What is reaction mechanism?

mechanism?

 A complete description of how a reaction occurs. A mechanism must account for all
starting materials & products & must describe the details of each individual step in the overall
reaction process.

A-B + C  A-C + B
A-B  A* + B*
A*  A-C + B

*C

Covalent bond:
bond: A bond, which formed by sharing electrons between two nuclei.

Covalent bond
Cleavage

Homolytic cleavage Heterolytic cleavage

(A* + B*) (: A- + B+ / A+ +: B-)

There are two types of covalent bonds, sigma (σ

(σ) & pi (π
(π). A single covalent bond consists
of a sigma bond; & multiple bonds have one σ & one or two π-bonds.

 A sigma (σ
(σ) bond (also called σ molecular orbital) results from end to end overlap of
atomic orbital.

 A pi (π
(π) bond (also called π molecular orbital) results from side to side overlap of p-
orbital.

 Bond energy is the energy (in Kcal/mol) requires breaking the bond in a molecule.

π (weaker)

C C

σ (strong)

 A covalent bond between two atoms can be broken in essentially following two ways –
homolytic & heterolytic cleavage.

Homolytic cleavage/Homolysis:
cleavage/Homolysis: When a covalent bond breaks by separating each
carbon atom with one electron, leading to the formation of highly reactive entities free radical.
This is referred to as homolytic cleavage or Homolysis or homolytic fission of bond.

A~B ------
------ A* + B*
Heat/light (free radicals)
A:B

Homolytic reactions are usually initiated by heat, light or Organic peroxides.

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 Free radical:
radical: Free radicals are paramagnetic, unpaired electron molecules which are
formed by breaking a covalent bond symmetrically or homolytically.

A~B / A : B -----
----- A* + B*

The products A* & B* are free radicals. They are electrically neutrals & have one unpaired
electron associated with them. Free radicals are extremely reactive because of the tendency of
these electrons to become paired at the earliest opportunity.

Heterolytic cleavage:
cleavage: When a covalent bond breaks in a fashion that both the bonding
electrons are taken over by one atom, leaving none for the other. As a result, a negative & a
positive ion is formed respectively is known as Heterolytic cleavage or heterolysis. Heterolysis
occurs most readily with polar compounds in polar solvents.

----- : A- + B+
A~B or A : B -----

What are the main types of organic reaction mechanism?

mechanism?

 There are two types organic reaction mechanism:

mechanism:

1. Polar or Ionic mechanism

2. Free radical mechanism

Polar or Ionic mechanism:

mechanism: In these types of mechanism; heterolytic bond fission takes
place. Here, the substrate molecule develops polarity (positive & negative centers) by the
electron shift of electrons due to inductive, mesmeric or electrometric effects. These positive &
negative centers can be attacked by electrophiles or nucleophiles. The mechanism of reactions
involving the attack of electrophilic and nucleophilic reagents on the polar substrates molecule is
referred to as polar or Ionic mechanism.
mechanism.

 Nucleophiles are negatively charged reagents. It attacks the positive centers in the
substrate molecules.

 Electrophiles (positively charged reagents) attack the negative centers in the substrate
molecules.

Free radical mechanism:

mechanism: In this types of mechanism homolytic fission takes place. The
first step is the formation of free radicals (R*) from a reagent by homolytic fission. These free
radicals can then attack the substrate to give the product.

R* + A~B -----
----- R~A + B*

The free radicals carry no charge. They can attack any part of the substrate molecule
regardless of the electronic distribution of the substrate. The mechanism of reactions involving
the attack of free radicals on the substrate molecule is referred to as a free radical mechanism.

 There are two main types of organic reagents:

reagents:

1. Electrophiles (also called electrophilic reagent)

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 2. Nucleophiles (also called nucleophilic reagent)
Electrophiles:
Electrophiles: A reagent which can accept an electron pair in a electrophilic reaction is
called an electrophile. The name electrophile means “electron-loving” and indicates that it
attacks regions of high electron density (negative centers) in the substrate molecule.
(E+) are electron-deficient. They may be positive ions (including carbonium ions) or
Electrophiles (E
neutral molecules with electron-deficient centers.
Examples are: H+, Cl+, Br+, I+, NO2+, R2C+, RN2+, +SO3H, AlCl3, BF3

Nucleophiles:
Nucleophiles: A reagent which can donate an (Nu (Nu :)
:) electron pair in a reaction is called a
nucleophile. The name nucleophile means “nucleus-loving” and indicates that it attacks regions of
low electron density (positive centers) in the substrate molecule. Nucleophiles are electron rich.
They may be negative ions (including carbanions) or neutral molecules with free electron pair.
Examples are: Cl-, Br-, I-, CN-, OH-, R~CH2-, R~NH2, NH3, H2O, ROH

What is a carbonium ion? Discuss the relative stabilities of 1°, 2°& 3° carbonium ions?
ions?

