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/ 19
BASIC PRINCIPLES OF ORGANIC CHEMISTRY
7.1 Introduction
7.2, Tetravalency of Carbon
7.3. Hybridisation and Hybrid Orbitals
7.4 Hybridisation in Carbon Atom and Shapes
of Organic Molecules.
7.4.1 Shape of sp’ hybrid orbitals and
bond
7.4.1.1 Shape of
molecule
7.4.1.2 Shape of ethane molecule
7.4.2, Shape of sp* hybrid orbitals and
bond.
7.4.2.1 Shape of ethene molecule
7.4.3 Shape of sp hybrid orbitals and
bond
7.4.3.1 shape of ethyne molecule
7.5 Functional Groups.
7.6 Homologous Series
7.6.1 Characteristics of Homologous
series
methane
7.7 Ysomerism.
7.7A Structural Isomerism
7.8 Nomenclature of Organic Compounds
7.9 Common and IUPAC Nomenclature of
Organic Compounds.
7.10 Blectronic Displacement (Substitution) in
Covalent Bond,
7.10.1 Inductive effect
7.10.2. Bletromeric effect
7.10.3 Resonance ot Mesomeric effect
7.10.4 Hyperconjugation
7.41 Fission of Covalent Bond
7.12 Eletrophile, Nucleophile, Carbocation or
Carbonium Ion, Carbanion
7.13 Main Types of Organic Reactions
7.1 Introduction
From the ancient times, the minerals, plants
and animals constitute the major important sources
‘of naturally occurring subtances. The compounds
‘biained from minerals ic. from nonlving sources
are called inorganic compounds. The compounds
‘obtained from animals and plants i.e. from living
sources are called organic compounds. Organic
‘compounds are essential (vital) for sustaining the
life on earth, During the ancient time it was believed
that there was some vital force within the living
beings which was needed for the formation of
‘organic compound, In 1828, Friedrich Wohler a
‘German scientist prepared organic compound urea
from inorganic compound ammonium cyanate. So
the ancient belief was rejected, Now 95% organic
substances are synthesised by human beings.
The basic constituent of organic compounds
is carbon. The basic organic compounds in
‘organic chemistry are hydrocarbon. Hydrocarbon
compounds comprise of carbon and hydrogen.
Variety of organic compounds are obtained by
subsitution of one or more hydrogen atoms of
hydrocarbon by elements like nitrogen, oxygen,
sulphur and halogen or by functional groups. So,
in real sense, the organic chemisty consists of
hydrocarbon and large variety of compounds
‘obtained from the subsitution of their hydrogens.
7.2 Tetravalency of Carbon
‘The knowledge of fundamental concepts of
molecular structure helps in understanding and
predicting the properties of an organic compound,
‘Therefore, itis necessary to have the knowledge
and information of the tetravalency of carbon.
The atomic number of carbon is 6 and hence,
the number of electrons in carbon is 6, so
the electronic configuration is 1s* 2s* 2p,' 2p,"
2p,°. Here, the number of electrons ‘in its
‘outermost orbit are four. In order to attain a
stable electronic configuration like inert gas,
carbon atom should either lose four electrons oF ‘gain four electrons. To achieve this, a very large
amount of energy Gonisation enthalpy AH and.
electron gain enthalpy A,H) is required.
Consequently it cannot form C* or C* ion.
However, the carbon atom shares four electrons
‘with some elements and forms four covalent bonds.
So generally the characteristic of carbon to
form four covalent bonds is called tetravalency
of carbon. To explain tetravalency of carbon, in
its electronic configuration having two electrons
‘in 2s orbital, one of its electron from 2s orbital
gets oxcited and enters in empty 2p, orbital.
‘Hence, the electronic configuration of carbon in
excited state is 18%, 2s", 2p,', 2p, 2p). In the
excited state electronic configuration of carbon
outermost orbit has all four electrons unpaired,
‘These four electrons arc in two different typos
of orbitals like s and p orbitals. If these unpaired.
electrons are to form four covalent bonds then
four bonds which are formed cannot be considered
‘equivalent, However, it has been experimentally
established that the four bonds formed by carbon
im the molecules like methane and carbon
tetrachloride are equivalent. The equivalent
character of these four bonds can be explained
by the hybridisation of orbitals of these four
‘unpaired electrons.
‘73 Hybridisation and Hybrid Orbitals
‘When in an atom there are different types
of orbitals having very less energy difference,
then such type of two or more than two orbitals
combine and form same number of orbitals
having simillar shapes and energies which are
‘mown as hybrid orbitals and the process is
mown as hybridisation.
