Class XI Chemistry

UNIT 12
ORGANIC CHEMISTRY – SOME BASIC
PRINCIPLES AND TECHNIQUES
Topics:-
• The Shapes of Carbon Compounds
• Hybridization in C
 Organic compounds

• Compounds of carbon were initially extracted from natural substances(living organism)

and it was thought that these carbon compounds could only be formed within living
organism .
• In 1815 Berzelius, a Swedish chemist suggested a theory which is known as the vital force
theory. According to this theory "organic compounds are produced only under the
influence of some mysterious force existing in the living organisms”.
• But in 1828 Friedrich Wohler, a German chemist rejected the vital force theory by
preparing urea from ammonium cyanate.
 Continue…
Organic compounds
• Acetic acid was synthesised by Kolbe (1845) and that of Methane by Berthelot (1856)
• Class of chemical compounds in which one or more atoms of carbon are covalently
linked to atoms of other elements, most commonly hydrogen, oxygen, or nitrogen are
known as organic compounds except carbides, oxides of carbon , carbonate ,
hydrogencarbonate and cyanides.
• Modern Definition of Organic Chemistry:- Branch of chemistry that deals with the study
of hydrocarbons and their derivatives
• Existence of large number of organic compounds is due to the self linking property
known as Catenation and due to tetravalency of carbon
 The Shapes of Carbon Compounds
1) Formation and the shapes of molecules like methane (), ethene (), ethyne () are explained in
terms of the use of hybrid orbitals by carbon atoms in the respective molecules
2) Hybridisation influences the bond length and bond enthalpy (strength) in organic compounds.
3) The sp hybrid orbital contains more s character and hence it is closer to its nucleus and forms
shorter and stronger bonds than the and hybrid orbital.
4) The change in hybridisation affects the electronegativity of carbon. The greater the s character
of the hybrid orbitals, the greater is the electronegativity. Thus, a carbon atom having an sp
hybrid orbital with 50% s character is more electronegative than that possessing (33 %) or
(25%) hybridised orbitals.
Problem 12.1
How many σ and π bonds are present in each of the following molecules?
(a) (b)
Solution
(a)
(b)
Problem 12.2
What is the type of hybridisation of each carbon in the following compounds?
(a) , (b) (c) , (d) , (e)
Solution
(a) , (b) (c) (d) , (e)
Problem 12.3
Write the state of hybridisation of carbon in the following compounds and shapes of
each of the molecules.
(a) , (b) , (c) .
Solution
(a) hybridised carbon, trigonal planar;
(b) hybridised carbon, tetrahedral;
(c) sp hybridised carbon, linear.
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC
PRINCIPLES AND TECHNIQUES
Topics:-
• Structural Representations Of Organic
Compound
• Structures of organic compounds are represented in several ways.
• The Lewis structure or dot structure, dash structure (complete structure ), condensed
structure and bond line structural formulas
Complete structural formulas

condensed structural formula

 bond-line structural representation
• In it carbon and hydrogen atoms are not shown and the lines representing carbon-carbon
bonds are drawn in a zig-zag fashion.
• The only atoms specifically written are oxygen, chlorine, nitrogen etc.
• The terminals denote methyl (–CH3) groups (unless indicated otherwise by a functional
group), while the line junctions denote carbon atoms bonded to appropriate number of
hydrogens required to satisfy the valency of the carbon atoms.
 bond-line structural representation

In cyclic compounds, the bond-line formulas may be given as follows:

Problem 12.4
Expand each of the following condensed formulas into their complete structural formulas.
(a) (b)
Problem 12.5
For each of the following compounds, write a condensed formula and also their bond-line
formula.
 Three-Dimensional Representation of Organic Molecules
1) by using solid and dashed wedge formula, the 3-D image of a
molecule from a two-dimensional picture can be understood.
2) In these formulas the solid-wedge is used to indicate a bond
projecting out of the plane of paper, towards the observer.
3) The dashed-wedge is used to depict the bond projecting out of
the plane of the paper and away from the observer
4) Wedges are shown in such a way that the broad end of the
wedge is towards the observer.
5) The bonds lying in plane of the paper are depicted by using a
normal line (—)
 Molecular Models
• Molecular models are physical devices that are used for a better visualisation and
perception of three-dimensional shapes of organic molecules.
• These are made of wood, plastic or metal and are commercially available.
• Commonly three types of molecular models are used:
• (1) Framework model, (2) Ball-and-stick model, and (3) Space filling model.
• In the framework model only the bonds connecting the atoms of a molecule and not the
atoms themselves are shown
 Continue…
Molecular Models

