Key-2-Chemistry by K Singh

Haloalkanes & Haloarenes

Haloalkanes → R−X where R is alkyl group &

X = halogen atom (F,Cl, Br, I )
IUPAC → haloalkanes.
Common name → Alkyl halides

1. Monohalide  eg R-X when one halogen atom present.

2. Dihalide  two halogen atom present.

(Alkylidences)

Gem-dihalid Vic-dihalide
(i-e two halogen (i.e. two halogen atom present
Atom present on single on two nearest Carbon atoms)
Carbon atom)
Ex. CH2Cl2 , CH3CHCl2 Ex. CH2 – CH2
│ │
Cl Cl
3. Trihalo compounds → Contain three halogen atom
Ex. CHCl3 (Chloroform)
CHI3 (Iodoform)

4. Polyhalides → Ex. CCl4. (Pyrene)

Preparation of alkyl halides →

1. From alcohols →
(a) By the action of halogen Acids → Alcohols can be converted into haloalkanes by
treatment of halogen acids (HX)
R – OH + HX → R-X + H2O
Alcohol Haloalkane
Anh ZnCl2
Ex. 1. CH3CH2–OH + HCl CH3CH2Cl + H2O
Ethanol Chloroethane
( I or Pri alcohol)
CH3 CH3
│ Anh ZnCl2 │
Ex. 2. CH3−CH2 –OH + HCl CH3−CH − Cl + H2O
2- propanol 2- Chloroethane

CH3 CH3
│ Anh ZnCl2 │
Ex. 3. CH3− C –OH + HCl CH3 −C – Cl + H2O
│ │
CH3 CH3
Tert – Butyalcohol tert – Butylocloride.

1 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

Note: (i) ZnCl2 (Anh.) is used to cleavage C–O bond to form carbocation. The
carbocation then readily reacts with chloride ion to form chloroalkanes.
(ii) The order of reactivity of halogen acids on alcohols is.
HI > HBr > HCl.
This is due to the less bond dissociation energy of HI than that of HBr which
in turn less than that of HCl. As we move down the group the size of halogen
atoms increases due to which the tendency to hold the small hydrogen atom
decreases & hence bond becomes weaker.

(iii) The Reactivity of alcohols towards halogen acids

Tertiary alcohol > Secondary alcohol > Primary alcohol
CH3
↓
CH3→C←CH3 CH3→CH←CH3 CH3→CH2OH
│ │
OH OH 1˚
3◦ 2˚
This is due to fact that greater the number of electron releasing groups on the
α-carbon atom of the alcohol more is the polarity of C-OH. As a result, the
Cleavage of C-O bond becomes easy or carbocation forms easy hence
reactivity increases.

Ex. 4. Bromo alkanes are obtained as

Conc. H2SO4 / 
CH3CH2–OH + HBr CH3CH2Br + H2O
Ethanol Bromoethane
Ex. 5. Iodoalkanes are obtained as
Reflux
CH3CH2OH + HI CH3CH2I + H2O.
Iodoethane
(b) By the action of Phosphorus halides → Haloalkanes can be prepared by the action of
phosphorus halides on the alcohols.
Ex. (i) R−OH + PX5 R – X + POX3 + HX
Alcohol Haloralkane
Eg. CH3CH2OH + PCl5 CH3CH2Cl + POCl3 + HCl
Ethanol Chloroethane
Eg. CH3CH2OH + PI5 CH3CH2- I + POI3 + HI
Ethanol
Ex. 3.R −OH + PX3 3.R – X + P(OH)3.
Alcohol holoroethane
Eg. 3.CH3CH2OH + PCl3 3CH3CH2 – Cl + P(OH)3
Ethanol Chloroethane
Ex. 3. CH3CH2 OH + PBr3 3CH3CH2Br + P(OH)3
Ethanol Bromoethane
Ex. 3. CH3CH2OH + PI3 3CH3CH2I + P(OH)3
Ethanol Iodoethane

2 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

(c) By the action of thionyl chloride → Chloroalkanes can be prepared from alcohols by
refluxing alcohols with thionyl chloride in the presence of Pyridine.

Ex. CH3CH2OH + SOCl2 Pyridine CH3CH2Cl + SO2 + HCl

Ethanol Thionylchloride
This method is best method for preparation of chloroalkanes because both the side products
(i.e. SO2 & HCl) are in gaseous form and are easily separated from alkyl-halide.

2. From Hydrocarbons → the haloalkanes can be prepared from alkanes & alkenes in
presence of ultraviolet light. This reaction is free radical substitution reaction & gives a
mixture of mono-, di-, or Polysubstituted haloalkanes.
Sunlight Cl2 Cl2 Cl2
CH4 + Cl2 CH3Cl CH2Cl2 CHCl3 CCl4 + HCl
- HCl - HCl - HCl - HCl
Methane Chloro methane Dichloro methane chloroform pyrene
CH3 CH3
│ UV Light │
Ex. 2. CH3 – C – CH3 + Cl2 or  CH3 – C – CH2Cl + HCl
│ │
CH3 CH3
Neopentane Neopentyl Chloride

3. From alkenes →
(i) Haloalkanes can be prepared by the electrophilic addition of halogen acids to alkenes.

Eg. C=C + HX –C–C–

│ │
Alkene X H
Haloalkane.
CH2 ═ CH2 + HCl CH3 – CH2 – Cl
Ethane Chloroalkane.

