Chapter 12

ORGANIC CHEMISTRY
SOME BASIC PRINCIPLES AND TECHNIQUES

Nomenclature
 Hydrocarbons
Organic compounds containing carbon and hydrogen atoms only are called hydrocarbons.

tax

-*☒i* *

Benzenoid
-BBEAa_A Non-benzenoid
the
Nomenclature
Tiff
CH₃-CH₂-CH₂-CH₃ Butane

But-1-enc
2 I

CH₃-CH₂-CH=CH₂

23
Pent-2ryne
&

CH₃-C=C-CH₂-CH₃ -
>
-
CH₂-CH₂-CH₂-CH₃ I-Bromobutane
Br
4
Chlorobutane
I 2
3

CH₃-CH-CH₂-CH₃ 2-

Cl

CH₃-CH₂-CH-CH-CH₃ Pentan-3-0
OH
CH₃-O-CH₃
T
Methoxymethane
T
Methoxybutane
CH₃-O-CH₂-CH₂-CH₂-CH₃
--
Y 4

Ketone
CH₃-CH₂-CO-CH₂-CH₃ Pentax-3-one
I 2 3 f
4
HCHO Methanal Aldehyde
·

CH₃-CHO Ethanal
-

CH₃-CH₂CH₂-CH₂-CHO Pertanal

4 3 2 I

CH₃-CH-CH₂-CH₂-CHO
5 CH₂ ↳ -Betty
the anal

6 CH₃
 Cl Br

Benzene chlorobenzene Bromobenzen

CH₃ NO₂ OH

Tduene Nitrobenzene -
-
pheno
-
-
 CHO COOH NH₂

Benzaldehyde Benzoic
acid ne

Cl Cl Cl
I
Cl ↑
z
N
2
2

3 S

Cl 4

Cl
1 2-Dichlorobenzene 13-Dichlorobenzene
,
meta-
-Dichlorobenzene .

Ortho- Para-
 OH
3-hexand
·
D
· -
-
3 f
⑰

6
5 ·

6
2 · D
/

*
3 5
I

veflel meth
.
· S 7

. · Cl Br

·
2 3-Bromo-3-chloroheptane
3-Edimethylcyclohexane
Hayl-
3 .

Ettyl
Chapter 12

ORGANIC CHEMISTRY
SOME BASIC PRINCIPLES AND TECHNIQUES

Isomerism
 Isomerism
The phenomenon of existence of two or more compounds having the same
molecular formula but different structural formula or spatial arrangement of atoms
is known as isomerism.

Isomerism
Structural isomerism Stereo isomerism

Chain isomerism
Geometrical isomerism
Position isomerism
Optical isomerism
Functional group isomerism

Metamerism
Structural isomerism
Compounds having same molecular formula but different structural
formula (arrangement of atoms) are called structural isomers and the
phenomenon is called structural isomerism.

a) Chain Isomerism
Isomers differ in carbon chain or skeleton are called chain isomers
and the phenomenon is called chain isomerism.

CH₃-CH₂-CH₂-CH₃ CH₃-CH-CH₃
-

Batane CH₃

2-methylpropane ·
b) Position isomerism
Isomers which differ in the position of the substituent or functional
group are called position isomers and the phenomenon is called
position isomerism.

CH₃-CH-CH₂-CH₂-CH₃ 2- pentano
OH

CH₃-CH₂-CH-CH₂-CH₃ 3-pentand
-
-
OH
c) Functional group isomerism
Isomers which differ in the functional group are called functional
group isomers and the phenomenon is called functional group
isomerism.

CH₃-CH₂-CHO CH₃-CH₂-CH₂-CH₂-CHO
CH₃-CO-CH₃ CH₃-CH₂-CH₂-CO-CH₃

HoO CH-O-CHty O

- CHO OH O
CH-CH2-ol
- -

-
co- -
O-
d) Metamerism
Isomers which differ in the carbon chain (alkyl groups) around the
functional group are called metamers and the phenomenon is called
metamerism.

CH₃-CO-CH₂-CH₂-CH₃

CH₃-CH₂-CO-CH₂-CH₃
Fission of a covalent bond

A. B

AB
>
-
+ .

- At +: B
1. Homolysis / Homolytic cleavage
The bond breaks in such a manner each of the bonded atoms gets one
of the electrons of the shared pair.

