Organic Chemistry (As)

Organic chemistry is the chemistry of carbon

compounds with carbon-carbon covalent
bonds..

Carbon forms a vast number of compounds

because it can form strong covalent bonds with
itself.

Carbon always forms 4 covalent bonds, which

can be single,double,
Or Triple Covalent bonds
 Ways of representing
organic molecules

1) Molecular 2) Empirical 3) Structural 4) Displayed 5) Skeletal

Formula Formula Formula formula Formula
It gives the It tells us about It is a way of It is a simplified
It gives the simplest whole how atoms are representing all version of the displayed
actual number number ratio bonded to each the bonds formula with all the
of each type of the different carbon atom in within a symbols for carbon
of atom in the atoms in the the molecule molecule as a and hydrogen removed
molecule. molecule. 2D model. and the C-H bonds
Eg: Eg: propene has Eg: Propene removed.
Eg: Propane – propene(C3H6) stuctural Eg: Butan-2-ol
C3H8 has empirical formula
formula CH2 CH3CH=CH2
 Isomerism
Types of isomerism

Compounds with same molecular Stuctural Isomers are compounds with Stereo Compounds with same structural and
molecular formula but with different
formula but different structural formula Isomerism the same molecular formulaIsomerism arrangements of groups in space
but with different structures.

Functional
Position Chain Geometric
group Optical
Isomerism isomerism Isomerism Isomerism Isomerism
 Stuctural
Isomerism

Position Functional group Chain

Isomerism isomerism Isomerism
In position isomerism it In this type of In this type of
is the location of the isomerism, the isomerism, the
functional group that compounds have structure of the carbon
varies in each different functional chain is different and
isomer.They have the groups to each other they have the same
same molecular and they have the same molecular formula.
formula molecular formula.

Eg: Molecular formula: C3H6Br2

Eg: Molecular formula: C3H8O Eg: Molecular formula: C4H10
 Types of isomerism
Compounds with same structural an
molecular formula but with differen
arrangements of groups in space

Compounds with same molecular Stuctural Stereo

formula but different structural formula Isomerism Isomerism

Functional
Position Chain Geometric
group Optical
Isomerism isomerism Isomerism Isomerism Isomerism
 Stereo
Isomerism

Geometric Optical
Isomerism Isomerism
Geometric isomerism A carbon atom attached
arises due to the to 4 different groups is
restricted free rotation of known as a chiral
the Carbon=Carbon centre.If a molecule has a
double bond.There also chiral centre,it can form 2
should be 2 different non super-imposable
groups attached on either isomers.
side of the 2 carbons.
Same molecular formula. Eg:

Eg:
 Naming Organic compounds
Number of Stem used
Carbon atoms in naming (Prefix) Examples

1 Meth- Methanol , Methane

2 Eth- Ethanol , Ethane

3 Prop- Propanol, Propane

4 But- Butanol , Butane

Nomenclature 5 Pent- Pentanol , Pentane

(Sytem of naming)
6 Hex- Hexanol , Hexane

7 Hept- Heptanol , Heptane

8 Oct- Octanol , Octane

9 Non- Nonanol , Nonane

10 Dec- Decanol , Decane

 Naming Organic compounds
Functioal Stem used
Group in naming (Suffix) Examples

Alkenes -ene Methene , Ethene , Pentene Functioal Stem used

Group in naming (Suffix) Examples
Halagenoalkane Chloro- Cloromethane ,
Fluoro- Bromoethane , Iodopentane
Iodo- Nitrile -nitrile Octanenitrile, Butanenitrile
Bromo-

Aldehyde -al Ethanal, Propanal, Butanal

Alcohol -ol Ethanol, Propanol , Butanol Look at the spelligs very

carefully. Don’t miss a letter
Ketone -one Propanone,Butanone when naming.

