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ASC0303

ORGANIC CHEMISTRY

Chapter 1

Introduction to Organic Chemistry


(Part 2)
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Learning Outcomes
a.

Identify classes of carbon and hydrogen atoms

b. Explain two types of covalent bond cleavage

c.

i.

Homolytic

ii.

Heterolytic

Define free radical, carbonion and carbocation

d. State the relative stabilities of primary, secondary and tertiary free


radical, carbonion and carbocation
e.

Define nucleophile and electrophile

f.

Identify types of electrophile


i.

Lewis acids

ii.

Cations

iii.

Electron deficient sites in organic compounds

g. Identify types of nucleophile:


i.

Lewis bases

ii.

Anions

iii.

Electron rich sites in organic compounds

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Learning Outcomes
h. State the main types of organic reactions
i.

Addition

ii.

Elimination

iii.

Substitution

iv.

Oxidation

i.

Explain inductive effect which can determine the properties and


reactions of functional groups

j.

use the concept of inductive effect to explain:


i.

NO2, -CN, -COOH, -COOR, C=O, -SO3H, -X(halogen), -OH, -OR, -NH2, -C6H5
are electron receptors

ii.

R(alkyl) is electron donor

k. Use the concept of induction to explain the difference in acidity


between

l.

i.

CH3COOH, ClCH2COOH, Cl2CHCOOH and Cl3CCOOH

ii.

Cl2CH2CH2CH2COOH and CH3CH2CHClCOOH

Use the concept of resonance to explain the difference in acidity


between

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SAINS
i.
CH
CH
3

OH and C6H5OH

Classification of C and H
Carbon
Carbon atoms can be classified by the number of other carbon
atoms that are directly attached to it.
In CH4, the carbon is unique (no other carbon attached), and there
is no classification for it.
1 - Primary carbons, are carbons attached to one other carbon.
2 - Secondary carbons are attached to two other carbons.
3 - Tertiary carbons are attached to three other carbons.
4 - Quaternary carbons are attached to four other carbons.
Since a carbon atom normally cannot bond to more than four other
carbons, there is no higher classification for carbon atoms than the
quaternary carbon.

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Classification of C and H
H

CH3

H3C

1C

CH3
2C

CH3

H3C

CH3

H3C

CH3

H3C

CH3

3C
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4C

Classification of C and H
Hydrogen
Primary hydrogen are the ones that are directly connected to a
primary carbon.
Secondary hydrogen connected to the secondary carbon.
Tertiary hydrogen connected to tertiary carbon.
There is no quaternary hydrogen due to limited bonding of carbon
atom to just four.

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Classification of C and H
o
1
H

1
H

1o
H C

H1

H2

C
o

H2

1o
H C

1o
H

o
3
H

1o
H C

1o
H

o
1
H

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Classification of C and H
EXERCISE 1.8: Classify all carbon and hydrogen atoms in the
following compounds.

H
H

H
H

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Classification of C and H
H
H

10

H
30

H
H

10

H
20

10

H
10

H
H

H
hydrogen's class follow
the carbon it attached to

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30

10
20

30
10

Covalent Bond Cleavage


Two ways of covalent bond cleavage (fission)
Homolytic Cleavage
enables each atom to retain one electron of the shared pair
formation of atoms or groups of atoms having unpaired electrons,
called free radicals

Heterolytic Cleavage
unsymmetrical
one of the fragments takes both the electrons
leaving none on the other.
The product of this bond-breaking are two charged particles

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Covalent Bond Cleavage


Homolytic Cleavage

h o m o ly t ic
c le a v a g e

Example:

Cl 2

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Cl

Cl

Covalent Bond Cleavage


Heterolytic Cleavage
X

X:Z
X
Example:

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Cl

H 2O

Cl

Electrophile and Nucleophile


Electrophile (E)
Electron deficient reagent (+ve charged cation);
seeks e- in reactions; electron lover,
Lewis acid

Nucleophile (:Nu-)
Electron-rich reagent (ve charged anion);
tries to donate e- to electrophile in reactions; proton/ nucleus
lover,
Lewis base

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Electrophile and Nucleophile

