ORGANIC CHEMISTRY

1. Chemistry of Carbon
 Introduction
 Organic chem. = study of carbon compounds
except CO, CO2 and metal carbides.
 Characteristics of carbon:
1. Group 14 element . Has 4 valence electrons
2. Achieves octet configuration thru sharing of
electrons = covalent bonding.
3. Forms 4 covalent bonds = single, double or
triple.
 Characteristics of organic
compounds
1. Low melting points and boiling points due to
weak van der Waal forces between molecules.
2. Low molar heat of fusion and vapourisation.
3. Dissolves in non polar solvents such as
benzene & methylbenzene.
4. Molecules with OH , COOH or NH2 groups may
dissolve in water.
5. May contain more than one functional group.
 Bonding Of the Carbon Atom
Carbon undergoes hybridisation.
1.sp3 hybrid orbitals = shape tetrahedral
angle = 109.50, 4 single bonds
2. sp2 hybrid orbitals = trigonal planar
angle = 1200 , double bonds
3. sp hybrid orbitals = linear
angle = 1800 , triple bonds
 Examples of orbital hybridisation
sp3 hybridisation
Alkanes – methane , ethane etc.

sp2 hybridisation
Alkenes – ethene. Butene etc.
- sigma bond & π bond
sp hybridisation
Alkynes – ethyne (C2H2) 1 sigma bond & 2 π
bond
 Benzene C6H6

- Undergoes sp2 hybridisation

- Flat and symmetrical molecule
- Contains delocalised electrons, all the
carbons lie in the same plane.
- 2pz orbitals overlap forming a continuous π
molecular orbital above and below the ring
structure.
- Bond length = 0.139 nm
- Angle = 1200
 Structure of Benzene

H H
C C
H C C σ H

C σ C
Bond length =
H H 0.139nm
 Structures of benzene
-1st cyclic structure proposed by Kekule
H H
C C
H- C C-H
C C
H H
Canonical
forms
Benzene exist as a resonance hybrid of
these 2 canonical forms, represented by:
 General, empirical, molecular and
structural formula
1.General formula is a common formula used for a
homologous series , example
alkanes = CnH2n + 2
alkenes = CnH2n
alcohol = CnH2n + 1 OH
2. Empirical formula
-simplest formula that shows the simplest mole ratio
of the no. of atoms of each element present in the
molecule.
- determined from the % of composition
3. Molecular formula
contains the actual no. of atoms of each
element in a molecule of a compound.

molecular formula = n x empirical formula

-n is calculated if relative molecular mass

is known.
n = relative molecular mass (Mr)
formula mass of empirical formula
 Structural formula
- formula which shows how the atoms are
arranged and bonded together.
- can be written in many ways.
i) Shorthand
ii) Displayed
iii) Ball and stick model
iv) Space filling model
v) 3 dimensional struture
vi) Skeletal formula
Examples of structural formulas for butane
(C4H10)
Shorthand = CH3CH2CH2CH3
Displayed H H H H
H–C–C–C–C–H
H H H H

Other structures = refer to CD.

 Calculations
1. An organic liquid, X has the composition
52.2% C, 13% H and 34.8% of oxygen by
mass. When 0.10g of liquid X was
vapourised at 900C and 101 kNm-2
pressure, the volume of vapour produced
was 64.9 cm3. Calculate the
(i) empirical formula
(ii) molecular formula of liquid X.
 Organic Cmpounds
Nomenclature
 Identify the longest continuous chain of carbons
in which the functional group(s) are attached to
one of the carbons in the chain.
 Number the chain so that the functional group(s)
are attached to the lowest numbered carbons.
 Identify and locate the other branches on the
chain so that they are named alphabetically and
their carbon number is hyphenated onto the front
of the name. If more than one of the same group
is present use the greek prefix attached to the
branch name. (di=2, tri=3, etc)
 After all the branches have been named
and located then attach the carbon
number that is attached to the functional
group onto the alkane name associated
with the number of carbons found in the
continuous chain in step 1
 drop the "e" on the alkane name and
attach the characteristic IUPAC ending
with the respective name for the
functional group to the rest of the alkane
name. Eg : -ol for alcohol
 Classification based on
Functional Groups
Types of Structure of Prefix / Example
compound Functional suffix
group
Alkane CH3 – CH2 - -ane butane