• In the ball-and-stick model, both the atoms and the bonds are shown.
• Balls represent atoms and the stick denotes a bond.
• Compounds containing C=C (e.g., ethene) can best be represented by using
springs in place of sticks. These models are referred to as Ball and-spring
model.
 Continue…
Molecular Models

• The space-filling model emphasizes the relative size

of each atom based on its van der Waals radius.
• Bonds are not shown in this model.
• It conveys the volume occupied by each atom in the
molecule.
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC
PRINCIPLES AND TECHNIQUES
Topics:-
• Classification of Organic Compounds
 Classification of Organic Compounds
On the basis of their structures, organic compounds are broadly classified as follows
 Acyclic or open chain compounds
• These compounds are also called as aliphatic compounds and consist of straight or
branched chain compounds
 Alicyclic compounds
Two types -Homocyclic and Heterocyclic

Homocyclic or carbocyclic:- Heterocylic

These compounds contain ring of three or more Atoms other than carbon are also
carbon atoms present in the ring .

• These exhibit some of the properties similar to those of aliphatic compounds

 Aromatic compounds
Aromatic compounds are special types of compounds. 3 types
 Functional Group
• The functional group is an atom or a group of atoms joined to the carbon chain
which is responsible for the characteristic chemical properties of the organic
compounds.
• The examples are hydroxyl group (–OH), aldehyde group (–CHO) and carboxylic
acid group (–COOH) etc.
 Homologous Series

• A series of similarly constituted compounds in which the members present have the same
functional group, same chemical properties and any two successive members in a particular
series differ in their molecular formula by –CH2 group.
• Some of these are alkanes, alkenes, alkynes, haloalkanes, alkanols, alkanals, alkanones,
alkanoic acids, amines etc.
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topics:-
• IUPAC Nomenclature of Straight
Chain Hydrocarbons
 Nomenclature Of Organic Compounds

• Common or trivial names of organic

compounds are based on their origin or
certain properties.
• For instance, citric acid - found in citrus fruits
• Formic acid - found in red ant (Latin word for
ant is formica.)
 The IUPAC System of Nomenclature
• IUPAC -International Union of Pure and Applied Chemistry.
• A systematic name of an organic compound is generally derived by identifying the
parent hydrocarbon and the functional group(s) attached to it

• Compounds containing carbon and

hydrogen only are called hydrocarbons.
• Saturated Hydrocarbons- C-C single
bond, Alkanes
• Unsaturated Hydrocarbons:- Two types
• Alkenes C=C
• Alkynes
 IUPAC Nomenclature of Alkanes
Straight chain Alkanes
General formula: Root word + Primary suffix (ane)
Root word:- indicates the number of carbon atoms in the straight chain.

From to ,the root words are derived from trivial

names
Alkenes:-
• Unsaturated hydrocarbons
• contain one or more Carbon-Carbon double bonds (C=C)
• General formula: IUPAC name :-Root word + Primary suffix (ene)
• n=2 C2H4 Ethene or Ethylene is the first member of alkene

• n=3 C3 H 6 OR Propene

• But-1-ene But-2-ene
Alkynes:-
• Unsaturated hydrocarbons
• contain one or more Carbon-Carbon triple bonds
• General formula:
• IUPAC name :-Root word + Primary suffix (yne)
• n=2 C2H2 Ethyne or Acetylene is the first member of alkyne

• n=3 C 3H4 Propyne

• But-2-yne But-1-yne
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topics:-
• Different Types of Alkyl Groups
 Alkyl Group
• An alkyl group is derived from a saturated hydrocarbon by removing a hydrogen
atom from carbon.
• An alkyl group is named by substituting ‘yl’ for ‘ane’ in the corresponding alkane.
 Types of Carbon Atoms

Primary C (1o):- attached to only 1 C atom (terminal)

Secondary C (2o):- attached to 2 C atoms
Tertiary C (3o):- attached to 3 C atoms
Quaternary C (4o):- attached to 4 C atoms
Branched Alkyl Group
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topics:-
• IUPAC Nomenclature of Branched Chain
Alkanes
 Nomenclature of branched chain alkanes

1) First of all, the longest carbon chain in the molecule is identified. it is considered as
the parent or root chain.
2) The carbon atoms of the parent chain are numbered in such a way that the branched
carbon atoms get the lowest possible numbers.
3) The names of alkyl groups attached as a branch are then prefixed to the name of the
parent alkane and position of the substituents is indicated by the appropriate numbers. If
different alkyl groups are present, they are listed in alphabetical order.
Locants-prefixes-root word-primary suffix(ane)