H
H

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H
H

-bond is electron-rich

acts as a nucleophile
attracts electrophiles

Electrophile and Nucleophile

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Electrophiles

Name

H+

Hydrogen ion

H3O+

Hydronium ion

R-C+

carbocation

R-C+=O

carbonyl ion

NO2+

Nitronium ion

Cl+

Chloronium ion

AlCl3

Aluminium trichloride

FeCl3

Iron trichloride

BF3

Boron trifluoride

H2SO4

Sulphuric acid

HCl

Hydrochloric acid

HBr

Hydrogen bromide

H2O

water

Electrophile and Nucleophile


Nucleophiles

Name

CNOHR-CXN3-

cyanide ion
hydroxide ion
carbonion
halide ion
azide ion
bisulfide
ammonia
amine
alcohol
-bond (alkene)
-bond (aromatic)
-bond (enols)
sodium borohydride
lithium aluminium hydride
water

HS
NH3
R-NH2
R-OH
R=C
C=C (aromatic)
R-C(OH)=C
NaBH4
LiAlH4
H2O
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Electrophile and Nucleophile


Example

Curved arrow indicate the


movement of electrons

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:Nu

Nu

Reaction Intermediates
an intermediate is a molecular entity that is formed from the
reactants (or preceding intermediates) and reacts further to give
the directly observed products of a chemical reaction.
Most chemical reactions are stepwise, that is they take more than
one elementary step to complete.

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Reaction Intermediates
Three types of reaction intermediates

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Reaction Intermediates
Free radicals
formed when one of the weak bonds is broken and odd number of
electrons remains in the valence shell of the bonded atoms
Instead of electron pair there is a movement of a single electron.
Free radicals are not stable which makes them highly reactive
species.
The most common organic reaction involving free radicals is the
free radical substitution reactions of alkane and alkyl halides.
A free radical carbon has 7 electrons in its valence shell (4+ 3
shared electrons from other atoms).
Indicated by a curved, halfheaded arrow
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-+

-+

+ -

-+ + -

Reaction Intermediates
Carbocation
carbon atom acquires a positive charge and also bears three
bonds such that it has a sextet of electrons.
Carbocations are electrophile
1 Primary carbocation: The positively charged carbon atom is attached
to only one alkyl group.
2 Secondary carbocation: attached to two alkyl groups.
3 Tertiary carbocation: attached to three alkyl groups.

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Reaction Intermediates
Carbonion
A molecule in which the carbon atom bears a negative charge.
Similar to carbocation, there are also primary, secondary and
tertiary carbonions.
Carbonions are nucleophiles
their stability depends upon various factors:
Inductive effect: If an electronegative atom is near to the charge then
it will stabilize the molecule
Hybridization of the charge bearing atom
The extent of conjugation

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-+

-+

+ -

-+ + -

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Reactions in Organic Chemistry


Several types of organic reactions:

Addition
Substitution
Elimination
Rearrangement

Oxidation
Reduction
Condensation

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Reactions in Organic Chemistry


Some terms
Selectivity due to the possible formation of isomers of the same
reaction product
Regioselectivity - preference of one direction of chemical bond
making or breaking over all other possible directions. A starting
material forms two (or more) structural isomers, and one
predominates.
Stereoselectivity - a single reactant forms an unequal mixture of
stereoisomers. The reaction is enantioselective when one
enantiomer is formed in preference to the other and
diastereoselective when one diastereomer is formed in preference
to another

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E
Cl

C
Cl

:Nu

Cl

Cl
E

H
H

Nu

Reactions in Organic Chemistry


dichloroethane

Addition Reaction
limited to chemical compounds that have multiple bonds, such as
alkenes or alkynes
2 types: electrophilic addition and nucleophilic addition.
General reaction mechanism:

:Nu

Nu

Example: addition of chlorine to ethene


H

Cl

+
H

Cl

Cl

Cl

H
H

dichloroethane
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Reactions in Organic Chemistry


Substitution Reaction
Also known as single-displacement (replacement) reaction
one functional group in a chemical compound is replaced by
another functional group
Nucleophilic Substitution
a nucleophile selectively attacks the positive charge on an atom or
a group of atoms.
replaces a weaker nucleophile leaving group (L-).
remaining positive atom becomes an electrophile.
Two mechanisms
SN1
SN2
PUSAT ASASI SAINS

Br
L

OH

H 2O
s lo w

HBr
:Nu
-

fa s t

Nu

Reactions in Organic Chemistry


SN1 (unimolecular rate-determining step)
1st order kinetics (ASC0302)
Has two steps:
1. the leaving group departs, forming a carbocation (C+).
2. nucleophile (:Nu-) attaches to the carbocation and forms a covalent
sigma bond
General reaction mechanism:
L
s lo w

