ORGANIC CHEMISTRY
SOME BASIC PRINCIPLES
AND TECHNIQUES
AND BONDS
TEST YOURSELF
Electronegativity and s- character
Electronegativity
of carbon depends
on its hybridization
state.
Hybrid orbitals having more s
character are
more electronegative because s or
bital is nearer to the nucleus and
hence more attracted by the
nucleus. ... Hence attraction of
electron in a bond towards the
nucleus decreases in the order
sp>sp2>sp3.
Hence electronegativity decreases
in above order.
IDENTIFY CARBONS
STRUCTURAL FORMULA, CONDENSED FORMULA AND BOND
LINE FORMULA
WHAT IS MEANT BY COMPLETE STRUCTURAL
HOW TO WRITE BOND-LINE FORMULAS?
FORMULA?
Complete structural formula shows all the Carbon atoms are depicted not by a
atoms and bonds present in the molecule. capital C, but by a ‘corner’ between two
bonds, or a free end of a bond.
Eg: Open-chain molecules are usually drawn
out in a ‘zig-zig’ shape.
Hydrogens attached to carbons are
generally not shown. Hydrogens bonded
WHAT IS MEANT BY CONDENSED FORMULA? to nitrogen, oxygen, sulfur, or anything
A condensed structural formula is a more compact other than carbon are shown, but are
way of drawing the structural formula of a molecule. usually drawn without showing the bond.
In condensed structural formulas the bonds to each carbon
are omitted, but each distinct structural unit (group) is
written with subscript numbers designating multiple
substituents, including the hydrogens.
Eg: CH3(CH2)3CH2CH=CH2
Write the complete structure, condensed and bond-line formulas of n-butane.
Complete structure Condensed formula Bond-line formula
Write the complete structure, and bond-line formula of CH3CH2CH2COOH.
Complete structure Bond-line formula
A FEW MORE EXAMPLES
Complete structure Bond-line formula Condensed formula Bond-line formula
Bond line formula of
TEST YOURSELF
1. Write bond-line formulas for:
a. Isopropyl alcohol b. 2,3-Dimethylbutanal c.Heptan-4-one.
2. Give the condensed structural formulas for the following
compounds:
a. 2, 2, 4-Trimethylpentane
b. 2-Hydroxy-1, 2, 3- propanetricarboxylic acid
c. Hexanedial
ANSWERS
1.
a b c
2.
CLASSIFICATION OF HYDROCARBONS
[CΞC]
NOMENCLATURE OF HYDROCARBONS
ALKANES General formula: CnH2n+2 C1H2(1)+2=CH4
where n=1,2,3…
NOMENCLATURE OF ALKENES AND ALKYNES
But-1-ene
Pent-1-ene
Hex-1-ene
Hept-1-ene
Oct-1-ene
ALKYL GROUP(R-):
Alkane- 1H gives alkyl group
METHANE CH4
Methyl CH3-
ETHANE CH3CH3
Ethyl CH3CH2-
PROPANE CH3CH2CH3
n- Propyl CH3CH2CH2-
(H is removed from end
carbon)
iso-Propyl
CH3CHCH3
|
( H is removed from the
middle carbon)
ISOMERISM-
The phenomenon of existence of two or more compounds
possessing the same molecular formula but different
properties is known as isomerism.
Compounds having the same molecular
formula but different structures are
classified as structural isomers.
CHAIN ISOMERS- Differ in the length of the carbon chain.
PLEASE NOTE:
Aldehydes and ketones are
functional isomers
POSITION ISOMERS-Differ in the Position of functional group CH3CH2CHO and
CH3COCH3
Alcohols and ethers are
functional isomers
FUNCTIONAL ISOMERS- Have different functional groups
CH3CH2OH and CH3OCH3
Carboxylic acids and esters
are functional isomers
CH3COOH and HCOOCH3
LET’S POLL
1. An isomer of ethanol is:
a) methanol
b) diethyl ether
c) acetone
d) dimethyl ether
2. The molecular formula C5H12 contains how many isomeric alkanes?
a) 1
b) 2
c) 3
d) 4
ANSWERS
1. An isomer of ethanol is:
a) methanol
b) diethyl ether
c) acetone
d) dimethyl ether
ANS: d
2. The molecular formula C5H12 contains how many isomeric alkanes?
a) 1
b) 2
c) 3
d) 4
ANS: c
Explanation: n-pentane, 2-ethylpropane, and 2-methylbutane are the 3 isomeric
alkanes of C5H12 (pentane)
Metamerism
This type of isomerism arises due to the presence
of different alkyl chains on each side of the
functional group.