• The numbers are separated from the groups by hyphens and there is no break between
methyl and nonane (one word)
4) If two or more identical substituent groups are present then the numbers are separated by
commas. The names of identical substituents are not repeated, instead prefixes such as di
(for 2), tri (for 3), tetra (for 4), penta (for 5), hexa (for 6) etc. are used.
5. If the two substituents are found in equivalent positions, the lower number is given to
the one coming first in the alphabetical listing.
6) The branched alkyl groups can be named as their trivial names like Isopropyl- , sec-Butyl- ,
Isobutyl- , tert-Butyl- , Neopentyl- , or as substituted substituents in that case the carbon
atom of the branch that attaches to the root alkane is numbered 1

• The name of such branched chain alkyl group is placed in parenthesis while naming the
compound. While writing the trivial names of substituents’ in alphabetical order, the prefixes
iso- and neo- are considered to be the part of the fundamental name of alkyl group.
• The prefixes sec- and tert- are not considered to be the part of the fundamental name.
• If there is more then one chain of equal size, then that chain is to be selected which contains
more number of side chains.
• After selection of the chain, numbering is to be done from the end closer to the substituent.

5-(2-Ethylbutyl)-3,3-dimethyldecane
[and not 5-(2,2-Dimethylbutyl)-3-ethyldecane]
Some Examples
 Nomenclature of Cyclic Compounds:
• A saturated monocyclic compound is named by prefixing ‘cyclo’ to the corresponding
straight chain alkane.
• If side chains are present, then the rules discussed are applied.
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topic:-
IUPAC Nomenclature of Organic Compounds
having One Functional Group
 Nomenclature of Organic Compounds having One Functional Group
Root word-primary suffix-secondary suffix
Alcohol
• Functional group - –OH
• Secondary suffix - -ol
• IUPAC Name- ‘e’ of the parent alkane is replaced by ‘ol’, i.e. Alkanol.
• CH3OH Methanol (Methyl alcohol)

• C2H5OH (CH3CH2OH) Ethanol (Ethyl alcohol)

Aldehyde
• Functional group - –CHO
• Secondary suffix - -al
• IUPAC Name- ‘e’ of the parent alkane is replaced by ‘al’, i.e. Alkanal.
• HCHO Methanal (Formaldehyde)
• CH3CHO Ethanal (Acetaldehyde)

• CH3 (CH2)2CHO Butanal

Ketone
• Functional group -
• Both Free valence of C are satisfied by Alkyl group
• R and R’ may be same or different.
• Secondary suffix - -one
• IUPAC Name- ‘e’ of the parent alkane is replaced by ‘one’, i.e. Alkanone
• First member contains 3 carbon atoms CH3COCH3 Propanone (Acetone)

• Second member CH3CH2COCH3 or CH3COCH2CH3 Butanone

• CH3CH2CH2COCH3 Pentan-2-one

• CH3CH2COCH2CH3 Pentan-3-one
Carboxylic acid
• Functional group :- –COOH
• Free valence of –COOH group is satisfied by H atom or R (Alkyl group)
• Secondary suffix - -oic acid
• IUPAC Name- ‘e’ of the parent alkane is replaced by ‘oic acid’, i.e. Alakanoic
acid
• First member:- HCOOH Methanoic acid (Formic acid)

Second member CH3COOH Ethanoic acid (Acetic acid)

