General Organic Chemistry-01 - Theory

Chemistry : General Organic Chemistry & Isomerism
GENERAL ORGANIC
CHEMISTRY & ISOMERISM
Concepts of hybridisation of carbon, sigma, pi bonds, resonance, homologous series, structural,

geometrical isomerism and optical isomerism of compound containing one and two asymmetric
carbons only, Keto-enol tautomerism of nomenclature (IUPAC). Inductive and resonance effect
on acidity and basicity of acids and bases respectively.
Reactive intermediates product during homolytic and heterolytic bond cleavage.
CONTENTS INTRODUCTION
 Introduction to organic compounds To understand the reaction mechanisms one
has to begin a study of reaction mechanisms
 Amines
by examining some of the basic principles. A
 Bond fission basic understanding of these concepts helps
largely on understanding of reactions and
 Reaction intermediates
their mechanisms.
 Organic reagents
This chapter describes certain fundamental
 Isomerism principles, so as to lay a good foundation on
which a study of reactions and their
mechanisms can be based.
2. INTRODUCTION TO ORGANIC COMPOUNDS

Organic Chemistry is the chemistry of the compounds of carbon, humans have used organic compounds
and their reactions for thousands of year. Not only are we composed largely of organic compounds, not
only are we derived from one nourished by them, we also live on age of organic chemistry. The clothing,
gasoline that propels our auto mobiles, the rubber of their tyres and plastic, most of the medicines are all
organic.
2.1 CLASSIFICATION OF ORGANIC COMPOUNDS

A carbon atom possess the significant virtue of forming covalent bond with itself and with H, N, O
halogen, S etc. This property result in the formation of many compounds with different physical and
chemical properties.
All organic compounds have been classified as :
Organic Compounds
Aliphatic, or Open-chain compounds e.g. n-butane and Iso-butane etc.
(In these carbons are joined to form open straight or branched chain.)
Cyclic or closed-chain compound e.g. Benzene, cyclohexane etc.

(They contain ring of atoms)
Homocyclic or carbocyclic (Ring of carbon atoms)
Aromatic compound e.g. Benzene, Naphthalene etc.

Alicyclic compound e.g. Cyclohexane, Cyclopentane etc.
Heterocyclic (Ring of carbon and other atom) e.g. Furan, Thiophene etc.
2.2 NOMENCLATURE OF THE ORGANIC COMPOUNDS

First we will learn how to name alkanes because they form the basis for the names of almost all organic
compounds.
Trivial System : In this system of nomenclature the straight-chain compounds are always designated
as normal compounds, and the word normal is usually abbreviated to “n”. If the compound contains the
grouping (CH3)2CH–, it is known as iso-compound , if it contains a quarternary carbon atom, the
compound is known as neo-compound. It is impossible to name many more complex alkanes by the
trivial system.
To avoid having to memorize the names of many different structural units, chemists have devised rules
that name compounds on the basis of their structure. This way only the rules have to be learned. This
method of nomenclature is called IUPAC nomenclature because it was designed by a commission of
the “International Union of Pure and Applied Chemistry.”
2
2.3 SYSTEMATIC NAME OF AN ALKANE IS OBTAINED USING THE FOLLOWING

RULES
1. Determine the number of carbons in the longest continuous carbon chain. This chain is called as
main chain or parent Hydrocarbon. The alkane name indicating the number of carbons in the
parent hydrocarbon becomes the alkane’s last name.
Number of Carbon Name (Prefix)

1. meth
2. eth
3. prop
4. but
5. pent
6. hex
7. hept
8. oct
9. Non
10. Dec
11. undec
12. dodec
13. tridec
20. eicos
6 5 6 5 4 3
_4 3 2 1
CH3 _ CH2 CH 2 _ CH _ CH2 _ CH3 CH3 _ CH2 _ CH2 _ CH _ CH3
_
CH3 CH2 CH3
2 1
Two Different way to draw 3-methyl hexane
2. Numbering should be started from that direction in the main, so, that the sum of the number of the
substituents or, number of the substituents no should be minimum. Name of the alkyl substituent
that hang off the parent hydrocarbon is cited before the name of the parent hydrocarbon with a
number to designate the carbon to which it is attached.
3. In case of same sum of locants in the substituents minimum number should be given in the
alphabetical order.
Note : Numbers are used only for systematic names and never for common names
CH 3
| Isobutane : common name
CH3  CH  CH3
2-methyl propane : Systematic name.
6 5 4 3 2 1
H 3 C— C H 2 — C H 2 — C H — C H 2 — C H 3
| 3-ethyl hexane
CH2 —CH3
2.4 LIST SUBSTITUENTS IN ALPHABETICAL ORDER