:Nu

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fa s t

Nu

Reactions in Organic Chemistry


Example: substitution reaction of 2-bromo-2-methylpropane in
water to produce 2-methyl-2-propanol:
Br

H 2O

OH

HBr

EXERCISE 1.9: Draw the reaction mechanism of SN1 reaction above

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Reactions in Organic Chemistry

Br

O H

+ Br

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H 3O

OH

HBr

Reactions in Organic Chemistry


SN2 (bimolecular rate-determining step)
2nd order kinetics (ASC0302)
One step
Nucleophilic attack and expulsion of leaving group happened
simultaneously
General reaction mechanism:

Nu
L

:Nu

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Nu

Reactions in Organic Chemistry


SN2 reactions depends on several circumstances
Stability of carbocation, more stable carbocation, higher chances for
SN2
Unhindered carbocation

Strength of nucleophile
Nature of leaving group
Nature of solvent

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Reactions in Organic Chemistry


Example: substitution reaction chloroethane with sodium hydroxide:

Cl

N aO H

OH

NaCl

EXERCISE 1.10: Draw the reaction mechanism of SN2 reaction


above

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Reactions in Organic Chemistry

HO
Cl

O H

Na

H
C
H

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Cl

OH

NaCl

Reactions in Organic Chemistry


Elimination Reaction
two substituents are removed from a molecule in either a one or
two-step mechanism.
the one-step mechanism is known as the E2 reaction,
the two-step mechanism is known as the E1 reaction.
Similar with nucleophilic substitution reaction, the number indicate
the kinetics of the reaction

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Reactions in Organic Chemistry


E1 Reaction
2 Steps
1. Ionization: the carbon-halogen bond breaks to give a carbocation
intermediate
2. deprotonation of the carbocation

E1 reactions are in competition with SN1 reactions because


they share a common carbocation intermediate

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Reactions in Organic Chemistry


General reaction mechanism:

Step 1
X

H3C

H3C

Z
Step 2
:B

C
H

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X
C

Reactions in Organic Chemistry


Example: elimination reaction of tert-butyl bromide with sodium
hydroxide
Br

N aO H

NaBr

EXERCISE 1.11: Draw the reaction mechanism for the above


reaction

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Reactions in Organic Chemistry


Step 1
CH3
H3C

CH3
Br

H3C

Br

CH3

CH3
Step 2
OH

CH3

H
H

C
H

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CH3

CH3

CH3

H2O

Na Br

Reactions in Organic Chemistry


E2 Reaction
1 step with a single transition state
typically uses a strong base. It must be strong enough to remove
weakly acidic hydrogen
E2 reactions are in competition with SN2 reactions if the base can
also act as a nucleophile (true for many common bases).

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Reactions in Organic Chemistry


General reaction mechanism:

:B

H
H

C
H

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C
L

B-H

Reactions in Organic Chemistry


Example: elimination reaction chloroethane with sodium hydroxide

H3C

Cl

NaO H

H2C

CH2

H2O

Cl

EXERCISE 1.12: Draw the reaction mechanism for the above


reaction

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Reactions in Organic Chemistry


HO

H
H

C
H

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H
C
Cl

H
H

H2O

Cl

Reactions in Organic Chemistry


Rearrangement Reaction
reaction in which an atom or bond moves or migrates, having
been initially located at one site in a reactant molecule and
ultimately located at a different site in a product molecule
key feature defining it as a rearrangement is that a bond shifts
from one site of attachment to another
Product can be a constitutional isomer of the reactant

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Reactions in Organic Chemistry


Example: rearrangement reaction of cyclohexanoxime to
caprolactam (Beckmann rearrangement)

OH

N H 2O H

cyclohexanone

O
H 2S O

cyclohexanoxime

caprolactam

rearrangement reaction

Notice that both cyclohexanoxime and caprolactam has the same


molecular formula of C6H11ON
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Reactions in Organic Chemistry


Oxidation Reaction [O]
the reactant lose a proton (H) or has an increase of oxidation
state.
occur to many types of organic compounds. Compounds that can
be oxidised can also be reduce (reduction reaction) and they are
usually reversible.
Several oxidising agents are commonly used as reagents in
oxidation reactions:
KMnO4-, CrO42-, K2Cr2O72, PCC, PDC or else
highly electronegative elements such as (O2, F2, Cl2, Br2)

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Reactions in Organic Chemistry


Example: producing carboxylic acid from primary alcohol through an
aldehyde:

[O ]
R

OH

10 alcohol

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[R ]

[O ]
H

aldehyde

[R ]

OH

carboxylic acid

Reactions in Organic Chemistry


Reduction Reaction [R]
the opposite of oxidation reaction
happens when the molecule accept an H atom, which decrease its
oxidation state.
involve reducing agents:
H2 gas in presence of metal catalyst (Pt, Pd, Ni)
H3O+ ion
hydride transfer reagents such as NaBH4 and LiAlH4.