Markownikoff rule →in case of unsymmetrical alkenes the negative part of the attacking
reagent attacks to that carbon atom which is highly alkylated or have less number of
hydrogen atoms it is k/as Markownikoff rule as-

Ex. CH3 – CH = CH2 + HBr CH3 – CH – CH2

│ │
Br H
2–Bromopropane
O O
║ ║
But in presence of organic peroxides such as (C6H5–C – O – O – CC6H5) the addition of
HBr takes places against the Markownikoff rule. This is known as anti-marknownikoff rule
or peroxide effect or also called Kharasch effect.
Peroxide
Ex. CH3 – CH = CH2 + HBr CH3-CH2 – CH2
│ │
H Br
1-Bromopropane

3 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

(ii) Haloalkanes also formed by addition of halogens as

CCl4
Ex. CH2 = CH2 + X2 CH2 – CH2
│ │
X X
(Vic dibromide)
CCl4
Ex. CH2 = CH2 + Br2 CH2 – CH2
│ │
Br Br
Vic-ethylene dibromide

Allylic chlorination → it is obtained when alkenes are heated with Cl2 at about 800 k
800K
Ex. CH2=CH–CH3 + Cl2 CH2 = CH–CH2Cl + HCl
Propene AllylChloride.

Allylic Bromination → with the help of N-bromosuccinamide (NBS) in presence of light

bromination of alkene takes places

Ex. CH2=CH–CH3 + CH2–CO CH2=CH–CH2 + CH2-CO

Propene │ NBr │ │ NH
CH2–CO Br CH2-CO

5. By Halide exchange → (i) Finkelstein reaction-

Acetone
Ex. CH3CH2Cl + NaI CH3CH2I + NaCl
Refuxl
(ii) Swarts reaction
CCl4
CH3Br + AgF CH3F + AgBr

6. From silver salt of acids → the silver salt of carboxylic acids dissolved in CCl4 are
decomposed by bromine to form bromoalkanes. This Rxn is called Borodine
Hunsdiecker Rxn
CCl4
Ex. CH3COOAg + Br2 CH3Br + CO2 + AgBr
Silver acetate Bromomethane

7. From alkanamines
R−NH2 + NOCl R−Cl + N2 + H2O
Alkanamine Tilden Reagent

8. From aldehyde & ketones

>C=O + SOCl2 >CCl2 + SO2
Or or
PCl5 POCl3

4 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

Preparations of Haloarenes → By following methods.

1. Direct halogenation of aromatic ring or electrophilic.

Substitution of arenas → direct halogenations of benzene ring takes places by
electrophilic substitution with the help of halogen carrier such as AlCl3 , FeCl3 , FeBr3 etc.
X
Ex. │
Halogen Carrier
+ X2 + HX

Benzene Halo benzene

Cl
│
AlCl3
+ Cl2 + HCl

Benzene Chlorobenzene

Br
+ Br2 FeBr3 + HBr

Benzene Bromobenzene

Mechanism of halogenation of arences → It is electrophilic Substitution reaction which

occurs in following steps-
Step-I Generation of Electrophile → In this step halogen carrier generate electrophile as
Cl2 + FeCl3 Cl+ + FeCl4¯
Chloroniumion (Electrophile)
Step – II Attack of electrophile on benzene ring takes place to form carbocation which get
resonance stabilized.
H H Cl H Cl H Cl
Slow + +
+ Cl+

+
H Cl

≡ resonance hybrid

Step – III In this step resonance stabilized carbocation proton (H+) to FeCl4- to give
chlorobenzene as.
H Cl Cl

Fast
+ FeCl4- + HCl + FeCl3.

Chlorobenzene

5 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

2. Preparation of aralkys-

CH3 CH2Cl

Sunlight/100˚ C
+ Cl2 + HCl

Chlorophenyl methane

3. From Diazonium salts:- chloro & bromoarenes are prepared by treating a freshly prepared
diazonium salt solution with cuprous chloride or cuprous bromide dissolved in HCl or HBr
respectively. This reaction is called Sand Meyer’s reaction

NH2 N2+Cl-

0-5˚,C
+ HONO + HCl + 2H2O

Aniline Benzenediazoniu Chloride salt

Ex N2+Cl- Cl

CuCl/HCl + N2 + HCl

Chlorobezene
N2+Cl- Br

CuBr/HBr + N2 + HCl.

Bromobenzene
Ex.
N2+Cl- Cl

+ Cu HCl + N2 + HCl

Chlorobezene
N2+Cl- Br

+ Cu HBr + N2 + HCl

4. Iodoarenes → It is prepared by warming the diazonium salt solution with aqueous KI sol.

N2+Cl- I

+ KI + N2 + KCl

Iodobenzene

6 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

5. Fluoroarenes → It is prepared by treating benzene diazonium chloride with fluoroboric

acid. This Rxn is called. Balz-schiemann Reaction.

N2+Cl- F

+ HBF4 + BF3 + N2 + HCl



6. By Hunsdiecker’s reaction 

COOAg Br
CCl
+ Br2 4 + AgBr + CO2

Bromobenzene
Physical Properties of Haloalkanes →
1. Haloalkanes in general are colourless. Sweet smelling liquids.
2. Solubility → haloalkanes are polar in nature, yet they are slightly soluble in water. This
is because they are not able to form hydrogen bonds with water.
But are soluble in organic solvents such as alcohol, ether, benzene etc. because of
intermolecular forces are similar to that of solvents.
3. Melting & boiling points. → M.Pt. & B.Pt. of chlorides, bromides & iodides are
considerably higher than those of parent hydrocarbon of comparable molecular mass.
Ex. of order of M.Pt & B.Pt.
(i) RI > RBr > RCl > RF. This is because with the increase in the size of the halogen,
the magnitude of vander waals forces increases.
(ii) In general the B.Pt of chloro, & iodo compounds increases with increase in the
number of halogen atoms.
Eg. CH3Cl < CH2Cl2 < CHCl3 < CCl4.
(iii) B.Pt. increases with increase in the size of alkyl gp.
Eg. CH3Cl < CH3CH2 Cl < CH3CH2CH2Cl < CH3CH2CH2CH2Cl
(iv) B.Pt decreases with increasing branching of alkane chain because
vander waals forces of attraction decreases.
Eg. n-Butyl bromide > Iso–Butyl bromide > tert-Butylbromide.