7.4 Hybridisation in Carbon Atom and
Shapes of Organic Molecules
7.4.1 Shape of sp’ hybrid orbitals and.
© bond ; As there is C~C single bond
in compounds of alkane series, the sp?
hybridisation taking place in them can be
explained as follows: In the excited state of carbon
having eletronic arrangement in outermost orbital
from which one 2s type and three 2p type of
and form four hybrid orbitals having equal
‘energies and simillar shape, it is known as sp
‘dination,
Buacied or ===
state
Save? (EITC)
sp" hybridisetion
The four hybrid orbitals having unpaired
electrons of equal energy are arranged
in tetrahedral shape having bond angle 109° 28°
74.11 Shape of methane molecule :
In methane (CH,) molecule the carbon atom
having four unpaired equivalent orbitals,
‘obtained by sp* hybridisation are arranged in a
tetrahedral shape. Here, the angle between any
‘two adjacent hybrid obital is 109° 28". The four
‘orbitals formed by sp° hybridisation of carbon
‘atom which axially overlap with each of the four
1s orbital of four hydrogen atoms containing
‘unpaired electrons with opposite spin to form
four covalent bonds of equal energy strength.
‘Thus, an axially overlapping bond formation by
sharing of the electrons of two valence orbitals
containing unpaired electrons with opposite spin
is called © bond. Hence, the shape of methane
molecule is tetrahedral and the four C-H 6 bonds
have equal energy, the four C-H bonds have
equal bond length of 112 pm and H-C -H
‘bond angle is 109° 28°
a
|
2ey
a
a
possesses
PVE
STS OSES
H H H H
74.1.2 Shape of ethane molecule :
‘The molecular formula of ethane is C,H, and
its molecular structure is CH,-CH, One of
the sp hybrid orbital on each of two carbon [Basic Principles of Organic Chemistry
atoms overlap each other axially by sharing of
‘the unpaired cletrons to form 6 bond. Remaining
three sp hybrid orbitals of both the carbon
overlap with each of the three 1s orbital of
three hydrogen atoms having unpaired eletrons
‘with opposite spin which results in total six
C-H o bonds. In ethane molecule the C-C and
C - Hi bond lengths are 154 pm and 112 pm
respectively and the bond angle is 109 28",
o on. 1"
sQnaetfeo« ee oy
OO O % i
7TA2 Shape of sp? hybride orbitals and x bond :
‘The compounds of alkene series contain
carbon-carbon double bond >C=C< involving sp?
hybridisation which can be explained as follows :
‘The carbon stom in excited state electronic
configuration of outermost, orbitals from which
ne orbital is of 2s type and two orbitals of 2p
type i.e. total three orbitals combine and three
orbitals having same shape and equal energy
formed is known as sp? hybridisation. The
‘unpaired electrons in three sp* hybrid arbitals have
same energy but the 2p, orbital having unpaired
electron of carbon atom which has not
‘participated in the formation of sp? hybridisation,
‘whose energy is not same as those of the
‘unpaired electrons of the sp? hybrid orbitals.
2s 2p, 2,
‘Three orbitals formed due to sp*hybridisation
are arranged in a planar triangular shape. The
angle between any two adjacent orbitals is 120°.
7.42.1 Shape of ethene molecule : The
molecular formula of ethene is C,H, and its
molecular structure is CH,=CH,, In each carbon
atom one orbital which is obtained by sp?
hybridisation having unpaired electron with
opposite spin overlap each other axially and form
6 bond between two carbon atoms. Now, both
the carbons have remaining two sp*hybrid orbitals
on each carbon atom which overlap with each
of the two 1s orbital of two hydrogen atoms
‘having unpaired electron with opposite spin result
in formation of total four C - Ho bond having
equal energy. The four C - H bonds have equal
bond length of 110 pm.
Further, doth the carbon atoms have 2p,
orbital containing unpaired electron which had
not participated in hybridisation. Now, due to
sharing of these electrons with opposite spin a %
bond is formed. Thus, in ethene molecule
‘between two carbon atoms, ane ¢ bond and
another bond ie double bond is formed. In
ethene molecule C = C bond length is 134 pm.
which is less than C-C bond length in ethene.
‘The shape of ethene molkcule is planar triangular
104 bond angle HCH is 116.6° and C-C-H is
ri.
74.3 Shape of gp- hybrid ortital and 7 bond :
‘The compound of alkyne series contains
carbor-carbon triple bond -C=C- involving sp
hybridisation which can be explained as follows : A
carbon atom in an excited state electronic
configuration of cuter most orbital from which one
orbital is of s type and one orbital is of 2p type.