Example: C4H10O can be represented as
ethoxyethane (C2H5OC2H5) and methoxy-propane
(CH3OC3H7)
2,2,4-Trimethylpentane 2,4,4-Trimethylpentane
Set of locants-2,4,4(incorrect)
Set of locants-2,2,4(correct) (2+4+4=10)
(2+2+4=8)
IUPAC NOMENCLATURE OF ORGANIC COMPOUNDS-
SOME IMPORTANT FUNCTIONAL GROUPS
ALCOHOLS ALDEHYDES CARBOXYLIC ACIDS
Alkane-e and add the suffix –ol Alkane-e and add the suffix-al Alkane-e and add the suffix -oic acid
Methane-e + ol =Methanol Methane-e+ al=Methanal Ethane-e + oic acid=Ethanoic acid
CH3OH HCHO CH3COOH
KETONES AMINES ESTERS
Alkane-e and add the suffix –one
Alkyl group (R’) +Carbon chain from the acid +
Propane-e + one= Propanone Alkane-e and add suffix suffix ‘oate’
amine CH3COOCH2CH3 Ethyl ethanoate
CH3CH2NH2 Ethanamine R R’
Ethers Halogens
Alkane + prefix alkoxy Alkane + prefix halo
CH3OCH3 Methoxymethane CH3Cl Chloromethane
CH3OCH2CH3 Methoxyethane
EXAMPLES
CH3-CH2-C-CH2-CH2-CH2-CH3 CH3-CH2-CHO
|| Propanal
O
Heptan-3-one
CH3-CH2-CH-CH2-CH3 CH3-CH2-CH2-COOH
| Butanoic acid
OH
Pentan-3-ol CH3-CH2COOCH3
Methylpropanoate
CH3-O-CH2CH2CH3
Methoxypropane
NOMENCLATURE OF COMPOUNDS HAVING MORE
THAN ONE FUNCTIONAL GROUP OF THE SAME KIND
Alkane + position of the groups + number of groups(as di/tri/tetra) +
suffix
H2NCH2CH2NH2 CH3CO CH2CH2 COCH3
Ethane-1,2-diamine Hexane-2,5-dione
NOMENCLATURE OF COMPOUNDS HAVING TWO DIFFERENT
FUNCTIONAL GROUPS
The order of decreasing priority for some functional groups is:
-COOH, –SO3H, -COOR (R=alkyl group), -COCl, -CONH2, -CN,-HC=O,
>C=O, -OH, -NH2, >C=C<, -CΞC-
CH3CCH2CH2COOH
||
O
3-Hydroxybutanal 4-Oxopentanoic acid
4-Chloropent-2-enoic acid
IUPAC NOMENCLATURE OF AROMATIC COMPOUNDS
Methylbenzene Hydroxybenzene Aminobenzene
EXAMPLES FOR PRACTICE
Benzene-1,4-dicarboxylic acid
2,4,6-Trichlorophenol Phenyl ethanoate
WHEN SIDE CHAIN HAS A FUNCTIONAL
GROUP,SIDE CHAIN WOULD BE THE
PARENT COMPOUND
2-Methyl-1,3,5trinitrobenzene
Lowest sum rule-1+2+3+5=11(correct)
1+3+5+6=15(incorrect)
NOMENCLATURE OF ALICYCLIC COMPOUNDS
2-
Alicyclic compound
with sidechain having
functional group
QUESTION TIME…
1. The IUPAC name of the compound
a) 3,3- dimethyl -1- hydroxycyclohexane
b) 1,1 – dimethyl -3- cyclohexanol
c) 3,3- dimethyl -1- cyclohexanol
d) 1,1 – dimethyl -3- hydroxycyclohexane
2. The systematic name of CH3-CHBr-CH2OH is
a) 3-hydroxy-2-bromopropane
b) 2-bromopropanol-1
c) 2-bromo-3-propanol
d) 3-hydroxy isopropyl bromide
3. The IUPAC name of CH3C ≡ N is
a) Acetonitrile
b) Ethanenitrile
c) Methyl cyanide
d) Cyanoethane
QUESTION TIME…
1. The IUPAC name of the compound
a) 3,3- dimethyl -1- hydroxycyclohexane
b) 1,1 – dimethyl -3- cyclohexanol
c) 3,3- dimethyl -1- cyclohexanol
d) 1,1 – dimethyl -3- hydroxycyclohexane
ANS: a
2. The systematic name of CH3-CHBr-CH2OH is
a) 3-hydroxy-2-bromopropane b) 2-bromopropan-1-ol
c) 2-bromo-3-propanol d) 3-hydroxy isopropyl bromide
ANS: b
3. The IUPAC name of CH3C ≡ N is
a) Acetonitrile b) Ethanenitrile
c) Methyl cyanide d) Cyanoethane
ANS: b
Fission of Covalent Bonds
A covalent bond can undergo fission in
two ways:
(i) By Homolytic Fission or Homolysis
(ii) By Heterolytic Fission or
Heterolysis
Homolytic Fission: Homolytic fission is where each atom of
the bond keeps an electron each resulting in species called
free radicals.
Heterolytic Fission: In this process one of atoms
acquires both of the bonding electrons when the bond is
broken.
If B is more electronegative than A which thereby aquires
both the bonding electrons and becomes negatively
charged.
The products of heterolytic fission are ions.
Reaction Intermediates
Heterolytic and homolytic bond fission results in the formation of
short-lived fragments called reaction intermediates.