Physical Properties of Haloarenes →

1. These are generally colourless liquids or crystalline solids.
2. The aryl halides are heavier than water.
3. These are insoluble in water but soluble in organic solvents.
4. Melting & Boiling points → B.Pt & M.Pt are nearly same as those of alkyl Containing
the same no. of carbon atoms.
Eg.1.
F Cl Br I

< < < <

7 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

eg. 2. Cl Cl Cl
Cl

Cl
Cl
b.Pt. 453 K 446 K 448 K
M.Pt. 256 K 249 K 325 K
The M.Pt of para- isomer is quite higher than that of ortho- or meta- isomer. This is due to the
fact that it has symmetrical structure & therefore, its molecules can easily pack closely in the
crystal lattice. As result of intermolecular forces of attraction are stronger & so more amount
of energy is required to break its lattice & it melts at higher temper.

Nature of C-X bond → Nature of C-X bond in alkyl halide is polar due to electro negativity
difference between the carbon and halogen atoms.
But the order of reactivity depends upon the dissociation energy. As we move down the
group the size of halogen atom increases due to which the tendency to hold H atom of alkyl gp
decreases or in other words the strength of C-X bond decreases & hence breaks easily. So the
order of reactivity is ═ (R-I > R-Br > R-Cl)

Chemical properties of Alkyl halides

A. Nucleophilic SubstitutionRxn of Alkyl halides-Nucleophilic substitution Rxn are those
chemical Rxn in which one weak nucleophile replaced by another strong – nucleophile
(ie. Electron rich sps). Are K/as Nu. Nucleophilic Substitution reactions.
Nucleophilic substitutions are of two types i.e. SN1 & SN2

(a) SN1 Rxn –

(1) SN1 Rxn are unimolecular Rxn it means the rate of Rxn depends only on one reactant i.e.
alkyl halide or [ R−Cl]
n
(2) These Rx occurs in two steps.
(3) SN1 Rxn takes places through carbonium ion or carbocation intermediate reacting species.
(4) The order of reactivity is = tertiary > secondary > Primary alkyl halide
(5) SN1 Rxn’ may be takes places by any direction i.e from back side or from front side. Due to
which the product formed is Racemic mixture or dextro- or leavo-forms are formed.
(6) Walden inversion absent.
Example.
CH3 CH3 CH3
│ K+OH- │ │
CH3 – C – Cl CH3 – C – OH + HO – C – CH3
│ │ │
CH3 CH3 CH3
50% d-form 50% l-form
(Racemic Mixture)

8 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

Mechanism:-
CH3 CH3 CH3 CH3
│ K +
│ OH -
│ │
CH3–C–Cl CH3–C+ CH3–C–OH + HO– C – CH3
│ -KCl │ │ │
CH3 CH3 CH3 CH3
Carboniumion d-form l-form
(Reacting
intermediate)
(b) SN2 Rxn’:-
1. SN2 Rxn are bimolecular Rxn it means the rate of Rxn depends upon the two reactants
i.e. upon nucleophile as well as alkyhalide. i.e Rate α [ Nu] [R-Cl]
2. These Rxn occurs in one step.
3. SN2 Rxn takes places through transition intermediate reacting species.
4. The order of reactivity is Primary > Secondary > tertiary (this is due to the presence of
steric hindrance in 3˚.
5. SN2 reaction takes places only through back side therefore dextro form change into
leavo form and vice versa.
6. Walden inversion takes places.(i.e d-form  l-form)
H H
│ │
H – C – Cl + KCN CN- C– H + KCl.
│ │
H H

Mechanism
H H CH3 CH3
│ ∂- ∂+ │
CH – C – Cl HO--------C---------Cl HO−C−H
│ │ │
H H H
d-form (unstable) l-form
(Transition intermediate)
Reacting sps

1. Substitution by hydroxyl group (formation of alcohols)


R – X + KOH (aq) R – OH + KX

Ex. CH3CH2Br + aq KOH CH3CH2OH + KBr

Bromoethane Ethanol
Ex. CH3CH2- Br + AgOH CH3CH2OH + AgBr.

Ex. CH3CH2 – Br + Ag2O (moist) CH3CH2OH + 2 AgBr

2. Substitution by alkoxy group (formation of ethers) .

R-X + NaOR R – O – R + Nax
Sod. Alkoxide Ether
Ex. CH3CH2-Br + NaOC2 H5 CH3CH2OC2H5 + NaBr

9 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

Ethoxyethane
This reaction is called Williamson’s synthesis and is quite useful for preparing ethers.
Ex. 2CH3CH2Br + Ag2 O CH3CH2OCH2CH3 + 2 AgBr.
Ethoxy ethane.

3. Substitution by carboxyl group (formation of ester’s)

O O
║ ║
R−C−O Ag + X-R R−C−OR + AgX
Ester
Ex. CH3COOAg + Br-CH2CH3 CH3COOCH2CH3 + AgBr
Silver acetate Bromo Ethane Ethylethanoate (ethyl acetate)

4. Substitution by cyano (-CN) Isocyano (-NC), Nitro (-NO2). & Nitrite (-ONO) group.
KCN
R−CN + KX
Alkylcyanide
R−X
AgCN
Alkyl halide R−NC + AgX.
Alkylisocyanide
KNO2
R−ONO + KX
Alkanenitrile
AgNO2 R−NO2 + AgX
Nitrolkane
Ex.2. CH3CH2−Br + AgCN CH3CH2−NC + AgBr
Ethylbromide Ethyl isocyanide.