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Reactions in Organic Chemistry


Example: hydrogenation reaction of alkene
H
H3C

H
CH3

(2Z)-but-2-ene

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H
2

Pt or Pd or N i

H3C

CH3
H

n-butane

Reactions in Organic Chemistry


Condensation Reaction
Two molecules or moieties, often functional groups, combine to
form a larger molecule, together with the loss of a small
molecule such as water and hydrogen chloride
Many follow the nucleophilic acyl substitution mechanism
Can be used to synthesize a variety of different products.
Condensation reaction is used to increase the chain length or amino
acids (become peptides or proteins) and polymers

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NHNu
3

:Nu
H3C

O O

O
ClL

H3C

+L

HCl

Nu NH
2

Reactions in Organic Chemistry


General reaction mechanism:

O
:Nu

Nu

Nu

Example: reaction between ethanoyl chloride with ammonia


O

+
H3C

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Cl

NH3
H3C

NH2

HCl

Reactions in Organic Chemistry


Polarization of Covalent Bond
The electron cloud in a -bond between two unlike atoms is not uniform
and is slightly displaced towards the more electronegative of the two
atoms.
This causes a permanent state of bond polarization, where the more
electronegative atom has a fractional negative charge (-) and the less
electronegative atom has a fractional positive charge (+).
For example, the water molecule H2O has an electronegative oxygen
atom that attracts a negative charge. This is indicated by - in the water
molecule in the vicinity of the O atom, as well as by a + next to each of
the two H atoms
The vector addition of the individual bond dipole moments results in a net
dipole moment for the molecule.

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Reactions in Organic Chemistry


Inductive Effect
If an electronegative atom is joined to a chain of carbon atoms:
the positive charge is relayed to the other atoms in the chain
electron-withdrawing inductive effect, also known as the -I effect.
some groups, such as the alkyl group, are less electron-withdrawing
than hydrogen considered as electron-releasing. This electronreleasing character is indicated by the +I effect.
In short, alkyl groups tend to give electrons, leading to induction
effect.

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Reactions in Organic Chemistry


The relative strength of inductive effect has been measured
experimentally against hydrogen, and is given below (in
decreasing order of I ):
-NH3+ > -NO2 > -SO2R > -CN > -SO3H > -CHO > -CO > -COOH > -COCl >
-CONH2 > -F > -Cl > -Br > -I > -OR > -OH > -NH2 > -C6H5 > -CH2=CH2 > -H

The strength of inductive effect also dependent on the distance


between the substituent and the main reactive group
Longer distance weaker effect

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H
Cl

O
O

H
ClCl
C
H
Cl

OH

Cl

OH OH

Reactions in Organic Chemistry


Example of inductive effect towards the acidity of carboxylic acids:

Effect of distance:

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Reactions in Organic Chemistry


Resonance Effect
observed in organic compounds with double bonds due to the
overlap p orbitals along the bond
molecule can stabilize itself by rearranging its double bond
If a molecule or compound can lose H and stabilize the resulting
ion through resonance, its acidity is higher than the ones that
dont.
Example such as between carboxylic acids and alcohols
Carboxylic acid can lose H easier than alcohol because of resonance
effect, therefore it is the stronger acid

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HO
O- H
H C
H3C
H3C H

C O
OH
OH
O
H

H3C

Reactions in Organic Chemistry

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Reactions in Organic Chemistry


Resonance can also occurs in aromatic compounds
phenol (aromatic) would be a stronger acid than ethanol, or
aniline (aromatic) would have stronger acidity (pKa = 4.6) than
methanamine (pKa = 10.64) as shown
H

NH2
H

NH2

H
aniline

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methanamine

Reactions in Organic Chemistry


Resonance structures of phenol:
OH

O
+

-H

phenol lose hydrogen to become phenoxide anion

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Reactions in Organic Chemistry


EXERCISE 1.13: Draw all resonance structures of aniline

NH2

NH2

NH2
-

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NH2

End of Chapter 1

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