Carboxylic acid -oic (Not oink) Ethanoic acid , Propanoic

acid
Ester Alkyl , -ate Ethyl methanoate , Propyl
butanoate
Amine Alkyl , -amine Ethyl amine,Propyl amine
 Naming Organic compounds
3) If there is more than one of
the same alkyl side-cahin
groups or functional groups,
1) Select the longest 2) Number this chain in such a
continuous carbon way that if an alkyl or functional Di (for 2), Tri(For 3) or
chain in the given groups are present,the carbon Tetra (For 4) is added in the
molecule and circle it. attached to this alkyl group front of the name. Adjacent
Eg: Longest is 6 carbons
receives the lowest number. numbers have a comma
Eg: between them and letters and
numbers are separated by a
Longest is 6 carbons hyphen.
Methyl groups
Longest is 6 carbons
Methyl Alkyl group
Eg: The side chain is named by CH3 CH3
putting ‘yl’ to the alkane stem
1 2 3 4 5 6
CH3 CH2 C CH CH2 CH3
CH3 CH CH2 CH3 Counting from right to left gives :
4-methylhexane.(Wrong for this compound) CH3 Methyl group
CH2CH2CH3
Counting from left to right gives : Name: 3,3,4-trimethylhexane
It is 3,3,4 because there are 3 identical
3-methylhexane.(Correct for this compound) alkyl groups and its trimethyl because
Longest is 5 carbon the 3 identical are methyl groups.
 Naming Organic compounds

4) If there is more than 1

Naming compounds
type of alky chain, Examples Longest chain,6 carbons
(like 1 propyl and 1 methyl CH3
group in a molecule,) they Draw the structure with 1 2 3 4 5 6 Name:
atoms for ease for this CH3 C = CH CH2 C CH3
are listed in alphabetical skeletal formula 2,5,5-trimethylhex-2-ene
CH3 CH3
order.(Ask Ms whether you
get marks if you don’t list it
3 identical methyl groups
in alphabetical order.)
Longest chain,6 carbons END Name:
CH3 2-propylpent-1-ene
6 5 4 3 2 1 Propyl alkyl group
CH3 CH2 CH CH2 CH CH3 5 4 3 2 • It’s ‘2-propyl’ because the
CH3 CH2 CH2 C CH2 CH2 CH3
CH2CH3 propyl group is on the 2nd

=
1 CH2 carbon.
Name: 4-ethyl-2-methylhexane
• It’s ‘pent-1-ene’ because there
Ask Ms if 2-methyl-4-ethylhexane are 5 carbon atoms in the
is corect. Longest chain ,5 carbons long chain (Pent) and the
alkene group is on the 1st
 Hydrocarbons
They are compounds made of
Carbon and hydrogen ONLY

Types of Hydrocarbons

Alkanes Alkenes
• Simplest hydrocarbon with no
• They are compunds with the
functional group
• They have limited reactions general formula CnH2n
compared to other organic • They are Unsaturated(cotaining
• All bonds In the alkane molecule double bonds) hhydrocarbons.
compounds.
are simple covalent. R is an atom or
groups of atoms
• They have general formula CnH2n+2 • They are more reactive than alkanes
because alkenes have a pi bond
 Alkanes
1) Hydrogenation of 4) Free radical
alkene 3) Combustion of alkanes
(Addition reaction)
substitution
Pt/Ni Complete combustion:
Alkene + H2
Catalyst
Alkane 2)Propagation
3)Termination
•1) Initiation 2) Cracking
It is a reaction in whichlargea hydrogen atom gets Alkane + Oxygen CO2 + H2O
Heat
substituted hydrocarbons
by a halogen (Clorine or bromine ) (Excess)
•• InThethis
freestep,the
radicalsCl-Cl
formed are very
or Br-Br reactive
bond and by
is broken will attack
Eg:the
• This alkanes.
unreactive is whenEg:the chain reaction stops due
Eg: Butane from But-1-ene U.V lightAl. O
Large toCatalyst
2 free radicals reacting together and
2 3

• ULTRAVIOLET
• Hydrocarbon
This produces light (sunlight)
Alkane
2 radicals + Alkene is needed
in a homolytic for thisreaction
fission reaction(a
forming
Heat a single unreactive molecule.
in which both the species at each end of the bondIncomplete leaves with onlycombustion:
reaction.
• A1 electron
C-H bond breaks homolytically
Hydrogenation is used to make from the pair that formed(each atom getsbond.)
the covalent an electron
Alkane + Oxygen CO + H2O
Steps from
Eg: the covalent
Octane and pair
Ethene, forming
from an alkyl free radical .
margarine and vegetable oil. (insufficient) Carbon
decane Eg: Monoxide
:•
This can attack another Chlorine / Bromine molecule to form the
halagenoalkane and regenerate the Chlorine / Bromine free
Initiationradical. Eg: Propagation Termination
 Alkenes

1) Hydrogenation of 3) Alkenes from

2) Alkenes from elimination dehydration reaction
alkene
(Addition reaction) reaction Al2O3
Pt/Ni Or Conc. H2SO4
Alkene + H2
Catalyst
Alkane Halagenoalkane + NaOH Alkene + water +NaX Alcohol Catalyst Alkene + Water
(Ethanolic) Heat
Heat Heat
X=Halogen
Eg:
Eg: Butane from But-1-ene Eg:

Hydrogenation is used to make

margarine and vegetable oil.
 Alkenes
Electrophilic addition
5) Alkenes reaction
4) Alkenes reaction with
steam reactions ofwith Hydrogen halides
alkenes
1-bromopropane 2-bromopropane

H3PO4(Phosphoric acid) It is the addition of an electrophile(Electron loving

Catalyst species).
Alkene + H2O(g) Heat
Alcohol
Propene
Hydrogenation This is the minor This is the major
product because product because
Eg:
OH H The is a The is a
H H H3PO4 Catalyst Reaction with steam (H2O)
secondary
H
C C
H
+ H2O(g) H C C H primary
Heat halagenoalkane halagenoalkane
H H
Ethene and is not(HX)
Reactions with Hydrogen halides very and is more stable
Ethanol
stable. than 1-
Bromopropane
Reactions with Halides (X2)
 Alkenes

Electrophilic addition mechanism of Alkenes for

reactions with Hydrogen Bromide.
H-Br is a polar molecule as Hydrogen and Bromine atoms have different
electronegativities.

So the Bromine atom has a stronger pull on the electrons in the H-Br bond

This causes a partial charge seperation in the molecule.

Pulls electrons strongly
towards it
Electr e-
ophile
electro It has a low .
negat er H e- Br
is elec ivity than B
tron d r
efficie so it
nt.
 Alkenes

Electrophilic addition mechanism of Alkenes for

reactions with Hydrogen Bromide.
In an addition reaction,the H atom acts as an electrophile and accepts a pair of
1)
electrons from the C-C bond in the alkene.The H-Br bond breaks heterolytically
Forming Br- C C

H Br
Electrophile

2) The above step results in the formation of a highly reactive carbocation

intermediate which reacts with Br- (nucleophile)
 Alkenes

Electrophilic addition mechanism of Alkenes for

reactions with Hydrogen Bromide.
Example reaction mechanism: Propene with HBr
Secondary carbocation.(More stable than primary)

H H H H H H H H H
H C C C H H C C C H H C C C H
+
H H H H Br H
Br -
2-bromopropane (Major product)
H Br
 Alkenes

Electrophilic addition mechanism of Alkenes for

reactions with Bromine.
Bromine is a non-polar molecule as it has 2 identical atoms(Br-Br)
1)

But when the Bromine molecule gets closer to the double bond of an alkene , it
2)
repels the electron pair in Br-Br away from the closest Br atom causing a slight
charge seperation.
 Alkenes

Electrophilic addition mechanism of Alkenes for

reactions with Bromine.
In an addition reaction the closest Br atom acts as an electrophile and accepts a
3)
pair of electrons from the C-C bond in the alkene.(Br-Br bond breaks
heterolytically.)

Example reaction mechanism: Ethene and Br2

H H H H
H H
C C H C C H H C C H
H H +
Br Br Br
Br Br
Br-
Electrophile
 Alkenes
7) Oxidation
6) Alkenes reaction with 1)2)With
WithCold
Hot dilute
concentrated
KMnO4KMnO4
Halogens
Eg:
Eg: If this segment is present in the The other segment is double
molecule, Carbon dioxide and bonded to oxygen as follows.
water are produced along with O
another compound.

=
C
(KMnO4)

Colour change: PURPLE COLOURLESS

for reaction
Heat and distill

Heat
under
reflux
 Alkenes
8) Testing for unsaturation
(This is also a test to differentiate between alkenes and alkanes)

Add Bromine water to both alkane and

alkene solutions at room temperature.

If the Bromine water decolourises , then

an alkene group is present,meaning that
the molecule is unsaturated.
Eg:
 Alkenes

