Basic Principal of Organic Chemistry

DEPARTMENT OF CHEMISTRY
Technical Chemistry
Subject Code: CH32
Unit: III, IV, V
DR. S. B. PATIL
Syllabus:
Unit-III
Basic Principles of Organic Chemistry:
1) Introduction : Homolytic and Heterolytic Cleavages
2) Reactive Intermediates: Carbocations , Carbanions and Free radicals (Structure, Stability and their
Reactivity)
3) Types of Reactions: a) Addition reactions

b) Elimination reactions (E1 & E2)
c) Substitution reactions (SN1 & SN2) in alkyl halides
4) Inductive and Resonance effects
5) Basics of Stereochemistry:
a) Isomerism -Structural-(Chain, Positional, Functional, Metamerism, Tautomerism and Ring-chain

isomerism.
b) Stereoisomerism- (Cis-trans)
c) Optical isomerism : Optical activity of organic compounds,, Configuration(R,S and E, Z

conformation)
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Classification of Organic Reactions:
On the basis of bond cleavage: 1) Free radical reactions (homolytic clevage) and
2) Ionic reactions (heterolytic cleavage)
On the basis of the products of the reactions: 1) Addition reaction: a) Electrophilic
b) Nucleophilic
2) Substitution reaction: 1) Free radical
2) SN1 and SN2
3) Electrophilic
3) Elimination reaction: E1 and E2
4) Rearrangement

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Introduction to Homolytic and Hetrolytic cleavages
Bond cleavage, or bond fission, is the splitting of chemical bonds. This can be generally referred to as
dissociation when a molecule is cleaved into two or more fragments.
There are two types of bond cleavage:
1) Homolytic and
2) Heterolytic.
Homolytic Cleavage: In homolytic or homolysis cleavage, the two electrons in the bond are divided equally
between the products.
Same electro negativity of atoms
Free radicals
e electro negativity of atoms
Free radicals
Conditions for Homolytic Cleavage:

1) Sunlight or uv rays
2) Same electro negativity of atoms
3) Presence of Peroxide (Ex: H2O2)
4) High Temperature ( >5000c)

Heterolytic Cleavage: In heterolytic cleavage, one atom gets both of the shared electrons.
More electro negativity of atom
Less electro negativity of atom heterolytic cleavage Ions
heterolytic cleavage
More electro negativity of atom
Less electro negativity of atom Ions
H-Cl → H+ + Cl–

•Heterolytic fission, also known as heterolysis, is a type of bond fission in which a covalent
bond between two chemical species is broken in an unequal manner, resulting in the bond
pair of electrons being retained by one of the chemical species (while the other species does
not retain any of the electrons from the bond pair).
•When a neutrally charged molecule undergoes heterolytic fission, one of the products will
have a positive charge whereas the other product will have a negative charge.

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Reactive intermediates:
A reactive intermediate or an intermediate is a short-lived, high-energy, highly reactive
molecule.
1. Reaction------->Reactants ------>Products
2. Reactive intermediate decides the final product.
3. Very short life
When generated in a Chemical reaction, it will quickly convert into a more stable molecule.
Following are the Reactive intermediates:

1) Carbocation
2) Carbanion
3) Free radical
4) Carbenes, Nitrenes etc.
Carbocations Carbanions Free radical

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Carbocations
A carbocation is a molecule in which a carbon atom has a positive charge and three
bonds is called as Carbocation.
Classification of carbocations :
a) Primary carbocation: In a primary carbocation the carbon bearing the positive
charge is attached to one carbon of an alkyl or aryl group.
b) b) Secondary carbocation: Here carbon with positive charge is attached to two
other carbons.
c) c) Tertiary carbocation: As the name suggest, in this case the positively charged
carbon is attached to three carbon atoms.

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Formation of Carbocation: by heterolytic cleavage

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Characteristics of Carbocation:
1) 6-electrons in valence cell – Electron deficient species-Electrophile
2) Sp2 hybridization ( 3 sigma bond)-Trigonal planar
3) Carbocation formation in popular reaction: Elimination (E1), Addition electrophilic
reaction and SN1
Stability of Carbocation:
1) Resonance/Mesomeric effect (More resonating Structures-More Stable)
2) Hyperconjugation or NO bond Resonance
3) Inductive effect
• Resonance is a way of describing bonding in certain molecules or ions by the
combination of several contributing structures (also variously known
as resonance structures or canonical structures) into a resonance hybrid.
• The delocalization of σ-electrons or lone pair of electrons into adjacent π-

orbital or p-orbital is called hyperconjugation.
• Inductive Effect: Displacement of sigma electrons towards more electronegative

atom of sigma bond (partial shifting).
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0-alpha hydrogen 3-alpha hydrogen 6-alpha hydrogen 9-alpha hydrogen
+ I effect + I effect + I effect
The order of stability of carbocations is : 30 >2o >1o >methyl.