Hence, total two orbitals combine and form two
orbitals having same shape and equal energy, these
are known a8 sp hybrid orbitals and this pheno-
‘menon is known as sp hybridsation. The unpaired
electrons in these two hybrid orbitals have same
enenrgy. Now, remaining 2p, and 2p, orbitals of
carbon atom which have not participated in
‘formation of sp hybridisation containing unpaired
electrons whose energies are not the same as chose
of the tmpaired electrons of the sp hybrid orbitals,
2», =,
2% %,
The two orbitals formed due to sp
hybridisation are arranged linearly and bond angle
‘between them is 180°. 7.4.3.1 Shape of ethyne molecule
‘The molecular formula of ethyne molecule is C,H,
and its molecular structure is HC=CH. In each
carbon atom orbital which is obtained by sp
hybridisation having unpaired electron overlap
axially with opposite spin and form 6 bond
between two cabon atoms. Now both the carbon
‘toms have remaining one sp hybrid orbital on
each carbon atom overlap with 1s orbital of
hydrogen atom having unpaired electron with
‘opposite spins result in formation of two C-H
‘6 bond having equal energy and equal bond length,
Further, both the carbon atoms have 2p,
and 2p, orbitals containing unpaired electron which
hhave not participated in hybridisation, These
‘unpaired electron orbitals when spin becomes
‘opposite to cach other sharing of electrons
results in two x bond formation. Thus in ethyne
molecule between two carbon atoms one 6 bond
and two 1 bands i.e triple bond is formed having
bond length 120 pm which is less than >C = C<
bond length in ethene, The shape of ethyne
molecule is linear and bond angle is 180°.
1 the plane
Shape of ethyne molecale
75 Functional Groups
‘An atom or group of atoms that determines
the characteristic reaction of an organic
‘compound is known as functional group. In alkane
hydrocarbons due to their saturation they do not
contain functional group for their characteristic
reaction. The different compounds have the same
functional group under similar reactions. Some
of the functional groups responsible for their
chemical reactions are given in table 7.1
‘Table 7.1 Classification of some functional groups Basic Principles of Organic Chemistry
95
‘Alcohol “OH | Jor CHO Methanol
CHCH.OH Ethanol
CHsCHCH.OH Propan-I-ol
CHsCHCHS
ox Propan 2.
Bther alkoxy / - CH -0- CH Methoxy methane
CHL -O- CH, CH, Methoxy ethane
CH - CH: -O-CH-CHs_|_Ethoxy ethane
Aldehyde | -CHO | -/al HCHO Methanal
CHsCHO Ethanal
CH.CH.CHO Propanal
Ketone -CO- | +f one CHsCOCHs Propanone
CHsCOCH.CHs Butan-2-one
CHsCH.COCH.CHs Pentan-3-one
Carboxylic | -COOH | -{ cic Acid HCOOH ‘Methanoic acid
acid CHsCOOH Ethanoie acid
CHsCH:COOH Propanoic acid
Ester -COOR | + cate HCOOCH, Methyl methanoate
CHsCOOCH: Methyl ethanoate
CH,COOCH.CHs Ethyl ethanoate
Amide -CONH, | -/ amide CHsCONH: Ethanamide
CHsCH:CONH2 Propanamide
Amine -NH; | (1°)-/ amine | CHsNHs Methanamine
(Primary) (CHsCH:NH2 Ethanamine
CHsCH.CH.NH: Propan-1-amine
Cl CH CH Propan-2-amine
Nib
-NH- | (2°) amine | CH; NHCH N-methyl methanamine
(Secondary) | CHs CH: NHCHs N-methyl ethanamine 96 Chemistry
ee
-N (3°) amine | CHs ~N- CH: CH: CH | N-N dimethyl ethanamine
(Tertiary) CH
cnc, NN cima metnaming
Nitro a (CHsCH:NO: Nitroethane
(CHsCH,CH:NO: LNitropropane
CHLCHCHs
No. 2-Nitropropane
Cynide N | -/nitrile CHsCN thane nitrile
OR CHACHLCN Propane nitrile
Nitrile CHsCHCH:CN Butane nitrile
7.6 Homologous Series
A series of organic compounds having same
functional group in which two successive
members differ from each other by fixed number
of carbon and hydrogen (CH.). Such series of
‘organic compounds is known as homologous
series. Almost all types of organic compounds form
‘homologous series and they have similar chemical
characteristics e.g. CH, CHy CH, etc.
7.6.1 Characteristics of Homologous series :
‘The elements and functional group present
in compound of a homologous series are same.
Each member of the series can be expressed
‘by common molecular formula. For example,
each member of alkane series can be
indicated by a common formula CH.»
The difference between the molecular
formula of two successive members of the
series will be of CH,.
The difference between the molecular
weights of two successive members of a
series will be of 14 amu (v)
The name of each member of a series
begins either with a common prefix or suffix.
‘The chemical reactions of each member of
series are same if the functional group
present in them is same and their methods
of preparation are also the same.