A
CH₃ — Br
•• •s

g.
•

CH₃ + Br

Free radical
Species which contain an odd electron or an unpaired electron
2. Heterolysis / Heterolytic cleavage
The bond breaks in such a manner that the shared pair of electrons
remains with one of the parts.

CH₃ — Br
• • +
CH₃ + Br •
•
−
Reagents
· Ni
Nucleophiles
A reagent that brings an electron pair is called a nucleophile.

− − − BO

Eg: Cl , Br , OH , NH₃ , H₂O

BO Bo •

•
Electrophiles
A reagent that takes away an electron pair is called an electrophile.

+ +
Eg: H , CH₃ , BF₃ , AlCl₃
Chapter 12

ORGANIC CHEMISTRY
SOME BASIC PRINCIPLES AND TECHNIQUES

Electron displacement effects in covalent bonds

1. Inductive effect (I effect)
It is a permanent effect arising due to the shifting of sigma electrons
through a carbon chain in presence of an atom or group of atom.

8867 8Sf & 8-

CH₃—CH₂—CH₂—Cl
I > ·

—I Effect cli FY, Ci NO , s

-CHO

Electron moves towards the electron withdrawing group

+I Effect CHjCHz
CHz- ,

Electron moves away from the electron donating groups

2. Resonance Effect or Mesomeric effect (R or M effect)
The polarity (charge) produced in the molecule by the interaction
of two π bonds or between a π-bond and lone pair of electrons
present on an adjacent atom.

They are two types : 1) -R effect

2) +R effect
1) -R effect
Electron moves towards atom or group attached to the conjugated system

O O O O O O

q
O OT O
-

N O. N
v
l

N N N-
4 I I
④ -

1 DI -I -
I

– R effect groups: – COOH, –CHO, >C=O, – CN, –NO₂ etc.

 2) +R effect
Electron moves away from the atom or group attached to the
conjugated system

s
B b
④
g.

OH OH OH OH .OH
G I I
-
&
o

I Ell -
↑
- L

a &

+R effect groups: – halogen, –OH, –OR, –NH₂, –NHR, –NR₂ etc.

Electromeric effect (E effect)
The complete transfer of a shared pair of π-electrons to the one of the
atoms joined by multiple bond in presence of an attacking reagent.
It is a temporary effect.

There are two types of E effects:

1) Positive Electromeric effect (+E effect)

2) Negative Electromeric effect (-E effect)

+E effect
The pi electrons are transferred to that atom to which the attacking
reagent gets attached

A + +

C==C + H C C
H
-E effect
The pi electrons of the multiple bonds are transferred to that atom to
which the attacking reagent does not get attached.

A −
C==C
-

+ CN C C
CN
Hyper conjugation H-EIT
It involves delocalisation of σ electrons of C—H bond of an alkyl
group directly attached to an atom of unsaturated system or to
an atom with an unshared p orbital.

⑲
Hyper-conjugative structures of CH₃ -CH₂+ (ethyl cation)
①
C C-CH2
+

CH - It City
-C-CHy
&
cits a kit
Hyper conjugation stabilises the carbocation
Greater the number of alkyl groups attached to a positively charged
carbon atom, the greater is the hyper conjugation interaction and
stabilisation of the cation.

The relative stability of carbocations is in the order:

Here tertiary carbocation has 9, isopropyl has 6, ethyl carbocation

has 3 and methyl carbocation has zero hyper conjugative structures.
Chapter 12

ORGANIC CHEMISTRY
SOME BASIC PRINCIPLES AND TECHNIQUES

PURIFICATION OF ORGANIC COMPOUNDS

PURIFICATION OF ORGANIC COMPOUNDS
The common techniques used for purification are as follows:

i. Sublimation

ii. Crystallisation

iii. Distillation

iv. Differential extraction

v. Chromatography
Chapter 12

ORGANIC CHEMISTRY
SOME BASIC PRINCIPLES AND TECHNIQUES

QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS

Chapter 12

ORGANIC CHEMISTRY
SOME BASIC PRINCIPLES AND TECHNIQUES

QUANTITATIVE ANALYSIS OF ORGANIC COMPOUNDS

CHAPTER 13

Hydrocarbons
Classification / Preparations of Alkanes
 Hydrocarbons
Organic compounds containing carbon and hydrogen atoms only are called hydrocarbons.

tax

-*☒i* *

Benzenoid
-BBEAa_A Non-benzenoid
the
Preparation of alkanes :
1. From Unsaturated hydrocarbons :
Alkenes and alkynes add Hydrogen in presence of finely divided
catalysts like Ni, Pd or Pt to form alkanes.
This process is called hydrogenation.

