – C – CH – CH3
(More stable) 2-Methylbutene-2
Illustration: 2. Explain why 2-halopentane on dehydrohalogenation yields 2-pentene as major product not
1-pentene?
Solution: X
CH3CH2CH2 – CH – CH3 Alc. KOH CH3CH2CH2CH = CH2
1-Pentene (Less stable)
Alc. KOH CH3CH2CH = CH – CH3
Δ, –HX 2-Pentene (More stable)
It is accordance to Saytzeff’s rule more highly substituted alkene is more stable.
Illustration: 3. Drazen’s reaction is:
(a) Reaction of alcohol with phosphorus tri-iodide
(b) Reaction of alkyl halide with sodium metal in presence of dry ether
(c) Hydrolysis of alkyl halide with moist silver oxide
(d) Reaction of alcohol with thionyl chloride.
Solution: (d) Reaction of alcohol with thionyl chloride.
Illustration: 4. Which of the correct method of the preparation of 2-bromo propane?
(a) HBr is treated with 1-propanol
(b) Propene is treated with HBr in presence of peroxides
(c) 1-Propanol is treated with conc. H2SO4 followed by the reaction with HBr.
(d) Ethylene is treated with Br2 (in CCl4) followed by the elimination of HBr.
Solution: (c) 1-Propanol is treated with conc. H2SO4 followed by the reaction with HBr.
Illustration: 5. The reaction : CH3Br + AgF CH3F + AgBr is called
(a) Sward’s reaction (b) Finkelstein reaction
(c) Gattermann reaction (d) Perkin’s reaction
Solution: (a) Sward’s reaction
The best method of preparation of haloalkanes from

DO YOU
YOU alcohols is using SOCl2. In this method, both the by-
DO
products (SO2 & HCl) are gaseous. They escape, leaving
KNOW
KNOW behind the product. Hence, the product, does not need
purification.
5 PROPERTIES OF HALOALKANES
 Physical Properties of Haloalkanes:
(1) Melting & Boiling point :-
Haloalkanes have higher boiling points as compared to these of corresponding alkanes. This is due to their
polar nature & strong dipole – dipole interactions between their molecules. The boiling points of
haloalkanes are in the order – (RCl < RBr < RI). It is because with the increase in size & mass of halogen
atom the magnitude of Van der Waal’s force of attraction increases.
Among isomeric alkyl halides, the boiling point is decreases with increases in branching in the alkyl group.
This is due to the reason that with increases in branching, the molecules attains a spherical shape with less
surface area. As a result, inter-particles forces becomes weaker resulting in lower boiling point.
For example, among isomeric butyl chlorides, the straight chain isomers, n-butyl chloride has highest
boiling point whereas tert-butyl chloride has the lowest boiling point.
(2) Density :-
Bromo, iodo & polychloro derivatives of hydrocarbon are heavier than water. The density increases with
increase in no. of C- atoms. Halogen atoms & atomic mass of the halogen atom.
(3) Solubility :-
Haloalkane & haloarenes are practically insoluble in water because they are not able to form the
intermolecular H-bonds with water molecules. Now, however they are soluble in organic solvents.
Illustration: 1. The arrangement of following compounds:

(i) Bromomethane (ii) Bromoform (iii) Chloromethane (iv) dibromomethane
In increasing order of their boiling point is:
(a) iv < iii < i < ii (b) i < ii < iii < iv (c) iii < i < iv < ii (d) ii < iii < i < iv
Solution: (c) The intermolecular forces of attraction become stronger with the increase in size of the
molecules. Hence the order of boiling points will be: CH3Cl < CH3Br < CH2Br2 < CHBr2.
Illustration: 2. Which one of the following alkyl halides has the lowest boiling point?
(a) n-Butyl chloride (b) iso-Butyl chloride
(c) sec-Butyl chloride (d) n-Pentyl chloride
(d) tert-Butyl chloride
Solution:(e) The boiling points of alkyl chlorides increases with the increase in the size of alkyl group.
In a group of isomeric alkyl chloride, the order of boiling point is :
Primary > Secondary > Tertiary
Illustration: 3. Which one of the following is not correct order of boiling points of the alkyl/aryl halides?
(a) CHCl3 > CH2Cl2
(b) CH3(CH2)3 Cl > CH3(CH2)2 Cl
(c) (CH3)3 CCl > (CH3)2 CHCH2Cl
(d) CH3(CH2)3Cl > CH3CH2CHClCH3
(e) C6H5Br > C6H5Cl
Solution: (c) (CH3)3CCl > (CH3)2CHCH2Cl is not correct as boiling point of (CH3)3CCl is smaller than
(CH3)2CHCH2Cl. It is due to large surface area of (CH3)2CHCH2Cl.
Illustration: 4. Alkyl halides are less soluble in water because
(a) they ionise in water
(b) they do not form H-bonds with water
(c) they are highly viscous
(d) they have very strong C – X bond
Solution: (b) They are polar but fail to form H-bonds with water.
Illustration: 5. In the group of isomeric alkyl halides, the order of boiling point is
(a) primary < secondary < tertiary
(b) primary > secondary < tertiary
(c) primary < secondary > tertiary
(d) primary > secondary > tertiary
Solution: (d) As on increasing branching, surface area is decreased, hence van der Waal’s forces of
attraction decreases. As a result, boiling point is also decreased. Thus, decreasing order of
boiling points among the isomeric alkyl halides follows the order: 10 > 20 > 30.
 Chemical Properties of Haloalkanes:

Reactions of Haloalkanes
1. Nucleophilic Substitution 2. Electrophilic Substitution 3. Reaction with metals

Reaction Reaction
The chemical reaction of haloalkanes can be divided into :-
(1) Nucleophilic substitution reaction :-
When an atom or a group of atom is replaced by a nucleophile, the reaction is called nucleophilic
substitution reaction.
In haloalkanes, the halogen atoms is attached to the C-atom. As the halogen atom is more
electronegative than carbon, the bond between carbon & hydrogen is polar in character.
𝛿+ 𝛿−
C–X
Due to the presence of partial positive charge on the C-atom, the nucleophiles can attack on electron
deficient carbon thereby resulting in the displacement of weaker nucleophile, the halide ion.
𝛿+ 𝛿−
C – X + 𝑍− C – Z + 𝑋−
(Substrate) (nucleophile) (Product) (Leaving group)
 Nucleophilic substitution of alkyl halides (R – X) :-
+ KOH (aq.) + KNO2

R – OH + KX R – O – N = O + KX
(Alcohol) (Alkyl nitrite)
+ Na+OR- + AgNO2
R – O – R + NaX
1
R – NO2 + AgX
(Ether) (Nitroalkane)
+ KCN (alc.) + LiAlH4
R – CN + KX R–H
(Alkyl cyanide) R–X (Alkane)
ALKYL HALIDE
+ AgCN + NH3
R – NC + AgX R – NH2 + H – X
(Alkyl isocyanide) (Alkyl amine)
+ NaSH O
R – SH + NaX + R – C – O – Ag
1
(Thioalcohol)
+ Na+C-≡ CH O
R – C ≡ CH + NaX R – C – O – R1 + AgX
(Higher Alkyne) (Ester)
(2) Elimination reaction :-

When haloalkane with 𝛽 − hydrogen atom is heated with ethanolic potassium hydroxide, there is
elimination of H – atom from 𝛽 − carbon atom & a halogen atom from 𝛼 − carbon atom. As a result,
an alkene is formed. Since 𝛽 − hydrogen atom is involved in elimination, it is often called
𝛽 − elimination reaction.
CH3 – CH2 – Cl + KOH (alc.) ∆ CH2 = CH2 + KCl + H2O
(3) Reaction with metals :-
(a) Reaction with magnesium –
R – X + Mg Dry ether RMgX
(Alkyl halide) (Alkyl magnesium halide)
(Grignard reagent)
CH3 – CH2 – Br + Mg Dry ether CH3 – CH2 - MgBr
(Ethyl magnesium bromide)
(b) Reaction with sodium (Wurtz reaction)
R – X + 2Na + X – R Dry ether R – R + 2NaX
(Alkane)
R – X + 2Na + X – R Dry ether CH3 CH2 CH2 CH3 + NaCl
(n-Butane)
Illustration: 1. Among the following compounds, which one is more easily hydrolyzed & why?
CH3CH2CH2CH2Cl & CH3CHClCH2CH3
Solution: In SN1 reactions, reactivity depends on the stability of carbocation intermediate. As 20
carbocation is more stable than 10 carbocation. So, CH3CHClCH2CH3 is more easily
hydrolysed.
In SN2 reaction CH3CH2CH2CH2Cl is more easily hydrolysed due to less stearic hindrance.
Illustration: 2. Which is a better nucleophile, a bromide ion or an iodide ion?
Solution: Iodide ion is a better nucleophile.
Illustration: 3. For SN1 reaction, the order of reactivity of haloalkanes is
(a) tertiary halide < secondary halide < primary halide
(b) tertiary halide < secondary halide > primary halide
(c) tertiary halide > secondary halide > primary halide
(d) tertiary halide > secondary halide < primary halide
Solution: (c) SN1 reaction is two steps reaction in which carbocation is formed as an intermediate in step I
(rate determining step). Greater the stability of carbocation, greater will be its ease of
formation from alkyl halide & faster will be the rate of reaction. thus, the order of reactivity
of haloalkanes towards SN1 reaction is: Tertiary > secondary > primary halide.
Illustration: 4. Which one of the following compounds cannot be used for the preparation of Grignard
reagent?
(a) C2H5Br (b) HO – CH2CH2Cl
(c) C6H5CH2Cl (d) CH2 = CH – CH2Cl
Solution: (b) Grignard reagent cannot be prepared from a compound which has reactive group such as –OH
because it will react rapidly with the Grignard reagent.
Illustration: 5. The hydrolysis of optically active 2-bromobutane with aqueous NaOH results in the
formation of :
(a) (−)-butan-2-ol (b) (±)-butan-2-ol
(c) (+)-butan-2-ol (d) (±)-butan-1-ol
Solution: (b)
6 PREPARATIONS OF HALOARENES
1. By direct halogenation of benzene :
H
+ X2 Fe or FeX3 / dark + HX (X = Cl, Br)
H
+ I2 HIO3 or HNO3 + HX (X = Cl, Br)
2. From Diazonium salt :
NH2 N+≡ 𝑁𝐶𝑙 −
H
NaNO2 /HCl (273-278K) + HX (X = Cl, Br)
CuCl/HCl Cl + N2
Sandmayer’s reaction
CuBr/HBr Br + N2
N+≡NC𝑙 −
(Benzene diazonium + KI I + KCl + N2

chloride)
+ NaBH4 F + BF3 + NaCl + N2
Illustration: 1. What halogen best delocalizes electron density to benzene ring?

Solution: The smaller size of halogen atom, smaller will be carbon-halogen bond. Also shorter the
carbon-halogen bond, more effective will be the overlap of p-orbitals & more extensive will
be delocalization. Therefore, order of best delocalization of electron density to benzene ring
should be F > Cl > Br > I.
Illustration: 2. Chlorination of toluene in the presence of light & heat followed by treatment with aqueous
KOH gives:
(a) o-cresol (b) m-cresol (c) p-cresol (d) benzyl alcohol
Solution:(d) CH3 CH2Cl CH2OH
Cl2 , / ℎ𝑣 aq. KOH
Toluene Benzyl chloride Benzyl alcohol

Illustration: 3. Conversion of chlorobenzene to phenol involves:
(a) Electrophilic substitution (b) Nucleophilic substitution
(c) free radical substitution (d) electrophilic addition
Solution: (b) When chlorobenzene is heated at 3500 under high pressure with caustic soda phenol is formed.
Illustration: 4. The major product obtained when chlorobenzene is nitrated with HNO3 + Conc. H2SO4 is
(a) 1-chloro-4-nitrobenzene (b) 1-chloro-2-nitrobenzene
(c) 1-chloro-3-nitrobenzene (d) 1-chloro-1-nitrobenzene
Solution: (a) Cl Cl Cl
NO2
HNO3 +
Conc. H2SO4
NO2
1-Chloro-2-nitrobenzene 1-Chloro-4-nitrobenzene
(Minor) (Major)
Illustration: 5. Predict the main product.
– Cl NH3 / Cu2O
(a) Phenyl cyanide (b) Nitrophenol (c) Aniline (d) Hydroxylamine