(a) If more than one substituent is attached to the parent hydrocarbon, the chain is numbered in the
direction that will result in the lowest possible number. The substituents are listed in alphabetical
order (not numerical order)
1 2 3 4 5 6 7 8
CH3 _ CH2 _ CH _ CH2 _ CH _ CH2CH2 CH3
CH3 CH2CH3
Incorrect Name : 4-ethyl -6- methyl octane
Correct Name : 5-ethyl -3- methyl octane
(b) If two or more substituents are the same, the prefix di, tri and tetra are used with the substituent
names. The prefixes di, tri, tetra, sec and tert are ignored in alphabetizing substituent groups, but
prefixes iso, neo and cyclo are not ignored.
(c) The number indicating the locations of the identical substituents are cited together, separated by
commas,
CH3 CH3
6 5 4 3 2 1
CH3 _ CH2 _ CH _ CH2 _ CH _ CH 3 H3C CH2 CH2 C C CH2 CH3
CH 3 CH3
CH3 CH3
2,4-dimethyl hexane 3,3,4,4-tetramethyl heptane
CH3
8 7 6 5 4 3 1
H3C CH2 CH2 CH CH2 CH2 CH CH3 (5- isopropyl-2-methyl octane)
2
CH CH3
CH3
(d) When both directions lead to the same lowest number for one of the substituents, the direction is
chosen that gives the lowest possible number to one of the remaining substituents.
CH3 CH 2 CH 3
| |
CH3  C  CH2  CH  CH3 CH 3  CH  CH  CH 2 CH 2  CH  CH3
| | | |
CH3 CH3 CH3 CH3
2, 2, 4  trimethyl pentane 3  ethyl  2, 6  dimethyl heptane
not not
2,4,4- trimethyl pentane 5-ethyl-2, 6-dimethyl heptane
(because 2 < 4 ) ( because 3 < 5 )
(e) If a compound has two or more chains of the same length, the parent hydrocarbon is the chain
with the greatest number of substituents
3 4 5 6
CH 3 – CH 2 CH  CH 2 – CH 2 – CH 3 3-ethyl-2-methylhexane
| not
CH  CH 3 3-isopropylhexane
2|
1
CH 3
4
(f) Names such as isopropyl, sec-butyl and tert butyl are acceptable substituent names in the IUPAC
system of nomenclature, but systematic names are preferable. Systematic substituent names are
obtained by numbering the substituents starting at the carbon that is attached to the parent
hydrocarbon. This means that the carbon that is attached to the parent hydrocarbon is always the
number 1 carbon of the substituent.
8 7 6 5 4 __3 2 1
CH3 CH 2 CH 2 CH 2 CH CH 2 CH 2 CH3 4  isopropyloctane
| _ or
CH CH3 4- 1-methylethyl  octane
|
CH3
1 2 3 4 5 6 7 8 9 10
CH3 _ CH 2 _ CH 2 _ CH2 _ CH _ CH 2 _ CH 2 _ CH2 _ CH2 _ CH3 5-(2-methylpropyl) decane
CH _ CH _ CH 2 3
CH3
CH3
10 _ 9 _ 8 _4 _ 3
_ 7
_ 2 _ 1 _ 6 _ 5
(g) CH 3 CH 2 CH2 CH2 CH CH2 CH CH2 CH2 CH3
H3C _ CH _ CH _ CH 3
CH3
6-(1,2-dimethylpropyl)-4-methyldecane
Illustration 1 : Write the structure of each of the following compounds :
(i) 2, 3-dimethylhexane (ii) 2, 2-dimethyl-4-propylocatne
CH3 CH3
| |
Solution : (i) CH 3  CH  CH  CH 2 CH 2 CH 3 (ii) CH3  C  CH 2 – CH – CH 2 – CH 2 – CH 2 – CH 3
| | |
CH3 CH3 CH 2 CH 2 CH 3
2.5 IUPAC RULES WE FOLLOWED IN NAMING ALKENES

IUPAC name of an alkene is obtained by replacing the “ane” with “ene” ending of the alkane.
(i) The longest chain containing the functional group (here it is C = C or C  C bond) is numbered in
a direction that gives the functional group suffix the lowest possible number.
5 4 3 2 1 6 5 4 3 2
CH3 – CH 2 – CH  CH  CH 3 CH3 _ CH 2_ CH2 _ CH 2 _ C _ CH2 _ CH 3
2-pentene
CH2
1
2-ethyl-1-hexene or 2-ethyl hex-1-ene
(ii) If a chain has more than one substituent, the substituents are cited in alphabetical order, using the
same rule as discussed for alkane.
1 2 3 4 5 6 7
CH 3  CH  CH  CH  CH  CH 2 CH 3 5  ethyl  2  methyl  3  heptene
| |
CH 3 CH 2 CH 3
(iii) If the same number for the alkene functional group suffix is obtained in both directions, the correct
name is the one that contains the lowest substituent number.
H3C CH2 CH2 C CHCH2 CH CH3 CH 3CH  CH  C  CH 2 CH 3

| |
CH3 CH3 CH 3 C2 H5
4-ethyl-2-methyl-3-hexene
2,5-dimethyl-4-octene
not
not
3-ethyl-5-methyl-3-hexene
4,7-dimethyl-4-octene  because 2 < 5 
(because 2 < 4)
(iv) If both directions lead to the same number for the alkene functional group suffix and the same low
numbers for one or more of the substituents, then those substituents are ignored and that direction
is chosen which gives the lowest number to one of the remaining substituents.
8 7 6 5 4 3 2 1
e.g., H3C CH CH2 CH C CH2 CH CH3 4-ethyl-2,7-dimethyl-4-octene
CH3 C 2 H5 CH3 not
5-ethyl-2,7-dimethyl-4-octene
2.6 NAMING OF ALKYNE