CHE
CH
, ifpd/pts CHz-Cl,
2. From alkyl halides : R-X Na
R-R
R X Na
Wurtz reaction
-

+ Nax

Alkyl halides react with metallic sodium in dry ether to form alkanes.
This reaction is known as Wurtz reaction.

2 Na
Ether CH5CH3 + [NaC
2 CHz-d +
3. From carboxylic acids :
Kolbe’s Electrolytic method:
An aqueous solution of sodium or potassium salt of a
carboxylic acid on electrolysis gives alkane containing even number
of carbon atoms.

Electrolysis
2CH₃COONa + 2H₂O CH₃–CH₃ + 2CO₂ + 2NaOH + H₂
Sodium acetate

H Oft
CHz-C00-Na

CHy-100 NC H of
CHAPTER 13

Hydrocarbons
Chemical properties of Alkanes
1. Substitution reaction
When an alkane is treated with halogen in the presence of sunlight or
uv light, we get haloalkane. This reaction is known as halogenations.

Chat else # CHBC + Hel

HC
chcl + de CHcIz +

Check+ Ch > CHC + He

CHc +
d H
2. Isomerisation :
Alkanes on heating in the presence of anhydrous aluminium chloride and
hydrogen chloride gas isomerise to branched chain alkanes.

r
 AnlyAll/Ac
CHy-CHE
CH
,
- CH
,
-

CHI CH, →
3. Aromatization :
Alkanes having six or more carbon atoms on heating to 773K
at 10-20 atmospheric pressure in the presence of oxides of
vanadium, molybdenum or chromium supported over alumina,
we get aromatic compounds.
This reaction is known as Aromatization or Reforming.

A-

↳ Higko-zate Fet
4. Pyrolysis :
c-cE
c-c - c -

Alkanes having six or more carbon atoms on heating at higher

temperature decompose to form lower alkanes, alkenes etc.
This reaction is known as pyrolysis.
\

+ Pentene
Methane
.

Ethane + Butene .

C₆H₁₄
Propane + Propere .

Butane + Ethere
CHAPTER 13

Hydrocarbons
Conformations of alkanes
 If
Conformations of Ethane CH₃—CH₃ C

A H
sawhorse BB
A
a "
F-←C
If
HH
1 H

H It
I

Eclipsed staggered. H
H H
,
.

It It
- -

Newman
H

O H

Eclipsed
Y H
staggered
H
Conformations
Conformation is a phenomenon in which the different structures are
obtained due to free rotation about the C-C sigma bond.

The different structures obtained are called

Conformers / Rotamers / Rotational isomers.

Staggered Conformation : The hydrogens of the two carbon atoms

are staggered with respect to one other. As a result they are maximum
distance apart and have minimum repulsion between them.

Eclipsed Conformation : The hydrogens of one carbon atom are

directly behind those of the other. Consequently,the repulsion in these
atoms is maximum.
Any conformations between eclipsed and staggered conformations are
called skew conformations.
To represent these conformations two simple ways are used;
H
H
H
(1) Sawhorse projection
of Ethane H
H H
H
H

H H
H H

HH H

(2) Newman projection 1 H

H

of Ethane
H /
it ¥ A H

H
 ▪
▪
Relative stability of Conformations

The repulsive interaction between the electron clouds is

called Torsional strain.

The staggered form has least tortional strain &

maximum stability.

The Eclipsed form has maximum torsional strain &

minimum stability.
CHAPTER 13

Hydrocarbons
Isomerism in alkenes
▪
Stereo isomerism
x =
c
Geometrical isomerism
Geometrical isomerism arising due to the restricted rotation about
carbon-carbon double bond.

There are two types of geometrical isomers

- cis isomer
- trans isomer

Isomer in which identical atoms or groups are on the same side of

the double bond is called cis isomer.