Alkene CH2= CH2 -ene ethene

Alcohol - OH -ol C2H5OH

Types Functional Prefix / Example
group suffix

Carboxylic -COOH -oic acid Ethanoic

acid acid

Carboxylate -COO- -oate Sodium

ion ethanoate

Ester -COO- oate Ethyl

ethanoate
Types Functional Prefix / Example
group suffix

Acid -COO-CO -oic Ethanoic

anhydride anhydride anhydride
aldehyde - CHO -al ethanal

Ketone C=O -one propanone

Ether -C-O-C- Ethoxy- ethoxyetha
ne
haloalkane -Cl / -Br / -I Chloro- / chloroethan
bromo- / e
iodo-
Types Functional Prefix / Example
group suffix

Acyl -COCl -oyl Ethanoyl

chloride chloride chloride

Amine -NH2 -amine or ethylamine

amino

Amide -C(NH2)O -amide propanamide

Nitro -NO2 nitro- nitrobenzene

 Isomerism
Isomers
= organic compounds that have the same
molecular formula but different
arrangement of atoms.

Types of isomers

Structural isomerism Stereoisomerism

 Structural Isomerism
1. Chain isomerism
= different carbon chains – straight chain
- branched chain
Eg: Butane
CH3CH2CH2CH3
CH - CH – CH
3 3

CH3
2-methyl propane
Pentane – how many isomers?
2. Position isomerism
- Same carbon skeleton, belongs to the same

homologous series but differ in the position of

the functional group.
Eg: alcohol – propanol
Isomers propan-1-ol and propan-2-ol
-position is important for aromatic compounds
3. Functional isomerism
- Shown by the same molecular formulas but

different functional groups.

Eg : C3H6O

CH3COCH3 CH3CH2CHO CH2=CHCH2OH

Ketone aldehyde alcohol
Propanone propanal propenol
 Stereoisomerism
Same molecular formula but different spatial
arrangements of their atoms.
- 2 categories = geometrical isomerism
= optical isomerism
Geometrical isomerism
-also known as cis-trans isomerism.
- Happens in compounds with
(i) Double bonds - rotation not possible
(ii) Ring structure
- Have distinctive physical properties
 Cis-trans isomerism
Example : 1,2-dibromoethane (C2H4Br2)

Br Br
Br H
C=C
C=C
H H
H Br
Cis 1,2-dibromoethane
Trans 1,2-dibromoethane
m.pt = -53 C b.pt =110 C
0 0
m.pt = -90C b.pt = 1080C
 Physical Properties of geometrical
isomers
a) Cis isomers- usually lower melting point ;
because
- molecular structure less symmetrical
- cannot be closely packed in the crystal lattice.
- reduces the contact between molecules
- attractive forces reduced
b) Cis isomers usually have higher boiling point because
- compound is more polar
-attractive forces between molecules increases
Trans isomers – dipole moment = 0 because structure
is symmetrical
 Chemical Properties
Chemical properties are similar because of
the same functional group.
BUT
It can differ due to spatial arrangements.
Eg : Cis-butenadioic acid forms anhydride
acid on heating but trans doesn’t because
the COOH group is far apart.
H COOH H O
C C C
O + H2O
C C C
H COOH H O
 Optical Isomerism
Any carbon atom with 4 different atoms or
groups attached to it is assymetric.
- Assymetrical atoms/molecules are known
as chiral atoms
H H