Rules for the systematic name of an alkyne is by almost similar to the alkene. The name of alkyne is
obtained by replacing the “ane” ending of the alkane name with “yne”.
Analogous to naming compounds with other functional group the largest continuous chain containing
the carbon-carbon triple bond is numbered in a direction that gives the alkyne functional group suffix as
low number as possible.
If the triple bond located at the end of the chain, the alkyne is classified as a terminal alkyne.
Alkyne with triple bonds located else where along the chain are called internal alkynes.
e.g. CH3 – CH2 – C  CH 1-butyene
6 5 4 3 2 1
CH3  CH  CH 2  C  C  CH 3 5-methyl-2-hexyne
|
CH3
Illustration 2 : Name each of the following compounds :
(i) CH 2  CH 2 C  CH (ii) CH3CH 2CH  C  CH

| |
CH 3 CH 2 CH 2 CH3
Solution : (i) 1-pentyne (ii) 3-ethyl-1-hexyne
Compounds containing more than one double bond the ending will be –“adiene”, “–atriene”, etc. The
generic names of these hydrocarbons are alkene, alkadiene, alkatriene etc,. The chain is so numbered
as to give the lowest possible numbers to the double bond.
5 3 1
6
1, 4-hexadiene
4 2
5 3 1
4 2
6 2-methyl hex- 2,4-diene
CH3
6
(a) Unsaturated acyclic hydrocarbons having both double and triple bonds are named by replacing the
ending “ane” of the name of the corresponding saturated hydrocarbon with the ending “–enyne”,
“adienyne”, “enediyne”, etc
(b) Number as low as possible are given to double and triple bonds.
(c) When double bond and triple bond comes at same number place when numbered from either side
then double bonds are given the lowest number.
2 4 5
e.g., 1
3 pent-3-ene-1-yne or 3-penten-1-yne
3 5
1
6
2-Hexen-4-yne
2 4
2 4
1
pent-1-ene-3-yne or 1-penten-3-yne
3 5
For branched unsaturated acyclic hydrocarbons, if there are two or more double bonds or triple
bonds or both, then selection will be done of the chain which has maximum number of unsaturated
bonds.
1 2 3 5 7
6
e.g., 4
8 5, 6-disopropyl-3,5-octadiene-1-yne
2 4 6 8
3
1 5 7 9 3-Ethynyl-1,4,8-nonatriene
2.7 NOMENCLATURE OF CYCLOALKANES:

(i) Cycloalkanes are named by adding primary prefix before parcent naver (alkane).
e.g.
Cyclopropane Cyclopentane Cyclohexane
(ii) In the case of alkyl substituted cycloalkanes, the ring is the parent hydrocarbon unless the substituent
has more carbon than the ring. In that case the substituent is the parent hydrocarbon and the ring
is named as a substituent.
1 3 5
2 4
propylcyclopentane 1-cyclopropyl pentane

(iii) If the ring has only two substituents and they are different, the substituents are cited in alphabetical
order and the number 1 position is given to the first cited substituent.
3 1-ethyl-3-methylcyclohexane
not
1 2
3-ethyl-1-methylcyclohexane
1-methyl-3-propylcyclopentane
1 2
not
3-methyl-1-propylcyclopentane
3
(iv) If there is more than one substituent on the ring, the substituents are represented in alphabetical
order. One of the substituents is given the number one position and the ring is numbered from that
position in a direction that gives a second substituents the lowest possible number.
5 1
4 1
4
2
3 2 3
1-ethyl-2-methylcyclopentane 1-butyl-4-ethyl-2-methylcyclohexane
1
4
2
3
4-ethyl-2-methyl-1-propyl cyclohexane
not 1-ethyl-3-methyl-4-propyl cyclohexane

because 1 + 2 + 4 = 7 and 1 + 3 + 4 = 8
2.8 NOMENCLATURE OF SUBSTITUED HYDROCARBONS (HAVING SECONDARY

PREFIX)
Substituent Secondary Substituent Secondary
Group Prefix Group Prefix
–F Fluoro – OR alkoxy

– Cl Chloro –N N diazo
– Br Bromo – NH2 amino
–I Iodo – CH3 methyl
– NO2 Nitro – C2H5 ethyl
– NO Nitroso – CHMe2 isopropyl
– CMe3 tert-butyl
8
ALKYL HALIDE
(a) They are named as substituted alkanes i.e. Haloalkanes.
5
H3C 3 CH3
2 1
4
CH3 CH2 CH CH3
Cl Br
Br
2-Bromobutane 2-Bromo-4-chloropentane
not
4-bromo-2chloropentane
(b) When the parent chain has both alkyl and halo group, number the chain from the end nearer
the first substituent, regardless of whether it is halo or alkyl group. If two substituents have
equal number from the end of the chain, then number chain from the end nearer the substituent
that has the alphabetical precedence.
Br Cl
CH3 CH3
2-bromo-3-methylpentane 2-chloro-4-methylpentane
Cl CH3
4 6
2
5
1 7
3
Br
F
2-bromo-2-chloro-5-fluoro-4-methyl heptane
2.9 ETHERS (ALKOXY ALKANE)

