11.

BASICS CONCEPTS OF ORGANIC CHEMISTRY

 What is Catenation?
The tendency of atoms to form a chain of bonds with the atoms of the same
element is called catenation. Carbon possesses maximum tendency for catenation.
Catenation order among the following is 𝐶 > 𝑆𝑖 ≈ 𝑆 > 𝑃 > 𝑁 > 𝑂.
 List the Characteristics of organic compounds.
1. Organic compounds are covalent in nature.
2. They are insoluble in water and readily soluble in organic solvent such as
benzene, toluene, ether, chloroform etc...
3. They are inflammable (except CCl4).
4. They possess low boiling and melting points due to their covalent nature.
5. They exhibit isomerism which is a unique phenomenon.
6. Organic compounds are characterised by functional groups.
 What are Homologous series? List the Characteristics of homologous
series?
 A series of organic compounds each containing a characteristic functional group
and the successive members differ from each other in molecular formula by a CH 2
group is called homologous series.
 They are represented by a general formula.
 They can be prepared by general methods.
 They show similar chemical properties and regular gradation in physical
properties.
Alkanes Alkenes Alkynes
CnH2n+2 CnH2n CnH2n-2
Methane (CH4) - -
Ethane (C2H6) Ethene (C2H4) Ethyne (C2H2)
Propane (C3H8) Propene (C3H6) Propyne (C3H4)
Butane (C4H10) Butene (C4H8) Butyne (C4H6)
Pentane (C5H12) Pentene (C5H10) Pentyne (C5H8)

BASICS OF ORGANIC CHEMISTRY-PART-I THE TURNING POINT 1

 Nomenclature of organic compounds
 The IUPAC name of an organic compound consists of three parts.
Prefix + Root Word + Suffix
 Root word denotes the number of carbon atoms in the longest chain in molecules.
 Prefix denotes the group(s) attached to the main chain.
 Suffix denotes the functional group.

ROOT WORD
No of C atoms Root word No of C atoms Root word
C1 Meth- C11 undec-
C2 Eth - C12 dodec-
C3 Prop- C13 tridec-
C4 But- C14 tetradec-
C5 Pent- C15 Pentadec-
C6 Hex- C16 Hexadec-
C7 Hept- C17 Heptadec-
C8 Oct- C18 Octadec-
C9 Non- C19 Nonadec-
C10 Dec- C20 Eicos-
SUFFIX
Primary suffix: It denotes the saturation/ unsaturation of organic compounds. It is
added immediately after the root word.
Type of carbon chain Primary suffix
Saturated
All 𝑪 − 𝑪 bonds ane
Unsaturated
One 𝑪 = 𝑪 bond ene
Two 𝑪 = 𝑪 bond diene
Three 𝑪 = 𝑪 bond triene
One 𝑪 ≡ 𝑪 bond yne
Two 𝑪 ≡ 𝑪 bond diyne
Secondary suffix: It is used to denote the nature of functional group present in the
organic compound. It is added to the primary suffix by removing its terminal ‘e’.

BASICS OF ORGANIC CHEMISTRY-PART-I THE TURNING POINT 2

 PREFIX
Substituents are denoted by adding prefix names before the root word. If the functional
groups are not part of the parent chain, they are considered as substituents. In such
cases its prefix name is added before the root word.

Substituent prefix Substituent prefix

-F Fluoro -CH3 methyl

-Cl Chloro -CH2-CH3 ethyl

-Br Bromo -CH2- CH2-CH3 1-propyl (n-propyl)

-I Iodo -CH(CH3)2 2-propyl (iso-propyl)

-NO2 Nitro -OH hydroxy

-NH2 Amino -O-CH3 methoxy

-O-CH2-CH3 Ethoxy

IUPAC RULES FOR NOMENCLATURE OF ORGANIC COMPOUNDS

"
 Choosing the longest carbon chain (parent chain)

If there are two chains of equal lengths. Choose the chain with maximum number of
substituents,

BASICS OF ORGANIC CHEMISTRY-PART-I THE TURNING POINT 3

 Compound contains functional group or multiple bond or both
 If a Compound contains functional group, choose the longest carbon chain in
such a way that it contains functional groups.

 If more than one functional group is present, the one with highest precedence
should be part of the parent chain. Order of precedence of functional group is
-COOH > CN > -CHO > -CO- > -OH >NH2 > -C=C- > -C≡C-> C-C > -O- > -X > -
NO2

 If the same functional group is present more than once, choose the very longest
carbon chain in such a way that it contains maximum number of that functional
group

 Numbering the parent chain from one end to another substituents.

' Numbering should be done in such a way that it gives the lowest possible number
to the carbon atom carrying the substituent

BASICS OF ORGANIC CHEMISTRY-PART-I THE TURNING POINT 4

 ' Numbering should start from terminal functional groups such as -CHO, -COOH, -
COOR, -CN etc.. (if present)

' More number of substituents / functional group present, Numbering should be

done in such a way that the sum of the number which indicates the position of
the substituents /functional group (Locant) gives the lowest number.