The important reaction intermediates are carbonium ions, carbanions,
carbon free radicals and carbenes.
Carbonium Ions (carbocations): Organic ions which contain a positively
charged carbon atom are called carbonium ions or carbocations. They are
formed by heterolytic bond fission.
where Z is more electronegative than carbon.
Carbanion
Organic ion which contains a negatively charged carbon atom are called carbanions.
They are also formed by heterolytic bond fission.
Where Z is less electronegative than carbon.
A primary carbanion is more
stable than a secondary,
which in turn is more stable
than a tertiary, because of +I
effect associated with alkyl
group.
ELECTROPHILES AND NUCLEOPHILES
Electrophile( electron seekingE+): It is positively charged or neutral
species which is electron deficient, e.g.,
CH3+ , NH4+, AICl3 , S03 etc.
Nucleophile(nucleus seeking NU:)It is negatively charged or neutral
species with lone pair of electrons e.g.,
(HO–), Cyanide CN-, H20: R3N, R2NH etc.
Electron Displacement Effects in Covalent Bonds
Electronic displacements in covalent bonds occurs under the
influence of an atom or a substituent group or in the presence of an
attacking reagent.
These lead to a number of effects which are as follows:
(i) Inductive effect
(ii) Electromeric effect
(iii) Resonance or Mesomeric effect
(iv) Hyperconjugation effect.
INDUCTIVE EFFECT
When a covalent bond is formed between atoms of different electronegativities,
the electrons are displaced towards the more electronegative atom.
This introduces a certain degree of polarity in the bond.
The more electronegative atom acquires a small negative charge (δ–). The less
electronegative atom acquires a small positive charge (δ+).
The inductive effect of C3 upon C2 is significantly less
than the effect of the chlorine atom on C.
Atoms or groups which lose electrons towards a carbon atom are said to have a +I
effect. Those atoms or groups which draw electrons away from a carbon atom are
said to have a -I Effect.
Some common atoms or groups which cause +I or -I effects are shown below:
ACID STRENGTH OF CARBOXYLIC ACID
Electron releasing Electron withdrawing
groups near carboxyl groups near the
group decrease the acid carboxyl group
strength of carboxylic increase the acidity
acid due to + I effect due to –I effect
Order of acid strength of substituted carboxylic acids with
reference to inductive effect
ORDER OF ACID STRENGTH OF CARBOXYLIC ACIDS REASON
More the number of electron releasing groups
HCOOH> CH3COOH>(CH3)2CHCOOH>(CH3)3CCOOH greater will be the +I effect, hence weaker will be
the acid.
Br3CCOOH>Br2CHCOOH>BrCH2COOH>CH3COOH More the number of electron withdrawing groups
greater will be the –I effect, stronger will be the
acid.
Inductive effect decreases with increase in
distance of electron withdrawing group
from the carboxyl group.
FCH2COOH > ClCH2COOH > BrCH2COOH > ICH2COOH Acid strength decreases as the
electronegativity of halogens decreases in
the order F>Cl>Br>I
Resonance Effect
The polarity produced in the
molecule by the interaction of two π-
bonds or between a π-bond and a
lone pair of electrons present on an
adjacent atom. There are two types
of resonance or mesomeric effects
designated as R or M effect.
Positive Resonance Effect (+R effect):
Those atoms which lose electrons
towards a carbon atom are said to
have a +M effect or +R effect. For
example:
—Cl, —Br, —I, —NH2, —NR2, —OH,
—OCH3
Negative Resonance Effect (-R effect): Those atoms or groups which
draw electrons away from a
carbon atom are said to have a -
M effect or -R effect.
HOMEWORK:
Draw the resonance structures of Phenol and
Benzaldehyde.
The complete transfer of a shared pair of pi
electrons to one of the atoms joined by a
ELECTROMERIC EFFECT multiple bond(double or triple) on the
demand of an attacking agent is called
electromeric effect
Orbital Concept of Hyperconjugation
It involves delocalisation of σ electrons of
C—H bond of an alkyl group which is
attached directly to an atom of unsaturated
system or to an atom with an unshared p-
orbital.
Let us consider CH3CH2 (ethyl
cation) in which the positively
charged carbon atom has an empty
p-orbital. One of the C—H bonds of
the methyl group can align in the
plane of this empty p-orbital and
electron constituting the C—H bond
in plane with this p-orbital can then
be delocalised into the empty p-
orbital as in Fig
HYPERCONJUGATION
.
The positive charge originally on carbon is dispersed to the hydrogen by shifting the bonding
electrons from an adjacent C —H bond to the electron deficient carbon . The structures formed
are called hyperconjugative structures
This way of electron release by assuming no bond character in the adjacent C—H bond is called
No-Bond Resonance or Hyperconjugation.
ORDER OF STABILITY OF PRIMARY, SECONDARY
AND TERTIARY CARBOCATIONS
TERTIARY > SECONDARY > PRIMARY > METHYL
Greater the number of alkyl groups attached to a
positively charged carbon atom more will be the
hyperconjugative structures and hence the stability
increases.