(a) The larger alkyl group is chosen as the parent alkane.
1 Br
4 O
2 2
O 3 1
5
3 Cl
2-ethoxypentane 2-bromo-2-chloro-1-methoxy-3-methylbutane
(b) Cyclic ether :

Br
2
4 3 1
O
2-bromo-3, 4-epoxyhexane
(c) Ether group substitutent to cyclo alkane.
OMe
3-ethyl-1-methoxycyclohexane
3. AMINES
Chemical abstracts has recently adopted a new system for naming amines that is more rational than
common system (alkylamine), IUPAC system (Amino alkane) and gain universal acceptance for the
nomenclature of these compound.
(i) The ‘e’ at the end of alkane name for the largest continuous carbon chain in the amine is replaced
by amine.
(ii) Position of nitrogen is denoted by the number in the largest possible carbon chain.
(iii) The name of any other alkyl groups bonded to nitrogen ( in sec and tert amine) is preceded by as
N to indicate that group is bonded to a nitrogen rather than to a carbon.
(iv) All substituents, whether they are attached to nitrogen or to the parent chain are listed in alphabetical order.
e.g., 5 3 1 1
4 2 3
4
2 NH2
NH2
4-methyl-2-pentanamine 3-methyl-1-butanamine
1
N
2 3
N-ethyl-2, 2-dimethyl propanamine
Illustration 3 : Name the following compounds

Br
(a) (b)
Cl Br NH2
N
(c)
H
Solutions : (a) 2-bromo-3-chloro-4-methylpentane
(b) 4-bromo-3, 3-dimethyl-2-pentanamine
(c) N-ethyl-1-propananine
3.1 NOMENCLATURE OF COMPOUND HAVING SECONDARY SUFFIX

(i) Select the largest possible chain of carbon atoms containing secondary suffix (i.e., functional
group) and maximum number of multiple bonds (if present) as the parent chain without caring
whether if also denotes the latest continuous carbon chain or not.
O
5 3 4
2
4 2 5
1 OH 1 3
6
2-ethyl-1-pentanol 7
5-(1-methylpropyl)hept-6-ene-2-one
(ii) Position of functional group should be denoted by least possible number and positions of substituents
and the primary suffix is determined with respect to the position of functional group.
Br
3 1
6 5
2
4
7
O
5-bromo-6, 6-dimethyl-2-heptanone
10
(iii) When a chain compound has terminating functional group. (The group in which carbon is present),
it is always given number 1 and number one is usually omitted from the final name of the compound.
3 1 3 1
CN CN
4 4
5 2 5 2
4-methyl pentanitrile 4-methyl pentanitrile
(iv) When compound contains two or more like groups, the numerical prepxes di, tri etc. are used and
the terminal ‘e’ form the primary suffix is retained while writing IUPAC name –
3 2 1
CH 3  CH  CH  CH 3 CH  CH 2  CH
| | || ||
OH OH O O
2,3-Butanediol propane-1,3-dial
(v) When an organic compound contains two or more different functional groups one is selected as
the principal function group (as per the preference order) and other are treated as substituents.
Table showing Secondary Suffix and Priority Order
The choice of principal functional group is made on the basis of the following order of preference
Functional Group Prefix Secondary Suffix

– COOH Carboxy –Oic acid
– CO – O – CO – –– –Oic anhydride
C  OR alkoxy carbonyl –Oate
||
O
or carbalkoxy
C  X formyl halo – oyl halide
||
O
C  NH 2 Carbamoyl – aneamide
||
O
–CN cyano – nitrile
– CHO formyl or aldo – al
CO Keto or oxo – one
|
–OH Hydroxy – ol
–SH mercapto –thiol
–NH 2 amino – amine
–OR alkoxy –
–NO 2 nitro –
– NO nitroso –
–X halo –
(a) The principal chain is selected in such a way that it includes the maximum number of functional
group (as substituents) including principal group.
(b) Numbering of the principal chain is done in such a way that principal functional group gets the
lowest number.
(c) Substituents side chains and secondary functional groups are arranged in alphabetical order.
Br 1
3 3-bromo-1-chloro-3-methyl-2-butanol
2
e.g.
4 Cl (_OH main functional group)
OH
6 4
8 2 5-hydroxy-2-methyl-7-octyn-3-one
5 3
7 1 ( = O is main functional group)
OH O
OH
2
4 2-ethyl-4-cyclopropyl-4-hydroxybutanoic acid
3 COOH
1
4 2
O ethyl-3-hydroxy butanoate
3 1
OH O
O isopropyl cyclopentyl methanoate
O
(vi) Acid halide in which carbonyl group of acid halide is attached
Cl
O
cyclopentyl methanoyl chloride
IUPAC name : cyclopentylmethanoyl chloride
NH 2
Carboxamide Cyclopentylcarboxamide
Cyclopentyl
OH
4 2 N 6-hydroxy-5-Keto-2-heptennitrile
6
5
7 3 1
O
12
CN Cyclopentyl methannitrile
2
6 5 1
NC 3 CN 3,3 -dimethylhexanedinitrile
4
COOH
HOOC COOH
3 1
5 3-carboxy pentanedioic acid
4 2
APPLICATION OF CONJUGATION AND RESONANCE
Aromatic character of compounds
According to Huckel Rule, Compound will be aromatic if it will fulfil the following four conditions.
(i) Compound should be cyclic
(ii) Compound should be planar
(iii) Compound should be conjugated and
(iv) Compound should have (4n + 2) conjugated or delocalised e– s where n is a whole no.
n = 0, 1, 2, 3, .......
O ' n (4n  2)  
0 2 