AAs the number of carbon and hydrogen atoms
increase with member of a given series the
molecular mass of the members increases,
Hence there will be gradual change in the
properties of the members which depend
upon their molecular mass which include
a
@
)
4
6)
©
o
boiling point, melting point, density, solubility
etc, The characteristics of homologous series
of alkane compounds are given in table 7.2.
‘Table 7.2 Characteristics of homologus
series of alkanes
Ss
es
Propane| cH, | 4¢ | #3 | 231 | as
pune | cH, | 58 | 13s [ams | ee
Pentane | CH, | 72 | 143 | 209 | ans,
ligt
7.7 Isomerism
The organic compounds having the same
‘molecular formula but different structural formula
are called isomers. This phemenon is called
isomerism. The isomerism has been classified
mainly in two types depending upon their
differences in structural aspects :
(1) structaral isomerism,
Q) stereo isomerism,
7.7.1 Structural Isomerism : Structural
isomerism is a result of different arrangments of
atoms or groups of atoms in. molecules of organic
‘compounds having same molecular formula.
Hence, the organic compounds having same
‘molecular formula but different structures are
called structural isomers and the phenomenon as
structural isomerism. There are five different
types of structural isomerism : Basic Principles of Organic Chemistry
(1) Skeletal or chain isomerism (2) Position
isomerism (3) Functional group isomerism
(4) Metamerism (5) Tautomerism.
(Q) Skeletal or chain isomerism ; The
organic compounds having same molecular
formula but arrangement of carbon atoms in a
linear or branch are different; such type
of isomerism is called chain isomerism, Methane,
ethane and propane do not exhibit chain isomeism
bbut butane has two isomers. Pentane has three
isomers, hexane has five isomers. For example
three isomers of pentane are given below.
(@ n- pentane (CH,CH,CH;CH;CH,
(i) 2 methyl butane CH,CHCH,CH,
i
CH,
(Gi) 2,2-dimethy] propane
a
Cli ¢-CH,
CH
(2) Position isomerism : Organic
compounds have same molecular formula and
similar carbon chain but differ in the position of
functional group. This type of isomerism is called
position isomerism. For example
@ CH,CH,CH,NH, Propan-I-amine
CH,CHCH,
NH, Propan-2-amine
(i) CH,CH,CH,CH,CH,OH Pentan-1-ol
CH,CH,CH,CHCH, —Pentan-2-01
OH
CH,CH,CHCH,CH,
OH Pentan-3-o1
(3) Functional group isomerism : The
‘organic compounds having the same molecular
formula but different functional groups are called
functional group isomers and this phenomenon is,
called functional group isomerism; for example.
@ CH,CH,CHOH ——CH,-0-CH,CH,
propan-I-ol methoxy ethane
(i) CH,CH,CHO CH,-CO-CH,
propanal propanone
Gi) CHCH,COOH CH,-COO-CH,
propanoic acid methyl ethanoate
(4) Metamerism : The organic
compounds having same molecular formula and
same functional group but different number of
carbon in alkyl group on either side of the
functional group are called metamers and such
isomerism is called metamerism. This type of
isomerism is shown by ethers, ketones and
amines, For example,
(@ CH;CH,COCH,CH, Pentan-3-one
CH,COCH,CH,CH Pentan-2-one
(il) CHy-0-CH,CHCH, Methoxy propane
CH,CH,-O-CH,CH, Ethoxy ethane
(ii) CH,NHCH,CH,CH, N-Methy propan-I-amine
CH,CH,NHCH,CH, N-Ethyl ethenamine
(5) Tautomerism : The organic compounds
having same molecular formula but isomers differ
in the arrangment of atoms and are in dynamic
cqullibrium with each other are called tautomers and
this phenomenon is called tautomerism. For exmple
0
Be "
H-C-C-H = H-C=C-H
H oH
ethanal vinyl alcohol
@CH-C-CH = Ci =C-CHs
° ou
propanone prop-l-en-2-o1
g g
CHy-C-Cih -C-Ch =
keto form
g
CH,-C-CH
enol form
In structure of organic compounds having
keto form and enol form in dynamic equllibrium
with each other is known as keto-enol
tautomerism.
7.8 Nomenclature of Organic Compounds
About a century ago a few number of
organic compounds were known. At that time
the naming of compounds was done as per their
properties, structures or their origin, During the
first half of the 20" century many types of Chemistry
organic compounds were synthesised, hence, the
nomenclature by old pattern became impossible.
Besides that the nomenclature of an organic com-
pound should be such that the structure of a
newly synthesised compound can be understood
by all the chemists. So, in 1889, a committee
‘was formed by International Chemical Congress
for laying down definite rules for nomenclature,
‘The report of this committee submitted, in 1892,
at Geneva was inadequate. So based on that, in
1930, International Union of Pure and Applied
Chemistry presented a more meaningful account.