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Factors affect the Carbocation Stability:
Three main factors increase the stability of carbocations:
1) Increasing the number of adjacent carbon atoms:
methyl (least stable carbocation) < primary < secondary < tertiary (most stable
carbocation)
2) Adjacent pi bonds that allow the carbocation p-orbital to be part of a conjugated
pi-system system (“delocalization through resonance”)
3) Adjacent atoms with lone pairs
Summary :
• Carbocations are reactive intermediates.
• Carbocations are electron deficient species with six electron.
• The order of stability of carbocations is 30 >2o >1o >methyl.
• Factors such as inductive effect (+I), hyperconjugation and resonance which can
decrease the positive charge on carbon stabilize a carbocation.
• Carbocation can undergo various types of reactions such as nucleophilic, elimination,

rearrangement.
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Carbanion
A carbanion is a molecule in which a carbon atom has a negative charge and three bonds
is called as Carbanion.
Less electro
negativity atoms

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Features of Carbanion :
• Carbanion possess an unshared pair of electron thus it is electron rich (Nucleophile)
• Diamagnetic in nature ( Presence of Paired electrons)
• Carbanion has octet of electron in outer shell
• The negatively charged carbon is trivalent
• Carbanion has a pyramidal geometry
• Carbanion formation in : Aldol condensation, Cannizaros reaction and Perkin reaction
•The negatively charged saturated carbon atom is sp3 hybridized in carbanion
• Stability order of alkyl carbanions is methyl>1o >2o >3o

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Stability of Carbanion:
Factors which can stabilize or disperse the negative charge on carbon will stabilize a
carbanion. The stability of carbanion depends on the following factors:
• Inductive effect
• Extent of conjugation of the anion
• Hybridization of the charge-bearing atom
Summary:
• Heterolytic cleavage of a bond with shared pair of electrons on carbon gives a carbanion.
• Carbanion has pyramidal geometry
• Factors affecting stability of carbanion are inductive effect, extent of conjugation of the
anion, hybridization of the charge bearing atom, aromaticity.
• Carbanions are part of most of the common reaction types such as displacement,
elimination, condensation, addition, rearrangement, polymerisation etc.
• Some example of reactions involving carbanion intermediate are aldol condensation,

Claisen condensation, Favoroskii rearrangement, Wittig reaction, Benzoin condensation,
Perkin reaction.

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Free radicals
The species formed as an intermediate in a chemical reaction which have one or more
unpaired electron are known as free radical (often called a radical).
Formation of free radicals:

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Characteristic of Free Radical:
1) The alkyl radical (·CR3) has (seven electron) 7 –electrons (Odd electron species)
2) They are usually uncharged
3) Electron deficient or Electrophile
4) Paramagnetic in nature (Presence of unpaired electron)
5) Unstable, short-lived
6) When they are formed?
H-Heat (5000 C more)
E- Electricity
L- Light( UV/Visible)
P-Peroxide(-O-O-)
R- Radical
7) In following reactions: Wurtz, Kolbe’s and Substitution in alkanes.

8) Alkyl Free Radical-Sp2 hybridized and Planar
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Stability of Free radical: (Resonance>Hyperconjugation>Inductive effect)
6 -Alpha Hydrogens
3 -Alpha Hydrogens 6-No bond Resonating Structures 9 -Alpha Hydrogens
0 -Alpha Hydrogen + I effect 9-No bond Resonating Structures
+ I effect
Thus, the order of stability is 3o >2o >1o

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Stability Order of Carbocation, Carbanion and Free Radicals:

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Reactivity of Free Radical:
(i) Initiation: In this step, free radicals required for the reaction are generated in situ by
irradiation or heating of the reagent or by carrying out the reaction in the presence of an
initiator like peroxides. The process is always endothermic. The first step is initiation which
involves bond dissociation in chlorine molecule. The bond dissociation energy of the
chlorine molecule is 58 kcal/mol, so chlorine readily undergoes a homolytic bond
dissociation.
(ii) Chain propagation: Second step is chain propagation. In this step the highly reactive
chlorine radicals with unpaired electron reacts further. They are electrophilic, thus each seeks
an electron to complete its unfilled shell of electrons. In a reaction with methane, a chlorine
atom readily removes a hydrogen from the methane. Free radical chain reactions work best
when all propagation steps are exothermic. The resulting methyl radical, which also is very
electrophilic, then removes a chlorine atom from a chlorine molecule.
(iii) Chain termination: The final step is chain termination in which two reactive radicals
combine together. Dr. S. B. Patil, Assistant Professor, MSRIT,
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On the basis of the products of the reactions: 1) Addition reaction: a) Electrophilic
b) Nucleophilic
c) Free radical
2) Substitution reaction: 1) Free radical

2) SN1 and SN2
3) Electrophilic
3) Elimination reaction: E1 and E2
4) Rearrangement

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Addition reactions: A reaction in which the substrate and the reagent add up to form a product
called addition reaction.
Or
An addition reaction is in its simplest terms an organic reaction where two or more molecules combine
to form a larger one.
•The reaction occurs at the site of unsaturation in a molecule. Thus, Compounds having multiple
bonds such as: C=C,C=O etc.
•Addition reactions are limited to chemical compounds that have multiple bonds, such as
molecules with carbon–carbon double bonds(alkenes) or with triple bonds.
• Molecules containing carbon—hetero double bonds like carbonyl (C=O) groups, or imine (C=N)

groups, can undergo addition, as they too have double-bond character.
• An addition reaction is the reverse of an elimination reaction.
• There are two main types of polar addition reactions: electrophilic addition and nucleophilic
addition.
• Two non-polar addition reactions exist as well, called free-radical addition and cycloaddition and
cycloadditions.
Saturated and Aromatic compounds in the ring will not show addition reactions.

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In this Three types:
1) Electrophilic addition reaction
2) Nucleophilic addition reaction
3) Free radical addition reaction
1) Electrophilic addition reaction : This is a characteristic reaction of Unsaturated

hydrocarbons. Both the reactants add to form a single product.
CH2=CH2 + Br2  CH2Br-CH2Br

Ethylene Ethylene bromide

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Markovnikov's rule or Markownikoff's rule describes the outcome of some
addition reactions.
The rule was formulated by Russian chemist Vladimir Markovnikov in 1870
The rule states that with the addition of a protic acid HX to an asymmetric alkene, the acid
hydrogen (H) gets attached to the carbon with more hydrogen substituents, and the
halide (X) group gets attached to the carbon with more alkyl substituents.
Alternatively, the rule can be stated that the hydrogen atom is added to the carbon with
the greatest number of hydrogen atoms while the X component is added to the carbon
with the fewest hydrogen atoms.
Anti-Markovnikov’s Rule(presence of HBr)

In presence of Peroxide linkage
Kharash effect or Peroxide effect
Anti-Markovnikov’s rule states that the halogen adds to the less substituted carbon, the
opposite of a Markovnikov reaction. Similar to a positive charged species, the radical species
is most stable when the unpaired electron is in the more substituted position.
Protic acid: a substance that yields hydrogen ions in solution and from which hydrogen may be displaced by a metal to form a salt. For the
various acids, see under the specific name, such as acetic acid.
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2) Nucleophilic addition reaction:
A nucleophilic addition reaction is a chemical addition reaction in which

a nucleophile forms a sigma bond with an electron deficient species. These reactions are
considered very important in organic chemistry since they enable the conversion of carbonyl
groups into a variety of functional groups.
Or
A nucleophilic addition reaction is an addition reaction where a chemical compound
with an electron-deficient or electrophilic double or triple bond, a π bond, reacts with
electron-rich reactant, termed a nucleophile, with disappearance of the double bond and
creation of two new single, or σ, bonds.
conjugation of electron-withdrawing groups activate the carbon-carbon multiple bonds
towards nucleophilic addition.
Slow Fast
Nucleophile Attack
Electrophile Attack
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•Nucleophilic addition reactions of nucleophiles with electrophilic double or triple bond (π bonds)
create a new carbon center with two additional single, or σ, bonds.
• Addition of a nucleophile to carbon–heteroatom double or triple bonds such as >C=O or -C≡N

show great variety.
•These types of bonds are polar (have a large difference in electronegativity between the two

atoms); consequently, their carbon atoms carries a partial positive charge. This makes the molecule an
electrophile, and the carbon atom the electrophilic center; this atom is the primary target for the
nucleophile.
•An adduct is a product of a direct addition of two or more distinct molecules, resulting in a single
reaction product containing all atoms of all components.