' When more than one functional group have same locant the following order of
priority should be followed.
-COOH > -SO3H > -COOR, -COX > CONH2 > -CN > -CHO > -CO- > -OH
> -SH -NH2 > -C=C- > -C=C-> C-C > -O- > -X > -NO2.

' Two substituents are present on identical position with respect to the parent
chain end. Assign the lowest number according to the alphabetical order of the
name of the substituent.

BASICS OF ORGANIC CHEMISTRY-PART-I THE TURNING POINT 5

 NOMENCLATURE OF AROMATIC COMPOUNDS

 Nucleus: The benzene ring present in aromatic compound is called nucleus.

H

H C H
C C
(or) (or) (or)
C C
H C H

 Side chain:
' Alkyl or any other aliphatic group attached to the benzene nucleus by replacing
one or more hydrogen atom is called the side chain
' If one hydrogen atom, (or) two hydrogen atoms or three hydrogen atoms are
replaced in the benzene ring by some other groups, they are termed as mono
substituted, di substituted or tri substituted derivative respectively.

Cl Cl
Cl

Cl

Cl Cl

(mono substituted) (di substituted) (tri substituted)

Cl Cl Cl

1 Cl 1 1
2

3 Cl
4
Cl
(Ortho substituted) (meta substituted) (Para substituted)
(1,2 substituted) (1,3 substituted) (1,4 substituted)

Nuclear substituted aromatic compounds:

Mono substituted benzene:

CH3

CH2CH3

Benzene Methyl bencene Eethyl bencene

(toluene)

BASICS OF ORGANIC CHEMISTRY-PART-I THE TURNING POINT 6

Di substituted benzene:
CH3
CH3
CH3
CH3

CH3 CH3
1,2 dimethyl benzene 1,3 dimethyl benzene 1,4 dimethyl benzene
(O-xylene) (m-xylene) (p-xylene)
Tri substituted benzene:
CH3 CH3 CH3

CH3 CH3

CH3 H3C CH3

CH3
1,2,3 trimethyl benzene 1,2,4 trimethyl benzene 1,3,5 trimethyl benzene
Side chain substituted aromatic compounds:
Cl
Cl Cl Cl Cl Cl
H2C CH C

Phenylchloromethane Phenyldichloromethane Phenylchloromethane

(Benzylchloride) (Benzaldichloride) (Benzotrichloride)

ARYL GROUPS

H2C CH C CH3 CH3 CH3

Phenyl Benzyl Benzal Benzo o- tolyl m- tolyl p- tolyl

2-tolyl 3-tolyl 4-tolyl

Rules for naming of alicyclic compounds:

 In the naming of such compounds a prefix cyclo is added to the word root.

Cyclopropane Cyclobutene Cyclopentene Cyclohexane Cycloheptene Cyclooctane

BASICS OF ORGANIC CHEMISTRY-PART-I THE TURNING POINT 7

 If only one substituent is present on the ring, then it is not required to give its
position
CH3
OH

C2H5

methylcyclobutene ethylcyclopentane Cyclohexanol

 If two or more substituents are present on the ring, the numbering of ring is
done according to lowest set of locant rule.
CH3
CH3 CH3
3 CH3
2 2 1 CH3
3 4 5
CH2CH3 CH2CH3
1 5 2
4 4
1 CH2CH3
5 6 3
1-ethyl-2-methylcyclopentane 1-ethyl-2,3-dimethylcyclohexane 2-ethyl-1,1-dimethylcyclopentane If
the ring contains lesser number of carbon atoms than that of alkyl group
attached to it, the compound is named as derivative of alkane and the ring
is considered as a substituent group to the alkane, otherwise it is named as
derivative of cycloalkane.
H3C CH3 H2
C CH3
CH H3C CH Cl

2-propylcyclobutane 2-cyclopropylbutane 3-chlorocyclobut-1-ene

(derivative of cycloalkane) (derivative of alkane) (double bond is more prefered)
 If the side chain contains a multiple bond or a functional group, then the
alicyclic ring is treated as the substituent irrespective of the size of the ring.
O
H2
C C
H3C CHO H3C CH CH3
CH

2-cyclobutylpropanal 3-cyclohexylpent-2-one
 If the alicyclic ring contains a multiple bond and the side chain contains a
functional group the compound is named as derivative of the side chain.
H3C CHO
CH
CH3
H2 H2
C C C COOH
H

2-(cyclobut-2-en-1yl)propanal 4-(cyclopent-3-en-1yl)-3-methylbutanoicacid

BASICS OF ORGANIC CHEMISTRY-PART-I THE TURNING POINT 8

 ISOMERISM
 What is isomerism? (or) what are isomers?
Existence of two or more compounds with the same molecular formula but different
structure and properties is called isomerism. Compounds exhibiting this isomerism
are called isomers.
 Explain various types of constitutional isomerism (structural isomerism) in
organic compounds
Chain or nuclear or skeletal isomerism:
compounds with the same molecular formula but differ in the nature of the
carbon skeleton are called chain or nuclear isomers.
CH3
H2 H2
C C H3C CH
H3C C CH3 C CH3
H2 H2