If the identical groups or atoms are on the opposite side of the

double bond, it is called trans isomer.
But-2-ene CH-CH = CH-CHIs
CH3 CH CHB H
- cu
- C- - c -

c
TH
-
-

-
I If H
CiS-Butl-zene trans-Butzene
-

1,2-Dichloroethene CH
CH-I
-

i
It H -d
dcut - C- -
-

- el
C--

~ d H

cis trans
=>
CHAPTER 13

Hydrocarbons
Preparations of Alkenes
2) From Alkyl halides :
Alkyl halides (R-X) on heating with alcoholic potash, eliminate one
molecule of hydrogen halide to form alkenes.
This reaction is known as dehydrohalogenation
Since hydrogen atom is eliminated from the β carbon atom,
the reaction is also known as β-elimination reaction.

Bx
CH₃- CH₂Br Alcoholic KOH
CH2 =
CHO

Bx

ChigcHz
Alcoholic KOH
CH₃- CH₂- CH₂Br
3) From alcohols :
Alcohols when heated with concentrated sulphuric acid undergo
dehydration (elimination of water molecule) to form alkenes.
This reaction is also the example of β-elimination reaction.

OH
B
Conc.H₂SO₄ + H
CH
X
CH₃- CH₂

B 2
Conc.H₂SO₄
CH₃- CH₂ - CH₂ CH3-CCHe --

OH
CHAPTER 13

Hydrocarbons
Chemical properties of Alkenes
1) Addition of hydrogen :
Alkenes add hydrogen in presence of finely divided Ni, Pd or Pt to
form alkanes.

&
& Ni / Pd / Pt
CH₂ = CH₂ + H₂ CHy-CHy

&
M Ni / Pd / Pt
CHz-CH2CHty
L
CH₃- CH = CH₂ + H₂
2) Addition of halogen :
Alkenes add halogen (Cl₂ or Br₂) to form vicinal dihalides.

↳ CH-CH2
CH₂ = CH₂ + X₂ 2

↓ k
D CCl₄

City-CH-CH
CH₃- CH = CH₂ + Br₂
3) Addition of hydrogen halide :
Alkenes add hydrogen halide to form alkyl halides.

-
&
CH₂ = CH₂ + HX → CH₃-CH₂X
-
L
CH₂ = CH₂ + HBr → CHz-CH2-By
CH₃-CH = CH-CH₃ + HBr → CH-CH-CH-Cty
w
- B
 I-Bromobatame
24
- CH2
CH₃-CH₂-CH = CH₂ + HBr → CHz-CH2-CH-
By
-
- minor

>
-

CHy-CHy-CH-CHy
Br
E-Bromobutane
⑳
May
Markownikoff’s rule :
The rule states that
“when an unsymmetrical reagent is added to an unsymmetrical
alkene, the negative part of the adding molecule gets attached to
the carbon containing lesser number of hydrogen atoms”.
Peroxide effect / Kharasch effect :
In presence of peroxide, addition of HBr to unsymmetrical alkenes takes
place against Markovnikov rule.
This is known as peroxide or Kharash effect or anti-Markovnikov addition
reaction.
Here the negative part goes to more hydrogenated carbon atom.

I-Bromobatame
anic ide
CH₃-CH₂-CH = CH₂ + HBr
org perof CHz
→
>
-
-

CH2-C-C
>
-

CHy-CH-CH-CHy
Br
2-Bromobutane
⑭or
4) Addition of water :
Alkenes add water in presence of a few drops of concentrated
sulphuric acid to form alcohols.
The reaction occurs according to the Markovnikov rule.

&
&
CH₃-CH₂-CH = CH₂ + H₂O
CH-CH2-CH.-C
-
6) Ozonolysis :
Alkenes add Ozone to form an ozonide which on hydrolysis in
presence of Zn to form carbonyl compounds (Aldehydes or ketones).

- O- Ozonide
CHz-CH aft
CH₃-CH= CH₂ + O₂
3
6 -
d

+ HCHO Zn + H₂O

-CHO
CHAPTER 13

Hydrocarbons
Preparations of Alkynes
 Preparation
1. From Calcium carbide (CaC2):
On large scale, ethyne is prepared by treating calcium carbide with water.