C C
CH3 HC
3

HO COOH HOOC OH
mirror plane
The central atom is asymmetric.
Whether the molecule is rotated, twisted or
turned, it cannot superimpose on its mirror
image.
The mirror images are isomers and called
enantiomers.
A mixture containing equal no. of moles of each
enantiomer is called a racemic mixture.
Separation of racemic mixture into 2 pure
enantiomers is known as resolution.
Enantiomers have the same physical and
chemical properties except optical activity.
 Optical Activity
Waves of a ray of normal light vibrate in
all directions at right angles ti the direction
in which the ray is travelling.
Light which vibrates in one plane is called
plane polarised light.
Compounds which can rotate plane
polarised light is optically active.
Enantiomers exhibit this property.
Clockwise rotation = dextrorotation (+)
Anti clockwise rotation = laevorotation (-)
Optical isomerism is important in biological
systems.
Amino acids are optically active, usually
the (+) isomers occur in nature.
chemical activity of each pair of
enantiomers may be different in reactions
with other optically active compounds. For
example : enzyme reactions are
stereospecific.
Nucleophile and Electrophile
Organic reactions are classified in terms of
the type of reagents that attack the
organic molecule.
- 3 types of reagents :
1) nucleophile
2) electrophile
3) radicals
 Nucleophiles
- Ions or molecules which have electron
rich areas.
- either negatively charged ions or have
atoms with a δ- charge.
- Lewis bases because Lewis bases can
donate a lone pair of ē to form a bond.
- compounds that have oxygen and
nitrogen atoms are Lewis bases.
Eg: H2O , NH3 , ROH , RNH2 , CN- , Br- , F- ,
Cl- , I- , CH3- , RO-
 Electrophiles

- ions or molecules which are electron

deficient (+vely charged) or have an
electron deficient atom (δ+) .
- Lewis acids because they can accept
an ē pair.
Eg: H+ , Cl+, Br+, CH3+ , NO2+ , RN2+ , R3C+ ,
AlCl3 , ZnCl2 , FeBr3 , BF3
 Radicals
- they are called free radicals
- species with unpaired electrons
-extremely reactive.
 Reaction Mechanism in Organic
Chemistry

Breaking of Covalent Bonds

Covalent bonds can be broken in 2 ways:
1) Homolytic fission

2) Heterolytic fission
 Homolytic Fission
- the 2 shared electrons are split equally between the
atoms.

-C:C- -C. + .C -

- radicals are produced.

- they are reaction intermediates (exist for a split
second).
- can occur with any type of single covalent bond.
- occur in reactions in the gas phase or non polar
solvents
- reactions are catalysed by light / other radicals
 Heterolytic Fission
- Essentially ionic reactions.
- 2 shared e in the bond are split unequally
between atoms.
- One atom keeps both the e, acquires –ve
charge,
- The other atom has the +ve charge
forming a carbocation / carbonium ion.
- Fission can occur in 2 ways:
 R – C – C – R` R–C- + C – R`
+

carbanion carbocation
- Movement of e is represented by a curly
arrow ;
- C – Cl C+ + Cl-

- takes place in polar solvents.

 Factors that affect breaking /
formation of Bonds
The Inductive Effect
- only for single covalent bonds between unlike
atoms.
- bonds are polarised because different in
electronegativity of the atoms.
Eg : - C – Cl represented by
- Cδ+ – Clδ- or by an arrow,
-C Cl arrow shows carbon atom
repels electrons and chlorine atom attracts the
electrons.
- Cl atom has a higher electron density
than carbon.
- the shift in density is called “inductive
effect”.
-withdrawal of electrons is called
negative inductive effect or –I.
- release of electrons to the carbon atom
is called positive inductive effect or +I
- eg: alkyl groups are +I .
- the effect increases with the number of
alkyl groups.
 Inductive effect
CH3 CH3
CH3 - CH2 - CH - CH3 - C–
CH3 CH3
Primary secondary tertiary