Stability of carbocations and

Markovnikov’s rule
Positive inductive effect.
Carbocations are + charged carbon atoms with
Since the alkyl groups push instead
electronsoftoward the + charged carbon
The alkyl onlygroups 3 covalent to the + charged
attachedbonds 4.carbon atoms are called
donating groups’.causes the carbon atom to become less + charged.
atom(carbocation),it
‘electron
Eg: H H H
There the
This causes are 3charge
types oftoCarbocations:
+
be more spreaded and causes Eitlectotronbedonating
H C C C C H
natingmore stable. up
Electron do
energetically This means that tertiary carbocations Methyl groare more
ro up
Ethyl g than primary carbocations.
stable H H H H Only 1 electron donating alkyl
group so it’s least stable as the
charge is distributed less across
Stabilty: R=Alkyl group the carbocation.
The attached alkyl groups push electrons towards the + charged carbon
There are 3 alkyl
Electron donating alkyl
atom. Primary e- e
Secondary
-
Tertiary
groups. Due to electron
e
Carbocation
- >e- e -
e- e-
> Carbocation
repulsion in alkyl
e- Carbocation
e e- e
- -
groups,the charge will be
Distributed more around
e--
the carbocation Tertiary e Secondary Primary
Carbocation Carbocation
 Alkenes

Stability of carbocations and

Markovnikov’s rule

Markovnikov’s rule

In addition reactions,an electrophile reacts with a double bond of

alkenes
Eg:

The electrophile will add to the carbon atom in such a way that it gives the
most stable carbocation(major product) or least stable(minior product)
 Alkenes

Stability of carbocations and

Markovnikov’s rule

Markovnikov’s rule
So the nucleophile will bond to the C-C atom which has the highest
number of alkyl groups bonded to it (This gives major produt)

This is Markonikov’s law.

In basics: Markonikov’s rule states that in the addition reaction

of a Halogen Halide(HX) to an alkene, the halogen(X) attaches
itself to the carbon atom with the most number of Hydrogen
atoms.
 HALOGENOALKANES

They are alkanes which have one or more halogens bonded.

They can be produced from :

• Free radical substitution of alkanes (UV light needed) Done on
previous
• Electrophilic addition of alkenes slides.

• Substitution of an alcohol
 HALOGENOALKANES
By substitution of Alcohols :
 HALOGENOALKANES

Classifying halagenoalkanes:
Decreasing stabilty

Most stable
> >
Least stable
TERTIARY SECONDARY PRIMARY
Halagenoalkane Halagenoalkane Halagenoalkane
X = Halogen( F , Cl ,Br , I)
 HALOGENOALKANES

Substitution reactions of
halagenoalkanes:
Halagenoalkanes are more reactive than alkanes due to the presence
of electronegative halogens.(Halogen-carbon bond is polar)

A Nucelophilic substitution is a reaction in which a nucleophile

attacks a carbon atom which carries a partial positive(+) charge
* Nucleophiles are electron rich species which carry a negative charge(or partial
negative charge), capable of donating a pair of electrons. Eg: OH- , CN-
Partial positive Partial negative charge
charge
C X
Carbon has a low
electronegativity Polar bond X = Halogen ( F , Cl ,Br ,
I)
 Reaction with KCN :
Reaction with NaOH (hydrolysis):
Nucelophile here is CN- ion
When reacted with Aqueous
alkali,it forms an alcohol Ethanolic solution of KCN is
The aquesous OH- behaves as a heated under reflux with the
nucleophile and replaces the halogen halagenoalkane
Eg: Eg:

Heat under Heat

reflux Under reflux
*note that an extra carbon is added to the chain.
HALOGENOALKANE’S
REACTIONS(Nucelophilic subs.)
Reaction with Aqueous silver nitrate
(AgNO3) : Reaction with NH3 :
It is a nucleophilic subs. reaction with H2O molecules Nucelophile here is NH3 molecule
in AgNO3 solution.This is also a hydrolysis reaction.
An ethanolic soution of excess
Eg: ammonia is reacted with the
halagenoalkane under pressure.
Heat
Under pressure
Reaction with NaOH (Ethanolic):
When heated with ethanolic
Alkali, C-X bond breaks
heterolytically

Eg:

HALOGENOALKANE’S
REACTIONS (Elimination)
 HALOGENOALKANES
SN1 and SN2 Mechanisms:
In nucleophilic substitution of halagenoalkanes, the reaction can
occur in 2 ways(SN1 and SN2) depending on the structure of the
halogen involved.

SN1 mechanism: SN2 mechanism:

• ‘S’ : Substitution • ‘S’ : Substitution

• ‘N’ : • ‘N’ :
Nucleophilic Nucleophilic
• ‘1’ : (Unimoleceular) • ‘2’ : (Bimoleceular)
only 1 reagent(the 2 reagents decide
halagenoalkane) the rate of reaction: the
determines the rate. nucleophile ion conc. and
halogenoalkane conc.
It is a 2 step reaction undergone by It is a 1 step reaction undergone by
Tertiary Halogenoalkanes. Primary Halogenoalkanes.