Solution: (c) Aniline
7 PROPERTIES OF HALOARENES
 Physical Properties of Alcohol:
(1) Melting point & Boiling point :
Boiling points of isomeric dihalobenzenes are very nearly same. However p-isomer have higher melting
point as compared to their ortho & meta-isomers. It is due to symmetry of para-isomers that fits in crystal
lattice better as compared to ortho & meta-isomers.
(2) Nature of C-X bond :
The C-X bond is polar as X is more electronegative than carbon. The carbon has partial positive charge
whereas halogen has slight negative charge because shared pair of electrons are more towards halogen
atoms.
𝛿+ 𝛿−
–C–X
 NOTE :- Dipole moment of CH3Cl is higher than CH3F due to greater bond length in C – C bond.
 Chemical Properties of Alcohol:
Reactions of Haloarenes
1. Nucleophilic Substitution 2. Electrophilic Substitution 3. Reaction with metals

Reaction Reaction
(1) Reaction with haloarenes :
(i) Nucleophilic substitutions :-
Aryl halides are extremely less reactive towards nucleophilic substitution reaction due to the following
Reason: –
In arylhalides C – X bond acquire a partial double bond character due to resonance.
As a result C – X bond cleavage in aryl halides is difficult than alkyl halides & therefore they are
less reactive towards necleophilc substitution reaction.
+ + +
X X X X X
CANONICAL FORM
𝛿+ X
𝛿− 𝛿−
𝛿−
(ii) Difference in hybridisation :-
X
Sp2 hybrid C-atom H
Sp3 hybrid carbon
C
R X
H
(iii) Intensity of phenyl cation :-
In case of haloarenes, the phenyl cation formed as a result of self-ionisation will not be stabilized by
resonance & therefore SN1 mechanism is ruled out.
(iv) Difference in hybridization of C-atom in C – X bond:
In haloarenes, carbon in C – X bond is sp2
hybridized which has greater s-character than sp3 hybridised carbon atom of alkyl halide. Due to this,
carbon in haloarene is more electronegative which leads to shortening of C – X bond length.
This makes the cleavage more difficult.
Cl
𝑠𝑝 2
CH3 – Cl ;
(v) Instability of phenyl cation:
Phenyl cation is highly unstable. This rules out SN1 mechanism.
(vi) Because of possible repulsion, it is less likely for the electron-rich nucleophile to approach
electron rich areas.
However, at high temperature & pressure several nucleophilic substitution reaction are carried out.
 Substitution by –OH group (Dow’s process)
Cl OH
(i) NaOH, 623K, 300atm

(ii) H+
(Chlorobenzene) (Phenol)
Substitution by –CN group
Cl CN
CuCN, DMF
473K
(Benzonitrite)
Substitution by –NH2 group
Cl NH3
NH3
CuO, 475K, 60atm
(Aniline)
(2) Reaction with metals :
+Na, Ether
(Fitting reaction)
(Diphenyl)
+Na, CH3-Cl CH3

Cl Ether
(Toluene)
(Chlorobenzene)
+ Mg/Ether MgCl
(Phenyl Magnesium chloride)
+Cu/Ether
(Ulmann reaction)
(Diphenyl)
(3) Electrophilic substitution reaction of haloarenes :
+ + +
X X X X X
CANONICAL FOR
Due to resonance, the electron density increases more at ortho & para positions than at meta position.
Therefore, electrophilic substitution reaction take place at ortho & para position.
Cl Cl
Cl
+Cl2/anhy.FeCl3
(Chlorination) +
Cl
(p-Dichlorobenzene) (Major product)
Cl Cl
NO2
HNO3(Conc.)/H2SO4(Conc.)
(Nitration) +
Cl
NO2
(p-Chloronitrobenzene) (Major product)
Cl
Conc. H2SO4 Cl SO3H + SO3H
(Chlorobenzene) (Sulphonation)
(p-Chloronitrobenzene)
(Major product)
Cl
CH3Cl / ∆ AlCl3 Cl CH3 + CH3
(Alkylation)
(p-Chlorotoluene)
(Major product)
Cl Cl
O COCH3
+CH3 – C – Cl / ∆ AlCl3 +
(Acetylation)
(p-Chloro acetophenone)
COCH3 (Major product)
Cl Cl
C
+ CCl4 + AlCl3/–2HCl
Benzene Benzene dichloro diphenyl methane
USES:
a) As a fire extinguishers (Pyrene)
b) As a lab reagent
c) As a solvent for fats, oils, resins.
d) As a dry cleansing agent.
e) In medicine a helminthicide.
f) As a fumigant.
8 IMPORTANT TERMS
(1) STERIOISOMERISM :
Isomerism exhibited by two or more compounds with the same molecular & structural formulae but
different spatial arrangements of atoms or groups in space is called stereoisomerism.
(2) PLANE POLARISED LIGHT :
The beams of light whose oscillations or vibrations are confined to one plane only is called plane-polarised
light. It is obtained by passing a monochromatic light (light of single wavelength) through a Nicol prism.
(3) OPTICALLY ACTIVE SUBSTANCES :
Those substances which rotate the plane of polarisation of plane polarised light when it is passed through
their solution are called optically active substance, & the phenomenon is called optically active.
(4) OPTICAL ROTATION :
The property of rotating the plane is polarisation either towards left or towards right is called optical
rotation.
(i) Laevorotatory :- Those substance which rotates the plane of polarisation of light towards the left
directions are called laevorotatory.
(ii) Dextrorotatory :- It can rotates polarisation of light towards right.
Note: Currently, dextro & laevo rotation sigh are represented by algebraic sign of (+) & (-) respectively.
(5) SPECIFIC ROTATION :
It is defined as the number of degrees of rotation observed when the concentration of optically active
substances is 1gm cm-3 & length of polarimeter tube is 1decimeter (dm) for D-line of sodium vapour
lamp at 250C.
𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑟𝑜𝑡𝑎𝑡𝑖𝑜𝑛 (𝑎 )
Specific rotation (𝛼) = 𝐿𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑡𝑢𝑏𝑒(𝑑𝑚) ×𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑏𝑠𝑣.
𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑔 𝑚𝐿−1 )
While reporting [𝛼], the wavelength of light used is given as subscript & the temperature in degree Celsius
as a superscript. It is also customary to designate the solvent & concentration.
Thus, [𝛼]25 0
𝐷 = −2.25 (𝐶; 0.05 ethanol) means that ′𝛼′ was measured at 25 C using sodium D-line & the
0
sample concentration was 0.50 g/mL in ethanol.

(6) ASYMMETRIC MOLECULE :
If all the four substituents attached the carbon are different, the resulting molecule will lack symmetry such
a molecule is called asymmetric molecule. Asymmetric of molecule is responsible for optical activity in
such organic compounds.
(7) CHIRAL :
An object which is non-superimposable on its mirror image is said to be chiral. The property of being chiral
is known as chirality.
(8) ASYMMETRIC CARBON :
The carbon atom which is attached with four different groups of atoms is called asymmetric carbon.
The molecule having asymmetric C-atom is called asymmetric.
(9) ENANTIOMERS :
The stereoisomer which are non-superimposable mirror image are called enantiomers.
Enantiomers rotates the plane of polarised light to the some extent but in opposite direction.
(10) RACEMIC MIXTURE :
An equimolar mixture of pair of enantiomers is called racemic mixture & the process of conversation
of enentiomers into racemic mixture is called racemisation.
(11) RESOLUTION OF A RACEMIC MIXTURE :
Resolution is a process of separating a racemic mixture into its enantiomers consitituents,
i.e., dextro(+) & laevo – rotatory (-) substances.
(12) MESOCOMPOUNDS :
The compounds containing two o more chirality centers but possessing achiral molecular structure because
of having plane of symmetry are called meso-compounds. A meso-compounds is optically active due to
internal compensation.
(13) DIASTERIOMERS :
The sterioisomers which are non-superimposable & do not bears a mirror image relationship.
(14) RETENTION :
If in an optically active molecule the relation configuration of the atoms / groups around a chiral centre
remains the same before & after a reaction, the reaction is said to proceed with retention of configuration.
Illustration: 1. 2-Chlorobutane obtained by chlorination of butane, will be

(a) meso-form (b) racemic form (c) d-form (d) l-form
Solution: (b) An optically inactive compound forming optically active compound during a reaction always
give racemic mixture.
Illustration: 2. In a mixture, two enantiomers are found to be present in 85% & 15% respectively.
The enantiomers excess (e, e) is
(a) 85% (b) 15% (c) 70% (d) 60%
Solution:(c) Enantiomeric excess is (85 - 15) = 70%.
Illustration: 3. When (–)-2-methylbutan-1-ol is heated with concentrated hydrochloric acid,
(+)1-chloro-2-methylbutane is obtained. The reaction is an example of:
(a) retention (b) inversion
(c) racemisation (d) resolution
(e) mutarotation
Solution: (a) During this reaction, no bond at the stereocentre is broken, thus the product has the same
general configuration of atoms or groups i.e., retention of configuration though sign of
optical rotation has changed.
Illustration: 4. During SN1 reaction which of the following species is produced?
(a) Free radical (b) Carbene
(c) Carbocation (d) Carbanions
Solution: (c) R – X – X– Solw R+ Nu– Fast R – Nu (SN1 reaction).
Illustration: 5. If there is no rotation of plane polarised light by a compound in a specific solvent, though
to be chiral, it may mean that:
(a) the compound is certainly meso
(b) there is no compound in the solvent
(c) the compound may be a racemic mixture
(d) the compound is certainly a chiral
Solution: (a) Meso compound does not rotate plane polarised light. Compound which contains tetrahedral
atoms with four different groups but has a plane of symmetry & is optically inactive. One of the asymmetric
carbon atoms turns the plane of polarised light to the right & other to the left & to the same extent so that the
rotation due to upper half is compensated by the lower half, i.e., internally compensated, & finally there is no
rotation of plane polarised light.
Polyhalogen compounds
The important polyhalogen compounds are methylene chloride (CH2Cl2), chloroform (CHCl3), iodoform
(CHI3), carbon tetra chloride (CCl4), Frorons (CF2Cl2, etc.) & DDT.
Methylene Chloride (Dichloromethane)
Uses Harmful Effects
It is widely used:  It harms the human central nervous system.
 As a solvent.  Exposure to its lower levels in air can lead to
 As a paint remover. slightly impaired hearing & vision.
 As a propellant in aerosols.  Its higher levels in air cause dizziness, nausea,
 As a process solvent in the manufacturing of tingling & numbness in the fingers & toes.
drugs.  In humans, its direct skin contact cause
 As a metal cleaning & finishing solvent. intense burning & mild redness of the skin.
 Direct contact with eyes can burn the cornea.
Chloroform (Trichloromethane)
 It is used as a solvent for fats, alkaloids,  Inhaling chloroform vapours depresses the
iodine & other substances. central nervous system.
 It is used in the production of the Freon  Breathing chloroform (900 ppm) for a short
refrigerant R-22. time can cause dizziness, fatigue & headache.
 It was once used as a general anaesthetic in  Chronic chloroform exposure may cause
surgery but has been replaced by less toxic, damage to the liver & to the kidneys & some
safer anaesthetics, such as ether. people develop sores when the skin is
immersed in chloroform.
 NOTE: Chloroform is slowly oxidised by air in the presence of light to an extremely poisonous
gas, carbonyl chloride, also known as phosgene.
light
2CHCl3 + O2 2COCl2 + 2HCl
Phosgene
It is therefore stored in closed dark coloured bottles completely filled so that air is kept out.
Carbon Tetrachloride (Tetrachloromethane)

It is used:  Its exposure cause liver cancer in humans.
 In the manufacture of refrigerants &  When inhaled it causes dizziness, light
propellants for aerosol cans. headedness, nausea & vomiting, which can
 As feedstock in the synthesis of cause permanent damage to nerve cells. In
chlorofluorocarbons. severe case, these effects can leads rapidly to
 As a solvent use. stupor, coma, unconsciousness or death.
 As a spot remover &  Its exposure can make the heart beat irregular
 As a fire extinguisher or stop. It may irritate the eyes on contact.
 When released into air, it depletes the ozone
layer.
Iodoform (Tri-iodomethane)
Earlier it was used as an antiseptic but due to its objectionable smell, it has been replaced by other
formulations containing iodine. The antiseptic properties are due to the liberation of free iodine &
not due to iodoform itself.
DDT (p, p’ – Dichlorodiphenyltrichloroethane)
It is a white powder insoluble in water, but soluble in oil.

