CHAPTER 2

Introduction to
Organic Reaction
 Reactions of the
Organic Compounds

There are four reactions of the organic

compounds:
1) Substitution
2) Elimination
3) Addition
4) Rearrangement
 Substitution Reaction
• One atom in a molecule is exchanged or
replaced by another atom.

H H
H C H + I2 H C I + HI

H H
methane iodomethane
 Elimination Reaction
• Two or more atoms or carbons are
removed from a molecule and the product
form a multiple bond.

H H H H
H2SO4 + HBr
H C C Br C C

H H H H
Bromoethane ethene
 Elimination Reaction: Formation of C=C

H Br OH- SO3H+
H2SO4 H C C H
H C C H
H H
H H
ethene
Bromoethane
1) The nucleophile (normally a strong base) + HBr
removes one atom (usually a proton, H+)
2) group on the adjacent carbon leaves
(the leaving group) and double bond is
formed between two adjacent carbon.
 Addition Reaction
• Two reactants are combined together to
form a single product.

• It is a reverse process of an elimination

reaction.

• The reaction occurs at carbon-carbon

multiple bond.
H H H H

C C + HBr H C C Br

H H H H
ethene Bromoethane

Formation of new single bonds or sigma bond

 Homolytic Bond Cleavage
▪ Breaking a bond by equally dividing the
electrons between the two atoms in the
bond, which results in species called free
radicals.
 Heterolytic Bond Cleavage
▪ Breaking a bond by unequally dividing the
electrons between the two atoms in the bond.
▪ When two atoms have different
electronegativities, the electrons end up on the
more electronegative atom.
 Bond Breaking–Heterolytic
• Heterolysis of a C—Z bond generates a
carbocation or a carbanion.

• A carbocation is an unstable intermediate

containing a carbon surrounded by only six
electrons.

• A carbanion is an unstable intermediate having

a negative charge on carbon, which is not a
very electronegative atom.
10
Reactive Intermediates Resulting from Breaking a
C-Z Bond

11
 Bond Breaking–Intermediates

• Radicals and carbocations are electrophiles because they

contain an electron-deficient carbon.
• Carbanions are nucleophiles because they contain a
carbon with a lone pair.

12
 Bond Forming
• Bond formation occurs in two different ways.
• Two radicals can each donate one electron to form a two-electron
bond.
• Two ions with unlike charges can come together, with the
negatively charged ion donating both electrons to form the
resulting two-electron bond.
• Bond formation always releases energy.

13
 Electrophiles (electron-loving)
• A reagent which attacks a negatively
charged carbon atom (carbanion) by
accepting an electron pair.

• They are positively ions that attack

electron rich area.

• Electrophiles accept electrons, therefore

they are called Lewis acids.
 Example of Electrophiles

+
X+ halonium ion C carbocation

H+ proton

NO2+ nitronium ion C carbon radical

 Nucleophiles (nucleus-loving)
• A reagent that attacks a positively charged
carbon atom (carbocation) by donating an
electron.

• They are either negative ions or molecules

that have lone pair of electrons.

• Nucleophiles donate electrons, therefore

they are called Lewis bases.
 Example of Nucleophiles
-
HO hydroxyl ion R3N amine
- H2O water
RO alkoxy ion
- C O* carbonyl group
CN cyanide ion
- C N * nitrile (N)
X halide ion

ROH hydroxyl ions H2C CH2 * double bond (C)

 Brønsted-Lowry Acids and Bases

• An acid is a proton (hydrogen ion) donor

(donate a proton).

• A base is a proton (hydrogen ion) acceptor

(accept a proton).
Example 1: HCl acts as an acid because it
donates a proton to a base (ammonia) to
form ammonium ion.

• Ammonia acts as a base because it

accepts a proton from an acid (HCl)
H+ + NH3 NH4+
from HCl
Example 2:

H2SO4 + H2O H3O+ + HSO4-

acid base conjugate conjugate
acid base

H2SO4 acts as acid because it donates a proton

to the water and is converted to its conjugate
base, hydrogen sulfate ion, HSO4-. The water
molecule acts as a base because its accepts a
proton from sulphuric acid and is changed into
its conjugate acid, H3O+.
 Conjugate Acid
• A species formed by the reception of a
proton (H+) by a base.

H+ + H2O H3O+
from H2SO4 base conjugate
acid

• H3O+ is the conjugate acid because it is

obtained by adding the H+ ion to the base,
H2O.
 Conjugate Base
• A conjugate base is what is left over after
an acid has donated a proton during a
chemical reaction.
• HSO4- is the conjugate base because it is
formed by the loss of the H+ ion from the
acid H2SO4.