‘After the naming of organic compounds was over,
a committee formed in 1947, recommended
various types of rules. The nomenclature done
by these rules is known today as IUPAC
(international Union of Pure and Applied
Chemistry) system. The changes in rules take
place from time to time, The IUPAC
nomenclature rules in order are given below :
(1) To determine the longest carbon chain.
Select the longest continuous chain of carbon
atoms in given structure of organic compound,
For example.
ews = C= CH,
|
CH
rh ==
La
In this structure, the longest chain of carbons is
seven and so orginal hydrocarbon will be heptane.
If in a given organic compound, the two
different chains but of equal length are possible,
the chain with maximum number of side branch
‘or alkyl groups is selected. For example
43 2 4
CH,- CH, -CH -CH-CH-CH- CH
i aa
CH, CH CHy CHy
i
-COOR > -CONH, > -CN >
-CHO> -CO_ > -OH > -NH, > Yo=C¢<
\
L
~C#C->-G -C -
For example,
@ 765 43 ad
(CHs-CH-CHy-CH-CH-CH-COOH
ai CHC
2,4,6-trichloro -3- methyl - heptanoic acid
@ 6 54 3 2 4
"H,-CH-CH,-COOH
Oo OH
S-hydroxy -5-oxo- hexanoic acid
76 5 4 3 24
(CH:-CH:-CH CH-CH-C-CH
CH Br O Br
1,4- dibromo -5- methyl - heptan-2-one
Bond-line strncture is a method in which
the structure of organic compounds can easily
be expressed. For the IUPAC nomenclature of
such structures is first converted into complete
structure by using points given below and then to
apply to the points of IUPAC nomenclature rules.
Alkyl groups or cabon and hydrogen atoms
in a chain are not shown but the remaining
atom or group of atoms present in functional
‘groups are shown,
i) Line at both the ends without any functional
‘group is considered as -CH, group.
(ii) Every junction indicates carbon atom and to
satisfy the tetravalency of carbon the required
number of hydrogen atoms are taken,
(jv) Double bond and triple bond are represented
by two and three parallel lines respectively. Basic Principles of Organic Chemistry
101
Complete structural formula
3, 3-diethyl pentane
3,3-dimethyl pentane
CH, CH, CH,-CH, Butane
1a as
CH, CH CH, CH CH,
cx, cH, 2,4-dimethyl pentane
on Br 4 23 as
CH, CH CH, CH CH,
oH Ags 4-bromopentan-2-0l
TUPAC Name
CH, -CH-CH-CH,-CHO
CH, CH,
3, 4-dimethyl pentanal
CH, = CHCH, CH-CH,
CH,
4-methyl pent-I-ene
CH, = CHCH,CHCH,
NH,
pent-4-en-2-amine 102 Chemistry
Go
ESLER SE a 4- methyl hex-5-yn-2-one
CH,-CH-CH-CHCH,COOH 4,5-dibromo-3-cthyl hexanoic acid
Br Br CH,CH,
5- bromo-1-nitrononan-2-one
7.9 Common and IUPAC Nomenclature of Organic Compounds
‘The common and TUPAC nomenclature of organic compounds based on functional
groups are given in table 7.3.
Table 7.3 Common and IUPAC names based on functional group
Alkene _ | Chk Ch ethylene ethene
CHACH = CH popylene propene
CHsCH.CH = CH | Butylene but-l-ene
CHCH= CH CH; | 2-butylene but -2-ene
Halide CHCH.CI ethyl chloride chloro ethane
(CHsCH: CH:C1 propyl chloride | -chloro propane
‘Alcohol -OH (CHsCH2OH ‘ethyl alcohol ethanol
(CHsCH:CH,0H propyl alcohol propant-1-ol
Ether -0- (CHs-O-CHs dimethyl ether methoxy methane
(CHh-O-CHs-CHs ethyl methyl ether | methoxy ethane
(CHsCH-O-CH.-CHs } diethyl ether ethoxy ethane
Aldehyde | -CHO HCHO formaldehyde ‘methanal
(CHsCHO acetaldehyde ethanal
Ketone -co CHsCOCHs acetone or propanone
Y
dimethyl ketone
(CHsCOCHCHs ethyl methyl ketone} butan -2-one
Carboxylic | coon | HCOOH formic acid methanoic acid
acid CHCOOH acetic acid cethanoic acid Basic Principles of Organic Chemistry 103
Amide -CONH, | HCONH: formamide /methanamide
CH,CONH: acetamide ethanamide
Amine -NH, | CHNH ‘methyl amine /methanamine
ay CHSCH:NE ethyl amine ethanamine
(CHsCHCH-CH 2-butyl amine fbutan -2- amine
NH
“NH. | CHNH CHS dimethyl amine [N-methyl methanamine|
@ CHSNH CH:CHs ethyl methyl amine {N-methyl ethanamine
(CH)N trimethylamine —_N, N-dimethyl
/methamine
(CH):NCH:CHs ethyl dimethyl amine]N, N-dimethyl
6 ethanamine
Gu.cn, diethyl methyl amine|N- methyLN-
CH, -N-CH,CH, ethyl ethanamine