CaC₂ + 2H₂O Ca(OH)₂ + CH = CH

-

It Olf
caC
- It off
CHAPTER 13

Hydrocarbons
Chemical properties of Alkynes
iv) Addition of water :

On warming with water, alkynes add one molecule of water in presence of

dil. H₂SO₄ and mercuric sulphate at 333K to form aldehydes or ketones.

CH CH + H₂O
dil.H₂SO₄ / HgSO₄

333K
it
CH,
=
,

↓
Chty-
⑭
CH3
Polymerisation
a) Linear polymerisation :
Ethyne undergoes linear polymerisation under suitable conditions
to form polyethyne or polyacetylene.

ECH I
polymerisation
n CH≡CH = CH-
acetylene n
-
--
b) Cyclic polymerisation :

Ethyne on passing through red hot iron tube at 873K,

undergoes cyclic polymerisation to form benzene (C₆H₆).

B-

Man .

fenestrated
CHAPTER 13

Hydrocarbons
AROMATIC HYDROCARBONS (ARENES)
Structure of Benzene
The molecular formula of benzene is C₆H₆.
August Kekulé proposed the following structure for benzene having cyclic
arrangement of six carbon atoms with alternate single and double bonds.

(A) (B) Resonance Structure

 Aromaticity
Aromaticity is defined by a rule called ‘Huckel rule’.

According to this rule, “cyclic, planar, conjugated systems containing

(4n+2) π electrons are aromatic”. n may be 1,2,3,....

For benzene n = 1, so it should contain 6 delocalised π electrons.

If n = 2, the no. of delocalised π electrons =10 and so on.

IT
( 2)
+

6
A

E D

ti
⑰ o
·
CHAPTER 13

Hydrocarbons
Preparation of Benzene
Preparation of Benzene
1) Cyclic polymerisation of ethyne (acetylene) :

Ethyne on passing through red hot iron tube at 873K,

undergoes cyclic polymerisation to form benzene (C₆H₆).

115

Mom
2) Decarboxylation of aromatic acids :
NaOHxCaO
Sodium salt of benzoic acid on heating with sodalime gives benzene.

-- Δ
3) Reduction of phenol :
Phenol is reduced to benzene by passing its vapours over
heated zinc dust.
CHAPTER 13

Hydrocarbons
Chemical Properties Of Benzene
1. Electrophilic Substitution Reactions
These are reactions in which a weak electrophile is replaced by
a strong electrophile.

The important electrophilic substitution reactions are

Nitration
Sulphonation
Halogenation
Friedel-Crafts alkylation
Friedel-Crafts acylation
1. Nitration :
Benzene is heated with a mixture of conc. HNO₃ and conc. H₂SO₄
(nitrating mixture).

NOz
I
Conc.HNO₃
BeBe
Conc.H₂SO₄
2. Sulphonation :

So
Conc.H₂SO₄
BeBe
3. Halogenation :
Benzene is treated with a halogen (Cl₂ or Br₂) in presence of Lewis acids
like anhydrous FeCl₃, FeBr₃ or AlCl₃.

d
I
Andy.AlCl₃
+ Cl₂ BeBe
4. Friedel-Craft’s Alkylation reaction :
It is the introduction of alkyl (-R) group to a benzene ring.

Here the reagents used are alkyl halide in presence of anhydrous AlCl₃.

Anhyd.AlCl₃
ty
CH₃- Cl
Hol

CH₃- CH₂- Cl
Anhyd.AlCl₃ Hect
Ol
L~
5. Friedel-Craft’s Acylation reaction :
It is the introduction of acyl (-CO-R) group to a benzene ring.

Here the reagents used are acyl halide in presence of anhydrous AlCl₃.

oct
E
Anhyd.AlCl₃
CH₃-CO-Cl
6. Benzene on treatment with excess of chlorine in the presence of
anhydrous AlCl₃ in dark to form hexachlorobenzene (C₆Cl₆).
2. Addition Reaction
1) Addition of H₂:
Benzene add hydrogen in presence of nickel catalyst at high
temperature and pressure to form cyclohexane.
2) Addition of halogen :
Benzene adds chlorine in presence of uv light to form
benzene hexachloride (BHC).
It is also known as Gammexane or Lindane or 666.

Coltscl
Thank you..!!
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