Ex.3. CH3CH2Cl + Ag-NO2 CH3−CH−NO2 + AgCl

Ethyichloride Nitroethane

Ex.4. CH3CH2Cl+ KNO2 CH3CH2ONO + KCl

Ethylchloride Ethynitrite

5. Substitution by amino group (formation amines): 

Ex. R−X + H–NH2 R−NH2 + HX
Ammonia alkanamine
CH3CH2−Br + NH3 CH3CH2NH2 + HBr
Ethanamine
When haloalkane is in excess, one or both or all the hydrogen atoms of the amino alkane
(Pri-amine) are replaced by alkyl groups & a mixture of Pri, Sec, & tertiary amines is
formed- CH3
+CH3Br +CH3Br │
CH3–Br + NH3 CH3–NH2 CH3−NH−CH3 CH3-N-CH3
-HBr 1˚amine -HBr 2˚ amine 3˚ amine
+CH3Br
[(CH3)4 N]+ Br- Tetramethyl ammonium Bromide (Quaternary salt)
This Rx also Called Hofmann ammonolysis Rxn
n

10 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

6. Substitution by alkyl group (formation of alkynes)

Ex. R−X + Na −C≡ CH R−C = CH + NaX.

Higher alkyne
Ex. CH3CH2−Cl + Na−C≡CH CH3 – CH2 – C≡ CH
Sod. Acetylide. But – 1 – yne.

7. Substitution by hydrosulphide gp (formation of thiroalcohols)

Ex. R− X + NaSH R−SH + NaX

ThioalCohol
CH3CH2Br + NaSH CH3CH2SH + Na Br
ethanethiol
8. Substitution by mercaptide gp (formation of thioether’s)

R – X + NaSR' R−SR' + NaX

Sod Mercaptide Thioether
Ex. CH3CH2Br + NOSC2H5 CH3 CH2SC2H5 + Na Br
Diethylioether.
B. Elimination Reactions (Dehydrohalogenation) Rxn’
When haloalkanes with β-hydrogen atom are boiled with alcoholic solution of
potassium hydroxide, the formation of alkenes takes place, it is Called β elimination
Rxn’.
H H H H
Ex. │ │ │ │
β
H – C − C – H + alc KOH
α H- C=C-H + KBr + H2O
│ │ Ethene
H Br
Bromoethane

Saytzeff’s Rule- In case of haloalkane can eliminate hydrogen halide in two different ways
then that alkene will be preferred in which carbon atoms joined by the double bond are
maximum alkylated. i.e contain largest number of alkyl gps. It is K/as Saytzeff’s rule

B A B
Ex. CH3 – CH2 – CH – CH3 CH3−CH ═ CH – CH3
│ Alc. KOH But -2-ene. (80%)
Br

2-Bromobutane
CH3−CH2−CH=CH2
But–1–ene (20%)
Ease of dehydrohalogenation. Acc. to Saytzeff’s Rule.The alkenes with greater number of
alkyl gps is the preferred product during dehydrohalogenation.
Ex.1. Ease of formation of alkenes-:
R2C = CR2 >R2 C = CHR > R2C = CH2 > RCH = CH2

The more stable the alkene the faster it is formed.

11 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

Ex. 2. The reactivity of haloalkanes towards elimination reaction i.e ease of

dehydrohalogenation follow the order.

Tertiary > Secondary > Primary alkyl halide

' R' R' H
│ │ │
R–C – X > R–C –X > R– C – X
│ │ │
R' H H

C. Reaction with Active Metals.-

(i) Action with magnesium (formation of Grignard reagent)
When a sol of an alkyl halide in dry ether is treated with magnesium an alkyl magnesium
halid formed. (i.e.G.R.)
Dry Ether
R-X + Mg R-Mg-X. (X = Cl, Br, I ).
(G.R.)
Dry Ether
Eg. CH3CH2Br + Mg CH3CH2Mg Br
Ethyl bromide Ethyl magnesium bromide
(ii) Action with Sodium- Two molecules of alkyl halides react with metallic sodium in
presence of ether to form alkane. This reaction is called Wurtz Rxn.
Dry ether
Ex. R-X + 2 Na +X-R R-R + 2 NaX.
C2H5–Br + 2Na + Br–C2H5 C2H5–C2H5 + 2NaBr.

(iii) Rxn with other active metals (OR Formation of organometallic compounds)
Dry ether
Ex. CH3CH2 Br + 2 Li CH3 CH2Li + LiBr
Ethyl Lithsum.

Ex. 4CH3CH2-Br + 4Na/Pb (CH3CH2)4 Pb + 4NaBr +3Pb.

Sodium lead Tetraethyl lead.
Alloy (TEL)
Note:- Tetraethyl lead (TEL) is used as an antiknocking agent in gasoline used for
running automobiles.

D. Reduction Rxn of alkyl halides:-

Ni or Pd
Ex.1. CH3CH2Br + H2 CH3–CH3 + H Br
525 K Ethane.
Zn-Cu
Ex.2. CH3–CH2–Br + 2H CH3–CH3 + HBr.
C2 H5 OH
Red P
Ex.3. CH3–CH2 I + HI CH3–CH3 + I2

12 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

E. Rearrangement or Isomerisation. In this Rxn haloalkanes undergoes rearrangement to

form isomeric haloalkanes.
Cl
AlCl3/573K │
Ex.1. CH3CH2CH2–Cl CH3–CH–CH3
1-Chloropropane 2-Chlopropane
Br
│
Ex. CH3–CH2CH2–CH2–Br CH3–CH2–CH–CH3

Chemical properties of Haloarenes:-

Q. Haloarenes are Chemically less reactive than haloalkanes. Due to following reasons:-
1. Resonance effect- There is delocalization of e-s in haloarenes so these stablised
by resonance as.

:Cl :Cl +Cl +Cl +Cl

The shortening of bond length imparts stability to aryl halides & as a result the
bond cleavage becomes difficult.
2. Different hybridization states of carbon atom.i.e SP2 & SP3
3. Polarity of carbon–halogen bond is less in aryl halides in comparison to
alkyl halides.
4. Repulsion between the electron rich attacking nucleophiles & electron rich
arenes ring..