CH3CH2COOH or CH3CH2CO2H Propanoic acid

CH3CH2CH2COOH Butanoic acid CH3(CH2)2COOH

Nitriles
• Functional group :-
• Free valence is satisfied by R (Alkyl group)
• Secondary suffix - -nitrile
• IUPAC Name- ‘e’ of the parent alkane is not dropped i.e. Alakanenitrile
• Ethanenitrile
• Propanenitrile
• Butanenitrile
• Pentanenitrile
Esters
• Functional group :-
• Free valence is satisfied by H or Alkyl groups
• Secondary suffix:- -oate
• IUPAC Name- Alkyl alkanoate
• R directly attached to ‘O’ is written as ‘alkyl’.
• Methyl methanoate
• Methyl ethanoate
• Ethyl ethanoate
• Methyl propanoate
Acyl halides
• Functional group :-
• -OH of carboxy group (-COOH) is replaced by halogen
• Free valence is satisfied by H or Alkyl groups
• Secondary suffix:- -oyl halide
• IUPAC Name- Alkanoyl halide (‘e’ of parent alkane is replaced by –oyl
halide)
• Methanoyl chloride
• Ethanoyl bromide
• Propanoyl chloride
• Butanoyl chloride
Acid anhydride
• Functional group:-
• Free valence is satisfied by H or Alkyl groups
• It is formed by removal of water molecule from two molecules of carboxylic acid.
• Secondary suffix:- -oic anhydride
• IUPAC name:- alkanoic anhydride
Amides
• Functional group :-
• -OH of carboxy group (-COOH) is replaced by
• Free valence is satisfied by H or Alkyl groups
• Secondary suffix:- -amide
• IUPAC Name- Alkanamide (‘e’ of parent alkane is replaced by –amide)
• Methanamide
• Ethanamide
• Propanamide
• Butanamide
Amines
• Functional group :-
• Free valence is satisfied by Alkyl group
• Secondary suffix:- -amine
• IUPAC Name- Alkanamine (‘e’ of parent alkane is replaced by –amine)
• Methanamine
• Ethanamine
• Propan-1-amine

• Butan-1-amine
• Butan-2-amine
Sulphonic acids
• Functional group :-
• Free valence is satisfied by Alkyl group
• IUPAC Name- Alkylsulphonic acid
• Methylsulphonic acid
• Ethylsulphonic acid

Some groups are written as prefixes

Prefix-Root word-primary suffix

Ethers
• Functional group :-
• Free valence is satisfied by Alkyl groups
• may be same or different
• IUPAC Name- Alkoxyalkane
• If both alky groups are different, smaller group is written as alkoxy
• Methoxymethane
• Methoxyethane
• 1-Methoxypropane
Nitro compounds
• Functional group :-
• Free valence is satisfied by Alkyl group
• It is named as prefix- nitro
• IUPAC Name- Nitroalkane
• Nitromethane
• Nitroethane
• 1-Nitropropane
Halides
• Functional group :-
• Free valence is satisfied by Alkyl group
• It is named as prefix-Halo
• IUPAC Name- Haloalkane
• Chloromethane
• 1-Bromopropane
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topic:-
IUPAC Nomenclature of Organic Compounds
having Poly Functional Group
• In the case of polyfunctional compounds, one of the functional groups is chosen as the principal
functional group and the compound is then named on that basis.
• The remaining functional groups, which are subordinate functional groups, are named as
substituents using the appropriate prefixes.
• The choice of principal functional group is made on the basis of order of preference. The order of
decreasing priority for some functional groups is:

• The etc. are always prefix substituents.

 Decreasing Priority order
Class of Functional group Suffix name Prefix name
Compound
Carboxylic acid -oic acid carboxy
Sulphonic acid sulphonic acid sulpho
ester -oate alkoxycarbonyl
Acyl halide -oyl halide halocarbonyl
amide -amide Carbamoyl
nitrile nitrile Cyano
aldehyde -al Formyl
ketone -one Oxo
Alcohol -ol Hydroxy
Amine -amine Amino
• Thus, a compound containing both an alcohol and a keto group is named as hydroxyalkanone since
the keto group is preferred to the hydroxyl group.
For example,

7-hydroxyheptan-2-one
not 2-oxoheptan -7-ol.
Similarly,
3-bromoprop-1-ene
not 1-bromoprop-2-ene.
• If more than one functional group of the same type are present, their number is
indicated by adding di, tri, etc. before the class suffix. ‘e’ is not dropped
• For example ethane–1,2–diol
• compounds having more than one double or triple bond; the ending – ne of the parent
alkane is dropped
buta–1,3–diene
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topic:-
Nomenclature of Substituted
Benzene Compounds
 Nomenclature of Substituted Benzene Compounds
• For IUPAC nomenclature of substituted benzene compounds, the substituent is placed as
prefix to the word benzene
• The common names (written in bracket below) of many substituted benzene compounds
are also universally used.
• In disubstituted benzene, the position of substituents is defined by numbering the carbon
atoms of the ring such that the substituents are located at the lowest numbers possible.
• For tri - or higher substituted benzene, the compounds are named by identifying substituent
positions on the ring by following the lowest locant rule.
• In some cases, common name of benzene derivatives is taken as the base compound.
• Substituent of the base compound is assigned number1 and then the direction of numbering is
chosen such that the next substituent gets the lowest number.
• The substituents appear in the name in alphabetical order.
• When a benzene ring is attached to an alkane
with a functional group, it is considered as
substituent, instead of a parent.
• The name for benzene as substituent is phenyl
, also abbreviated as Ph).
Problem 12.10
Write the structural formula of:
(a) o-Ethylanisole, (b) p-Nitroaniline, (c) 2,3 - Dibromo -1 -
phenylpentane,