 Organic ions which contain a positively charged carbon atom are called carbonium
ions/corbocations. They are formed by heterolytic bond fission.

C:Z ----------- C+ + : Z-
-----------
Heterolytic fission
Here Z is more electronegative than carbon.

2
SP R
C+ R C
120°
R

 The positively charged carbon atom in a carbonium ion uses sp2 hybrid orbital to form
three covalent (σ
(σ) bonds. An empty p-orbital extends above & below the plane of the σ bonds.
This empty p-orbital makes the carbon atom electron deficient & gives it a positive charge. Thus
a carbonium ion will combine with any substance. e.g. - Nucleophiles. This can donate a pair of
electrons. For example: - Methyl carbonium ion, ethyl carbonium ion etc.

Stability of carbonium ion:

ion: - The stability of carbonium ions depends on 2 facts –
resonance & inductive effects. For examples, Allyl & benzyl carbonium ions are more stable n-
propyl car1bonium ion. Because Allyl & Benzyl carbonium ions can be stabilized by resonance
but n-propyl carbonium ions have no resonance structure.
CH2 = CH ~ +CH2 +
CH2 ~ CH = CH2
+
CH2 CH2 CH2 CH2
+ +

+
Fig: Resonance structure of Allyl & Benzyl carbonium ion.
ion.

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 CH3 CH3 CH3 H
CH3 C+ CH3 C+ H C+ H C+

CH3 H H H
3° (tert) 2° (sec) 1° (pri)
Electron – attracting groups (-I groups) like – NO2 and – Br will make carbonium ion less stable.

Preparation:
Preparation:  From heterolysis:
heterolysis: - (1)
R R

R~C~X R ~ C + + X-

R R
 Protonation:
Protonation: - (2)
R
R R R
C=C + H+ C+ ~ C ~ H
H H H
H

R~OH + H+ R+OH2 R+ + H2O

 (3) R~N≡N~X R+ + N 2

Reaction:
Reaction: -

 Proton less:
less: - A propyl car1bonium ion less a proton to produce propylene as: -
+
-H
CH3 ~ CH ~ +CH2 CH3 ~ CH = CH2
Propylene

H
Propyl corbocations

 Combination with nucleophiles:

nucleophiles: A highly reactive ethyl carbonium ions reacts with a
bromide ion to form ethyl bromide.
CH3 ~ +CH2 + : Br - CH3 ~ CH2 ~ Br

Another example: A neutral nucleophile, H2O, reacts1 with tertiary butyl carbonium ion to
produce protonated tertiary butyl Alcohol and further loses H+ to produce tertiary butyl Alcohol.

CH3 CH3 CH3

+
-H
CH3 ~ C+ + :O~H CH3 ~ C ~ O+ ~ H CH3 ~ C ~ OH

CH3 H HC 3 H CH3
Tert. Ethyl Alcohol (Protonated) Tertiary butenol.

 Addition to alkenes:
alkenes: To produce a bigger carbonium ion as: -
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 CH3 CH3 CH3 CH3
+
CH3 ~ C = CH2 + C ~ CH3 CH3 ~ C+ ~ CH2 ~ C ~ CH3

CH3 CH3
 Molecular rearrangement:
rearrangement: -

 From 1°
1° into 2° carbonium ion

CH3 ~ CH2 ~ CH2 ~ +CH2 CH3 ~ CH2 ~ +CH ~ CH3

 From 1° into 3° carbonium ion

CH3 CH3

CH3 ~ CH2 ~ CH ~ +CH2 CH3 ~ CH2 ~ +C ~ CH3

 From 2° into 3° carbonium ion

CH3 H3C CH3

CH3 ~ C ~ +CH ~ CH3 CH3 ~ +C ~ C ~ H

CH3 CH3

 Abstraction of a hydride ion:

ion: -

CH3 CH3 CH3 CH3 CH3 CH3

CH3 ~ C ~ CH2 ~ +C + H : C ~ CH3 CH3 ~ C ~ CH2 ~ C ~ C ~ H + CH3 ~ +C

CH3 CH3 CH3 CH3 CH3 CH3

 Carbanions:
Carbanions: Organic ions which contain a negative charged carbon atom are called
carbanions. They are formed by heterolytic fission.

~C:Z ~ C : + Z+

Where Z is less electronegative than carbon.

sp3 hybridized
C

Fig: Structure of carbanions

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 The negatively charged carbon atom in a carbanion uses sp 3 hybrid orbital to form 3σ 3σ
bonds. A completely filled p-orbital to extend above & below the plane of the σ bonds. This
completely filled p-orbital makes the carbon atom electron-rich & gives it a negatively charges.
Thus a carbanion will combine with any substance (e.g. – electrophiles) which can accept a pair
of electrons. For example - Methyl & Ethyl carbanion.