A. Nucleophile substitution Rxn of haloarenes.

1. Replacement by hydroxyl gp (formation of phenol)-

Cl ONa OH
High T&P dil HCl
+ NaOH + NaCl

2. Substitution by amino group – (formation of aniline)

Cl NH2
475K
+ 2NH3 + Cu2O 2 + Cu2Cl2 +H2O
60 atm

Aniline

13 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

3. Substitution by cyano gp (formation of cyanobenzene)

Br CN Complete hyds
Pyridine
+ CuCN Incomplete hyds
475K
cycanobenzene
reduction
B. Rxn with metals:-
Ex.1. Br MgBr.
Ether
+ Mg

Phenyl magnesium bromide (G.R.)

Ex.2. Li
Br
Dry ether
+ 2Li + LiBr

Fittig Rxn
Cl

Ether
+
+ 2 Na

Diphenyl
Wurtz-Fittig Rxn
Cl

+2 Na+ + Cl–CH3 CH3 + 2 NaCl

Toluene
C. Reduction:- Haloarenes reduces to hydrocarbons.
Cl

Ni - Al
+2H. + HCl
NaOH
Chlorobenzene Benzene

14 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

D. Ring substitution or electeophilic substitution Rxn.

In halo benzene resonance str the electron density increases on ortho-& para- position
due to which the halogen atom is ortho & para directing in nature & hence substitution
takes places at O–& p–position.

Cl2/AlCl3 o-dichlorobenzene + p-dichlorobenzene

(Halogenation)

Cl HNO3+H2SO4 o-chloronitrobenzene + p-chloronitrobenzene

(Nitration)
H2SO4 o-chlorobenzene sulphonic acid +
(sulphonation) p-chlorobenzene sulphonic acid
CH3Cl/AlCl3 o-chlorotoluene + p-chlorotoluene Chlorobenzene
(alkylation)

CH3COCl/AlCl3 o-chloroacetophonone +
(acylation) p- chloroacetophonone

1. Trichloromethane (CHCl3) or chloroform:-

Reagent. (i) NaOH + Cl2 or NaOCl
Or OCl- or Cl2 / OH-
Or Cl2 / alkali or Cl2 / K2CO3.

(ii) CaOCl2 (Bleaching powder) Calcium oxy chloride.

HOH
CaOCl2 Ca (OH)2 + Cl2.
oxidation of only alcohols.
Function
Halogenation = + Cl

CHI3 NaOH + I2 or NaoI

I2/OH- or I2 / alkali + I

Which compounds gives Haloform reactions.

1. In aldehyde only CH3CHO.

2. In Ketone presence of CH3–C – gp.
║
O
3. 1˚alcohol only CH3CH2OH.
4. 2˚alcohol only once of CH3–CH–gp
│
OH
5. 3˚ alcohol no haloform reaction.

15 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

Preparation of CHCl3 :- 1. Haloform reaction : CHCl3 is prepared from ethanol or

propanone with bleaching powder or NaOCl this reaction is K/as Haloform reaction. Rxn
occurs in three step In alcohols & In two step in aldehyde & ketones..

NaOH +Cl2
2. CH3CHO CHCl3 + HCOONa
NaOH +Cl2
3. CH3 –CH –CH3 CHCl3 +CH3COONa
│
OH
4. by chlorination of methane:- .
Cl2
CH4 CH3Cl + CH2Cl2 + CHCl3 +CCl4
675.k

5. By reduction of carbon tetrachloride:-.

Fe / H2O
CCl4 +2H CHCl3 +HCl .
Chloroform
Chemical properties of CHCl3:-

1. Oxidation: - Chloroform oxidized into poisonous gas phosgene (i.e. COCl2 carbonyl
chloride) in the presence of air or light.

CHCl3 + 1/2 O2 COCl2 + HCl .

Light
phosgene.
Note:- Small amount of alcohol mixed with chloroform to preserve it , because alcohol
decompose phosgene (COCl2) in to HCl as .
Cl C2H5OH
+ (C2H5)2CO3 + 2HCl.
O═ C
Cl C2H5OH
And CHCl3 stored in dark coloured bottles & completely filled upto brim to protect from light
& air respectively.

2. Reduction:-
Zn/HCl
CHCl3 + 2H CH2Cl2 + HCl
Methylene chloride.
3. CHCl3 + aq KOH HCOOH or HCOOK + HCl

4. 2CHCl3 + 6Ag CH ≡ CH + 6AgCl
.
5. Chloroform + acetone chloretone . CCl3
CHCl3 + CH3 – C – CH3 │
║ CH3 – C – CH3
O │
OH

16 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

6. Carbide amine reaction or isocyanide test:- pri. Amines on treatment with chloroform
In presence of KOH gives alkane isocyanides.
CHCl3/KOH
R –NH2 R-NC

Mechanism:-
Step – 1 CHCl3 + alc KOH *CCl2 (reacting species) chlorocarbeen
Alc. KOH
Step- II R – NH2 + *CCl2 R – NH2 – CCl2 R–NC

7. Reamer-Tiemann Rxn or Rxn with phenol :-

OH OH
KOH
+ CHCl3
CHO
Phenol Salisaldehyde
OH OH
KOH
+ CCl4
COOH
Salicyclic acid.
Uses of Chloroform:-
(i) In industry, chloroform is used as an imp. Solvent particularly for fats, alkaloids,
Iodine, waxes, rubber etc.
(ii) It is used as an anesthetic.
(iii) It is used in medicines.
(iv) It is used in the production of Freon, refrigerant ( R-22)
(v) It is used in the preparation of chloropicrin, chloretone etc.