It is used as an insecticides.
Many species of insects developed resistance to DDT.
It is non-bio-degradable many species of insects developed resistance from DDT, & it was also
discovered to have high toxicity in fish.
The chemical stability of DDT & its fat solubility compounded the problems.
DDT is not metabolised rapidly by animals.
IUPAC Name: 1, 1, 1, -Trichloro – 2, 2 – di (4-chlorophenyl) ethane
Common Name: 𝑝, 𝑝′ − Dichlorodiphenyltrichloroethane
Structure:
Cl
Cl
Cl 1 2 Cl (Structure of DDT)
Cl H
Preparation of DDT:
Cl H Cl Cl Cl
Cl – C – CH O + H+ Cl – C – CH
Cl H Cl Cl Cl
DDT
Freons or CFC (Chlorofluorocarbon)

Chlorofluoro derivatives of methane & ethane are called freons.
Properties & Uses of Freons:
 Freons are colourless, odourless, unreactive & non-combustible liquids.
 They are also used as solvents.
 They have very low boiling points & are easily converted from gaseous state to liquid state,
therefore they are used as a coolant in A.C & Refrigerant.
 They are used as a aerosole propellant in aeroplane & rockets.
Nomenclature of Freons:
 The common name of freons is F-cba,
Where c = number of carbon atoms – 1
b = number of hydrogen atoms + 1
a = total number of atoms of fluorene
Example: CFCl3 : C – 1 ⇒ 1 – 1 = 0, H + 1 ⇒ 0 + 1 = 1, F = 1 ⇒ F-11
CF2Cl2 : C – 1 ⇒ 1 – 1 = 0, H + 1 ⇒ 0 + 1 = 1, F = 2 ⇒ F-12
Preparation of Freons:
SbCl5
CCl4 + HF FCl3 + HCl
F – 11
SbCl5
CFCl3 + HF CF2Cl2 + HCl
F – 12
SbCl5
C2Cl6 + 2HF C2F2Cl4 + 2HCl
Hexachloroethane F – 112
9 IMPORTANT NAME REACTIONS

(a) SANDMEYER’S REACTION :
Benzene diazonium chloride is converted to the chlorobenzene, bromobenzene, cyanobenzene or
treatment with CuCl / KCN respectively.
Cl
CuCl / HCl
+ N2
(Chlorobenzene)
𝑁2+ 𝐶𝑙 − Br
CuBr / HBr
+ N2
(Bromobenzene)
(Benzene Diazonium CN
Chloride)
CuCN / KCN
+ N2
(Cyanobenzene)
(b) FINKELSTEIN REACTION :

Chloroalkanes & Bromoalkanes are converted into the corresponding Iodoalkanes by treating with sodium
iodide dissolved in acetone.
CH3 CH2 Cl + NaI Dry acetone CH3CH2I + NaI
(Ethyl chloride) (Ethyl Iodide)
CH3 CH2 Br + NaI Dry acetone CH3CH2I + NaBr
(Ethyl bromide) (Ethyl iodide)
(c) WURTZ REACTION :
Alkyl halides reacts with metallic sodium in the presence of dry ether to form alkanes this reaction is used
for preparation of higher alkanes.
For example :
CH3Br + 2Na + Br – CH3 Dry ether CH3CH3 + 2NaBr
(Methyl bromide) (Ethane)
CH3 CH Br + 2Na + Br – CH – CH3 Dry ether CH3 - CH - CH - CH3 + 2NaBr
CH3 CH3 CH3 CH3
(Iso-propyl bromide) (2,3-dimethyl butane)
 Wurtz reaction is only useful for preparation of alkanes containing even no. of carbon & not for all the
alkanes containing odd no. of C-atom.
(d) WURTZ-FITTING REACTION :
Aryl halide when treated with alkyl halide & sodium in dry ether give alkyl benzene.
Cl + 2Na + Cl – CH3 Dry ether CH3 + 2NaCl
Cl + 2Na + Cl – C2H5 Dry ether C2H5 + 2NaCl
(e) FITTING’S REACTION :

In this reaction two molecules of haloarens combines with metallic sodium in the presence of dry ether to
give diphenyl or biphenyl.
Cl + 2Na + Cl Dry ether
(Diphenyl or biphenyl)
(f) FRIEDEL-CRAFTS ALKYLATION :
Benzene & other aromatic compounds react with alkyl halides in the presence of anhydrous AlCl3 to form
Alkyl benzene.
CH3
+ CH3Cl ∆AlCl3 + HCl
(Benzene) (Toluene)
CH3 CH3 CH3

CH3
CH3Cl
∆AlCl3 +
(o-xylene) CH3 (p-xylene)
(g) CARBYLAMINE REACTION :
When a primary amine (aliphatic or aromatic) is warmed with chloroform & alcoholic KOH, it forms
isocyanide or Carbylamine having extremely offensive smell.
CH3CH2NH2 + CHCl3 + 3 alco. KOH ∆ CH3CH2NC + 3KCl + 3H2O
(Ethylisocyanide)
NH2 NC
+ CHCl3 + 3KOH ∆ + 3KCl + 3H2O
(Aniline) (Phenylisocyanide)
(h) DOW’S PROCESS :
When chlorobenzene is treated with an aqueous solution of NaOH at 623K, 300atm pressure sodium
phenoxide is formed which on acidification gives phenol.
Cl ONa OH
+ 2NaOH (Aq.) -NCl, -H2O H+

623K, 300atm
(i) HUNDSIEKER’S REACTION :

Bromoalkanes are obtained by this method by refluxing silver salts of fatty acids with Br2 in CCl4.
R – COOAg + Br2 CCl4 / Reflux RR – Br + AgBr + CO2
CH3CH2COOAg + Br2 CCl4 / Reflux CH3CH2Br + AgBr + CO2
This method can employed to decrease number of the C-atoms.
(j) GATTERMAN’S REACTION :
The reaction of diazonium salt’s with ‘Cu’ powder in the present of corresponding halogen acids is
known as the Gatterman’s reaction.
N2Cl Cu / HCl Cl + N2
N2Cl Cu / HBr Br + N2 + HCl
 Distinguish between pairs of organic compound containing halogen :

SILVER NITRATE TEST :
In this test, the halide is warmed with aqueous or alcoholic KOH. The solution is then acidified with
dil.HNO3 followed by addition of AgNO3 solution.
Alkyl, benzyl & allyl halides give precipitate. Aryl & vinyl halides do not give precipitate. It may be noted
that the precipitate formed should be insoluble in HNO3.
Optical Isomerism
Nicol prism or or
Ordinary light Plane polarised zero Left Right

Light rotation rotation rotation
Optically inactive
(does not rotate plane polarised light)
Organic compound Laevorotatory [rotates the plane polarised

(𝑙 or –) light towards left]
Optically active + & – isomers of an
(rotate plane polarised light) organic compound
Dextrorotatory [rotates the plane polarised are optical isomers
(𝑑 or +) light towards right]
CHIRALITY
Chiral: The objects which are not superimposable on their mirror image are called Chiral & this property of
non-superimposability is called Chirality.
Achiral: The objects Which are superimposable on their mirror image are called Achiral.
 NOTE: The concept of chirality can also be applied to organic molecules also.
ASYMMETRIC CARBON
As sp3 hybridused carbon in which all the four valencies are satisfied by different atoms or groups is called
Asymmetric carbon or Stereocentre.
 If a molecule contains symmetric carbon & all the elements of symmetry are absent, the molecule as a whole
will be asymmetric & chiral. Such compounds are optically active.
 The stereoisomers related to each other as non-superimposable mirror images are called enantiomers.
 A mixture containing two enantiomers in equal proportions will have zero optical rotation due to external
compensation. Such a mixture is known is known as racemic mixture or racemic modification.
 The process of conversion of an enantiomer into a racemic mixture is known as racemisation.
Example: −(±) Butan-2-ol or (𝑑𝑙) Butan-2-ol.
MECHANISM OF NUCLEOPHILIC SUBSTITUTION REACTIONS
INVERSION :
If the relative configuration of atoms / groups around a stereo center in the product is opposite to that in
the reactant, the reaction is said to proceed with inversion of configuration. There are three outcomes for a
reaction at an symmetric C-atom. Consider the replacement of a group X by Y in the following reaction :-
C2H5 C2H5 C2H5
Y Y
H H H
Y X Y
CH3 CH3 CH3
(B) (A)
Y
A+B
If (A) is the only compound obtained, the process is called retention of configuration. If (B) is the only
compound obtained, the process is called inversion of configuration, the process is called racemisation
& the product is optically inactive is one isomer will rotate light in the direction opposite to another.
[I] Mechanism of Nucleophilic substitution reaction in Alkyl Halides :-

It can be take place by either of two mechanism; SN1 or SN2.
(i) Substitution nucleophilic unimolecular (SN1) :
It takes place in two steps & reaction is of first order. In the first step, alkyl halide undergoes slow
heterolysis to produce carbonium ion intermediate & a halide ion. In the second step nucleophile rapidly
combines with the carbonium into complete the substitution reaction. A nucleophilic substitution reaction
can proceed through either of the following two mechanisms:
* R1 R1
R11 C–X Slow R11 C+ + X--
R111 R111
(Carbonium ion)
1
**R R1
R11 C+ + Nu- R11 C+ - Nu
R111 R111
SN1 reaction of optically active halides are accompanied by racemisation. This is because the carbonium
formed in the slow step being sp2 hybridised is plane (achiral) therefore, the attack of nucleophile on it
can occur from both the faces with equal ease giving a mixture containing two enantiomers in equal
amounts. This may be illustrated by hydrolysis of optically active 2-bromobutane, which gives (±)
butan-2-ol.
H3C CH3
H R + H + Br
Br
H3CH2C CH2CH3
(+) or (-) 2-bromobutane Carbonium ion
CH3 CH3 CH3

OH-(Inversion) OH-(Rettention)
H rear attack + H Frontal attack H
OH HO
CH2CH3 CH2CH3 H3CH2C
(ii) Substitution nucleophilic bimolecular (SN2) :

It takes place in one steps & the reaction is of second order. In this process the nucleophile attack the
partially positive carbon of the C – X bond of the substrate, alkyl halide, from the back side of the
C – X bond & the leaving group, X- , departs simultaneously.
H H H
Nu + H X Nu X Nu H+ + X--
H H H H
2
SN reaction of optically active halides are accompanied by inversion of configuration. This is because
the attack of nucleophile occurs from a direction opposite to the one from where the halogen atom leaves.
The order of reactivity of alkyl halides towards SN1 & SN2 is as follows :-
SN1 reactivity increases
R11
CH3X RCH2X R – CH – X R–C–X
1
R R1
0 0
1 2 30
SN2 reactivity increases
Order of reactivity: For the same halide group
For SN1 mechanism: 30 > 20 > 10 (According to the stability of intermediate carbonium ion)
For SN2 mechanism: 10 > 20 > 30 (According to steric hindrance)
 NOTE: For the same alkyl group R – I > R – Br > r – Cl > R – F (for both SN1 & SN2)
An alkyl group at the 𝛼-Carbon, being bigger in size, than H-atom, tends to block the approach of the
nucleophile to carbon due to steric hindrance in SN2 mechanism & makes the reaction difficult to occur.
In the SN1 mechanism, a carbocation is formed in the first, slow step. The more stable the carbocation,
more easily is the product formed. Tertiary alkyl halides undergoes SN1 reaction very fast because of the
high stability of tertiary carbocation.
CH3 < R – CH2 < R – CH – R < R – C – R1
R11
Primary allylic & benzylic halides shows higher reactivity in SN1 reaction than other primary halides.
This is due to stabilisation of allylic & benzylic carbocation intermediate by resonance.
CH2 = CH – CH2 CH2 – CH = CH2
(Resonance in allyl carbocation)
CH3 CH2 CH2 CH2 CH3
CANONICAL FORM
RESONANCE STABILIZATION IN BENZYL CARBOCATION
Thus, primary alkyl halides almost always react predominantly by SN2 mechanism. Tertiary alkyl halides
react predominantly by SN1 mechanism. Secondary alkyl halides may react by both the mechanisms
without much preference. Polar solvents favour SN1 , & non-polar solvent favours SN2 reaction.
USES OF HALOGEN DERIVATIVES

This class of compounds finds wide applications in laboratories, industries, health care & medicines.
 As Solvent: Chloroform CHCl3, Carbon tetrachloride CCl4 are used as solvent.
 As Insecticides: DDT & BHC (contain chlorine in them) are used as insecticides.
 As Medicine: Chloramphenicol (contains chlorine & used in the treatment of typhoid fever), Chloroquine
(used in treatment of malaria).
 As Hormone: Thyroxine, an iodine containing hormone, is produced by our body. Its deficiency cause a
disease called Goitre.
Aliphatic Hydrocarbons (Aliphatic halogen compounds)

Halogen compounds may be derived form
Aromatic Hydrocarbons (Aromatic halogen compounds)
1
Classification of Halogen Compounds
On the basis of number of Halogen atoms
Halogen derivatives of alkanes i.e., Haloalkanes may be classified as:
Monohaloalkanes Dihaloalkanes Trihaloalkanes Tetrahaloalkanes
General formula: General formula: General formula: General formula:

–2H –3H – 4H
–H
𝐶𝑛 𝐻2𝑛+2 𝐶𝑛 𝐻2𝑛+1 𝑋 𝐶𝑛 𝐻2𝑛+2 𝐶𝑛 𝐻2𝑛 𝑋2 𝐶𝑛 𝐻2𝑛+2 𝐶𝑛 𝐻2𝑛−1 𝑋3 𝐶𝑛 𝐻2𝑛+2 𝐶𝑛 𝐻2𝑛−2 𝑋4
Alkane +2X Alkane +3X Alkane +4X
Alkane +X
Example: C2H5Cl Example: CH2Cl2 Example: CHCl3 Example: CCl4
Aromatic Halogen Compounds can be classified as:

Monohaloarene Dihaloarene Trihaloarene Benzyl halide Benzal halide Benzo halide
X X X CH2 – X CHX2 CX3

X X
Factors which tend to favour substitution & elimination in alkyl halides
S. No. Factors SN1 SN2 E1 E2
1. Structure of alkyl halide 30 >> 20 > 10 10 > 20 > 30 30 30 or 20

2. Nature of reagent Weak nucleophile Strong nucleophile Strong base Strong base
3. Concentration of reagent Low High Low High
4. Nature of solvent Highly polar Lower polarity Polar Low polarity
5. Temperature Moderate Moderate High High
From Alkene
Addition of HX Allylic halogenation

HBr CH3 – CH = CH2
RCHBrCH3
NBS. U.V. Peroxide
(According to Markovnikov’s rule)
RCH = CH2 Or,
Peroxide SO2Cl2 + Peroxide. U.V.
RCH2CH2Br
(Anti Markovnikov’s rule)
Cl – CH2 – CH = CH2 + HCl
(Allyl bromide)
SOME OF THE IMPORTANT REACTIONS OF HALOALKANE
Name of reaction Reagents used Equation

& conditions
Hydrolysis of NaOH (Aq) CH3CH2CH2Cl + NaOH Reflux
CH3CH2CH2OH + NaCl
Haloalkane under reflux 1-Chloropropane Sodium Propan-1-ol
hydroxide
Ethanol
Formation of KCN/ethanol CH3CH2CH2Br + KCN Reflux CH3CH2CH2CN + KBr
Nitrile under reflux 1-Bromopropane Potassium Butanenitrile
cyanide
Ethanol
Formation of Conc. NH3/ CH3CH2CH2Br + NH3 Reflux CH3CH2CH2NH2 + HBr
Amine Ethanol 1-Bromopropane Conc. Butanamine
Ammonia
Ethanol + NaOH
Formation of NaOH / CH3CH2CH2Cl Reflux CH3CH = CH2 + HCl
Alkene Conc. ethanol 1-Chloropropane Propene
ALKYL HALIDES (RX)

 General formula – 𝐶𝑛 𝐻2𝑛+1 𝑋.
 They can show chain, position & optical isomerism.
 Due to electronegativity difference between the carbon & the halogen, the shared pair of electron lies closer
to the halogen atom.
 As a result, the halogen carries a small negative charge, while the carbon carries a small positive charge.
Consequently, C – X bond is a polar covalent bond.
Method of Preparation of Alkyl Halides
From Alcohol
(a)
By reaction with HX By reaction with PX3 or PX5 By reaction with SOCl2
HCl + anhy. ZnCl2 +PX3 Darzen reaction
RCl RX + H3PO3 ROH + SOCl2
HBr + H2SO4 +PX5
ROH RBr ROH RX + POCl3 + HX Pyridine
HI + reflux +P4 /X2 RCl + SO2 + HCl

RI RX
 ZnCl2 acts as dehydrating agent to promote C – O bond cleavage.

 Alkyl chlorides are best prepared by SOCl2 because SO2 & HCl formed as by product are gases which can
be easily removed.
 The reactivity of alcohols – 30 > 20 > 10.
 The reactivity of alkyl halides – HI > HBr > HCl.
Borodine – (Hunsdiecker reaction)

CCl4 / reflux
RCOOAg + Br2 R – Br + AgBr + CO2
 Reaction proceeds via free radical
 Reaction is used in descending of homologous series.
 Yield of alkyl bromides follow the order; 10 > 20 > 30
SUMMARY OF THE REACTIONS OF HALOALKANES
Reaction with metals Nucleophilic Substitution Reactions

Alkanes
Na, Ether Aq. KOH
CH3CH2CH2CH3 C2H5OH
Wurtz reaction Alcohols
+
Na OCH3
C2H5OCH3
Ethers
Mg, Ether KNO2
CH3CH2MgBr C2H5ONO
Grignard reagent Alkyl nitrites
AgNO2
C2H5NO2
Nitroalkanes
CH3COOAg
Elimination Reaction C2H5COOCH3
Ester
Alc. KOH C2H5Br NH3
CH2 = CH2 C2H5NH2 (C2H5)2NH
Alkene 10 amine 20 amine
(C2H5)4N+Br– (C2H5)3NH
30 amine
H2 , Ni NaSH
C2H6 C2H5SH
Thioalcohols
HI , Red P AgCN
C2H6 C2H5NC
Isocyanides
Zn/Cu (Couple) CH3C ≡ CNa
C2H6 C2H5C ≡ CCH3
Alkynes
Sn/HCl KCN
C2H6 C2H5CN
Cyanides
Reduction
Conc. HCl
/alk. H2O2 Dil. HCl Ni, H2
C2H5CN C2H5COOH C2H5CH2NH2

Amide Acid Amine
ARYL HALIDES (ArX)

Reactions of haloarenes: Aryl halides are extremely less reactive towards nucleophilic substitution
reaction due to following reasons:
(a) Resonance effect: In haloarenes, the lone pair of electron on the halogen atom are delocalized on
the benzene ring as:
Cl +Cl +Cl +Cl Cl
As a result, C – Cl bond acquires some double bond character. Consequently, C – X bond in aryl
halides is little stronger than in alkyl halides, & hence cannot be easily broken.
(b) In haloalkane, the halogen is attached to sp3 – hybridised carbon while in haloarenes the halogen is
attached to sp2 – hybridized carbon. Since sp2 – hybridized orbital is smaller in size as compared to
sp3 – carbital of carbon, therefore, the C – Cl bond in haloarenes should be shorter & hence
stronger than in methyl chloride.
(c) In haloarenes, the phenyl cations formed as a result of self-ionisation will not be stabilised by
resonance & therefore, SN1 mechanism is ruled out.
Method of Preparation of Aryl Halides (ArX) Chemical Properties
(a) From diazonium salt: OH

Cl Br
7% NaOH, 623 K, 300 atm
CuCl/HCl or CuBr/HBr or + N2 Dil. HCl
Sandmeyer reaction (Dow’s process)
Chlorobenzene Bromobenzene NH2
Cl Br NH3 , Cu2O, 573 K, Press.
Cu/HCl or Cu/HBr or + N2 (Dow’s process)

Gattermann reaction CN
Diazonium salt
C6H5N2Cl
Chlorobenzene Bromobenzene
CuCN, 475 K, Pyridine
F
HBF4 + N2 + BF3 Cl
Balz Schiemann reaction KNH2 *
Fluorobenzene
I (i) NH2 , (ii) NH3 (Solvent)

o & p –Benzyne
Aq. KI / Δ + N2 CH3Cl , anhy. AlCl3
o & p – chloro
Iodobenzene Toluene
(b) Nuclear halogination: Cl CH3COCl , anhy. AlCl3
o & p – chloro
Cl2 / AlCl3 + HCl acetophenone
Fluorobenzene Mg (Tetrahydrofuran)
I C6H5MgCl
Benzene I2 / HIO3 + HI Na / Dry ether
C6H5C6H5
Iodobenzene Diphenyl
(Fitting reaction)
(c) Side chain substitution: occurs in absence of Lewis 2[H]
acid & in presence of light. Side chain hydrogen
Zn / Cu or Ni – Al; NaOH Benzene
are substituted by halogen atoms.
Conversations Related to Alkyl Halides

RCH2CH2CH2OH
RCH2CH3 H+ HCHO (10 Alcohol)
R CH2CH2 – CH – OH
R’CHO R’
(20 Alcohol)
R – CH2CH2MgBr R’’
Mg, Dry ether [Grignard reagent] R’COR’’
R – CH2CH2 – C – OH
R’
CO2 (30 Alcohol)
R CH2CH2COOH
RCH2CH2Br + 2Na + BrCH2CH2R Dry ether RCH2CH2CH2CH2R Wurtz reaction
Alkyl halide –NaBr (Alkane)
AgF/Δ R CH2CH2 F
[Swarts reaction] (Fluoroalkane)
Alc. KOH R CH = CH2 Br2 R – CHBr – CH2Br NaNH2/KNH2 RC ≡ CH

(Alkene) or 2 alc. KOH (Alkyne)
Aq. KOH RCH2CH2OH Cu/573K RCH2CHO Aldehyde

Acidic KMnO4 Alk. KMnO4
RCH2COOH
NH3 RCH2CH2NH2
– HCl (10Amine)
KCN RCH2CH2CN H2O / H+ RCH2CH2COOH

(Cyanide) (Carboxylic acid)
AgCN RCH2CH2NC H2/Ni/Pb RCH2CH2 – NH – CH3

(Cyanide) or LiAlH4 / Ether (20 Amine)
 Reaction of alcohol with thionyl chloride (SOCl ) is best method to prepare escaped out
2
& pure haloalkanes is formed.
 According to Markovnikov’s rule negative part of chemical reagent is attached with that
carbon of alkene or alkyne having least number of hydrogen atom so it is used to shift a
group from outside to inner side.
 According to Antimarkovnikov’s rule (peroxide effect) positive part of chemical reagent
is attached with that carbon of alkene or alkyne having least number of hydrogen atom
so it is used to shift a group from innerside to outside but it is used only with HBr and
in presence of organic peroxide. Example., Propan-2-ol to Propan-1-ol.
 Haloalkane are polar compound but immiscible with water because they can not form
hydrogen bond with H2O molecule.
 Grignard reagent should be prepared in anhydrous condition because it reacts with
moisture & form alkane.
Conversion Related to Aryl Halides

CHO ̅ Na+
O OH
NaOH Dil. HCl

623K , 300atm (Dow’s Process)
(Benzaldehyde) (Phenol)
(i) CrO2Cl2/CCl4 CuCN, Pyrimidine H 2O/H+ O H+

(ii) H3O+
CH3 SN reaction CN C – NH2 COOH
(Etard reaction)
(Toluene) (Benzonitrile) (Benzamide) (Benzoic acid)
` Cl
+ 2Na + Cl
CH3Cl + 2Na
– 2NaCl
(Wurtz-Fitting rkn) (Diphenyl) (Fiiting reaction)
Chlorobenzene
AgCN 2H/Ni-Al (Benzene)
N C
CH3COCl COCH3
(Acetophenone)
(Isonitrile)
H2 / Ni / Pd Cl2 / Anh. FeCl3 Cl + Cl Cl
NH – CH3 Cl (p-dichlorobenzene)
(o-dichlorobenzene)
Conc. H2SO4 Cl + HO3S Cl