Nitro -No, | CHNO: nitromethane nitromethane
CHSCH.NO: nitroethane nitroethane
CELCH:CH:NO: nitropropane 1 nitropropane
cH, CHCH,
NO, 2 nitropropane |2- nitropropane
Cynide CN HCN ‘methyl cynide ethane nitrile
Nitrile CHSCH:CN ethyl cynide propane nitrile
CHLCH:CH:CN propyl cyanide butane nitrile
Ester -coor | HCOOCH ‘methyl formate | methyl methanoate
CHsCOOCHs methyl acetate methyl ethanoate
CHsCOOCHCHs ethyl acetate ethyl ethanoate
ge
nea Yo | ci,-c-o-c-c, acetic anhydride Jethanoie anhydride
g
arene 2 0 . oe anmari
4 reer formic anyhydride |methanoic anhydride
7.10 Electronic Displacement (Subsitution)
in Covalent Bond
Organic compounds contain mostly
covalent bond. Hence the subsitution of hydrogen
atom or of functional group with or without
electron pair takes place in different ways. Four
types of electronic displacement are generally
noticed in the mechanism of organic reactions.
7.10.1 (1) Inductive eftect : In organic
compound if a carbon atom is covalently bonded
to an atom of higher eletronegetivity (like halogen)
the bond becomes polar due to large difference in
clectronegativities and the polar effect of this
spreads over the carbon atoms arranged in the
chain, This effect is called an inductive effect
L-effect). It is shown by > sign. For example,
in propyl chloride (I-chloropropane) this effect is.
shown as under: Inductive effect is the
permanent effect
yoR OH
HC + CHC
i i 104
We know that chlorine is more
eletronegative than carbon. Due to large
cloctronegativity of chlorine atom the electron
‘pair which is shared betweea C-Cl, is displaced
‘towards chlorine atom. As a result of this,
chlorine atom acquires a partial negative charge
(Band carbon atom acquires a partial positive
charge (6°). This displacement is however not
limited to C-C1 bond but is transmitted to other
carbon atom along the chain, This effect goes
con decreasing on moving from near carbon to
farther carbon from chlorine atom generally after
‘three carbon. From fourth carbon this effect
‘becomes negligible. For comparing the relative
effect hydrogen atom is taken as a standard
and the atoms or groups can be classified into
‘two categories.
@ Negative I effect (-I effect) : Atoms
or group of atoms having electron
attraction capacity more than that of hydrogen
are referred wo as. (electron attracting) atoms or
electron negative (I) effect For example :
-NO, > -CN > -COOH > -F > Cl > Brot
> -OH > -OCH; >-C,H;>-H
(U) Positive I effect (+1 effect) : Atoms
or group of atoms having less electron attracting
‘power than that of hydrogen are refeered to as
a (cletron repelling) atom or possitive I effect
(HI effect). For example
(CH,),C - > (CH,), CH- > CH, CH, ->- CH,
7.102 Eletrameric effect ; An electron
‘Pair bonded between two atoms with more than
one bond shifis to a more electronegative atom
4a presence of a reagent depending upon its
characteristics. This effect is termed as
clectromeric (B-effect) effect. For example,
ekeciron pair of double bond between carbonyl
group C=O present in aldchydes and ketone
shift t the original atom which is more
eletronegative when comes in contact with a
reagent having higher eletronegative charge. This
effect is termed as an electromeric effect. This
effect is due to the presence of reagent so it
is a temporary effect.
Blectromeric effect can be classified into
‘two categories :
(® Positive electromerie effect (+E
effect) : When the transfer of electrons takes
place towards the attacking reagent, it is
called positive electromeric effect. For exmaple,
(Negative clectromeric effect (-E effect) :
When the transfer of electron takes place away
from the attacking reagent, it is called nogative
cletromeric effect (-E effect). For example
O -
>c4+0 +N 30-8
CN
7.10.3 Resonance or Mesomeric effect :
‘A molecule of some organic compound can be
represnted by two or more electronic structures,
however, all of its properties cannot be explained.