1 6  The numbers are known as Huckel numbers
2 10 

3 14 
e.g. : (i)  no. of conjugated e–s (6) 

  Aromatic
(ii)  no. of conjugated e–s (6) 

  Aromatic
Anti-aromatic compounds
(i) Compound should be cyclic.
(ii) Compound should be planar.
(iii) Compound should be conjugated and
(iv) Compound should have (4) conjugated or delocalised e–s where n is a whole no...
e.g. (i)  no. of conjugated e–s (4) 

  Anti-aromatic
(ii)  no. of conjugated e–s (4) 

  Anti-aromatic
EXERCISE – 1
O
1. || 2. CH3  CH  CH2  CH  CH3
H  C  CH2  CH2  CH3 | |
CH3 CHCH3
|
CH3
O O O
|| ||
3. CH3 – CH – CH – CH 2 – CH 3 4. HO  C  CH2  CH2  CH2  C  OH
|
Cl
3.2 NOMENCLATURE OF AROMATIC COMPOUNDS

Common names of most of the aromatic compounds are accepted as their IUPAC names.
CH 3
CH 3 CH 3
CH 3 CH 3
Benzene Methyl benzene 1,2-dimethyl benzene (m-xylene)
(Toluene) (o-xylene)
CN OH
OCH 3
OH
Benzehyde anisole Benzonitrile Catechol
OH OH
OH OH CHO
COOH
OH
OH
Resorcinol Hydroquinone Salicylic acid Salicyldehyde
or
quinol
OH
COOH COOH
COOH COOH HOOC

Phthalic acid Isophthalic acid Terephthalic acid
SO3H
H3C SO3H
Benzenesulphonic 4-toluenesulphonic acid

acid or
p-toluenesulphonic acid
14
Illustration 4 : Name the compound

COCl
Solution : 3-tert-butyl-4-methyl benzolychloride
EXERCISE – 2
1. Which of the following is aromatic species ?
(a) (b)
N
|
(–) H
(c) (d) All
2. Which of the following is anit-aromatic species?
(a) (b)
N S
+
(c) (d)
3. Which of the following is non-aromatic?
(a) (b)
+
(c) (d)
4. Which of the following is non-aromatic?
(a) (b)
N
(c) (d)
5. Which is the most aromatic in character?

(a) (b)
N S
|
H
(c) (d) All having same aromatic character
O
4. BOND FISSION
Organic reaction is a process in which breaking and formation of covalent bond/bonds take place. In
organic reaction, the main organic compound which is converted into a new compound by breaking and
formation of covalent bonds is known as the reactant or substrate and the new compound formed is
known as the product. The chemical species which causes the change is called the reagent.
 
CH 3  CH 2  Br + O H  CH 3  CH 2  OH  B r
Substrate or Reagent Pr oduct
Reactant
Breaking of covalent bond of the compound is known as bond fission. A covalent bond can be broken by
two ways :
4.1 HOMOLYTIC FISSION OR HOMOLYSIS

In this fission, the covalent bond is broken in such a way that each resulting species gets its own
electron. This leads to the formation of odd electron species known as free radical.
A : B 
 A B
free radical
The factor which favors homolysis is zero or a small difference in electronegativity between A and
B. Homolytic bond fission takes place in gaseous phase or in the presence of non polar solvents
(CCl4, CS2).
Condition for homolytic Bond Fission : Homolysis takes place in the presence of peroxide, UV
 o

light, heat  500 C , electricity and free radical. The process is known as initiation of free radical
reaction,
(i) Peroxide
A : B   A o  Bo
(ii) h
(iii) 
(iv) Electricity
or
(v) Free radical
h
e.g. CH 3  H   C H3  H

Methyl free radical
(i) Homolytic bond fission gives free radical as the reaction intermediate.
(ii) Reaction mechanism reaction is known as free radical or homolytic mechanism.
4.2 HETEROLYTIC BOND FISSION OR HETEROLYSIS

In heterolysis, the covalent bond is broken in such a way that one species (i.e., less electronegative) is
deprived of its own electron, while the other species gains both the electrons. This types of fission
occurs when more electronegativie atom is attached with less electronegative atom consequently more
elecronegative get negatively charge and less electronegative atom gets positively charged. When
carbon is attached with more or less electronegative atom respectively, if forms carbocation or carbanion.
 