(20 amine)
(arylalkylamine) SO3H (p-chlorobenzene sulphonic acid)
(o-chlorobenzene sulphonic acid)
HNO3/H2SO4 Cl + NO2 Cl
NO2 (p-chloronitrobenzene)
(o-chloronitrobenzene)
CH3Cl / AlCl3 Cl + CH3 Cl
CH3 (p-chlorotoluene)
(o-chlorotoluene)
 Boiling point of haloalkanes are not very high due to dipole-dipole attraction and it is
directly proportional to size and molecular mass so order of boiling point among different
halide is R – I > R – Br > R – Cl > R – F.
 Haloarenes are less reactive than haloalkanes for nucleophilic substitution reaction
because in Haloarenes C – X bond acquire a partial double bond character due to
resonance. As a result the bond in haloarene is difficult to break than haloalkanes.
 Required conditions for a compound to be optically active are presence of chiral carbon,
non-superimposability and absence of plane of symmetry.
1. Name of the following halides according to IUPAC System and classify them as alkyl, allyl, benzyl
(primary, secondary, tertiary), vinyl or alkyl halides:
(a) (CH3 )2 CHCH(Cl)CH3
(b) CH3 CH2 CH(CH3 )CH(C2 H5 )Cl
(c) CH3 CH2 C(CH3 )2 CH2 I
(d) (CH3 )3 CCH2 CH(Br)C6 H5
(e) CH3 CH(CH3 )CH(Br)CH3
(f) CH3 C(C2 H5 )2 CH2 Br
(g) CH3 C(Cl)(C2 H5 )CH2 CH3
(h) CH3 CH = C(Cl)CH2 CH(CH3 )2
(i) CH3 CH = CHC(Br)(CH3 )2
(j) p − ClC6 H4 CH2 CH(CH3 )2
(k) m − ClCH2 C6 H4 CH2 C(CH3 )3
(l) o − Br − C6 H4 CH(CH3 )CH2 CH3
Ans: (a) CH3 Cl
4 3 2 1
CH3 – CH – CH – CH3
2 − Chloro − 3 − methylbutane
(Secondary alkyl halide)
(b) CH3 Cl
6 5 4 3 2 1
CH3 – CH2 – CH – CH – CH2 – CH3
3 − Chloro − 4 − methylhexane
(c) H3C
4 3 2 1
CH3 – CH2 – C – CH2 – I
1 − Iodo − 2,2 − dimethylbutane
(Primary alkyl halide)
(d) H3C
4 3 2 1
CH3 – C – CH2 – CH
1 − Bromo − 3,3 − dimethyl − 1 − phenylbutane
(e) CH3 Br
4 3 2 1
2 − Bromo − 3 − methylbutane
(f) C2H3
2 1
CH3 – C – CH2 – Br
3
CH2
4
CH3
2 − Bromo − 2 − ethyl − 2 − methylbutane
(Primary alkyl halide)
(g) Cl
3 4 5
CH3 – C – CH2 – CH3
2
CH2
1
CH3
2 − Chloro − 3 − methylpentane
(Tertiary alkyl halide)
Cl CH3
1 2 3 4 5 6
(h) CH3 – CH = C – CH2 – CH – CH3 (C = C − Cl)
3 − Chloro − 5 − methylhex − 2 − ene Vinylic
(Vinyl halide)
Br
1 2 3 4 5
(i) CH3 – CH = CH – C – CH3 (C = C − C − Cl)
CH3
3 − Bromo − 4 − methylpent − 2 − ene Allylic
(Allyl halide)
CH2 – CH – CH3
4
CH3
5 3
(j) 6 2 (Ph − Cl)
1
Cl
1 − Chloro − 4 − (2 − methylpropyl) benzene Arylic
CH3
1 2 3
(k) CH2 – C – CH3
3
CH3
4 2
5 1 (Ph − CH2 − Cl)
6 CH2Cl
1 − Chloro − 4 − (2 − methylpropyl) benzene Benzylic
1 2 3
(l) CH3 – CH – CH2 – CH3
2
1 Br
3
4 6
5
1 − Bromo − 2 − (1 − methylpropyl) benzene
2. Give the IUPAC names f the following compounds:
(a) CH3 CH(Cl)CH(Br)CH3
(b) CHF2 CBrClF
(c) ClCH2 C ≡ CCH2 Br
(d) (CCl3 )3 CCl
(e) CH3 C(p − ClC6 H4 )2 CH(Br)CH3
(f) (CH3 )3 CCH = CClC6 H4 I − p
Ans: (a) Cl Br
4 3 2 1
2 − Bromo − 3 − chlorobutane
(b) F Cl
2 1
F – CH – C – F
Br
1 − Bromo − 1 − chloro − 1,2,2 − trifluoroethane
4 3 2 1
(c) Cl – CH2 – C ≡ C – CH2 – Br
1 − Bromo − 4 − chlorobut − 2 − yne
Cl
Cl – C – Cl
(d) Cl Cl
1 2 3
Cl – C – C – C – Cl
Cl Cl Cl
2 − (Trichloromethyl) − 1,1,1,2,3,3,3 − heptachloropropane
3’ 2’
CH3
4’ 1’ 3
(e) Cl C Cl
5’ 6’ 2
CH – Br
1
CH3
2 − Bromo − 3,3 − bis(4′ chlorophenyl) butane
CH3
1 2 3 4
(f) Cl – C = CH – C – CH3
1’
CH3
2’ 6’
3’ 5’
4’
I
1 − Chloro − 1 − (4 − iodophenyl) − 3,3 − dimethylbut − 1 − ene
3. Write the structures of the following organic halogen compounds.
(a) 2 − Chloro − 3 − methyl pentane
(b) p − Bromochlorobenzene
(c) 1 − Chloro − 4 − ethylcyclohexane
(d) 2 − (2 − Chlorophenyl) − 1 − idodooctane
(e) 2 − Bromobutane
(f) 4 − Tert − butyl − 1 − 3 − idoheptane
(g) 1 − Bromo − 4 − sec − butyl − 2 − methyl benzene
(h) 1,4 − Dibromobut − 2 − ene
Ans: (a) CH3 – CH – CH – CH2 – CH3
Cl CH3
Cl
(b)
Br
Cl
(c)
Et
(d) CH2 – CH – CH2 – CH2 – CH2 – CH2 – CH2 – CH3
I Cl
(e) CH2 – CH – CH2 – CH3
Br
I
(f) CH3 – CH2 – CH – CH – CH2 – CH2 – CH3
CH3 – C – CH3
CH3
Br
(g) CH3
CH3 – CH – CH2 – CH3

(h) CH2 – CH = CH – CH2
Br Br
4. Which of the following has the highest dipole moment?
(a) CH2 Cl2
(b) CHCl3
(c) CCl4
Ans: H H H Cl Cl Cl
C C C
Cl Cl Cl Cl Cl Cl
Dichloromethane(CH2 Cl2 ) Trichloromethane(CHCl)2 Carbon tetrachloride (CCl4 )
𝜇 = 1.60𝐷 𝜇 = 1.08𝐷 𝜇 = 0𝐷
CCl4 < CHCl3 < CH2Cl2
5. A hydrocarbon C5 H10 does not react with chlorine in dark but gives a single monochloro compound
C5 H9 Cl in bright sunlight. Identify the hydrocarbon.
Ans:
Cyclopentane (C5H10)
The reactions involved in the question is:

Cl2 /dark
No reaction
Cl
Cl2 /Sunlight
Cyclopentane
Mono chlorocyclopentane (C5H10)

6. Write the isomers of the compound having formula C4 H9 Br.
Ans: There are four isomers of the compound having the formula C4H9Br.
These isomers are given below.
(a) (b) Br
4 3 2 1 4 3 2 1
CH3 – CH2 – CH2 – CH2 – Br CH3 – CH2 – CH – CH3
1 − Bromobutane 2-Bromobutane
(c) CH3 (d) Br
3 2 1 3 2 1
CH3 – CH – CH2 – Br CH3 – C – CH3
CH3
1 − Bromo − 2 − methylpropane 2-Bromo −2 − methylpropane
7. Write the equations for the preparation of 1 − iodobutane from
(a) 1 − butanol
(b) 1 − chlorobutane
(c) but − 1 − ene
Al O H-Br
Ans: (a) CH3 – CH2 – CH2 – CH2 – OH 2 3 CH3 – CH2 – CH = CH2
R2O2 /∆
NaI
CH3 – CH2 – CH2 – CH2 – I CH3 – CH2 – CH2 – CH2 – Br
Dry acetone
(b) CH3 – CH2 – CH2 – CH2 – Cl + NaI (Finkelstein reaction) NaCl + CH3 – CH2 – CH2 – CH2 – I
1 − Chlorobutane 1 − Iodobutane
Peroxide
(c) CH3 – CH2 – CH = CH2 + HBr CH3 – CH2 – CH2 – CH2 – Br
(Anti-Markownikoff’s addition)
1 − 𝐵romobutane
NaI / Dry acetone
NaBr + CH3 – CH2 – CH2 – CH2 – I
1 − 𝐼odobutane
8. What are ambident nucleophiles? Explain with an example.
Ans: Ambident nucleophiles are nucleophiles having two nucleophilic sites.
Example, Nitrite ion is an ambident nucleophile.
[𝑂̅ − 𝑁̈ = 𝑂]
9. Which compound in each of the following pairs will react faster in SN2 reaction with OH − ?
(a) CH3 Br or CH3 I
(b) (CH3 )3 CCl or CH3 Cl
Ans: (a) CH3 – I is more reactive because I Θ is better leaving group than Br Θ .
CH3
(b) H3C – C – Cl < CH3 – Cl
CH3
In case of (CH3)3CCl, the attack of the nucleophile at the carbon atom is hindered of the
presence of bulky substituents on that carbon atom bearing the leaving group.
10. Predict all the alkenes that would be formed by dehydrohalogenation of the following halides with
sodium ethoxide in ethanol and identify the major alkene.
(a) 1 − Bromo − 1 − methylcyclohexane
(b) 2 − Chloro − 2 − methylbutane
(c) 2,2,3 − Trimethyl − 3 − bromopentane
Br CH3 CH3
Ans: (a)
C2H5ONa / C2H5OH
(Only one alkene)

CH3 CH3 CH3
C2H5ONa / C2H5OH
(b) CH3 – CH2 – C – CH3 CH3 – CH = C – CH3 + CH3 – CH2 – C = CH2
−𝐻𝐵𝑟
CH3 2− Methyl−2 −butene 2 −Methyl−1 −butene
(Major) (Major)
H3C Br CH3 H3C CH2

C2H5ONa / C2H5OH
(c) CH3 – C – C – CH2 – CH3 CH3 – C – C = CH – CH3 + CH3 – C – C – CH2 – CH3
−𝐻𝐵𝑟
H3C CH3 H3C CH3 CH3
3,4,4 − Trimethyl−2 − ene 2 − Ethyl−3,3 − dimethylbut
(I) (Major) −1 − 𝑒𝑛𝑒 (II) (Minor)
11. How will you bring about the following conversion?
(a) Ethanol to but − 1 − yne
(b) Ethane to bromoethene
(c) Propene to 1 − nitropropane
(d) Toluene to benzyl alcohol
(e) Propene to propyne
(f) Ethanol to ethyl fluoride
(g) Bromoethane to propanone
(h) But − 1 − ene to but − 2 − ene
(i) 1 − Chlorobutane to n − octane
(j) Benzene to biphenyl
SOCl2 , Pyridine
Ans: (a) CH3 – CH2 – OH CH3 – CH2 – Cl + SO2 + HCl
Ethanol Chloroethane
Liq. NH3
(i) HC ≡ CH + NaNH2 HC ≡ CNa
Ethylene Sodium acetylide
CH ≡ CNa + CH3 – CH2 – Cl CH3 – CH2 – C ≡ CH + NaCl
But −1 − yne
(ii) CH ≡ CMgBr + CH3 – CH2 – Cl CH3 – CH2 – C ≡ CH + MgClBr
But −1 − yne
Br2 / UV Light −H-Br
(b) CH3 – CH3 CH3CH2Br + HBr CH2 = CH2
or heat KOH(alc.) /∆
Ethane Bromoethane Ethene
KOH (alc.) Br2 / CCl4

CH2 = CHBr BrCH2 – CH2Br
∆
Bromoethene Vic − Dibromide
Or,
ℎ𝑣 KOH (alc.) Br2 / CCl4
CH3 – CH2 + 2Cl2 CH3 – CHCl2 ∆ CH ≡ CH CH2 = CH – Br
Peroxide AgNO2
(c) CH3 – CH = CH2 + HBr CH3 – CH2 – CH2Br AgBr + CH3 – CH2 – CH2NO2
Propene 1 − Bromopropane 1 − Nitropropaane
CH3 CH2Cl CH2OH
(d) Cl2 /UV Light NaOH (Alc.)

or Heat NaCl

Br2 / CCl4 NaNH2
(e) CH3 – CH = CH2 CH3 – CH – CH2 CH3 – C ≡ CH
Liq. NH3
Propene Br Br Propyne
1,2 − Dibromopropane
PCl5 AgF
(f) CH3 – CH2 – OH −POCl , −𝐻𝐶𝑙 CH3 – CH2 – Cl CH3 – CH2 – F
3
Ethanol Chloroethane Ethyl fluoride
KOH (alc.) CH3 – MgBr Hydrolysis
(g) CH3 – Br CH3 – CN CH3 – C = NMgBr CH3 – C = O
𝐻3 𝑂 +
Bromomethane Acetonitrile CH3 CH3
Propanone
HBr KOH (alc.)/∆
(h) CH3CH2CH=CH2 (Markownikoff’s
CH3CH2CHCH3 −𝐻𝐵𝑟
CH3 – C ≡ CH
But − ene addition) Br 2 − Butene
2 − Bromobutane
Dry ether
(i) 2CH3CH2CH2CH2 – Cl + 2Na CH3CH2CH2CH2CH2CH2CH2CH3
– 2NaCl
1 − Chlorobutane n − Octane
Br
(j) Br2 / Fe Na + 2NaBr
Dark Dry ether
Benzene Bromobenzene Diphenyl

