13.

2 Characteristics of organic reactions

Organic chemistry
 CONTENTS

• Homologous series

• Alkane

• Alkene and alkyne

• Organic reactions

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Homologous series
A series of compounds that have the same
functional group, and each member differs from
the next by a common repeating –CH2 unit in their
formula
• all share the same general formula
• Formula of a homologue differs from its
neighbor by –CH2 group
• Contains same functional group
• Similar chemical properties
• Shows a gradual change in physical properties
as molar mass increases
• Can be prepared by similar methods

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Alkane
• Organic compound with only single bonds are called saturated compounds
• The alkanes are homologous series of saturated compounds
• Names all end with -ane

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Alkenes and alkynes
• Unsaturated compounds contain at least one double or triple bond
• Alkenes have double bonds, names end in –ene
• Alkynes have triple bonds, names end in -yne

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 Organic reactions

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Organic reactions and mechanisms
• Are chemical reactions involving organic compounds
• The basic organic chemistry reactions types are addition reactions, elimination
reactions, substitution reactions, pericyclic reactions, rearrangement reactions and
redox reactions
• A reaction mechanism is the step by step process of elementary reactions by which
overall chemical change occurs
• Although only the net chemical change is directly observed for most chemical
reactions, experiments can often be designed that suggest the possible sequence of
steps in a reaction mechanism

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Nucleophile
• A reagent which can donates an electron pair
• Nucleophile means nucleus loving and indicates that it attacks regions of low electron
density (positive centers) in the substrate molecule
• They are electron rich
• They may be negative ions including carbanions or neutral molecules with free
electron pair
• Symbol: Nu:
• Example: Cl-, Br-, CN-, OH-, RCH2-, NH3, RNH2, H2O

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Electrophile
• A reagent which can accept an electron pair
• Electrophile means electron loving and indicates that it attacks regions of high
electron density (negative centers) in the substrate molecule
• They are electron deficient
• They may be positive ions including carbonium ions or neutral molecules with
electron deficient centers
• Symbol: E+
• Example: H+, NO2+, R3C+, AlCl3, BF3

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Categories of simple organic reacitons
• Substitution reaction
• Addition reaction
• Condensation/elimination reaction
• Hydrolysis
• Mild oxidation and strong oxidation reaction
• Combustion
• Acid-base reactions

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Categories of simple organic reacitons
Reaction Type Sub-Type Comments
Addition reaction Electrophilic Halogenation,
Nucleophilic hydrohalogenation and
Radical hydration
Elimination reaction Dehydration
Substitution reaction Nucleophilic aliphatic With Sn1, Sn2
Substitution
Nucleophilic aromatic
substitution
Nucleophilic acyl substitution
Electrophilic substitution
Electrophilic aromatic
substitution
Radical substitution
Organic redox reaction Redox reactions specific to
organic compounds
Rearrangement reactions 1,2-rearrangements pericyctic
reactions metathesis

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Elimination/Condensation reaction
• Involves the elimination and removal of the adjacent atoms
• Example: conversion of ethyl chloride to ethylene
• In this reaction the eliminated molecule is HCl which is formed b the combination of H+
from the carbon atom which is on the LHS and the Cl- ion from the carbon atom on the
RHS

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Substitution reaction
• A substitution reaction occurs when one atom of an organic molecule is replaced by
another
• Often requires heat and/or a catalyst
• Example

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Substitution reaction
Substitution of benzene
• Due to strong bonding arrangement between the carbon atoms in a benzene ring, the
ring cannot easily be broken during chemical reactions
• The hydrogen atoms that are bonded to each carbon can be substituted for other
atoms and groups

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Substitution reaction: Nucleophilic
• It is a fundamental class of substitution reaction in which electron rich nucleophile
selectively bonds with or attacks the positive or partially positive charge atom attached
to a group or atom called the leaving group
• Nucleophilic substitution reaction are classified as:
1. Nucleophilic substitution reaction at saturated carbon atom
2. Nucleophilic substitution reaction at unsaturated carbon atom

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Substitution reaction: Nucleophilic
• In Sn1 reaction, the addition of the nucleophile and the elimination of leaving group take
place simultaneously
• Sn2 reaction occurs where the central carbon atom is easily accessible to the
nucleophile
• By contrast Sn1 involves 2 steps
• Sn1 reactions tend to be important when the central carbon atom if the substrate is
surrounded by bulky groups because such groups interfere sterically with the Sn2
reaction and because a highly substituted carbon forms a stable carbocation

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Substitution reaction: Nucleophilic Sn1

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Substitution reaction: Nucleophilic Sn2

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Substitution reaction: Energy diagrams
Energy diagram Sn1 mechanism Energy diagram Sn2 mechnism