A : B 
 A + B
16
Thus formation of opposite charged species takes place. In case of organic compounds, if positive
charge is present on the carbon then cation is termed as carbocation. If negative charge is present on
the carbon then anion is termed as carbanion. Carbocation and carbanion are the reaction intermediates.
The factor which favours heterolysis is a greater difference of electronegativity between A and B.
1. Heterolytic bond fission gives carbocation or carbanion as reaction intermediate.
2. Mechanism of the reaction in which hereolytic bond fission takes place is known as heterolytic
mechanism or ionic mechanism.
3. The energy required for heterolytic bond fission is always greater than that for homolytic bond
fission due to electrostatic force of attraction between ions.
4.3 VARIOUS EFFECTS

(i) Inductive Effect : In a covalent bond between two atoms having different electronegatives, the
electron pair shift towards the more electronegative atom resulting in the origin of small fractional
charges on the atoms.
“This induction of polarity in an otherwise non polar bond due to presence of an electronegative
element is known as inductive effect”
This effect is transmitted through the chain of -bonds and diminishes with increasing chain
length.


C – C – C – C non planar C C C X
Induced electronegative
character by X.
Inductive effect is thus

(a) permanent effect
(b) Operates through  bond (electron never leave their original atomic orbital)
(c) Its magnitude (i.e., electron withdrawing or donating power) decreases with increase in
distance.
On the basis of inductive effect, groups can be of two types
–I group : The group which withdraws electron
–I power of groups in decreasing order :
  
 N R 3  SR 2   N H 3   NO 2  CN  SO3 H  CHO  CO  COOH
  F  Cl   Br  I  OBr  OH  OR   NH 2
  C6 H 5  H
+ I group : The group which denotes electron.
+I power of groups :

O  COO   CR 3  CHR 2  CH 2 R  CH 3  H
It can be seen that compared with hydrogen most groups are electron-withdrawing. The only
electron donating groups are groups with a formal negative charge V, atoms (but not even all
these) of low electronegativity such as Si, Mg etc and perhaps alkyl groups. Alkyl groups were
formely regarded as electron donating but many examples of behaviour have been found that can
be interpreted only by the conclusion that alkyl groups are electron withdrawing compared with
hydrogen. In accord with this is the value of 2.472 for the group electronegatively of CH3 compared
with 2.176 of H.
(ii) Electromeric Effect : Electrons of  -bond are loosely held (due to sidewise ways overlapping)
and easily polarisable. Therefore, when a compound having  -bond is approached by a charge
reagent (electrophiles or nucleophiles), the electrons of the bond are completely polarised or
displaced towards the constituent atoms due to electrostatic attraction or repulsion.
Polar
C=C 
Reagent
 C=C 
 C=C
“Thus the effect involving the complete transfer of shares pair of electrons of  -bond in presence
of attacking reagent is known as electromeric effect (E effect)”
It is a temporary effect and it comes into play instantaneously at the demand of the attacking
reagent.
+ E effect : When the electron transfer takes place towards the attacking reagent.
_
H
+ +
C __ C + H C __ C
 
C=C + H
– E effect : When the electron transfer takes place away from the attacking reagent.
C = O + CN C __ O
CN
(iii) Resonance Effect : Formation of a centre of high and low electron density by the transfer of  -
electron from one part of conjugated  -system to other is called “Resonance” or “Mesomeric
effect.
A given atom or group is said to be in conjugation with an unsaturated system if :
(i) It is directly linked to one of the atoms of the multiple bond through a single bond.
OR
(ii) It has  bond, positive charge, negative charge, odd electron or lone pair of electron.
CH 2 = CH CH = CH 2
Unsaturated Carbon is linked to unsaturated system by
system single bond and carbon has multiple bond