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In this reaction the formation of an electrophile X+ that forms a covalent bond with an electron-rich
unsaturated C=C bond.
The positive charge on X is transferred to the carbon-carbon bond, forming a carbocation during the
formation of the C-X bond.
In step 2 of an electrophilic addition, the positively charged intermediate combines with (Y) that is
electron-rich and usually an anion to form the second covalent bond. Step 2 is the same nucleophilic
attack process found in an SN1.

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3) Free radical addition reaction:
Free-radical addition is an addition reaction in organic chemistry which involves
free radicals. The addition may occur between a radical and a non-radical, or
between two radicals

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Elimination reactions:
When two groups or atoms from adjacent carbons are eliminated with the formation of
unsaturated compounds (alkene or alkyne), the reaction is called elimination reaction.
Or
An elimination reaction is a type of organic reaction in which two substituent’s are removed from a
molecule in either one or two-step mechanism. The one-step mechanism is known as the E2 reaction, and
the two-step mechanism is known as the E1 reaction.
•Smaller atoms or groups are eliminated
•Saturated compounds are converted to unsaturated compounds
•Elimination reaction is reverse process of Addition reaction
-HX

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•“Elimination reactions”, these are organic chemical reactions in which a pair of atoms
or groups of atoms (leaving group) are removed (eliminated) from a
molecule, usually through the action of acids, bases, or metals and, in some cases, by
heating to a high temperature.
•In most organic elimination reactions, at least one hydrogen is lost to form the
unsaturated bond and It is one of the main methods used for the formation of unsaturated
compounds (alkene or alkyne) from substrates containing single carbon-carbon bonds
(saturated compounds).
•Based on the position of the leaving group, these may be α-eliminations, β-

eliminations, but most common are the β-eliminations(1,2-elimination) in which a
leaving group from α-carbon and a proton from the β-carbon are eliminated.

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E1 mechanism
E1 is a model to explain a particular type of chemical elimination reaction. E1 stands for unimolecular
elimination
The elimination reaction in which the rate of reaction is dependent on the concentration of the
substrate only, i.e., kinetically of the first order, is designated E1.
Since the rate of reaction is independent of the concentration of the reagent, it is interpreted, as in
SN1, that the first step of the reaction is the slowest step involving ionization of the substrate. This
followed by the rapid removal of a proton from the by the reagent in the second step.
E1 has the following specifications:

1) It is a two-step process of elimination: ionization and deprotonation.
Ionization: the carbon-halogen bond breaks to give a carbocation intermediate.
deprotonation of the carbocation.
2) E1 typically takes place with tertiary alkyl halides, but is possible with some secondary alkyl halides.
The reaction rate is influenced only by the concentration of the alkyl halide because carbocation
formation is the slowest step, as known as the rate-determining step. Therefore, first-order kinetics
apply (unimolecular).
3) The reaction usually occurs in the complete absence of a base or the presence of only a weak base
(acidic conditions and high temperature).
4) E1 reactions are in competition with SN1 reactions because they share a common carbocationic
intermediate.
5) Carbocation reaction with Nucleophile –Gives to SN1 reaction(Exotherimic reaction, Low temperature(<200)
 Base – E1 reaction(Endotherimic, High temp (>50 o)

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Elimination reaction is reverse process of Addition reaction
•Why weak base?
•If strong base will not wait for removal of X-
(MeOH, EtOH, H2O)
•Polar solvents are used
E1 mechanism:
+ H2 O
HO-
Step 1
Step 2
• The t-butyl bromide undergoes slow ionization in the first step. This is followed
by a rapid extraction of a proton from the carbocation by the base or solvent in the
second step.
•It is seen that a carbocation is formed in the first step in both E1 and SN1
reactions. Hence the carbon to give substitution product and also can accept a proton to
give elimination product.
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E2 mechanism
During the 1920s, Christopher Kelk Ingold proposed a model to explain a peculiar type of chemical
reaction: the E2 mechanism. E2 stands for bimolecular elimination.
When the rate of elimination reaction is dependant on both the substrate and the reagent, the reaction
is kinetically of the second order or bimolecular. Such bimolecular elimination reaction is designated E2
on its similarity with SN2.
The reaction involves a one-step mechanism in which carbon-hydrogen and carbon-