(d) 4-Ethyl-1-fluoro-2-nitrobenzene.
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC
PRINCIPLES AND TECHNIQUES
Topic:-
ISOMERISM
 ISOMERISM
• The phenomenon of existence of two or more compounds possessing the same
molecular formula but different properties is known as isomerism. Such compounds are
called as isomers.
Structural Isomerism
• Compounds having the same molecular formula but different structures (manners in
which atoms are linked) are classified as structural isomers.
(i) Chain isomerism:
• When two or more compounds have similar molecular formula but different carbon
skeletons, these are referred to as chain isomers and the phenomenon is termed as
chain isomerism. For example, represents three compounds:
(ii) Position isomerism:
• When two or more compounds differ in the position of substituent atom or functional
group on the carbon skeleton, they are called position isomers and this phenomenon is
termed as position isomerism.
• For example, the molecular formula represents two alcohols:
(iii) Functional group isomerism:
• Two or more compounds having the same molecular formula but different functional
groups are called functional isomers and this phenomenon is termed as functional group
isomerism.
• For example, the molecular formula represents an aldehyde and a ketone:

• Alcohols and ethers are functional group isomers of each other. For example represents
(iv) Metamerism:
• It arises due to different alkyl chains on either side of the functional group in the molecule.
• For example, represents

• represents
 Stereoisomerism
• The compounds that have the same constitution and sequence of covalent bonds but
differ in relative positions of their atoms or groups in space are called stereoisomers.
This special type of isomerism is called as stereoisomerism
• It can be classified as geometrical and optical isomerism.
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topic:-
• Fission or Cleavage of a Covalent
Bond
 Fundamental Concepts In Organic Reaction
Mechanism
• In an organic reaction, the organic molecule (also referred as a substrate) reacts with an
appropriate attacking reagent and leads to the formation of one or more intermediate(s)
and finally product(s)

• In general, a molecule whose carbon is involved in new bond formation is called substrate
and the other one is called reagent.
• If both the reactants supply carbon to the new bond then choice is arbitrary and in that
case the molecule on which attention is focused is called substrate.
• In such a reaction a covalent bond between two carbon atoms or a carbon and some other
atom is broken and a new bond is formed.
• Reaction Mechanism:- A sequential account of each step, describing details of electron
movement, energetics during bond cleavage and bond formation, and the rates of
transformation of reactants into products (kinetics) is referred to as reaction mechanism.
• The knowledge of reaction mechanism helps in understanding the reactivity of organic
compounds and in planning strategy for their synthesis.
 Fission or Cleavage of a Covalent Bond
Two types:- (i) heterolytic cleavage (ii) homolytic cleavage.

• In heterolytic cleavage, the bond breaks in such a fashion that the shared pair of electrons
remains with one of the fragments.
• After heterolysis, one atom has a sextet electronic structure and a positive charge and the other,
a valence octet with at least one lone pair and a negative charge.
• For example, heterolytic cleavage of bromomethane

• The organic reactions which proceed through heterolytic bond cleavage are called ionic or
heteropolar or just polar reactions.
• In homolytic cleavage, one of the electrons of the shared pair in a covalent bond goes with
each of the bonded atoms.
• Thus, in homolytic cleavage, the movement of a single electron takes place instead of an
electron pair.
• The single electron movement is shown by ‘half headed (fish hook: ) curved arrow.
• Such cleavage results in the formation of neutral species (atom or group) which contains an
unpaired electron. These species are called free radicals.

• Organic reactions, which proceed by homolytic fission are called free radical or homopolar
or nonpolar reactions.
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topic:-
• Reactive Intermediates
 Reactive Intermediates
• In chemistry, a reactive intermediate or an intermediate is a short-lived, high-energy, highly
reactive species which is formed during the reaction and is consumed to form product.
• For examples, carbocations, free radicals, carbanions and carbenes.
Carbocations:-
• A species having a carbon atom possessing sextext of electrons and a positive charge is
called a carbocation (earlier called carbonium ion).
• It is formed by heterolytic bond cleavage.

• The ion is known as a methyl cation or methyl carbonium ion.

 Continue… Carbocations

• Carbocations are classified as primary, secondary and tertiary depending on whether one,
two or three carbons are directly attached to the positively charged carbon.
 Continue… Carbocations

• Carbocations are highly unstable and reactive species.