12. Explain why:
(a) The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride?
(b) Alkyl halides, though polar, are immiscible with water?
(c) Grignard reagent should be prepared under anhydrous conditions?
Ans: (a) δ− 𝛿−
Cl Cl
δ+ δ+
sp2 sp3
Chlorobenzene Cyclohexylchloride
+𝑀 of – 𝐶𝑙 and – 𝐼 of – 𝐶𝑙 are in opposite direction so 𝑑. 𝑚. is decreased in chlorobenzene.
(b) No 𝐻 − bonding of halide with water.
(c) Grignard reagents in the presence of moisture, they react with H2O to give alkanes.
𝛿− 𝛿+ 𝛿−
𝑅 𝑀𝑔 𝑋 + 𝐻2 𝑂 𝑅 − 𝐻 + 𝑀𝑔(𝑂𝐻)𝑋
Grignard reagent Alkane
13. Give the uses of Feron 12, DDT, Carbon tetrachloride and iodoform.
Ans: Uses of Feron – 12: Feron – 12 (dichlorodifluoromethane, CF2 Cl2 ) is commonly known
as CFC. It is used as a refrigerant in refrigerators and air conditioners.
Uses of DDT: (𝑝 − 𝑝 − dichlorodiphenyltrichloroethane) is one of the best known insecticides.
Uses of carbontetrachloride (CCl4):
(a) It is used for manufacturing refrigerants and propellants for aerosol cans.
(b) It is used as a solvent in the manufacture of pharmaceutical products.
(c) It is used as a fire extinguisher.
Uses of iodoform (CHI3 ): Iodoform was used earier as an antiseptic. The antiseptic
property of iodoform is only due to the liberation of free iodine
when it comes in contact with the skin.
14. Write the structure of the major organic product in each of the following reactions.
Acetone heat
(a) CH3 CH2 CH2 Cl + NaI
Ethanol heat
(b) (CH3 )3 CBr + KOH
Water
(c) CH3 CH(Br)CH2 CH3 + NaOH
Aqueous acetone
(d) CH3 CH2 Br + KCN
(e) C6 H5 ONa + C2 H5 Cl
(f) CH3 CH2 CH2 OH + SOCl2
(g) CH3 CH2 CH = CH2 + HBr
(h) CH3 CH = C(CH3 )2 + HBr
Acetone heat
Ans: (a) CH3 CH2 CH2 Cl + NaI (Finkelstein reaction) CH3CH2CH2I + NaCl
1 − Chloropropane 1 − Iodopropane
Ethanol heat
(b) (CH3 )3 CBr + KOH (Dehydrohalogenation) CH3 – C = CH2 + KBr + H2O
2 −Bromo−2 − CH3
methylpropane 2 − 𝑀ethylpropane
Water
(c) CH3 CH(Br)CH2 CH3 + NaOH CH3CH(OH)CH2CH3 + NaBr
2 − 𝐵romobutane Butan−2 −ol
Aqueous acetone
(d) CH3 CH2 Br + KCN (Nucleophilic substitution) CH3CH2CN + KBr
Cyanoethane
(Williamson synthesis)
(e) C6 H5 ONa + C2 H5 Cl C6H5 – O – C2H5 + NaCl
Sodium Chloroethane Phenetole
phenoxide
(f) CH3 CH2 CH2 OH + SOCl2 CH3CH2CH2Cl + SO2 + HCl
1 − Propanol 1 − Chloropropane
(g) CH3 CH2 CH = CH2 + HBr CH3CH2CH2CH2 – Br
But−1 −ene 1 − Bromobutane
Br
Acetone heat
(h) CH3 CH = C(CH3 )2 + HBr CH3 – CH2 – C – CH3
(Markownikoff’s addition)
2 − 𝑀ethylbut−2 − 𝑒𝑛𝑒 CH3
2 − Bromo−2 −methylbutane
15. Write the mechanism of the following reaction:
EtOH – H O
nBuBr + KCN 2
nBuCN
Ans: The given reaction is : An SN2 reaction. In this reaction, CN − acts as the nucleophile
and attacks the carbon atom to which Br in attached. CN − ion is an ambident nucleophile
and can attack through both C and N. In this case, it attacks through the 𝐶 − atom.
C3H5 C3H5 C3H5
H – C – Br NC --- C --- Br NC – C – H + Br −
H H H H
16. Arrange the compound of each set in order of reactivity towards SN2 displacement:
(a) 2 − Bromo − 2 − methylbutane, 1 − Bromopentane, 2 − Bromopentane
(b) 1 − Bromo − 3 − methylbutane, 2 − Bromo − 2 − methylbutane,
3 − Bromo − 2 − methylbutane
(c) 1 − Bromobutane, 1 − Bromo − 2 − dimethylpropane,
1 − Bromo − 2 − methylbutane, 1 − Bromo − 3 − methylbutane
1
Ans: (a) 𝑆𝑁2 ∝ 𝐻𝑖𝑛𝑑𝑟𝑎𝑛𝑐𝑒 𝑜𝑛 𝑐𝑎𝑟𝑏𝑜𝑛
Br Br
CH3CH2CH2CH2CH2 – Br > CH3CH2CH2CHCH3 > CH3CH2CCH3
Br
1 − Bromopentane (10 ) 2 − Bromopentane (20 ) 2 − Bromo−2 − methylbutane (30 )
(b) CH3 Br Br
CH3CHCH2CH2 – Br > CH3CHCHCH3 > CH3CCH2CH3
CH3 Br
1 − Bromo−3 − 2 − Bromo−3 − 2 − Bromo−2 −
methylbutane (10 ) methylbutane (20 ) methylbutane (30 )
Since steric hindrance in alkyl halides increases in the order of 10 < 20 < 30 , increasing
order of reactivity towards SN 2 displacement is 30 < 20 < 10 . Reactivity towards SN2 is:
2-Bromo-2-methylbutane < 2-Bromo-3-methylbutane < 1-Bromo-3-methylbutane.
CH3
(c) CH3 – CH2 – CH2 – CH2 – Br CH3 – CH – CH2 – CH2 – Br
1 − 𝐵romobutane (10 ) 1 − 𝐵romo−3 −methylbutane (10 )
CH3 CH3
CH3 – CH2 – CH – CH2 – Br CH3 – C – CH2 – Br
CH3
1 − 𝐵romo−2 −methylbutane (10 ) 1 − 𝐵romo−2,2 −dimethylbutane
(More branching at nearer distance)
Hence, the increasing order of reactivity of the given compounds towards SN2 is:
1-Bromo-2,2-dimethylpropane < 1-Bromo-2-methylbutane
< 1-Bromo-3-methylbutane < 1-Bromobutane.
17. Out of C6 H5 CH2 Cl and C6 H5 CHClC6 H5 , which is more easily hydrolysed by aqueous KOH?
Ans: C6H5CHClC6H5 (more reactive)
C6H5 – CH2 – Cl C6H5 – +CH2

𝐶𝑙 −
Benzyl chloride 10 Carbocation
Cl
C6H5 – CH – C6H5 C6H5 – +CH – C6H5
𝐶𝑙 −
Chlorodiphenylmethane 20 Carbocation
(More stable intermediate)
18. p − Dichlorobenzene has higher melting point and lowersolubility than those of o − and
m − isomers. Discuss.
Ans: Cl Cl Cl
Cl
Cl
Cl 𝑜 − Dichlorobenzene 𝑚 − Dichlorobenzene
𝑝 − Dichlorobenzene
𝑝 − Dichlorobenzene is more symmetrical than 𝑜 − and 𝑚 − isomers.
For this reason, molecules of 𝑝 − Dichlorobenzene are more closely than 𝑜 − and
𝑚 − isomers in the crystal lattice. Therefore, more energy is required to break the
crystal lattice of 𝑝 − Dichlorobenzene.
19. How the following conversions can be carried out?
(a) Propene to propan − 1 − ol
(b) 1 − Bromopropane to 2 − bromopropane
(c) Benzene to 4 − bromonitrobenzene
(d) Benzyl alcohol to 2 − phenylethanoic acid
(e) Ethanol to propanenitrile
(f) Aniline to chloro benzene
(g) 2 − Chlorobutane to 3,4 − dimethylhexane
(h) 2 − Methyl − 1 − propene to 2 − chloro − 2 − methyl propane
(i) Ethyl chloride to propanoic acid
(j) But − 1 − ene to n − butyliodide
(k) 2 − Chloropropane to 1 − propanol
HBr/Peroxide
Ans: (a) CH3CH = CH2 CH3CH2CH2CH2Br or CH3CH=CH2
Propene 10 − Bromopropane
Aqueous KOH / ∆ (i) BH3 / THF
(Nucleophilic substitution) (ii) H2O2 / OΘ H
CH3CH2CH2 – OH CH3CH2CH2 – OH
Propan −1 − ol
Br
Alc. KOH / ∆ HBr
(b) CH3CH2CH2Br (Dehydrogenation) CH3CH=CH2 (Markownikoff addition)
CH3 – CH – CH3
1-Bromopropane Propene 2-Bromopropane
Br Br
(c) Br2 /FeBr3 HNO3 /H2SO4

Dark (Nitration)
NO2
Benzene Bromobenzene 4 − 𝐵romonitrobenzene
CH2OH CH2Cl CH2CN CH2COOH
(d) PCl5 KCN, aq. Ethanol 𝐻 + / H2O

−POCl3 ,−HCl – 𝐾𝐶𝑙 (Hydrolysis)
NO2
Benzyl alcohol Benzyl cyanide 2 − Phenylethanoic acid
Red P KCN, aq. Ethanol

(e) CH3CH2 – OH Br2
CH3CH2 – Br CH3CH2 – CN
Ethanol Bromoethane Propionitrile
NH2 N2+ Cl− Cl
(f) NaNO2 + 2HCl 𝐶𝑢2 𝐶𝑙2

273-278 K + N2
Aniline Benzenediazonium Chlorobenzene
chloride
Cl H3C CH3
2Na / Dry ether
(g) CH3CHCH2CH3 CH3CH2CH – CHCH2CH3 + 2NaCl
(Wurtz reaction)
2-Chlorobutane 3,4 −Dimethylhexane
CH3 CH3
HCl
(h) CH3 – C = CH2 CH3 – C – CH3
(Markownikoff’s addition)
2-Methyl-1-propene Cl
2-Chloro-2-methylpropane
Aq. KCN, Ethanol H + /H2 O

(i) CH3CH2 – Cl (Nucleophilic substitution) CH3CH2 – CN + KCl (Hydrolysis) CH3CH2 – COOH
Ethylchloride Propionitrile Propanoic acid
HBr/Peroxide NaI / Dry acetone

(j) CH3CH2CH=CH2 (Anti-Markownikoff addition) CH3CH2CH2CH2 – Br (Finkelstein reaction)
But-1-ene Bromobutane I
CH3CH2CH2CH2
𝑛 − Butyl iodide
Cl
Aq. KOH / ∆ (i) BH3 / THF
(k) CH3CHCH3 (Dehydrohalogenation) CH3CH = CH2 CH3CH2CH2OH
(ii) H2O2 / OΘ H
2-Chlororo- Propene
propane HBr / Peroxide
(Anti-Markownikoff add.)
Aq. KCN, Ethanol

CH3CH2CH2 – OH CH3CH2CH2 – OH
(Nucleophilic substitution)
Propan −1 − ol 1 − 𝐵romopropane
20. What happens when:
(a) n − butyl chloride is treated with alcoholic KOH,
(b) bromobenzene is treated with Mg in the presence of dry ether,
(c) chlorobenzene is subjected to hydrolysis,
(d) ethyl chloride is treated with aqueous KOH,
(e) methyl bromide is treated with sodium in the presence of dry ether,
(f) methyl chloride is treated with KCN.
Alc. KOH / ∆
Ans: (a) CH3CH2CH2CH2 – Cl (Dehydrogenation) CH3CH2CH = CH2 + KCl + H2O
𝑛 −Butyl chloride But −1 −ene
(b) Phenylmagnesium bromide is formed.
Br MgBr
Na
+ Mg
Dry ether
Bromobenzene Phenylmagnesium bromide

(c) Chlorobenzene does not undergo hydrolysis under normal conditions. However, it
undergoes hydrolysis when heated in an aqueous sodium hydroxide solution at a
temperature of 623 K and a pressure of 300 atm to form phenol.
Cl OH
(i) NaOH, 623K, 300 atm