H H

H ~ -C : CH3 ~ -C :

H H
Methyl carbocation Ethyl carbocation

 Stability:
Stability: The stability of carbanion depends on the both resonance & inductive effects.
For example- The benzyl carbanion is much more stable than n-propyl carbanion is stabilized by
resonance; n-propyl carbanion has no resonance structures.

CH2 CH2 CH2 CH2

─: ─:

:─
Fig: Benzyl carbanion

Stabilization of carbanions by inductive effects is in opposite direction from the carbanion

ions. Electron releasing groups (+I groups) makes the carbanions less stable. Thus a primary
carbanion is more stable than a secondary, which in turn is more stable than a tertiary because of
+I effect associated with Alkyl groups.

H R R
R ~ C─: R ~ C─: R ~ C─:

H H R
1° 2° 3°

Electron attracting groups (-I groups) like - NO2 & -Br will stabilized carbanion by partial
removal of the negative charge on the carbon.

 Preparation:
Preparation: From organometallic compound ─

~C:M ~ C─: + M+

Where >C = O, ─ CN,

CN, ─ COOH,
COOH, ─ NO2 groups present, it can produce carbanion.
Example, H O H H
─
-OH
H~C~H~C~H H~C~C~O : CH2 ~ CHO
Carbanion

H H H
 Reaction:
Reaction: With proton: -
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 C2H5 + H+ C2H6

 Addition reaction to C = C

>C = C< + R─ R ~ C ~ C─ ~

 Rearrangement: -
C6H5

C6H5 ~ C ~ ─CH2 C6H5 ~ ─C ~ CH2 ~ C6H5

C6H5 C6H5

 Free radicals:
radicals: Free radicals are paramagnetic, unpaired electron molecules which are
formed by breaking a covalent bond symmetrically or homolytically.

A~B / A:B A* + B*

Here, A* & B* are free radicals. They have no charge (electrically neutrals) & have one
unpaired electron associated with them. Free radicals are extremely reactive because of the
tendency of this electron to become paired at the earliest opportunity.

sp2 hybridized
C

Fig: Structure of carbon free radicals

The carbon atom in a carbon free radical uses sp2 hybrid orbital to form three σ bonds.

 Stability:
Stability: Like carbonium ion, a tertiary free radical is more stable than a secondary,
which in turn is more stable than a primary. Free radicals are stabilized by resonance.
R R H H
R ~ C* R ~ C* H ~ C* H ~ C*

R H R H
 Resonance effect:
effect: -
+
CH2 = CH ~ *CH2 CH2 ~ CH = CH2

 Preparation:
Preparation: -
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  Pyrolysis of peroxide: - ∆
R~O~O~R 2RO*

 Photochemical cleavage: - UV
Cl ~ Cl Cl* + Cl*

 Reaction:
Reaction: In substitution, addition, polymerization reaction mechanism occur free
radicals.
radicals.

H ~ CH3 + Cl* *CH3 + HCl

*CH3 + Cl* CH3Cl

 Electron displacement effects:

effects: There are four types of electron displacement effects
observed in organic molecules.

 Inductive effect
 Mesomeric effect
 Electromeric effect
 Hyper conjugative effect

 Inductive effect:
effect: The inductive effect referred to the polarity produced in a molecule as
a result of higher electro negativity of one atom compared to another.

C ~ H or C : H (Standard)
δ+ δ─
C ~ X or C : X ( ─I)
δ─ δ+
C ~ Y or C : Y (+I)

Here, C ~ H bond is used as a standard. It has no effect because the shared electron pair
is symmetrically place between two them. Instead of hydrogen atom, we have a substituent aving
higher electronegativity (electron attracting power) than the carbon atom. The shared electron
pair will be displacing toward the substituent X.
On the other hand, if a substituent Y has lower electronegativity (electron releasing group)
than the carbon atom, the shared electron pair will be displacing toward the carbon atom from the
Y & that means increase the electron density toward the carbon atom.

δ─ δ+ δ+ δ─
X <~ C ~ Y ~> C ~

When the substituent, linked to carbon is electron attracting (X (X), it develops a negative
charge as known (negative) inductive effect simply (─I) (─I) effect. On the other hand, if the
substituent linked to carbon, is electron releasing. It develops a positive charge. The inductive
effect is called positive inductive effect simply (+I)
(+I) effect. For example,
 (─ I) effect groups  NO2, F, Cl, Cl, Br, I, OH, C2H5. (Electron attracting groups)
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 NO2 > F > COOH > Cl > Br > I > OH > C6H5

 (+I) effect groups  (CH3)3C─, (CH3)2CH─, CH3CH2–, CH3─ (Electron releasing

groups)

Tertiary (3°) alkyl groups exert greater +I effect. The secondary (2°) which in turn exert a
greater effect than primary (1°)