by a single structure. The actual structure is
represented by an intermediate stage between two
or among more electronic structures. These
structures are called resonance or mesomeric
‘structures and the resulting characteristic is known
as resonance or mesomeric effect. Resonance
effect is shown by a symbol ¢+. For example
‘Two resonance structures of benme :
O-O
‘Three resonance structures of CO, +
‘Two resonance structures of carboxylic seid +
R Be rte
oe
7.10.4 Hyperconjugation + In some
‘organic compounds wien a C-C single bond is
aligned with C=C double bond or attached to &
benzene ring, the electron pair of the & bond
between C-H single bond is attracted towards
the double bond. This effect is termed
hyperconjugation. If an alkyl group carrying at
least one hydrogen atom is attached to an
‘unsaturated carbon aiom, it releases clectrons of
carbon hydrogen single bond (6 bond) toward
the double bond. For example, hyperconjugation
in propene is shown below : Basie Principles of Organic Chemistry
105
‘Hyperconjugation in propene
K 0
wPotn, © nc = aren o 8
i h
The hyperconjugation is very useful in
explaining stabilities of some organic molecules.
For example
() The order of stability for -CH, subsituted
alkene as given below :
cH cH,
peace
5 CH,
2-methyl propene
Structure IIL
hy. ‘ x
Aa
Propene
Structure -IV
Hence, the structure I has 12 hyperconjugation
C-H bond in structure II 9 C-H o bond and
hence structure I has more C-H_ 6 bond so
the hyperconjugation effect being more which
makes it more stable. Same way structure [Il
‘has 6 C-H o bond and structure IV has only
3 C-H bonds, hence the descending order
of stability can be explained.
Gi) The stability of carbocation and free radicals
can be explained by hyperconjugation.
Gi). Shortening of carbon-carkon single bond
adjacent to carbon having YC = C% dobule
bond or -C=C- triple bond is also explained
by hypercongugation.
‘ ns
ii H-C =CH-CHy
H Ou
7.11 Fission of Covalent Bond
‘The fission of covalent bond can occur in
two ways.
(1) Homolytic fission : A covalent bond
is formed by sharing of two electrons between
same two electronegative atoms then during
fission of that covalent bond both atoms
separated by gaining one-one electron each is
called homolytic fission. The atoms separated in
this way possessing unpaired electron are called
free radicals. ‘These free radicals have unpaired
electrons so they have strong tendency to pair
the electrons. Hence, they are very reactive and
have a very short life.
lav ight
acd ch + ck
he
five race
Alkyl free radicals are classified into three
categories : primary (1°) secondary (2°)
and tertiary (3°), For example
i co Ge
CH-Ge CH= Ce CH Ce
h a cit,
ay @ °
‘The order of stability for free radical is
CH,. 1° < 2° < 3° which can be explained by
hyperconjugation
(2) Heterolytic fission : A covalent
bond is formed by sharing of two electrons
between two different electronegative atoms
then during fission of that covalent bond
more electronegative atom acquires shared
electrons paired and less electronegative atom
has shortage of electron and such fission is
known as heterolytic fission. The atoms get two
electrons resulting into negative (-ve) ion and
atoms having shortage of electron results into
positive (+ve) ion; so heterolytic fission results
into +ve and -ve ions. For example,
Tommie Ho , 2
fc eM 8 O 4a
H 106
Chemistry
Hence, the breaking of C-Cl covalent bond
{in which chlorine atom is more electronegative
compared to carbon atom results into shared
electron pair with chlorine atom as (Cr’ion while
carbon atom has shortage of electron which
results into CH," positive ion.
7.12, Electrophile, Nucleophile, Carbocation
or Carbonium Ton, Carbanion
Electrophile : The part of positive charge
(positive ion) obtained during a heterolytic fission
or some neutral molecules having capacity to
accept pair of electrons are called clectrophiles.
Electrophiles are also called Lewis acid. For
example
sve ions :7NO,,C1", *SO3H, “CH,,CH,"CO,
H,, HO" ete.
Neutral molecules : AICI,, BF,, SO, ete.
Nucleophile : The part of negative charge
(negative ions) obtained during heterotic fission
or some neutral molecules having capacity to
donate electron pair are called nucleophiles.
Nucleophiles are also called Lewis base, For
example
sve fons +X, : OH, : “CN, : "NH ete.
Neutral molecules : NH,, H,0, ROH, R
RN, R,NH etc.
Carbocation or earbonium ion : A group
having several atoms in which a carbon atom
has six electrons and consequently has positive
charge is called a carbocation or carbonium ion.
It is highly reactive and is very short lived. For
example,
Carbocations are classified into three
‘categories: primary (1°), secondary, (2°) tertiary (3°)
‘When a positively charged carbon atom is
directly attached to one, two or three carbons such
carbocation is called Primary (1°), Secondary (2°)
and Tertiary (3°) respectively for example,
Now methyl (alkyl) group has (tH-effect)
positive inductive effect. So alkyl group attached
to positively charged carbon atom tends to
release electrons towards carbon. As a result it
decreases the +ve charge on the carbon atom
Dut itself becomes positively charged so the
positive charge on carbon atom gets dispersed.