halogen bonds break to form a double bond (C=C Pi bond).
The specifics of the reaction are as follows:
•E2 is a single step elimination, with a single transition state.
•It is typically undergone by primary substituted alkyl halides, but is possible with some
secondary alkyl halides and other compounds.
•The reaction rate is second order, because it's influenced by both the alkyl halide and the
base (bimolecular).
•Because the E2 mechanism results in the formation of a pi bond, the two leaving groups
(often a hydrogen and a halogen) need to be antiperiplanar. An antiperiplanar
transition state has staggered conformation with lower energy than a synperiplanar
transition state which is in eclipsed conformation with higher energy. The reaction
mechanism involving staggered conformation is more favorable for E2 reactions (unlike E1
reactions).
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•E2 typically uses a strong base. It must be strong enough to remove a weakly acidic
hydrogen.
•The C-H bond is weakened in the rate determining step and therefore a primary
deuterium isotope effect much larger than 1 (commonly 2-6) is observed.

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Substitution reactions :
A reaction in which one group or atom is replaced by another is called a

substitution reaction. The incoming group bonded to the same carbon to
which the leaving group was bonded.
Substitution reaction has been classified according to the nature of the

substituent's involved.
. .
2) Substitution reaction: 1) Free radical Substitution: A:B + Q ->A:Q + B
- -
2) Nucleophilic substitution: A:B + :Q ->A:Q + :B
+ +
3) Electrophilic substitution: A:B + Q ->A:Q + B

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Nucleophilic substitution reaction: SN1 and SN2
At saturated carbon: Nucleophilic substitution reaction involves the displacement of a

nucleophile by another. These reactions have great synthetic importance. A classical
example is the hydrolysis of alkyl halides.
The nucleophile furnishes an electron pair to the carbon from which the leaving group
departs with the bonding pair of electrons. In that two types:SN1 and SN2
-OH:+ R:X -> OH:R + :X

-

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SN1 reaction :
The SN1 reaction is a substitution reaction in organic chemistry. "SN" stands for "

nucleophilic substitution", and the "1" says that the rate-determining step is unimolecular.
Thus, the rate equation is often shown as having first-order dependence on electrophile and
zero-order dependence on nucleophile.
The reaction involves a carbocation intermediate and is commonly seen in reactions of

secondary or tertiary alkyl halides under strongly basic conditions or, under strongly acidic
conditions, with secondary or tertiary alcohols. With primary and secondary alkyl halides,
the alternative SN2 reaction occurs.
This reaction does not depend much on the strength of the nucleophile unlike the S N2
mechanism. This type of mechanism involves two steps. The first step is the reversible
ionization of alkyl halide in the presence of aqueous acetone or ethyl alcohol. This step
provides a carbocation as an intermediate.

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Mechanism:
An example of a reaction taking place with an SN1 reaction mechanism is the hydrolysis of tert
-butyl bromide forming tert-butanol:

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SN2 Mechanism:
•The SN2 reaction is a type of reaction mechanism that is common in organic chemistry. In

this mechanism, one bond is broken and one bond is formed synchronously, i.e., in one
step.
•SN2 is a kind of nucleophilic substitution reaction mechanism. Since two reacting species

are involved in the slow (rate-determining) step, this leads to the
term substitution nucleophilic (bi-molecular) or SN2.
•The reaction type is so common that it has other names, e.g. "bimolecular nucleophilic
substitution", or, among inorganic chemists, "associative substitution" or "interchange
mechanism".
•The breaking of the C–X bond and the formation of the new bond (often denoted
C–Y or C–Nu) occur simultaneously through a transition state.