• Order of stability

• Alkyl groups directly attached to the positively charged carbon stabilise the carbocations
due to inductive and hyperconjugation effects
• Carbocations have trigonal planar shape.
• Positively charged carbon of carbocation is hybridized.
• There is one empty un-hybrid p-orbital perpendicular to the plane.
 Carbanions
• Carbon species carrying a negative charge on carbon atom is called carbanion.
• It is formed by heterolytic bond cleavage in which carbon gets the shared pair of electrons.

• The ion is known as a methyl anion.

• Carbanions are also

classified as primary,
secondary and tertiary
 Continue… Carbanions

• Carbanions are also unstable and reactive species.

• Carbon in carbanion is generally hybridised and its
structure is distorted tetrahedron
 Alkyl free radical
• Neutral species (atom or group) formed by homolytic cleavage of a covalent bond
and which contains an unpaired electron are called free radicals.
• If the unpaired electron is with carbon of hydrocarbon part , it is called alkyl free
radical

• Free radicals are also very reactive.

• Alkyl radicals are classified as primary, secondary, or tertiary.
Continue… Alkyl free radical
 Continue… Alkyl free radical

Structure:-
• Carbon is hybridized
• Structure is planar
• Un-hybrid p-orbital contains one electron
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topic:-
• Attacking Reagents
• Reagents attack the reactive site of the substrate.
• The reactive site may be electron deficient portion of the molecule (a positive reactive site)
e.g., an atom with incomplete electron shell or the positive end of the dipole in the
molecule. If the attacking species is electron rich, it attacks these sites.
• If attacking species is electron deficient, the reactive site for it is that part of the substrate
molecule which can supply electrons, e.g., electrons in a double bond.
• The species that attacks a substrate molecule or intermediate and forms a product is
called attacking reagent.
• It is of two types:
• Electrophilic reagent or electrophiles.
• Nucleophilic reagent or nucleophiles.
 Electrophiles
• A reagent that takes away an electron pair from reactive site is called electrophile i.e.,
electron seeking and the reaction is called electrophilic.
• Electrophile=“electron-loving”, or “negative-charge loving”.
• An electrophile is a species that accepts a pair of electrons to form a new covalent bond. It is
a Lewis acid
• Examples:- carbocations, electron deficient species like and neutral molecules having
functional groups like carbonyl group (>C=O) or alkyl halides .
 Nucleophiles
• A reagent that brings an electron pair to the reactive site is called a nucleophile (Nu:) i.e.,
nucleus seeking and the reaction is then called nucleophilic.
• Nucleophile = “nucleus loving”, or “positive-charge loving”.
• A nucleophile is a reactant that provides a pair of electrons to form a new covalent
bond. It is a Lewis base
• Examples:-negatively charged ions with lone pair of electrons such as hydroxide, cyanide
ions and carbanions . Neutral molecules such as etc., can also act as
nucleophiles due to the presence of lone pair of electrons.
• During a polar organic reaction, a nucleophile attacks an electrophilic centre of the
substrate which is that specific atom or part of the substrate which is electron deficient.
• Similarly, the electrophiles attack at nucleophilic centre, which is the electron rich centre
of the substrate.
• Thus, the electrophiles receive electron pair from the substrate when the two undergo
bonding interaction.
• A curved-arrow notation is used to show the movement of an electron pair from the
nucleophile to the electrophile.
 Electron Movement in Organic Reactions
• The movement of electrons in organic reactions can be shown by curved-arrow notation.
• To show the change in position of a pair of electrons, curved arrow starts from the point
from where an electron pair is shifted and it ends at a location to which the pair of electron
may move.
 Continue…Electron Movement in Organic Reactions

• Movement of single electron is indicated by a single barbed ‘fish hooks’ (i.e. half
headed curved arrow).
Problem 12.11
Using curved-arrow notation, show the formation of reactive intermediates when the
following covalent bonds undergo heterolytic cleavage.
(a) , (b) , (c)
Problem 12.12
• Giving justification, categorise the following molecules/ions as nucleophile or electrophile:

Solution
Nucleophiles:
These species have unshared pair of electrons, which can be donated and shared with an
electrophile.
Electrophiles:
Reactive sites have only six valence electrons; can accept electron pair from a nucleophile.
 Problem 12.13
Identify electrophilic centre in the following:

Solution
Among

the starred carbon atoms are electrophilic centers as they will have partial positive
charge due to polarity of the bond.
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topic:-
• Electron Displacement Effects in Covalent
Bonds
• Inductive Effect
 Electron Displacement Effects in Covalent Bonds