Positive inductive effect increases

 Delocalisation of Electrons
- Shift of electrons can also occur in Π
bonds.
- The shift is known as the resonance effect

or mesomeric effect.
- Eg : aldehyde

H H
C = O C+ - O-
H H
I II
It exist as a resonance hybrid / resonance form
The aldehyde molecule is represented by:
H
Cδ+ O δ-
H
partial double bond
Carboxylate ion:
O O-
R–C R–C
O- O
Carboxylate ion is represented as :
O
R–C -
O
Effect of Structure & Delocalisation of
Electrons on the Relative Strength of
Acids.
Carboxylic acids has 2 functional groups :
- Carbonyl group ( -C=O)

- Hydroxide group (-OH )

Carboxylic acid dissociates easily to form the

carboxylate ion.
O +H2O O
R- C - OH R - C – O- + H3O+

Dissociation is caused by 2 factors :

a) Inductive effect b) delocalised e
The inductive Effect
- Makes it easier to loose a proton, oxygen
is more electronegative.
O
R - C
O - H
- Delocalised electrons at the anion
stabilises the carboxylate ion.
- The anion has less tendency to accept
protons.
- So, carboxylate acids are stronger than
alcohols.
Strength of carboxylic acids is influenced by
substituents on the carboxylic acids.
-If the substituents are electron
withdrawing groups, eg: halogens, it
withdraws electron density from the
carboxylate anion and delocalise the
negative charge.
-this stabilises the carboxylate anion, hence
acidity increases.
Eg: pKa values indicates acidity
pKa = - log Ka
 pKa

CH3COOH + H 2O = CH3COO- + H3O+

Ka = [ CH3COO-] [H3O+]
[ CH3COOH]
Acid pKa
Ethanoic acid 4.74
Chloroethanoic acid 2.87 acidity
Dichloroethanoic acid 1.26 increases
Trichloroethanoic acid 0.63

The effect of the –I group also depends on

the distance of the group from the
carboxylic group.
- if the group is near = effect is greater
- if the group is far = effect is less
Acid pKa
4-chlorobutanoic acid 4.52 acidity
3-chlorobutanoic acid 4.05 increases
2-chlorobutanoic acid 2.86
 Acidity of Phenol & Alcohol

C2H5OH + H2O C2H5O- + H3O+

Ethanol

OH + H2O = O- + H3O+

Phenol
pKa = 10.0
Ethanol , pKa = 16.0 , phenol is a stronger acid
than ethanol because of the delocalised
electrons which stabilises the phenoxide ion.
 Relative strength of Bases
A Lewis base is a proton acceptor,

RNH2 + H2O RNH3+ + OH-

Base acid conjugate conjugate
acid base
Aliphatic amines
Amines are bases = nitrogen has a lone
pair
can form coordinate bond
- Primary amines stonger bases than
ammonia.
- due to the +I effect of the alkyl group,
- stabilises the ion.

CH3 – NH2 + H2O CH3 – NH3+ + OH-

- Secondary amines are stronger than 10

amines because of the increase of the +I
effect .
 pKb Values
Compound pKb Type
NH3 4.74
CH3NH2 3.36 10 amines
C2H5NH2 3.28
(CH3)2NH 3.23 20 amines
(C2H5)2NH 3.07

(CH3)3N 4.20 30 amines

(C2H5)3N 3.36
-30 amines are weaker bases because in
aqueous solutions, 30 amines only form
one hydrogen bond compared to 20
amines. So, it is less soluble.

Aromatic amines
Phenylamine, C6H5NH2 , pKb = 9.30 ,
weaker than ammonia because of overlap
of the lone pair of electrons with the
delocalised pi electrons in the ring.
- Presence of electron releasing substituents
( +I) effect on the ring will
- increase base strength, ion more
stable

- presence of electron withdrawing

substituents on the ring ( -I) effect on the
ring will
- reduce base strength