3. DDT: - It is synthesized by heating a mixture of chloral with chlorobenzene in

Presence of conc. H2SO4.
Cl2 2C6H5Cl
C2H5OH CCl3 – CHO DDT
chloral conc.H2SO4
Cl Cl Cl Cl

+ Conc. H2SO4

H O H H-C–CCl3
║
Cl3C-C-H PP'-Dichlorodiphenyl trichloroethane

(i) It is used as an insecticide .the use of DDT increased enormously after world war–II
because of its effectiveness against mosquito that spreads malaria.

17 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

6. Carbon tetrachloride (CCl4) or Pyrene

Preparation:- 1. From methane.
CH4 + 4Cl 2 CCl4 + 4HCl.
2. from Chloroform .
CHCl3+Cl2 CCl4 +HCl
3. from Carbon disulphide .
CS2 + 3Cl2 CCl4 + S2Cl2

Chemical properties
Red Fe/ HCl
CHCl3 + HCl
2(H), Fe/H2O
CHCl3 + HCl
Aq KOH
K2CO3
H2O(steam) air
CCl4 COCl2 + 2 HCl
SbF2, SbCl5
CCl2F2 + 2 SbCl3.

HF, SbCl3
CCl4 CCl2 F2 + HCl.
C6H5OH, 3KOH OH
CCl4
COOH Salicyclic acid
Uses.- (1) CCl4 is used to extinguish fire under the name pyrene.
(2) CCl4 resists hydrolysis with boiling water due to non availability of d- orbital in Carbon.
(3) CCl4 is an anti-helminthes medicine against–Hookworm.
(4) It is used in the preparation of Freon

2 Freon’s:-
(i) It is chloroflouro derivative of methane & ethane which is represented by
CFC.
(ii) It is used in refrigeration & air-conditioning.
(iii) It is nontoxic, odorless, and non-rusting.

HF
Preparation :- (i) CCl4 CCl3F. 011
SbFCl4 CCl2F2 012

(ii) C2Cl6 C2Cl5F 111

C2Cl4F2 112
C2Cl3F3 113
(iv) These have also been used extensively as propellants for aerosols & as foam to spray
out deodorants, cleansers, shaving creams, & insecticides.

18 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

Haloalkanes & Haloarenes

Q 1 . Write short note on Gemdihalid & Vic dihalide
Dihalide  two halogen atom present.
(Alkylidences)

Gemdihalid Vic dihalide

(i-e two halogen (i.e. two halogen atom present
Atom present on single on two nearest Carbon atoms)
Carbon atom)
Ex. CH2Cl2 , CH3CHCl2 Ex. CH2 – CH2
│ │
Cl Cl
Q 2 . Write short note on order of reactivity of halogen acids & Reactivity of alcohols
towards halogen acids
1. The order of reactivity of halogen acids on alcohols is.
HI > HBr > HCl.
This is due to the less bond dissociation energy of HI than that of HBr which in turn less
than that of HCl. As we move down the group the size of halogen atoms increases due to
which the tendency to hold the small hydrogen atom decreases & hence bond becomes
weaker.
2. The Reactivity of alcohols towards halogen acids
Tertiary alcohol > Secondary alcohol > Primary alcohol
CH3
↓
CH3→C←CH3 CH3→CH←CH3 CH3→CH2OH
│ │
OH OH 1˚
3◦ 2˚
This is due to fact that greater the number of electron releasing groups on the α-carbon
atom of the alcohol more is the polarity of C-OH. As a result, the Cleavage of C-O bond
becomes easy or carbocation forms easy hence reactivity increases.

Q 3 .Write short note on Markownikoff rule

Markownikoff rule →in case of unsymmetrical alkenes the negative part of the attacking
reagent attacks to that carbon atom which is highly alkylated or have less number of
hydrogen atoms it is k/as Markownikoff rule. As

Ex. CH3 – CH = CH2 + HBr CH3 – CH – CH2

│ │
Br H 2–Bromopropane
O O
║ ║
But in presence of organic peroxides such as (C6H5–C – O – O – CC6H5) the addition of
HBr takes places against the Markownikoff rule. This is known as anti-marknownikoff rule
or peroxide effect or also called Kharasch effect.
Peroxide
Ex. CH3 – CH = CH2 + HBr CH3-CH2 – CH2
│ │
H Br 1- Bromopropane

19 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

Q 4.
Write short note on Allylic chlorination & Allylic Bromination
Allylic chlorination → it is obtained when alkenes are heated with Cl2 at about 800 k
800K
Ex. CH2=CH–CH3 + Cl2 CH2 = CH–CH2Cl + HCl
Propene AllylChloride.

Allylic Bromination → with the help of N-bromosuccinamide (NBS) in presence of light

bromination of alkene takes places
Ex. CH2=CH–CH3 + CH2–CO CH2=CH–CH2 + CH2-CO
Propene │ NBr │ │ NH
CH2–CO Br CH2-CO
Q 5 . Explain Solubility , Melting & boiling points & Nature of C-X bond
Solubility → haloalkanes are polar in nature, yet they are slightly soluble in water. This is
because they are not able to form hydrogen bonds with water.
But are soluble in organic solvents such as alcohol, ether, benzene etc. because of
intermolecular forces are similar to that of solvents.

Melting & boiling points. → M.Pt. & B.Pt. of chlorides, bromides & iodides are considerably
higher than those of parent hydrocarbon of comparable molecular mass.
Ex. of order of M.Pt & B.Pt.
1. RI > RBr > RCl > RF. This is because with the increase in the size of the halogen, the
magnitude of vander waals forces increases.
2. In general the B.Pt of chloro, & iodo compounds increases with increase in the number
of halogen atoms.
Eg. CH3Cl < CH2Cl2 < CHCl3 < CCl4.
3. B.Pt. increases with increase in the size of alkyl gp.
Eg. CH3Cl < CH3CH2 Cl < CH3CH2CH2Cl < CH3CH2CH2CH2Cl
4. B.Pt decreases with increasing branching of alkane chain because
vander waals forces of attraction decreases.
Eg. n-Butyl bromide > Iso–Butyl bromide > tert-Butylbromide.