• Two types of electron displacement effects:

1. Permanent Electron Displacement Effects:-
• The electron displacements due to the influence of an atom or a substituent group
present in the molecule cause permanent polarisation of the bond.
• Examples :-Inductive effect resonance effects Hyperconjugation
2. Temporary electron displacement effects :-
• Electron displacement in the presence of an appropriate attacking reagent
• For example:-electromeric effect or polarizability effect.
 Inductive Effect
• When a covalent bond is formed between atoms of different electronegativity, the electron
density is more towards the more electronegative atom of the bond. Such a shift of electron
density results in a polar covalent bond.
• consider cholorethane in which the C–Cl bond is a polar covalent bond.
• The polar C – Cl bond induces polarity in the adjacent bonds.

• Polarisation of σ- bond caused by the polarisation of adjacent σ-bond is referred to as the

inductive effect.
 Continue… Inductive Effect

• The inductive effect is related to the ability of substituent(s) to either withdraw or

donate electron density to the attached carbon atom.
• Based on this ability, the substitutents can be classified as
• electron-withdrawing groups ( Have negative Inductive effect, – I effect)
• Examples:- Halogens, nitro , cyano, carboxy, ester, aryloxy
• electron donating groups (Have positive Inductive effect, +I effect)
• Examples:- alkyl groups like methyl and ethyl .
Problem 12.14
Which bond is more polar in the following pairs of molecules:
(a) (b) (c)
Solution
(a) C–Br (b) C–O (c) C–O
Problem 12.15
In which C–C bond of , the inductive effect is expected to be the least?
Solution
Magnitude of inductive effect diminishes as the number of intervening bonds increases.
Hence, the effect is least in the bond between carbon-2 and carbon-3.
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topic:-
Resonance Structure & Resonance Er
 Resonance Structure

• There are many organic molecules whose behaviour cannot be explained by a single
Lewis structure.
• An example is that of benzene.
• Benzene should exhibit two different bond lengths, due to C–C single and C=C double
bonds. However, as determined experimentally benzene has a uniform C–C bond
distances of 139 pm, a value intermediate between the C–C single(154 pm) and C=C
double (134 pm) bonds.
• Thus, the structure of benzene cannot be represented adequately by the above structure.
 Resonance Structure

• Further, benzene can be represented equally well by the energetically identical structures I
and II.

• According to the resonance theory the actual structure of benzene cannot be adequately
represented by any of these structures, rather it is a hybrid of the two structures (I and II)
called resonance structures.
• The resonance structures (canonical structures or contributing structures) are hypothetical and
individually do not represent any real molecule.
• They contribute to the actual structure in proportion to their stability.
 Resonance Structure

• Another example of resonance is provided by nitromethane which can be represented by

two Lewis structures, (I and II).

• There are two types of N-O bonds in these structures.

• However, it is known that the two N–O bonds of nitromethane are of the same length
(intermediate between a N–O single bond and a N=O double bond).
• The actual structure of nitromethane is therefore a resonance hybrid of the two canonical
forms I and II.
 Resonance Energy

• The energy of actual structure of the molecule (the resonance hybrid) is lower than that of
any of the canonical structures.
• The difference in energy between the actual structure and the lowest energy resonance
structure is called the resonance stabilisation energy or simply the resonance energy.
• The more the number of important contributing structures, the more is the resonance
energy.
• Resonance is particularly important when the contributing structures are equivalent in
energy.
 The following rules are applied while writing resonance structures:

• The resonance structures have (i) the same positions of nuclei and (ii) the same number of
unpaired electrons.
• Among the resonance structures, the one which has following characteristics is more stable
than others:-
• more number of covalent bonds,
• all the atoms with octet of electrons (except hydrogen which has a duplet),
• less separation of opposite charges, (a negative charge if any on more electronegative
atom, a positive charge if any on more electropositive atom) and
• more dispersal of charge,
Problem 12.16
Write resonance structures of and show the movement of electrons by curved arrows.
Solution
• First, write the structure and put unshared pairs of valence electrons on appropriate atoms.
• Then draw the arrows one at a time moving the electrons to get the other structures.
Problem 12.17
Write resonance structures of . Indicate relative stability of the contributing structures.
Solution

Order of stability: I > II > III

• I: Most stable, more number of covalent bonds, each carbon and oxygen atom has an octet and
no separation of opposite charge
• II: negative charge on more electronegative atom and positive charge on more electropositive
atom;
• III: does not contribute as oxygen has positive charge and carbon has negative charge, hence
least stable.
Problem 12.18
Explain why the following two structures, I and II cannot be the major contributors
to the real structure of .