(ii) 𝐻 +
Chlorobenzene Phenol
Alc. KOH
(d) CH3CH2 – Cl CH3CH2 – OH + KCl
(Hydrolysis)
Ethyl chloride Ethanol
Dry ether
(e) 2CH3 – Br + 2Na CH3 – CH3 + 2NaBr
(Wurtz reaction)
Methyl bromide Ethane
Dry ether
(f) CH3 – Cl + KCN (Wurtz reaction)
CH3 – CN + KCl
Methyl chloride Methyl cyanide
Multiple Choice Questions:

1. Which nomenclature is not according to IUPAC system?
(a) Br – CH2 – CH = CH2
1-Bromoprop-2-ene
CH3
(b) CH3 – CH2 – C – CH2 – CH – CH3
Br CH3
4-Bromo-2,4-dimethylhexane
(c) CH3 – CH – CH – CH2 – CH3
CH3
2-Methyl-3-phenylpentane
(d) CH3 – C – CH2 – CH2 – CH2COOH
O
5-Oxohexanoic acid (J & K CET)
2. Chlorobenzene can be prepared by reacting aniline with
(a) hydrochloric acid in the presence of nitrous acid
(b) cuprous chloride in the presence of aluminium chloride
(c) chlorine in the presence of aluminium chloride
(d) nitrous acid followed by heating with cuprous chloride (UP CPMT)
3. Assertion: Alkyl iodine can be prepared by treating alkyl chloride/bromide with NaI in acetone.
Reason: NaCl/NaBr are soluble in acetone while NaI is not.
(a) If both assertion & reason are true & reason is the correct explanation of assertion.
(b) If both assertion & reason are true but reason is not the correct explanation of assertion.
(c) If assertion is true but reason is false.
(d) If both assertion & reason are false. (AIIMS)
4. In a group of isomeric alkyl halides, the order of boiling points of the alkyl/aryl halides?
(a) primary < secondary < tertiary
(b) primary > secondary < tertiary
(c) primary < secondary > tertiary
(d) primary > secondary > tertiary (J & K CET)
5. Consider the reaction, CH3CH2CH2Br + NaCN → CH3CH2CH2CN + NaBr.
This reaction will be the fastest in
(a) ethnol
(b) methanol
(c) N, N-dimethylformamide (DMF)
(d) water (NEET Phase-II)
6. Optically active compounds among the following compounds are
(i) 1-phenylethanol
(ii) 2-phenylpropan-1-ol
(iii) 2-phenylpropan-2-ol
(iv) 2-methylpropan-2-ol
(a) (ii) & (iii)
(b) (i) & (ii)
(c) (iii) & (iv)
(d) (ii) & (iv) (J & K CET)
7. The carbocation formed in SN1 reaction of alkyl halide in the slow step is
(a) sp3 hybridised
(b) sp2 hybridised
(c) sp hybridised
(d) sp3d hybridise (AMU (Med.))
8. Identify the product of the following reaction:

F (i) Ph Li , Et2O
* (ii) H3O+
Ph
(a) Only *
*
Ph
(b) Only
Ph * Ph
(c) * +
Ph
(d)
* (J & K CET)
9. In a mixture, two enantiomers are found to be present in 85% & 15% respectively.
The enantiomeric excess (e, e) is
(a) 85%
(b) 15%
(c) 70%
(d) 60% (WB JEE)
10. Which of the following is dehydrohalogenated readily at the highest rate?
(a) Br
(b) Br
(c) Br
(d) Br
(JIPMER)
11. An incorrect statement with respect to SN1 & SN2 mechanisms for alkyl halide is
(a) a strong nucleophile in an aprotic solvent increases the rate of favour SN2 reaction
(b) competing reaction for an SN2 reaction is rearrangement
(c) SN1 reaction can be catalysed by some Lewis acids
(d) a weak nucleophile & a protic solvent increases the rate or favour SN1 reaction (Karnataka CET)
12. meso-2,3-Dibromobutane on dehalogenation gives
(a) but-1-yne
(b) cis-but-2-ene
(c) butane
(d) trans-but-2-ene (UP CPMT)
13. 2,4,6-Trinitrochlorobenzene on warming with water produces

(a) chlorobenzene
(b) picric acid
(c) phenol
(d) no compound since C – Cl bond is stable. (AMU (Med.))
14. Which one of the following compounds cannot be used for the preparation of Gignard reagent?
(a) C2H5Br
(b) HO – CH2CH2Cl
(c) C6H5CH2Cl
(d) CH2 = CH – CH2Cl (AIPMT (Mains))
15. Assertion: 1,2-dichloroethane is optically active.
Reason: Meso compound is optically active.
16. An aromatic compound C7H6Cl2 (A), gives AgCl on boiling with alcoholic AgNO2 solution & yields
C7H7OCl on treatment with sodium hydroxide. (A) on oxidation gives monochlorobenzoic acid.
The compound (A) is:
(a) CH2Cl
Cl
(b) CH2Cl
Cl
Cl
Cl
(c) CH2Cl
Cl
Cl
(d) CH2Cl
(AIIMS)
17. A nucleophilic substitution reaction proceeds through SN1 mechanism. So, the reaction is
(a) unimolecular
(b) bimolecular
(c) tertmolecular
(d) rate depends on concentration of incoming nucleophile. (J & K CET)
18. When (-)-2methylbut-1-ol is heated with concentrated hydrochloric acid, (+)1-chloro-2-methylbutane is
obtained. The reaction is an example of
(a) retention
(b) inversion
(c) racemisation
(d) resolution
(e) mutarotation (Kerala PMT)
19. Consider the reaction:
(i) (CH3)2 CH – CH2 Br C2H5OH (CH3)2 CH – CH2 O C2H5 + HBr
(ii) (CH3)2 CH – CH2 Br C2H5O- (CH3)2 CH – CH2 O C2H5 + Br-
The mechanisms of reactions (i) & (ii) are respectively
(a) SN1 & SN2
(b) SN1 & SN1
(c) SN2 & SN2
(d) SN2 & SN1 (AIPMT (Mains))
20. Assertion: CH3 CH3
CH3 – C – CH2 – Br + NaOH CH3 – C – CH2 – CH3
OH
Reason: It follows with formation of more stable carbocation.
21. Which of the following is the correct order for reactivity of halogen atom?
(a) Vinyl chloride < Chloroethane < Chlorobenzene
(b) Vinyl chloride < Chlorobenzene < Chloroethane
(c) Chloroethane < Chlorobenzene < Vinyl chloride
(d) Chlorobenzene < Vinyl chloride < Chloroethane (AFMC)
22. In alkaline hydrolysis of a tertiary alkyl halide by aqueous alkali, if concentration of alkali is doubled, then
the reaction rate at constant temperature
(a) will be doubled
(b) will be halved
(c) will become four times greater
(d) will be tripled
(e) will remain constant. (Kerala PMT)
23. The ease of dehydrohalogenation of alkyl halide with alcoholic KOH is
(a) 30 < 20 < 10
(b) 30 > 20 > 10
(c) 30 < 20 > 10
(d) 30 > 20 < 10 (WB JEE)
24. Alkyl halides undergoing substitution nucleophilic bimolecular reaction involves
(a) formation of carbocation
(b) racemic mixture
(c) inversion of configuration
(d) retention of configuration (J & K CET)
25. When 2-phenylethylbromide is heated with NaOEt, elimination takes place. No deuterium exchange takes
place when the reaction is carried out in C2H5OD solvent. The mechanism will be
(a) E1 elimination
(b) E2 elimination
(c) E1 cB elimination
(d) E2 or E1 cB (AIIMS)
26. Predict the main product
Cl NH3/Cu2O ..........................
(a) Phenyl cyanide

(b) Nitrophenol
(c) Aniline
(d) Hydroxylamine (AMU (Med.))
27. Chlorination of toluene in the presence of light & heat followed by treatment with aqueous KOH gives
(a) o-cresol
(b) m-cresol
(c) p-cresol
(d) benzyl alcohol
(e) 2-chloro-4-hydroxytoluene (Kerala PMT)
28. If there is no rotation of plane polarised light by a compound in a specific solvent, though to be chiral,
it may mean that,
(a) the compound is certainly meso
(b) there is no compound in the solvent
(c) the compound may be a racemic mixture
(d) the compound is certainly a chiral (AIPMT)
29. CH3 – CHCl – CH2 – CH3 has a chiral centre. Which one of the following represents its R-configuration?
(a) C2H5
H – C – CH3
Cl
(b) C2H5
Cl – C – CH3
H
(c) CH3
H – C – Cl
C2H5
(d) C2H5
H3C – C – Cl
H (AIPMT)
30. Pick out the correct statements.
(i) If a compound has no asymmetric carbon atom it is always achiral.
(ii) If a compound has just one asymmetric carbon atom, it is chiral.
(iii) If a compound has more than one asymmetric carbon atoms, it may or may not be chiral.
(a) (i), (ii)& (iii) are correct.
(b) (i) & (ii) only are correct
(c) (ii) & (iii) only are correct.
(d) only (ii) is correct.
(e) only (i) is correct. (Kerala PMT)
31. Which of the following is optically inactive?

(a) H
H3C Cl
Cl CH3
H
(b) H
Cl CH3
H3C Cl
H
(c) H
H3C Cl
H3C Cl
H
(d) None of these (AIIMS)
32. What happens when chloroform is left open in air in the presence of sunlight?
(a) Explosion takes place.
(b) Phosgene, a poisonous gas is formed.
(c) Polymerisation takes place.
(d)No reaction takes place. (AIIMS)
33. Assertion: Chloroform is stored in dark coloured bottles.
Reason: Chronic chloroform exposure may cause damage to liver & kidneys.
34. A sample of chloroform before being used as an anaesthetic agent is tested by
(a) Fehling’s solution
(b) ammoniacal cuprous chloride
(c) silver nitrate solution in the cold
(d) silver nitrate solution after boiling with alcoholic KOH. (AFMC)
35. The organic halogen compound used as refrigerant in refrigerators & air-conditioners is
(a) DDT
(b) Freon
(c) BHC
(d) BFC
(e) CCl4 (Kerala PMT)
36. Chemical formula of phosgene is
(a) COCl2
(b) CaOCl2
(c) CaCO3
(d) COCl (AFMC)
37. Chronic chloroform exposure may cause damage to liver & kidney, due to the formation of
(a) phosgene
(b) methylene chloride
(c) methyl chloride
(d) carbon tetrachloride
(e) phosphoryl chloride (Kerala PMT)
38. Which of the compounds is synthesised by chloral?
(a) DDT
(b) BHC
(c) Chloroform
(d) Michlers ketone (AIIMS)
39. CCl4 is well known fire exhauster. However after using it to extinguish fire, the room should be well
ventilated. This is because
(a) it is flammable at higher temperatures
(b) it is toxic
(c) it produces phosgene by reaction with water vapour at higher temperatures
(d) it is corrosive
(e) it is anaesthetic (Kerala PMT)
40. Assertion: Chloral reacts with phenyl chloride to form DDT.
Reason: It is an electrophilic addition reaction.
-
41. In solvents like DMSO, acetonitrile, F ion of dissolved NaF is more reactive than in methyl alcohol
explains
(a) CH3OH is more polar than DMSO & CH3CN
(b) CH3OH is less polar than DMSO & CH3CN
(c) Unsolvated F- ion in DMSO or CH3CN acts more effectively as nucleophile
(d) –OH group is a better leaving group than F- ion (AIIMS)
42. Arrange the given compounds in decreasing order of boiling points
CH3
CH3 CH2 CH2 CH2 Br CH3 – C – Br CH3 – CH2 – CH - Br
CH3 CH3
(I) (II) (III)
(a) I > III > II
(b) II > I > III
(c) I > II > III
(d) III > I > II (AIIMS)
43. Assertion: Chlorobenzene is more reactive than benzene towards the electrophilic substitution reaction.
Reason: Resonance destabilises the carbocation.
44. The products expected to be formed in the Wurtz reaction of a mixture of neopentyl bromide &
isobutyl bromide are
(i) 2,2,4-trimethylpentane
(ii) 2,2,5,5-tetramethylhexane
(iii) 2,2,4,4-tetramethylhexane
(iv) 2,5-dimethylhexane
(v) 2,2,5-trimethylhexane
(a) (ii), (iii) & (v)
(b) (ii), (iv) & (v)
(c) (i), (iv) & (v)
(d) (i), (iii) & (v)
(e) (i), (ii) & (iv) (Kerala PMT)
45. The correct sequence of reactions to be performed to convert benzene into m-bromoaniline is
(a) nitration, reduction, bromination
(b) bromination, nitration, reduction
(c) nitration, bromination, reduction
(d) reduction, nitration, bromination (Karnataka CET)
46. Alkyl halide can be converted into alcohol in a single step reaction. It’s an example of ................. reaction.
(a) electrophilic substitution
(b) nucleophilic substitution
(c) electrophilic addition
(d) free radical substitution (OJEE)
47. Which of the following compounds undergoes nucleophilic substitution reaction most easily?
(a) Cl
NO2
Cl
(b)
CH3
Cl
(c)
OCH3
(d) Cl
(AIPMT (Mains))
48. Which of the following will give yellow precipitate on shaking with an aqueous solution of NaOH
followed by acidification with dil. HNO3 & addition of AgNO3 solution?
(a) Cl
Br
(b) CH2 – Cl
(c) I
Br
CH3
(d) Cl
(OJEE)
49. Find the major product in the following reaction:

CCl3
Cl2/FeCl3
(a) CCl3
Cl
(b) CCl3
Cl
(c) CCl3
Cl
(d)
(OJEE)
50. AgNO3 does not give precipitate with CHCl3 because
(a) CHCl3 does not ionise in water
(b) AgNO3 is chemically inert
(c) CHCl3 is chemically inert
(d) None of these. (UP CPMT)
3 2 1
1. (a) Br – CH2 – CH = CH2
3-Bromopropene
2. (d) NH2 𝑁2+ 𝐶𝑙 −
+ NaNO2 + 2HCl 0–5 C 0
+ H2O + NaCl
Aniline Benzene diazonium

Chloride
Cl
Cu2Cl2
Chlorobenzene
3. (c) This is Finkelstein reaction which involves the conversion of an alkyl chloride/bromide to an alkyl iodide by
the addition of sodium iodine in acetone. Because sodium iodide is soluble in acetone & NaCl & NaBr are
not, the equilibrium is shifted by the precipitation of insoluble salt.
4. (d) As on increasing branching, surface area is decreased hence van der waal’s forces of attraction decreases.
As a result, boiling point is also decreases. Thus, decreasing order of boiling points among the isomeric alkyl
halides follows the order: 10 > 20 > 30.
5. (c) The reaction, CH3CH2CH2Br + NaCN → CH3CH2CH2CN + NaBr,
Follows SN2 mechanism which is favoured by polar aprotic solvent i.e., N, N’ – dimethylformamide (DMF),
O
H – C – N(CH3)2
H
6. (b) CH3*CHOH H3C – C – CH2OH
*
1-Phenylethanol 2-Phenylpropan-1-ol
OH CH3
H3C – C – CH3 H3C – C – CH3
OH
2-Methylpropan-2-ol
2-Phenylpropan-2-ol
7. (b) The carbocation formed in SN1 reaction of alkyl halide is sp2 hybridised & trigonal planar in shape.
R
C+
R R
8. (c) F F Li Ph Ph
PhLi/-PhH –LiF PhLi + H2O/–LiOH
Ph
Biphenyl
9. (c) Enantiomeric excess is (85 – 15) = 70%.

10. (d) Br
– HBr
Br
Among given compounds only gives the most stable product.
11. (b)
12. (d) CH3
H Br Zn/Cu
H Br Heat + ZnBr2
CH3
Meso-2,3-Dibromobutane trans-But-2-ene
Cl OH
13. (b) O2N NO2 O2N NO2
+ H2O Heat
NO2 NO2
2,4,6-Trinitrochlorobenzene 2,4,6-Trinitrophenol
(Picric acid)
14. (b) Grignard reagent cannot be prepared from a compound which has reactive group such as –OH because it
will react rapidly with the Grignard reagent.
15. (d) CH2 – CH2
1 2
Cl Cl
Since, it has no chiral carbon, it is optically inactive. Meso compound are optically inactive.
CH2Cl CH2NO2
16. (a)
AgNO2/Δ + AgCl
Cl Cl
(A) (B)
CH2
NaOH(Aq.)
Cl
CH2Cl COOH
[O]
KMnO4/[H+]
[A] Monochlorobenzoic acid
17. (a) SN1 stands for substitution nucleophilic unimolecular reaction.

18. (a) During this reaction, no bond at the stereocentre is broken, thus the product has the same general
configuration of atoms or groups i.e., retention of configuration though sig of optical rotation has changed.
19. (c) If reaction in SN1 , there will be the formation of arbocation & the rearrangement takes place.
In these reactions there is no rearrangement hence, both are SN2 mechanism.
CH3 CH3 CH3 CH3

20. (a) CH3 – C – CH2 – Br + NaOH SN1 CH3 – C – CH2 CH3 – C – CH2 – CH3 OH CH3 – C – CH2 – CH3
CH3 CH3 OH
0 0
1 alkyl halide alkyl migration 3 alkyl carbocation 2-methylbutan-2-ol
21. (d) The reactivity of halogen atom is in the order: Chlorobenzene < Vinyl chloride < Chloroethane.
This is because in chlorobenzene & vinyl chloride, the C – Cl bond acquires some double bond
character due to resonance & resonance is more dominated in chlorobenzene than in vinyl chloride.
22. (e) Tertiary alkyl halides undergoes SN1 mechanism. Here the rate depends only on the concentration
of the substrate.
23. (b) The ease of dehydrohalogenation of alkyl halide with alcoholic KOH is 30 > 20 > 10.
This order of alkyl halides can be explained on the basis of the stability of the alkene formed after
dehydrohalogenation of haloalkanes. 30 alkyl halides on dehydrohalogenation form more substituted
alkenes, which being more stable are formed at faster rate, while primary alkyl halides yield least
substituted alkenes, which being less stable are formed at slower rate.
24. (c) SN2 reactions takes place via inversion of configuration.
25. (b) CH2 – CH2 – Br EtO–/-HBr CH = CH2

2-phenyl ethyl bromide
26. (c) Cl NH2
2 + 2NH3 + Cu2O 2000C/60atm 2 + 2CuCl + H2O
27. (d) CH3 CH2Cl CH2OH
Cl2/ℎ𝑣 aq. KOH

28. (a) Meso compound does not rotate plane polarised light. Compound which contains tetrahedral atoms with
four different groups but has a plane of symmetry & is optically inactive. One of the asymmetric carbon
atoms turns the plane of polarised light to the right & other to the left & to the same extent so that the
rotation due to upper half is compensated by the lower half, i.e., internally compensated, & finally there
is no rotation of plane polarised light.
29. (b)
30. (c)
31. (c) Due to internal compensation, this compound is strictly inactive.
H
H3C 1 Cl
H3C 2 Cl
H
Meso
32. (b) CHCl3 + [O] → COCl2 + HCl
phosgene
33. (b) Chloroform is slowly oxidised by air in the presence of light to an extremely poisonous gas ‘phosgene’.
Therefore, it is stored in dark bottles, completely filled so that air is kept out.
34. (c) Chloroform is tested before use for the presence of extremely poisonous gas phosgene, that may be formed
on storage. If CHCl3 sample contains phosgene then it will give a white ppt. when treated with AgNO3
solution in the cold. However, after boiling CHCl3 with alcoholic KOH, the resulting solution will always
give white ppt. with AgNO3 solution whether it contains COCl2 or not.
35. (b) Chlorofluorocarbon’s (CFC’s) or feron are used as refrigerant in refrigerators & air-conditioners.
36. (a) Carbonyl chloride is commonly known as phosgene & its chemical formula is COCl 2.
37. (a) Chronic chloroform exposure causes damage in liver & kidney as CHCl3 decomposes slowly into
phosgene & hydrogen chloride.
CHCl3 + [O] Light & air / CCl3OH COCl2 + HCl
Chloroform Phosgene
38. (a) Cl
2C6H5Cl + Cl3CCHO H2SO4 Cl3C – H
Cl
DDT
39. (c) Carbon tetrachloride vapours react with steam above 5000C to form phosgene, a poisonous gas.
CCl4 + H2O 5000C COCl2 + 2HCl
Phosgene
It is used as fire extinguisher. The dense vapour form a protective layer on the burning objects & prevent
the oxygen or air to come in contact with the burning objects, hence after using CCl4 to extinguish fire
the room or windows should be well ventilated.
40. (c) When chlorobenzene is heated with chloral in the presence of conc. H2SO4 , a powerful insecticide,
DDT is formed with the elimination of water molecule.
H Cl Cl
CCl3CHO + H2SO4/Δ CCl3CH
H Cl Cl
It is electrophilic aromatic substitution reaction.

41. (c) In methyl alcohol, F- ion is solvated but in DMSO or CH3CN (aprotic solvents), F- ion is not solvated.
Unsolvated F- ion acts more effectively as a nucleophile.
42. (a) Magnitude of van der Waal’s forces goes on decreasing with branching. Hence, the order of boiling points is:
CH3 CH3
CH3CH2CH2CH2Br > CH3CH2 – CH – Br > CH3 – C - Br
CH3
43. (d) Chlorobenzene is less reactive than benzene towards the electrophilic substitution reactions due to –I effect.
44. (b)
45. (c) NO2 NO2 NH2
Conc. HNO3 + H2SO4 Br2/H2O Sn/HCl

Step-1 (Nitration) Step-2 (Bromination) Step-3 (Reduction)
Benzene Nitrobenzene m-Bromonitrobenzene m-Bromoaniline
46. (b)
47. (a) Electron withdrawing group like –NO2 facilitate nucleophilic substitution reaction in chlorobenzene.
48. (c)
49. (b)
50. (a) AgNO3 does not precipitate with CHCl3 because CHCl3 does not ionise in water.

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Chapter – 1

(Vinyl halide) (1-Halocyclohex-1-ene)

3 COMMON & IUPAC NAMES OF SOME HALIDES

COMMON NAME STRUCTURE IUPAC NAME

Benzyl chloride CH2 – Cl Chlorophenyl methane

Alkyl halides: CH3CH2CH2Br Benzylic halides:

4 METHODS OF PREPARATION OF HALOALKANES

3C2H5OH + PCl3 3C2H5Cl + H3PO3

From 2C2H5Cl + Hg2F2 2C2H5F + Hg2Cl2

Illustration: 1. 2-Bromo-3-methylbutane on heating with alcoholic KOH yields 2-methyl-2-butene as the

The best method of preparation of haloalkanes from

Illustration: 1. The arrangement of following compounds:

 Chemical Properties of Haloalkanes:

1. Nucleophilic Substitution 2. Electrophilic Substitution 3. Reaction with metals

 Nucleophilic substitution of alkyl halides (R – X) :-

+ KOH (aq.) + KNO2

(2) Elimination reaction :-

(Benzene diazonium + KI I + KCl + N2

+ NaBH4 F + BF3 + NaCl + N2

Illustration: 1. What halogen best delocalizes electron density to benzene ring?

Cl2 , / ℎ𝑣 aq. KOH

Toluene Benzyl chloride Benzyl alcohol

(a) Phenyl cyanide (b) Nitrophenol (c) Aniline (d) Hydroxylamine

1. Nucleophilic Substitution 2. Electrophilic Substitution 3. Reaction with metals

(i) NaOH, 623K, 300atm

+Na, CH3-Cl CH3

(Phenyl Magnesium chloride)

Benzene Benzene dichloro diphenyl methane

sample concentration was 0.50 g/mL in ethanol.

Illustration: 1. 2-Chlorobutane obtained by chlorination of butane, will be

Carbon Tetrachloride (Tetrachloromethane)

DDT (p, p’ – Dichlorodiphenyltrichloroethane)

It is a white powder insoluble in water, but soluble in oil.

Freons or CFC (Chlorofluorocarbon)

9 IMPORTANT NAME REACTIONS

(b) FINKELSTEIN REACTION :

Cl + 2Na + Cl – CH3 Dry ether CH3 + 2NaCl

Cl + 2Na + Cl – C2H5 Dry ether C2H5 + 2NaCl

(e) FITTING’S REACTION :

Cl + 2Na + Cl Dry ether

+ CH3Cl ∆AlCl3 + HCl

CH3 CH3 CH3

+ CHCl3 + 3KOH ∆ + 3KCl + 3H2O

+ 2NaOH (Aq.) -NCl, -H2O H+

(i) HUNDSIEKER’S REACTION :

N2Cl Cu / HBr Br + N2 + HCl

 Distinguish between pairs of organic compound containing halogen :

Ordinary light Plane polarised zero Left Right

Organic compound Laevorotatory [rotates the plane polarised

[I] Mechanism of Nucleophilic substitution reaction in Alkyl Halides :-

CH3 CH3 CH3

(ii) Substitution nucleophilic bimolecular (SN2) :

USES OF HALOGEN DERIVATIVES

Aliphatic Hydrocarbons (Aliphatic halogen compounds)

General formula: General formula: General formula: General formula:

Aromatic Halogen Compounds can be classified as:

X X X CH2 – X CHX2 CX3

Factors which tend to favour substitution & elimination in alkyl halides

S. No. Factors SN1 SN2 E1 E2