PENTANE ISOPENTANE
Position Isomerism:
Compounds with the same molecular formula and carbon skeleton, but differ in
the position of substituent or functional group or an unsaturated linkage are
called position isomers.
O

Cl
Pent-1-ene 2-pentanone 1-chlorobutane
Cl
O

Pent-2-ene 3-pentanone 2-chlorobutane

Functional isomerism:
Compounds with same molecular formula but different functional groups are said
to exhibit functional isomerism.
O
H2
C O
H3C C
H3C C
H C OH
H2
Propanal Propanoic acid

O
O

C CH3
C
H3C O
H3C CH3

Propanone methyl acetate

BASICS OF ORGANIC CHEMISTRY-PART-I THE TURNING POINT 9

 Metamerism:
Compounds with same molecular formula but unequal distribution of carbon atoms
(or) alkyl groups on either side of the functional group are called metamers. Ethers,
ketones, esters and secondary amines show Metamerism.
O O
O

diethylether methylpropylether methylisopropylether

O O O

Methyl propyl ketone diethyl ketone methyl isopropyl ketone

Tautomerism:
It is a special type of functional isomerism in which a single compound exists in two
readily inter convertible structures that differ markedly in the relative position of at
least one atomic nucleus. The two different structures are known as tautomer.
(i) Dyad system:
In this system hydrogen atom oscillates between two directly linked polyvalent
atoms. Eg:
H C N H N C

Hydrogen Cyanide Hydrogen isoCyanide

(ii) Triad system: (Write a note on keto-enol tautomerism)
In this system hydrogen atom oscillates between three polyvalent atoms. It involves
1,3 migration of hydrogen atom from one polyvalent atom to other within the
molecule. The most important example system is keto–enol tautomerism.
The polyvalent atoms involved are one oxygen and two carbon atoms. Enolisation is
a process in which keto-form is converted to enol form. Both tautomeric forms are
not equally stable. The less stable form is known as labile form.
H

H2C H H2C H
C C

O OH

Keto form Enol form

(100%) (Trace)
(f) Ring chain isomerism:
In this type of isomerism, compounds having same molecular formula but differ in terms of
bonding of carbon atom to form open chain and cyclic structures for eg:
H2
H2 H2C CH2
H C
C C
H3C CH2 H2C CH2 H2C CH
H2C CH2
CH3
Propene Cyclopropane cyclobutane Methyl cyclopropane

BASICS OF ORGANIC CHEMISTRY-PART-I THE TURNING POINT 10

 STEREOISOMERISM:
The isomers which have same bond connectivity but different arrangement
of groups or atoms in space are known as stereoisomers.

GEOMETRICAL ISOMERISM:

 Briefly explain geometrical isomerism in alkene by considering 2- butene as an

example.
 Geometrical isomers are the stereoisomers which have different arrangement of
groups or atoms around a double bonds.
 Geometrical isomerism occurs due to restricted rotation of double bonds.
 The isomer in which two similar groups are on the same side of the double bond
is called cis isomer.
 The isomer in which two similar groups are on the opposite sides of the double
bond is called Trans isomer.
H3C H H3C H

H3C H H CH3

Cis-2-butene Trans-2-butene

 These cis and Trans isomers have different chemical properties.

 These isomers are interconvertible at high temperatures or when absorbs light.
The heat supplies the energy (about 62kcal/mole) to break the π bond so that
rotation about σ bond becomes possible.
 Upon cooling, the reformation of the π bond can take place in two ways giving a
mixture both cis and Trans forms of trans-2-butene and cis-2-butane.
 Generally the Trans isomer is more stable than the cis isomers. The steric
repulsion of the groups makes the cis isomers less stable.

BASICS OF ORGANIC CHEMISTRY-PART-I THE TURNING POINT 11

 OPTICAL ISOMERISM
 What is chiral carbon?
A carbon atom which is connected to four different substituents is called
asymmetric carbon or chiral carbon.
COOH

Chiral Carbon
C
CH3
H
OH
 What is chirality or dissymmetry?
A molecule possessing chiral carbon and non-super impossible to its own mirror
image is said to be a chiral molecule or asymmetric, and this property
is called chirality or dissymmetry.
 Describe optical isomerism with suitable example.
 The ability of some organic compounds to rotate the plane of the plane polarized
light is called optical activity. Compounds having same physical and chemical
property but differ only in the rotation of plane of the polarized light are known
as optical isomers and the phenomenon is known as optical isomerism.
 The optical isomer, which rotates the plane of the plane polarised light to the
right or in clockwise direction is said to be dextrorotary (d) (+),
 The optical isomer which rotates the plane of the plane polarised light to the left
or anticlockwise is said to be leavo rotatory (l) (-).
 What are enantiomers? (What is Enantiomerism?)
 Optical isomers which rotate the plane of polarized light with equal angle but in
opposite direction are known as enantiomers and the phenomenon is known as
Enantiomerism.
 Enantiomers are non-super impossible mirror images of each other.
 They have same physical and chemical properties.
M
COOH COOH

H C OH HO C H

CH3 CH3

d- Lactic acid l- Lactic acid

BASICS OF ORGANIC CHEMISTRY-PART-I THE TURNING POINT 12