Solution
The two structures are less important contributors as they involve charge separation.
Additionally, structure I contains a carbon atom with an incomplete octet.
 Resonance Effect (R effect)
• The resonance effect is defined as ‘the polarity produced in the molecule by the
interaction of two -bonds or between a -bond and lone pair of electrons present on an
adjacent atom’.
• The effect is transmitted through the chain.
• It is also known as mesomeric effect, designated as M effect.
• There are two types of resonance effect:-
(a) Positive Resonance effect
(b) Negative Resonance effect
(i) Positive Resonance Effect (+R effect)
• In this effect, the transfer of electrons is away from an atom or substituent group attached to
the conjugated system.
• This electron displacement makes certain positions in the molecule of high electron
densities. This effect in aniline is shown as :

• The presence of alternate single and double bonds in an open chain or cyclic system is
termed as a conjugated system.
(ii) Negative Resonance Effect (- R effect)
• This effect is observed when the transfer of electrons is towards the atom or
substituent group attached to the conjugated system.
• For example in nitrobenzene this electron displacement can be depicted as :
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topic:-
Electromeric Effect
 Electromeric Effect (E effect)
• It is a temporary effect.
• The organic compounds having a multiple bond (a double or triple bond) show this effect
in the presence of an attacking reagent only.
• It is defined as the complete transfer of a shared pair of π-electrons to one of the atoms
joined by a multiple bond on the demand of an attacking reagent.
• The effect is annulled (cancelled) as soon as the attacking reagent is removed from the
domain of the reaction.
• It is represented by E and the shifting of the electrons is shown by a curved arrow
• There are two distinct types of electromeric effect:-+ E and -E
(i) Positive Electromeric Effect (+E effect)
• In this effect the π-electrons of the multiple bond are transferred to that atom
to which the reagent gets attached. For example :
 (ii) Negative Electromeric Effect (–E effect)
• In this effect the π- electrons of the multiple bond are transferred to that
atom to which the attacking reagent does not get attached. For example

• When inductive and electromeric effects operate in opposite directions, the

electomeric effect predominates.
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topic:-

Hyperconjugation
 Hyperconjugation

• Hyperconjugation is a general stabilising interaction.

• It involves delocalisation of 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.
• The electrons of C—H bond of the alkyl group enter into partial conjugation with the
attached unsaturated system or with the unshared p orbital.
• Hyperconjugation is a permanent effect.
• The hyperconjugation may also be regarded as no bond resonance.
• For example (ethyl
cation) in which the positively charged
carbon atom has an empty p orbital.
• The electrons of one of the C-H bond of
an alkyl group can be delocalised into the
empty p orbital .

• This type of overlap stabilises the carbocation because electron density from the
adjacent bond helps in dispersing the positive charge.
• In general, greater the number of alkyl groups attached to a positively charged carbon
atom, the greater is the hyperconjugation interaction and stabilisation of the cation.
• Thus, we have the following relative stability of carbocations :
 • Hyperconjugation is also possible in alkenes and alkylarenes.
• Delocalisation of electrons by hyperconjugation in the case of alkene can be
depicted as

• hyperconjugative effect also explain

the partial ionic character in organic
molecule due to resonance.
 Class XI Chemistry
UNIT 12
ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES
AND TECHNIQUES
Topic:-

Types of Organic Reactions

 Types of Organic Reactions
Organic reactions can be classified into the following categories:
(i) Substitution reactions
(ii) Addition reactions
(iii) Elimination reactions
(iv) Rearrangement reactions
Depending upon the mechanism and attacking reagent substitution and addition
reactions are further classified as
• Nucleophilic reaction
• Electrophilic reaction
• Free radical reaction
 Types of Organic Reactions
(i) Substitution reactions
• Free radical substitution reactions:- Alkanes
• Nucleophilic substitution reactions:- Haloalkanes
• Electrophilic substitution reactions:- Arenes

(ii) Addition reactions

• Electrophilic addition reactions:- Alkenes and alkynes
• Free radical addition reactions:- Alkenes with HBr in presence of organic peroxide
• Nucleophilic addition reactions:- carbonyl compounds (aldehydes and Ketones)
 Types of Organic Reactions

(iii) Elimination reactions:-

• 1, 1-elimination or α-elimination
• 1, 2-elimination or β-elimination

(iv) Rearrangement reactions

• There are two types of rearrangements: hydride shift and alkyl shift.