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Substitution reaction
Nucleophilic substitution at unsaturated carbon centers
• Nucleophilic substitution via the Sn1 and Sn2 mechanism does not generally occur with
vinyl or aryl halides or related compounds
• When the substitutions occur at the carbonyl group, the acyl group may undergo
nucleophilic acyl substitutions
• This is the normal mode of substitution with carboxylic acid derivatives such as acyl
chlorides, esters and amides

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Substitution reaction: Nucleophilic aromatic
Nucleophilic aromatic substitution
• Is a substitution reaction in which the nucleophile displaces a good leaving group such
as a halide on an aromatic ring

Nitration
• It is a general process for the introduction of a nitro group into a chemical compound
• Example: conversion of toluene to trinitrotoluene
• In aromatic nitration, aromatic organic compounds are nitrated via an electrophilic
aromatic substitution mechanism involving the attack of the electron rich benzene ring
by the nitronium ion
• Benzene is nitrated by refluxing with concentrated sulphuric acid and concentraded
nitric acid at 50ᵒC

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Substitution reaction: Nucleophilic aromatic

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Addition reaction

• New atoms or groups are bonded to the

atoms of the organic molecules
• The organic molecule must be
unsaturated (double or triple bonds)
• New bonds can be made to the carbon
atoms involved in the double or triple bond
if the part of the bond is first broken

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Addition reaction: Electrophilic
• An electrophilic addition reaction is an addition
reaction where, in a chemical compound a π bond
is broken and 2 new σ bonds are formed
• The substrate of an electrophilic addition reaction
must have a double bond or triple bond
• The driving force of this reaction is the formation of
an electrophile X+ that forms a covalent bond with
an electron-rich unsaturated C=C bond
• The positive charge on the X is transferred to the
carbon-carbon bond forming a carbocation

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Addition reaction: Electrophilic

• Step 1: the δ+ H atoms attacks the electron-rich region (π bond) causing it to break and
forming a carbocation and the H covalently bonds to the carbon atom
• Step 2: the carbocation combines with the anion (Br-) to form a second covalent bond
• Sn1 reaction

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Addition reaction: Electrophilic

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Markovnikov’s Rule
• If the double or triple bond is part of a
molecules with three or more carbon
atoms in the chain, the most likely addition
reaction products can be predicted using
a rule first formulated by Russian chemist,
V. V. Markovnikov
• RULE: the more electronegative atom will
predominantly bond to the carbon atom of
the double bond that has fewer hydrogen
atoms

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Markovnikov’s Rule
• The driving force behind the reaction is the formation of carbocation on addition of H
to the alkene, in the first step of the reaction.
• The most stable carbocation is formed when H is added to carbon having more
number of hydrogen atoms already attached – due to factors like induction and
hyperconjugation – which gives the major product with Br added to less hydrogen-rich
carbon
• Less stable carbocation (H added to less hydrogen-rich carbon) is also present in
small quantity, forming minor product on addition of Br to carbon having more
hydrogen attached

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Markovnikov’s Rule

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Markovnikov’s Rule in alkynes

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Anti-Markovnikov’s Rule
• The most common type of mechanism for
anti-Markovnikov reactions is that of free
radical addition.
• This mechanism is only applicable for HBr –
not HCl or HI – with the presence of either
benzoyl peroxide (C14H10O4) or hydrogen
peroxide (H2O2)
• Peroxide is essential as it acts as a catalyst
which breaks HBr into Br and H radicals (a
radical is any chemical species with one
unpaired electron).

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Anti-Markovnikov’s Rule
• The Br radical attacks the alkene first. It attacks
the less substituted carbon, as the carbon
radical so formed will be at the more
substituted carbon, for greater stability. The
carbon radical then attacks the hydrogen of
another HBr molecule, liberating another Br
radical and so the reaction is carried forward
• As with Markovnikov reactions, there are also
trace amounts of product formed by the less
stable carbon radical, with Br attacking the
more substituted carbon

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Addition reaction: Electrophilic
Aromatic substitution: Sulphonation
• Unlike other electrophilic substitution reaction, sulphonation is reversible
• Removal of water from the system favors the formation of the sulphonation products
• Heating sulphonic acid with aqueous sulphuric acid can result in the reverse reaction –
desulphonation
• Sulphonation with fuming sulphuric acid strongly favors formation of the product the
sulphonic acid
• Reagents: for benzene, H2SO4/heat or SO3/H2SO4/heat = fuming sulphuric acid
• Electrophile species: SO3 which can be formed by the loss of water from the sulphuric
acid

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Addition reaction: Electrophilic
STEP1:
• The p electros of the aromatic C=C act as a nucleophile, attacking
the electrophile S, pushing charge out onto an electronegative O
atom.
• This destroys the aromaticity giving the cyclohexadienyl cation
intermediate
STEP 2:
• Loss of the proton from the sp3 C bearing the sulfonyl-group reforms
the C=C and the aromatic system
STEP 3:
• Protonation of the conjugate base of the sulphonic acid by sulphuric
acid produces the sulphonic acid