‘Therefore, more the number of alkyl groups,
the greater will be the dispersion of charges
decreasing the positive charge of carbon and
stability of carbon (carbocation) increases. Thus
the order of stability for caorbocation is
“CH, < P< 2 < 3,
Carbanion : A group of atoms in which a carbon
atom has eight electrons and hence has a negative
charge, such a group is called carbanion, Tt is
highly active and is very short lived. For example
Carbanions are classified into three categories
‘as primary (1°), seconday (2°) and tertiary (3°)
When a negatively charged carbon atom is
directly attached to one, two or three alkyl groups
are called primary (1°), secondary (2°) and
tertiary (3°) respectively. For example
Now alkyl group has positive inductive
effect (+1 effect); alkyl group has electron
releasing tendency, and therefore, increases the
‘electron density on the negatively charged carbon
‘atom and hence stability decreases; more the
‘number of alkyl groups attached to the negatively
‘charged carbon atom greater will be the electron
density on the carbon atom and lower will be
its stability. So the order of stability for carbanion
is “CH, > 1° > 2° > 3°,
7.13 Main Types of Organic Reactions
There are four main types of organic
reactions :
(1) Substitution reaction : An atom or
group of atom in an organic compound is substituted
by different atoms or group of atoms in a reaction
is called substitution reaction. For example, Basic Principles of Organic Chemistry
107
cHy+c,—_
Methane
CH,C1+HC1
(Coronet
CH,CH,I + KOH ~ CH, CH,OH + KI
Todoethane Ethanol
In the above reactions the Hof methane
is substituted by - Cl and -I of iodoethane is
subsituted by -OH functional group.
(2) Addition reaction : During a
chemical reaction with a molecule containing a
double bond or a triple bond, if the x bond of
the double or a triple bond breaks and a new
organic compound is formed by addition of
another molecule, the reaction is called addition
reaction. In this type of reaction two molecules
are reacted to form a product having single
molecule. For example
CH, = CH, + Cl, > CH,~CH,
bee aia
12 diehloro eave
formation of additional new bond between two
carbon atoms, the reaction is called elimination
reaction. This reaction is also known as
B-climination reaction. For example,
any
CH,CH, OH > CH, =CH, +H,0
iy CBr SEEM C= CH + KB HO
(4) Rearrangement reaction : In a
molecule of organic compound the migration
of atom or group of atoms to another position
takes place within the same molecule
under suitable conditions, the reaction is called
rearrangment reaction. For example,
CH;
Here, the x bond breaks and chlorine “S) cHy-cH cH,
molecule is added and the product formed is 1,2
dichloro ethane,
@) Blimination reaction :Tn an organic
reaction, atom or group of atoms is removed
from adjacent carbon atom resulting in the
CH,CH, CH, CH,
1 butane inobutane
uc -cucu,cu, 4, cu, ence,
SUMMARY
Organic chemistry is in fact the science of hydrocarbons formed by carbon and
hydrogen, The compounds of several types are obtained by the substitution of hydro-
gen in them. It also gives the information of tetravalency of carbon and structures of
organic: molecules.
‘The information about the shapes of molecules of alkane, alkene and alkyne
formed by sp’, sp? and sp hybridisation in carbon can be obtained. Tt also gives
information about & and x bonds. Homologous series and the study of its characteristics
fare useful in understanding the properties of compounds. IUPAC nomenclature can be
carried out by the study of isomerism and detailed information about its types and
obtaining their complete structural formulas and also the information about the
nomenclature of compounds or information about structure from nomenclature suggested
by TUPAC. The inductive effect, electromeric effect, mesomeric effect and
hyperconjugation are useful for the study of stability of certain organic molecules and
ions as well as the study of chemical reactions. The free radicals produced during
homolytic and heterolytic fission of organic compounds containing covalent bond provides
explanation of clectrophillic and nucleophillic reagents. There are four main types of
‘organic rections which can be understood by many reactions. 108 Chemistry
EXERCISE
1. Select the proper choice from the given multiple choices
(1) Bute ene molecule carbon has which type of hybridisation ?
(A) sp* B) sp?
(©) sp and sp* ©) sp
(2) Pent -2-yne has how many 6 and bonds ?
(A) 106, 26 @) 120, 2
© 150, 2 ©) 36, 3
() Which molecule has longest carbon chain ?
(A) Neopentane (B) Isopentene
(©) Neohexane (©) Nepentane
(4) The TUPAC nomenclature of //\I\/ is
te
(A) 2.3-dimethyl 7-bromo octane (B) 2-bromo-5,6-dimethyl octane
(©) 2-bromo-6,7-