CH 2  CH  C H 2
+ve charge is in conjugation to C = C
..
CH 2  CH  OH
lone pair is in conjugation to C = C
This is a permanent effect
When groups, with draw electron from the conjugation system are said to possess negative
mesomatic effect (–H) or – R. (e.g., – NO2, – CN, > C = O).
When groups donates electrons to the conjugated system are said t posses + M or + R
(e.g., – NH2, – OH, –OR).
(iv) Rules of Resonance : In drawing canonical form or resonating structure, certain rules to be
followed
18
(a) All the cononical forms must be bonafide Lewis structures. For instance none of them may
have a carbon with five bonds.
(b) The position of the nuclei must be the same in all the structure. This process means we are
putting the electrons in different way when we drawing various resonating structure. It
means the position of the atoms are fixed in all resonating structure.
For this reason, shorthand ways of representing resonance are easy to devise
+
:
OH + +
OH OH OH OH OH
:
In resonance -bonds are not involved and only the  or most unshared electrons are put
in different ways. It shown above.
(c) All canonical forms or resonating structure must have the same number of unpaired electrons.
(d) All atoms taking part in the resonance i.e., covered by delocalized electrons, must lie in a
plane or nearly so. The reasons of polarity is maximum overlap of the p-orbitals.
(e) The energy of the actual molecule is lower than that of any form. Therefore delocalisation
is a stabilising phenomenon.
(f) All canonical forms do not contribute equally to the true molecule. Each form contributes in
proportion to its stability, most stable form contributing most.
For benzene
1 2 3 4 5
Ke kule structure Dewar structure
Structure 1 and 2 participate equally and contribute 39% each to actual molecule and the
other (3, 4 and 5) 7.3% each.
It is not always easy to decide relative stability of imaginary structures, the chemists are
often guided by intuition. However, the following rule may be helpful :
(i) Structure with more covalent bond are ordinarly more stable, then that of lesser number
of covalent bond..
_
_ __ _+
CH2 = CH CH = CH2 CH2 CH = CH CH2
More stable Less stable
(ii) Stability is decreased by an increase in charge separation. Structure with formal charge
are less stable than uncharged structures.
(iii) Structures with octet are more stable than that of other structures having number
octel.
(iv) Structure that carry a negative charge on a more electron negative atoms are more
stable than those in which the charge is on a less electronegative atom.
_ _ _ _
CH2 C H CH2 C H
|| ||
O O
:
less stable more stable

(v) Hyper Conjugation : When ( C— H) sigma electrons are in conjugation to  bond, this conjugation
is known as  (C —H),  -conjugation, excessive conjugation or hyperconjugation. It is also
called as no bond resonance because in the different canonical forms, no bond exists between
carbon and H atom of alkyl group.
H H+ H
_ _  _ 
:
:
_ ___ +
H C CH = CH2 H C = CH CH2 H C = CH CH2
H H H
:
_ __ _
H C CH CH2
H+
Structural Requirement for Hyperconjugation :
(i) Compound should have at least one sp2 hybrid carbon of either alkene, alkyl carbocation or alkyl
free radical.
(ii)  -carbon with respect to sp2 hybrid carbon should have at least one hydrogen.
Hyper Conjugation is of three types :
(i)  (C–H),  conjugation : ( It occurs in alkenes)
CH 3
 |
CH3  CH  CH 2 , CH 3  CH  CH  CH 2 , CH 3  C  CH  CH 2
 | |
CH 3 CH 3
No hyperconjugation
(ii)  (C–H), positive charge conjugation : It occurs in alkyl carbocations

   +   
CH3  CH 2 , CH3  CH  CH 2 , CH 3  CH  CH 3
| |
CH3  CH 3
(iii)  (C – H), odd electron conjugation : (It occurs in alkyl free redicals)
CH3  C H 2 , CH 3  C H  CH 3
As we have seen, the inductive effect of alkyl groups is in the order R3C – > R2CH – > RCH2 –
> CH3 –. This inductive effect order has been used satisfactorily to explain many phenomenon
like the dipole moments in gas phase of PhCH3, PhC2H5, PhCHMe2, which are 0.37, 0.53, 0.65
and 0.70 D respectively. However in same reactions, the inductive order is reversed. For example
E

E
R R
In above reaction methyl substituted reacted faster than iso-propyl substituted compound and t-
butyl substituted reacts slowest.
According to Hyper-conjugation effect or Baker Nathen effect the order of electron releasing of
alkyl group is as follows
Me – > CH3CH2– > isopro > t-Bu.
20
Explanation of Acidity and basicity of different compounds on the basis of

inductive, electromeric and resonance effects.
I. Acidity of Carboxylic acid
(i) Electron-releasing group (+I-effect) increases the –ve charge on carboxylate ion, and thus
destablized it. The equilibrium shifts to the left and hence the acidic strength decreases.
e.g. Acetic acid is less acidic than formic acid but is more acidic than propanoic acid.
i.e. H — COOH  CH3 — COOH  CH3 — CH2 — COOH  CH3 — CH2 — CH2 — COOH
(More acidic ) (Least acidic )
(ii) Electron-withdrawing group (–I-effect) increases acidity of acid.

e.g. Chloro-acetic acid is more acidic than acetic acid
i.e. Cl — CH2 — COOH > CH3COOH
II. Acidity of Phenols and alcohols

Phenols are much more acidic than alcohols. This is because alcohols give alkoxide ions on loss of a
proton. The alkoxide ions so formed are not resonance-stablized.
Electron-releasing substituents (+I-effect) decrease the acidity of phenols.
Electron-withdrawing substituents (–I-effect) increase the acidity of phenols.
OH OH OH
e.g.
NO 2 CH3
(More acidic) (Least acidic)
I. Basicity of Aliphatic Amines

Electron releasing group on the N-atom of amines increases the basicity of amine and electron
with drawing groups on the N-atom decrease the basicity.
e.g. (CH 3 )2NH > CH3 — NH2  (CH3 )3 N
(Most basic ) (Least basic )
e.g. CH 3 — CH2 — NH2 > Cl — CH2 — CH2 — NH2  O2N — CH2 — CH2 — NH2
(Most basic ) e  withdrawing group (Least basic )
II. Basicity of aromatic amines