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Addition reaction: Nucleophilic

• A nucleophilic addition reaction is an addition reaction where in a chemical compound a

π bond Is removed by the creation of 2 new covalent bonds by the addition of a
nucleophile
• Addition reactions are limited to chemical compounds that have multiple-bonded atoms
• Molecules with carbon hetero multiple bonds like carbonyls, amines or nitriles
• Molecule with carbon-carbon double bonds or triple bonds
• Example: nucleophilic reaction that occurs at the carbonyl group of a ketone by
substitution with hydroxide based compounds

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Addition reaction: Nucleophilic
Carbonyl
• Carbonyl compounds undergo nucleophilic addition reactions because of the C=O bond’s
polarity.
• The polar bond allows partial charges on the carbon and oxygen atoms, making it easy for
the nucleophile to attack at the 1,2-positions.
• Most favored in aldehydes and ketone
• The reactivity of carbonyl compounds towards nucleophilic addition reactions is influenced
by the groups attached to the carbonyl carbon.
• The reactivity depends on the magnitude of the positive charge on the carbonyl atom and is
high for electron-deficient carbon.
• The functional group, like alkyl, hinders the nucleophilic attack and decreases the electron
deficiency and reactivity.

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Addition reaction: Nucleophilic
• The reactivity of carbonyl compounds towards nucleophilic addition reactions is influenced
by the groups attached to the carbonyl carbon.
• The reactivity depends on the magnitude of the positive charge on the carbonyl atom and is
high for electron-deficient carbon.
• The functional group, like alkyl, hinders the nucleophilic attack and decreases the electron
deficiency and reactivity.
• Example: the order of reactivity of formaldehyde (methanal, HCHO), acetaldehyde (ethanal,
CH3CHO) and acetone ((CH3)2CO)
• Formaldehyde is the most reactive
HCHO > CH3CHO > (CH3)2CO

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Addition reaction: Nucleophilic
1. Nucleophilic addition of water
• The nucleophilic addition of water to a carbonyl compound like an aldehyde or ketone
results in a geminal diol (hydrate).
• The reaction is usually slow under neutral conditions.
• However, the rate can be significantly increased through the addition of an acid or a base
catalyst.
RCOR’ + H2O → RC(OH)2R’
• Example: Acetaldehyde (CH3CHO) hydrolyses propane-2,2-diol (C3H8O2)
CH3CHO + H2O → C3H8O2

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Addition reaction: Nucleophilic
1. Nucleophilic addition of alcohol
• Aldehydes and ketones undergo a nucleophilic addition reaction with alcohols to give
hemiacetal, which reacts with another alcohol molecule to give acetal (geminal diethers).
• This reaction takes place in the presence of an acid catalyst.
RCOR’ + 2R’OH → RC(OR’)2R’ + H2O

• Example: Acetone (CH3COCH3) reacts with ethanol (C2H5OH) to produce 2,2 diethoxy
propane ((CH3)2C(OC2H5)2) and water
CH3COCH3 + C2H5OH → (CH3)2C(OC2H5)2 + H2O

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Addition reaction: Nucleophilic

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Radical reaction
• Most organic reactions involve radicals and their movememtn
• Addition of halogen to a typically saturated hydrocarbon involves free radical mechanism
• There are usually 2 stages involved in a radical reaction
1. Initiation
2. Propagation
3. Termination
• Initially when the weak bond is broken, initiation of the reaction takes place with the
formation of free radicals
• When the halogen is added to the hydrocarbon a radical is produced and give a alkyl
halide

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Oxidation-reduction reactions
• Can often be identified by the change in the oxidation numbers or oxygen atoms at a
particular position in the hydrocarbon skeleton or in the number of bonds between the
carbon and oxygen at that position
• Increase in either corresponds to an oxidation whereas a decrease corresponds to a
reduction
• Increase in the number of hydrogen atoms in a hydrocarbon is often an indication of a
reduction

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Combustion
Combustion are of two:
1. Complete combustion
• All organic compounds can combust or burned
• Complete combustion will take place
• Carbon and hydrogen oxidized to CO2 and H2O
• Due to the release of large amount of heat, alkanes are used as fuels

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Combustion
2. Incomplete combustion
• When organic compounds are burnt in only a limited supply of oxygen
• Incomplete combustion occurs where not all the carbon is fully oxidized
• Some carbon is only partially oxidized to form carbon monoxide (CO)
• CO is a toxic gas a it will bind to the haemoglobin in the blood which can then no longer
bind to oxygen
• As no oxygen can be transported around the body, victims' feel dizzy, loss of
consciousness and if not recovered, it can be fatal
• CO is extra dangerous odorless gas

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Combustion

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