H2SO4 HSO4- + H+
acid conjugate
base
 Lewis Acids and Bases
• Lewis Acid: electron pair acceptor
• Lewis Base: electron pair donor
• Curved arrows show movement of electrons
to form and break bonds
 The Use of Curved Arrows in Reactions

• Curved arrows show the flow of electrons in

a reaction
• An arrow starts at a site of higher electron
density (a covalent bond or unshared
electron pair) and points to a site of electron
deficiency.
Example: Mechanism of reaction of HCl and
water
 Strengths of Acids and Bases
• A strong acid or strong base is one that
ionizes rapidly and completely in aqueous
solution.

• For Example, hydrochloric acid (HCl) is a

strong acid. When placed in water, every
HCl molecule splits into a H+ ion and a Cl-
ion in the reaction.
 Strength of Organic Acids

• Organic acids are weak acids and dissociate

only slightly in aqueous solution.

• For Example, dilute ethanoic acid contains

about 99% of ethanoic acid molecules, only
1% have actually ionised.
 • The dissociation of ethanoic acid in water:

• The equilibrium equation for this reaction is:

- +
[CH3COO ] [H3O ]
Kc =
[CH3COOH] [H2O]

K = Acid dissociation constant/acidity constant/acid ionization constant

• Dilute acids have a constant concentration
of water (about 55.5 M) and so the
concentration of water can be factored
out to obtain the acidity constant (Ka).
• Ka for acetic acid is 1.76 X 10-5
[CH3COO-] [H3O+]
Ka = Kc [H2O] =
[CH3COOH]

• Any weak acid (HA) dissolved in water fits

the general Ka expression.
• Using a generalized acid, HA, the reaction
with water is given by:

HA + H2O H3O+ + A-

and the expression for the acid dissociation

constant, Ka, is:

[H3O+] [A-] [H+] [A-]

Ka = or Ka =
[HA] [HA]
• The strength of a weak acid in dilute
solution is normally expressed by quoting
Ka values. The smaller the Ka value, the
weaker the acid.

• pKa is used to measure the strength of an acid

in solution, where pKa is the acid dissociation
constant at logarithmic scale. pKa is the
negative log of Ka.

pKa = -log Ka
• The pKa for acetic acid is 4.75.
• There is an inverse relationship between
the magnitude of the pKa and the strength
of acid. The smaller the value of pKa, the
stronger the acid.

• The unit of Ka is mol dm-3 while pKa has no

unit.
• The values of pKa for some acids are given
in the next slide.
Stronger acid
 Predicting the Strength of Bases
• The stronger the acid, the weaker its
conjugate base will be. An acid with a low
pKa will have a weak conjugate base.
• Chloride is a very weak base because its
conjugate acid HCl is a very strong acid.
• Example:
+
RNH2 + H2O RNH3 + OH-
base acid conjugate conjugate
acid base

• The primary amine, RNH2 reacts with

water to form the alkylammonium ion
(RNH3+) and the hydroxide ion.

• Primary amine is a base because it accepts

a proton from water which act as acid.
• The base dissociation constant (Kb) and pKb
are: [RNH +] [OH-]
3
Kb = mol dm-3
[RNH2]

pKb = -log Kb

• The larger the value of Kb, the greater is the

tendency of amine to accept a proton from
water, and the greater will be the
concentrations of RNH3+ and OH- in the
aqueous solution. The smaller the value of
pKb, the stronger the base.
 Predicting the Outcome of
Acid-Base Reactions

• The acid-base reaction always favors the

formation of the weaker acid/weaker base
pair.

• The weaker acid/weaker base is always on

the same side of the equation.
• Example: Acetic acid reacts with sodium
hydroxide to greatly favor products.

• Thus, the stronger the base, the weaker its

conjugate acid.
• The weaker the base, the stronger its
conjugate acid.
Acidity increases from left to right in a row of
the periodic table.
 Most electronegative

Most stable

Strong acid

Strong base
• The hybrids are defined by the p to s ratio of the contributing orbitals.
• Thus, an spm hybrid is composed of m+1 parts: one part of s and m parts of p.
• For example, an sp3 hybrid has ¼ (25%) of s and ¾ (75%) of p.
• This fraction is called an s (or p) character of the orbital.
• Thus, an sp3 hybrid has 25% s character.

Note: Electronegativity is directly proportional to s character as it is directly

proportional to the closeness to the nucleus of its last orbital.
• The hydrocarbon is viewed as a proton donor.
• In alkanes, the Carbon atom is sp3 hybridized, sp2 in alkenes, and sp in
alkynes.
• Now, the more the s character, the more the electronegativity of the
carbon.
• The more the electronegativity, will be the more acidity as the release
of H+ becomes easier.

• S character is highest in alkynes, then in alkenes, and least in

alkanes.
• As a result, the order of acidity from greatest to least is:
• Alkynes>Alkenes>Alkanes