REACTIONS OF ORGANIC COMPOUNDS

Learning Outcomes: At the end of the lesson the students should be able to :  Explain covalent bond cleavage:
homolytic heterolytic

Lecture 7 12.5 Reactions of Organic Compounds

Types of Covalent Bond Cleavage/Fission  All chemical reactions involved bond breaking and bond making.  Two types of covalent bond cleavage : Homolytic cleavage  Heterolytic cleavage

a)

Homolytic Cleavage

Occurs in a non-polar bond involving two atoms of similar electronegativity. A single bond breaks symmetrically into two equal parts, leaving each atom with one unpaired electron. Formed free radicals.

Example:

X : X

X• + X•
free radicals

X• •X

b) Heterolytic cleavage

Occurs in a polar bond involving unequal sharing of electron pair between two atoms of different electronegativities. A single bond breaks unsymmetrically. Both the bonding electrons are transferred to the more electronegative atom. Formed cation and anion.

 

A:B

A: + B+ anion cation A is more electronegative. A + + B: cation anion B is more electronegative.

Reaction Intermediates
 a) Carbocation  b)

Carbanion  c) Free Radical They are unstable and highly reactive.

a)

Carbocation

 Also

called carbonium ion.  A very reactive species with a positive charge on a carbon atom.  Carbocation is formed in heterolytic cleavage.

Example : δ + δ −  (CH3)3C — Cl carbocation

(CH3)3C+ + anion

Cl-

Chlorine is more electronegative than carbon and the C—Cl bond is polar. The C—Cl bond breaks heterolitically and both the bonding electrons are transferred to chlorine atom to form anion and carbocation.

b) Carbanion

 is

an anion counterpart  a species with a negative charge on a carbon atom.  Carbanion is formed in heterolytic cleavage.

example: δ + δ −  (CH3)3C — Li kation

(CH3)3C- + carbanion

Li+

b)

Free Radical

A very reactive species with an unpaired electron. Formed in homolytic cleavage. Examples:
i)

free radicals

Cl

uv

Cl

+

Cl

Cl –

ii)

C
iii)

C

●C

+

●C

H3C

H

H3C ● + ●H

Learning Outcomes:

Lecture 7 12.5 Reactions of Organic Compounds

At the end of the lesson the students should be able to:  State the relative stabilities of primary, secondary and tertiary free radicals, carbocations and carbanions.  Explain the inductive effect of alkyl group towards the stability of carbocations and carbanions.  Define electrophile and nucleophile.

Relative Stabilities of Carbocations, Carbanions and Free Radicals

 Carbocation,

carbanion and free radical can be classified into:  Primary  Secondary  Tertiary

Carbocation Stability
 The

alkyl groups (electron-releasing group) stabilise the positive charge on the carbocation. stability of carbocation increases with the number of alkyl groups present.

 The

Carbocation Stability: H H R R H C H < H C R <H C R < R C R + + + + Methyl Primary Secondary Tertiary cation 10 20 30

Increasing stability

Carbanion Stability
o

Alkyl group and other electron-donating groups destabilise carbanions. Electron withdrawing group (e.g: halogen) stabilise carbanions through the inductive withdrawal of electron density

o

Carbanion Stability: H H R R H C H < H C R <H C R < R C R Methyl anion Primary 10 Secondary 20 Tertiary 30

Increasing stability

Free-radical stability
 The

stability of free radical increases as more alkyl groups are attached to the carbon atom with unpaired electron.

H H C H < H C R < H . . methyl radical Primary 10

Free Radical Stability : R H C .

R R <R C R . Tertiary 30

Secondary 20

Increasing stability

Reagents and sites of organic reactions
A) Electrophile  Means ‘electron loving’.  An electron-deficient species and accepting electron from an attacking nucleophile.  Can be either neutral or positively charged

Examples of electrophiles :  cations such as H+, H3O+, NO2+ etc.
 carbocations.  Lewis

acids such as AlCl3, FeCl3, BF3 etc. agents such as Cl2, Br2 and etc.

 oxidizing

electrophilic sites are molecules with low electron density around a polar bond Examples: ii) + δ i) δ + δ δ -C = O (carbonyl) ; -C – X (haloalkanes)
iii)δ

+ δ -C – OH (hydroxy compounds)

 b) Nucleophile  means

‘nucleus loving’  An electron-rich species and electron-pair donor.  A nucleophile can be either neutral or negatively charged.

Examples of nucleophiles :
 anions

such as OH-, RO-, Cl-, CN- etc.

 carbanions

( species with a negative charge on carbon atoms ).

Learning Outcomes: At the end of the lesson the students should be able to explain the main types of organic reactions:  addition: electrophilic and nucleophilic  substitution: electrophilic, nucleophilic and free radical  elimination  rearrangement

Lecture 7 12.5 Reactions of Organic Compounds

4 Types of Organic Reactions
    Addition Substitution Elimination Rearrangement

I) Addition Reaction
 A reaction in which atoms or groups add to adjacent atoms of a multiple bond.  Two types of addition :-

a) b)

Electrophilic Addition Nucleophilic Addition

a)Electrophilic Addition
 Initiated by an electrophile accepting electron from an attacking nucleophile.  Typical reaction of unsaturated compounds such as alkenes and alkynes.

Example : CH3CH=CH2 + Br2 electrophile
CCl4 CH3CHBrCH2Br Room temperature

b)

Nucleophilic Addition

 Initiated

by a nucleophile, which attacks an electrophilic site of a molecule.
– Typical reaction of carbonyl compounds.

CH3

O δ − C CH3 + HCN δ +

CN CH3 C OH CH3

II) Substitution Reaction
 A reaction in which an atom or group in a molecule is replaced by another atom or group.  Three types of substitution :-

a) b) c)

free radical substitution. electrophilic substitution. nuclephilic substitution.

a)

Free-radical Substitution

 Substitution which involves free radicals as intermediate species. Example :

CH3CH3 + Cl2

uv light

CH3CH2Cl + HCl

b)

Electrophilic Substitution
reaction of aromatic compounds.

 Typical

– The aromatic nucleus has high electron density, thus it is nucleophilic and is prone to electrophilic attack.
Example:

+ Br2 electrophile

Fe Br catalyst

+ HBr

c)

Nucleophilic Substitution

Typical reaction of saturated organic compounds bearing polar bond as functional group, such as haloalkane with alcohol.
Example : δ +δ − CH3CH2Br + OH-(aq) nucleophile

Δ

CH3CH2OH + Br-(aq)

III)

Elimination Reaction

– An atoms or groups are removed from adjacent carbon atoms of a molecule to form a multiple bond (double or triple bond). – Results in the formation of unsaturated molecules. – Example :

CH3CH2OH

conc. H2SO4 CH2= CH2 + H2O ∆

IV)

Rearrangement Reaction

 A reaction in which atoms or groups in a molecule change position.  Occurs when a single reactant reorganizes the bonds and atoms. Example :

H

C H

tautomerisme C R H C OH

H C R O

H

Exercises
1.

Explain how the free radicals are formed in homolytic cleavage.

2. Write an equation for the brominebromine bond cleavage in the bromination of methane. State the type of bond cleavage.

3. Which would you expect to be the most stable free radical ? • CH2CH3 , (CH3)2 CH• , • CH3 , •
CH3

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