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In an example of the SN2 reaction, the attack of Br− (the nucleophile) on an ethyl chloride (the
electrophile) results in ethyl bromide, with chloride ejected as the leaving group.
SN2 attack occurs if the backside route of attack is not sterically hindered by substituents on the substrate.
Therefore, this mechanism usually occurs at unhindered primary and secondary carbon centres.
If there is steric crowding on the substrate near the leaving group, such as at a tertiary carbon centre, the
substitution will involve an SN1 rather than an SN2 mechanism, (an SN1 would also be more likely in this case
because a sufficiently stable carbocation intermediary could be formed).
SN2 reaction of chloroethane with

bromide ion

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“Protic” Solvents Have O-H or N-H Bonds And Can Hydrogen-Bond With Themselves. ...
Additionally, these O-H or N-H bonds can serve as a source of protons (H+). Aprotic
solvents may have hydrogens on them somewhere, but they lack O-H or N-H bonds, and
Dr. S. B.
therefore cannot hydrogen bond with Patil, Assistant Professor, MSRIT,
themselves.
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Electronic displacement effect:
Electron displacement effects in covalent bonds: The electron displacement due to the
influence of an atom or a substituent group present in the molecule cause permanent
polarization of the bond.
Dr. S. B. Patil, Assistant Professor, MSRIT, +E -E

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Inductive effect:
Defn: Displacement (Partial shifting) of sigma bond electrons towards more electronegative
atom of sigma bond.
Partial charges are developed.
C-C-C-X (Electron withdrawing group)- Negative Effect(-I)

EN of X>EN of C
C-C-C-Y (Electron donating group)-Positive Effect (+I)
EN of Y<EN of C

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Inductive effect has the following characteristics:
1) It is a permanent effect.
2) It travels and decrease with distance.( Up to 3 carbon)
3) Group attached to Carbon chain should have tendency to release or withdraw electrons.
4) Inductive effect represent by an arrow head in the middle of the covalent bond pointing
in the direction of the displacement of electron.
5) It operates through sigma bonds. (Note that all the single, double and triple bonds have
a sigma bond in them.)
6) Its magnitude goes on decreasing with increase in distance from the atom/group
responsible for the same. Inductive effect is almost negligible after the third or fourth
atom.
7) Presence of multiple bond not necessary.

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8. Polarity of bond essential. (bond polarity is the separation of electric charge along
a bond, leading to a molecule or its chemical groups having an electric dipole or dipole
moment. Electrons are not always shared equally between two bonding atoms).
9. Partial charge separation takes place.
10. Ions are not formed.
11. Attacking reagent not required.
12. Types of Inductive effect:

1) Positive inductive effect (+I)-It is due to electron donating groups
Ex: CH3, C2H5
2) Negative inductive effect (-I)- It is due to electron Withdrawing groups
EX: -NO2, -CN
13. -I effect of some groups is in the order
-H < -C6H5 < -OCH3 < -OH < -I < -Br < -Cl < -F < -COOH < -CN < -NO2 < -N+ (CH3)3
14. +I effect of some of the groups is in the following order:

H- < -CH3 < -CH2R < CHR2 < -CR3 < -COO

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2. Stability of Carbanions
3. Stability of Free radicals
4. Stability of Carboxylic acids

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Resonance Effect
Resonance effect is the polarity produced in a molecule due to interaction between a lone pair of
electron and a pi bond or it is produced due to interaction of two pi bonds between two adjacent atoms.
In a normal bond, the electrons are localized between the constituent atoms. However, if double and single
bonds are present alternately in a molecule, it is called conjugation.
Resonance is a way of describing bonding in certain molecules or ions by the combination of

several contributing structures (or forms,[also variously known as resonance structures or canonical
structures) into a resonance hybrid (or hybrid structure) .
The atoms/groups in which lone pair(or electrons of negative charge) is in conjugation with double or triple
bond are electron donating and gain a formal positive charge in the resonating structure in the process and
are known to exert +M/+R Effect.

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Types Of Resonance Effects
There are two types of Resonance effects namely positive resonance effect and negative
resonance effect.
Positive Resonance Effect- Positive resonance effect occurs when the groups release
electrons to the other molecules by the process of delocalization. The groups are usually
denoted by +R or +M. In this process, the molecular electron density increases.
For example- -OH, -SH, -OR,-SR.
Negative Resonance Effect- Negative resonance effect occurs when the groups withdraw
the electrons from other molecules by the process of delocalization. The groups are
usually denoted by -R or -M. In this process, the molecular electron density is said to
decrease.
For example- -NO2, C=O, -COOH, -C≡N.