Nature of C-X bond → Nature of C-X bond in alkyl halide is polar due to electro negativity
difference between the carbon and halogen atoms.
But the order of reactivity depends upon the dissociation energy. As we move down the
group the size of halogen atom increases due to which the tendency to hold H atom of alkyl Gp
decreases or in other words the strength of C-X bond decreases & hence breaks easily. So the
order of reactivity is ═ (R-I > R-Br > R-Cl)

Q 6 . What is Nucleophilic SubstitutionRxn ? Explain SN1 Rxn & SN2 Rxn

Nucleophilic SubstitutionRxn of Alkyl halides-Nucleophilic substitution Rxn are those
chemical Rxn in which one weak nucleophile replaced by another strong – nucleophile (ie.
Electron rich sps). Are K/as Nu. Nucleophilic Substitution reactions.
Nucleophilic substitutions are of two types i.e. SN1 & SN2

(a) SN1 Rxn – (1) SN1 Rxn are unimolecular Rxn it means the rate of Rxn depends only on one
reactant i.e. alkyl halide or [ R−Cl]
(2) These Rxn occurs in two steps.
(3) SN1 Rxn takes places through carbonium ion or carbocation intermediate reacting species.
(4) The order of reactivity is = tertiary > secondary > Primary alkyl halide

20 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

(5) SN1 Rxn’ may be takes places by any direction i.e from back side or from front side. Due
to which the product formed is Racemic mixture or dextro- or leavo-forms are formed.
(6) Walden inversion absent.

Example.
CH3 CH3 CH3
│ K+OH- │ │
CH3 – C – Cl CH3 – C – OH + HO – C – CH3
│ │ │
CH3 CH3 CH3
50% d-form 50% l-form
(Racemic Mixture)
Mechanism:-
CH3 CH3 CH3 CH3
│ K+ │ OH- │ │
CH3–C–Cl CH3–C+ CH3–C–OH + HO– C – CH3
│ -KCl │ │ │
CH3 CH3 CH3 CH3
Carboniumion d-form l-form
(Reacting intermediate)
(b) SN2 Rxn’:-
7. SN2 Rxn are bimolecular Rxn it means the rate of Rxn depends upon the two reactants
i.e. upon nucleophile as well as alkyhalide. i.e Rate α [ Nu] [R-Cl]
8. These Rxn occurs in one step.
9. SN2 Rxn takes places through transition intermediate reacting species.
10. The order of reactivity is Primary > Secondary > tertiary (this is due to the presence of
steric hindrance in 3˚.
11. SN2 reaction takes places only through back side therefore dextro form change into
leavo form and vice versa.
12. Walden inversion takes places.(i.e d-form  l-form)
H H
│ │
H – C – Cl + KCN CN- C– H + KCl.
│ │
H H

Mechanism
H H CH3 CH3
│ ∂- ∂+ │
CH – C – Cl HO--------C---------Cl HO−C−H
│ │ │
H H H
d-form (unstable) l-form
(Transition intermediate)
Reacting sps

21 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

Q 7 . What is Saytzeff’s Rule ?

Saytzeff’s Rule- In case of haloalkane can eliminate hydrogen halide in two different ways
then that alkene will be preferred in which carbon atoms joined by the double bond are
maximum alkylated. i.e contain largest number of alkyl gps. It is K/as Saytzeff’s rule

B A B
Ex. CH3 – CH2 – CH – CH3 CH3−CH ═ CH – CH3
│ Alc. KOH But -2-ene. (80%)
Br

2-Bromobutane
CH3−CH2−CH=CH2
But–1–ene (20%)
Q 8. Haloarenes are Chemically less reactive than haloalkanes why?
Due to following reasons:-
1. Resonance effect- There is delocalization of e-s in haloarenes so these stablised
by resonance as.
:Cl :Cl +Cl +Cl +Cl

The shortening of bond length imparts stability to aryl halides & as a result the
bond cleavage becomes difficult.
2. Different hybridization states of carbon atom.i.e SP2 & SP3
3. Polarity of carbon–halogen bond is less in aryl halides in comparison to
alkyl halides.
4. Repulsion between the electron rich attacking nucleophiles & electron rich
arenes ring.

Q 9 . Explain following name reactions

1. Wurtz Rxn
Two molecules of alkyl halides react with metallic sodium in presence of ether to form alkane.
This reaction is called Wurtz Rxn.
Dry ether
Ex. R-X + 2 Na +X-R R-R + 2 NaX.
C2H5–Br + 2Na + Br–C2H5 C2H5–C2H5 + 2NaBr.
2. Fittig Rxn :
Ex. Cl

Ether
+ 2 Na+

Diphenyl
3. Wurtz-Fittig Rxn:
Cl

+2 Na+ + Cl–CH3 CH3 + 2 NaCl

Toluene

22 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

4. Finkelstein reaction-
Acetone
Ex. CH3CH2Cl + NaI CH3CH2I + NaCl
Refuxl

5. Swarts reaction :-
CCl4
CH3Br + AgF CH3F + AgBr

6. Borodine Hunsdiecker Rxn → the silver salt of carboxylic acids dissolved in CCl4 are
decomposed by bromine to form bromoalkanes. This Rxn is called Borodine
Hunsdiecker Rxn
CCl4
Ex. CH3COOAg + Br2 CH3Br + CO2 + AgBr
Silver acetate Bromomethane
7. Sand Meyer’s reaction:- chloro & bromoarenes are prepared by treating a freshly
prepared diazonium salt solution with cuprous chloride or cuprous bromide dissolved
in HCl or HBr respectively. This reaction is called Sand Meyer’s reaction”