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Hyperconjugation or No bond resonance or sigma-p-orbital resonance
Hyperconjugation Observed in a) Carbocation b) Free radical c) Alkene
More hyperconjugation-More stability
In organic chemistry, hyperconjugation refers to the delocalization of electrons with the

participation of bonds of primarily σ-character
Or
Hyperconjugation is the stabilising interaction that results from the interaction of the
electrons in a σ-bond (usually C-H or C-C) with an adjacent empty or partially filled p-orbital
or a π-orbital to give an extended molecular orbital that increases the stability of the system
The delocalization of σ-electrons or lone pair of electrons into adjacent π-orbital or p-orbital
is called hyperconjugation.
It takes place because of overlapping of -bonding orbital or the orbital containing a lone
pair with an adjacent unfilled p-orbital. It is also called as "no bond resonance" or "Baker-
Nathan effect".

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Number of No bond Resonance Structure = No of Alpha Hydrogen

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It explains stability of alkenes, carbocations and free radicals:
The dipole moment of the molecules and bond length is greatly affected due to
hyperconjugation since the contributing structures show considerable polarity and change
in bond order.
 Hyperconjugation also explains the reactivity & orientation of electrophilic substitution

on alkyl substituted benzene ring.

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Basic Principal of Organic Chemistry

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Basic Principal of Organic Chemistry

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DEPARTMENT OF CHEMISTRY

Subject Code: CH32

Unit: III, IV, V

Basic Principles of Organic Chemistry:

1) Introduction : Homolytic and Heterolytic Cleavages

3) Types of Reactions: a) Addition reactions

4) Inductive and Resonance effects

a) Isomerism -Structural-(Chain, Positional, Functional, Metamerism, Tautomerism and Ring-chain

c) Optical isomerism : Optical activity of organic compounds,, Configuration(R,S and E, Z

2) Ionic reactions (heterolytic cleavage)

On the basis of the products of the reactions: 1) Addition reaction: a) Electrophilic

2) Substitution reaction: 1) Free radical

2) SN1 and SN2

3) Elimination reaction: E1 and E2

Dr. S. B. Patil, Assistant Professor, MSRIT,

Same electro negativity of atoms

Conditions for Homolytic Cleavage:

2) Same electro negativity of atoms

3) Presence of Peroxide (Ex: H2O2)

4) High Temperature ( >5000c)

More electro negativity of atom

Less electro negativity of atom heterolytic cleavage Ions

H-Cl → H+ + Cl–

Dr. S. B. Patil, Assistant Professor, MSRIT,

Following are the Reactive intermediates:

Carbocations Carbanions Free radical

Dr. S. B. Patil, Assistant Professor, MSRIT,

Dr. S. B. Patil, Assistant Professor, MSRIT,

Dr. S. B. Patil, Assistant Professor, MSRIT,

• The delocalization of σ-electrons or lone pair of electrons into adjacent π-

• Inductive Effect: Displacement of sigma electrons towards more electronegative

The order of stability of carbocations is : 30 >2o >1o >methyl.

Dr. S. B. Patil, Assistant Professor, MSRIT,

• Carbocations are electron deficient species with six electron.

• The order of stability of carbocations is 30 >2o >1o >methyl.

• Carbocation can undergo various types of reactions such as nucleophilic, elimination,

Dr. S. B. Patil, Assistant Professor, MSRIT,

• Carbanion possess an unshared pair of electron thus it is electron rich (Nucleophile)

• Diamagnetic in nature ( Presence of Paired electrons)

• Carbanion has octet of electron in outer shell

• The negatively charged carbon is trivalent

• Carbanion has a pyramidal geometry

• Carbanion formation in : Aldol condensation, Cannizaros reaction and Perkin reaction

•The negatively charged saturated carbon atom is sp3 hybridized in carbanion

• Stability order of alkyl carbanions is methyl>1o >2o >3o

Dr. S. B. Patil, Assistant Professor, MSRIT,

• Carbanion has pyramidal geometry

• Some example of reactions involving carbanion intermediate are aldol condensation,

Dr. S. B. Patil, Assistant Professor, MSRIT,

Formation of free radicals:

Dr. S. B. Patil, Assistant Professor, MSRIT,

2) They are usually uncharged

3) Electron deficient or Electrophile

4) Paramagnetic in nature (Presence of unpaired electron)

6) When they are formed?

H-Heat (5000 C more)

7) In following reactions: Wurtz, Kolbe’s and Substitution in alkanes.

Thus, the order of stability is 3o >2o >1o

Dr. S. B. Patil, Assistant Professor, MSRIT,

Dr. S. B. Patil, Assistant Professor, MSRIT,

2) Substitution reaction: 1) Free radical

3) Elimination reaction: E1 and E2