NH2 N2+Cl-

0-5˚,C
+ HONO + HCl + 2H2O

Aniline Benzenediazoniu Chloride salt

Ex N2+Cl- Cl

CuCl/HCl + N2 + HCl

Chlorobezene
8. Hofmann ammonolysis Rxn
or Substitution by amino group (formation amines):
Ex. R−X + H–NH2 R−NH2 + HX
Ammonia alkanamine
CH3CH2−Br + NH3 CH3CH2NH2 + HBr
Ethanamine
When haloalkane is in excess, one or both or all the hydrogen atoms of the amino alkane
(Pri-amine) are replaced by alkyl groups & a mixture of Pri, Sec, & tertiary amines is
formed- CH3
+CH3Br +CH3Br │
CH3–Br + NH3 CH3–NH2 CH3−NH−CH3 CH3-N-CH3
-HBr 1˚amine -HBr 2˚ amine 3˚ amine
+CH3Br
[(CH3)4 N]+ Br-
Tetramethyl ammonium Bromide (Quaternary salt)
This Rxn also Called Hofmann ammonolysis Rxn

9.Haloform reaction : CHCl3 is prepared from ethanol or propanone with bleaching powder
or NaOCl this reaction is K/as Haloform reaction. Rxn occurs in three step In alcohols & In
two step in aldehyde & ketones..

23 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

NaOH +Cl2
2. CH3CHO CHCl3 + HCOONa
NaOH +Cl2
3. CH3 –CH –CH3 CHCl3 +CH3COONa
│
OH
10. Carbide amine reaction or isocyanide test:- pri. Amines on treatment with chloroform
In presence of KOH gives alkane isocyanides.
CHCl3/KOH
R –NH2 R-NC
Mechanism:-
Step – 1 CHCl3 + alc KOH *CCl2 (reacting species) chlorocarbeen
Alc. KOH
Step- II R – NH2 + *CCl2 R – NH2 – CCl2 R–NC

11. Reamer-Tiemann Rxn or Rxn with phenol :-

OH OH
KOH
+ CHCl3
CHO
Phenol Salisaldehyde
OH OH
KOH
+ CCl4
COOH
Salicyclic acid.
12. By Hunsdiecker’s reaction
COOAg Br
CCl
+ Br2 4 + AgBr + CO2

Bromobenzene
Q 10. Write short on Ring substitution or electeophilic substitution Rxn.
In halo benzene resonance str the electron density increases on ortho-& para- position
due to which the halogen atom is ortho & para directing in nature & hence substitution
takes places at O–& p–position.

Cl2/AlCl3 o-dichlorobenzene + p-dichlorobenzene

(Halogenation)

Cl HNO3+H2SO4 o-chloronitrobenzene + p-chloronitrobenzene

(Nitration)
H2SO4 o-chlorobenzene sulphonic acid +
(sulphonation) p-chlorobenzene sulphonic acid
CH3Cl/AlCl3 o-chlorotoluene + p-chlorotoluene Chlorobenzene
(alkylation)

CH3COCl/AlCl3 o-chloroacetophonone +
(acylation) p- chloroacetophonone

24 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

Q 11 .Write short note on Oxidation of Chloroform

Oxidation: - Chloroform oxidized into poisonous gas phosgene (i.e. COCl2 carbonyl chloride)
in the presence of air or light.

CHCl3 + 1/2 O2 COCl2 + HCl .

Light
phosgene.
Note:- Small amount of alcohol mixed with chloroform to preserve it , because alcohol
decompose phosgene (COCl2) in to HCl as .
Cl C2H5OH
+ (C2H5)2CO3 + 2HCl.
O═ C
Cl C2H5OH
And CHCl3 stored in dark coloured bottles & completely filled upto brim to protect from light
& air respectively.

Q 12. Write uses of chloroform & CCl4

Uses of Chloroform:-
(vi) In industry, chloroform is used as an imp. Solvent particularly for fats, alkaloids,
Iodine, waxes, rubber etc.
(vii) It is used as an anesthetic.
(viii) It is used in medicines.
(ix) It is used in the production of Freon, refrigerant ( R-22)
(x) It is used in the preparation of chloropicrin, chloretone.
Uses of CCl4 :- (1) CCl4 is used to extinguish fire under the name pyrene.
(2) CCl4 resists hydrolysis with boiling water due to non availability of d- orbital in Carbon.
(3) CCl4 is an anti-helminthes medicine against–Hookworm.
(4) It is used in the preparation of Freon

Q 12 .Write short note on

DDT: - It is synthesized by heating a mixture of chloral with chlorobenzene in
Presence of conc. H2SO4.
Cl2 2C6H5Cl
C2H5OH CCl3 – CHO DDT
chloral conc.H2SO4
Cl Cl Cl Cl

+ Conc. H2SO4

H O H H-C–CCl3
║
Cl3C-C-H PP'-Dichlorodiphenyl trichloroethane

(ii) It is used as an insecticide .the use of DDT increased enormously after world war–II
because of its effectiveness against mosquito that spreads malaria.

25 Subscribe on key 2 chemistry

Key-2-Chemistry by K Singh

Q 14. Write short note on Freon’s:-

(i) It is chloroflouro derivative of methane & ethane which is represented by
CFC.
(ii) It is used in refrigeration & air-conditioning.
(iii) It is nontoxic, odorless, and non-rusting.
HF
Preparation :- (i) CCl4 CCl3F. 011
SbFCl4 CCl2F2 012

(ii) C2Cl6 C2Cl5F 111

C2Cl4F2 112
C2Cl3F3 113
(iv) These have also been used extensively as propellants for aerosols & as foam to spray
out deodorants, cleansers, shaving creams, & insecticides.

26 Subscribe on key 2 chemistry