Aromatic amines are less basic than aliphatic amines. This is because the lone pair of e–s on N-atom in
aromatic amines is less available due to delocalization.
e.g. CH 3 — NH2 > C6H5 — NH2
(Most basic ) (Least basic )
Ques. Explain why amines are most basic than amides and cyanides.
Ans. In simple amines, the lone pair of e–s is usually localised on nitrogen and hence available
for protonation.
In amides, the lone pair of e–s is delocalised to the carbonyl oxygen through resonance.
In cyanides, the lone pair of e–s in nitrogen is in sp-hybrid orbtial. Such e–s in orbital of high
s-character are held closer to the nucleus and are less available for protonation.
EXERCISE – 3
1. What is the correct order of acidity of the following hydra-acid?
(a) HF > HCl > HBr > HI (b) H2O > H2S > H2Se > H2Te
(c) H2SO4 < H2S < H2Se < H2Te (d) HI > HCl > HBr > HF
2. Which of the following is the correct order of acidity regarding oxyacid?
(a) HOCl > HClO2 > HClO3 > HClO4 (b) H3PO2 > H3PO3 > H3PO4
(c) H2SO4 < H2SO3 but HNO3 > HNO2 (d) All are correct
3. What is the correct order of acidity of the following compounds?
Cl
|
CH3CO2 H CHBr2 CO2 H CH3CHCO2 H
1. 2. 3.
Me2CH - CO2 H Me - CH - CO2 H CH2 - CH2 CO2 H

4. | |
N + R3 N + R3
5. 6.
(a) 2>5>3>6>1>4 (b) 5 > 3 > 2 > 1 > 6 > 4

(c) 6>1>2>5>4>3 (d) 2 > 6 > 5 > 1 > 3 > 4
4. What is the correct order of –I effect of the following groups?
(a) F > Cl > Br > I (b) N+H3 > –C  C – H > –CH = CH2 > H
(c) –NO2 > –CN > CO2H > –OH (d) All
5. Which one of the following is the correct order of acidity of the following compound?
(a) CH3–C  N > CH3CH2NH2 > CH3–NH2 > CH3CH = NH
(b) HN3 > NH2OH > N2H4 > NH3
(c) FCH2CO2H > HCO2H > CH3CO2H > ICH2CO2H > CHMe2CO2H
(d) H2O > CH3OH > Me2CHOH > Me3COH > EtOH > OH–
6. What is the correct order of pKa values of the following compounds?
(a) CH2  NH2 CH2  NH2

|  |  CH3NH2  NH3

SMe2 Br
(b) NH3 > CH3NH2 > CH2 = CH–NH2 > NH2–CH2–CH2–N+R3
Cl
|
(c) CH2  CH2NH2  CH2  CH2NH2  CH  C  NH2
|
CN
(d) None
22
5. REACTION INTERMEDIATES
Reaction intermediates are generated by the breaking of covalent bond of the substrate. They are
short-lived species and are highly reactive. There are six important types of reaction-intermediates.
1. Carbocation 2. Carbanion
3. Free radical 4. Carbene
5. Benzyne and 6. Nitrene
5.1 CARBOCATIONS
1. An organic species which has a carbon atom bearing six electrons in its outermost orbit and has a
positive charge is called a carbocation.
2. Carbocations can be classified into the following groups :
(A) Alkyl Carbocations :
(i) When positive charge is present on the alkyl carbon, carbocation is known as alkyl carbocation.
(ii) Alkyl carbocation is of four types :

Methyl Carbocation C H3

Primary alkyl carbocations R  C H2

Secondary alkyl carbocations R  CH  R

Tertiary alkyl carbocations R  C R
|
R
(iii) Stability of alkyl carbocations can be explained by
(a) Inductive effect and
(b) Hyperconjugation.
(iv) According to these two effects the stability order is follows :
   
R  C R R CH R R  CH 2  R CH 3
|
R

Stability in decreasing order


(v) If  -atom with respect to carbcationic carbon has lone pair of electrons then lone pair of
electrons strongly stabilises a carbocation due to the delocalisations.
Alkoxy and amino groups are important substituents for such types of carbocations.
CH3  
N _ CH2 is more than R  C R
:
CH3 |
R

_ _ 
: :
CH3 O CH2 is more stable than R  C R

|
R
(B) Vinyl carbocation : When positive charge is present on vinylic carbon then carbocation is known

as vinyl carbocation; CH 2  CH .
This carbocation is the least stable because positive charge is present on the more electronegative
carbon.

(C) Allyl carbocation : (CH2 = CH – CH2 )
(i) When positive charge is present on the allylic carbon of the allyl group, the carbocation is
known as allyl carbocation.
(ii) Allyl carbocations are more stable than the alkyl carbocations due to the resonance. Allyl
carbocations are stabilised by delocalisation (or resonance).
(iii) Allyl carbocations are of the following types :

CH 2  CH  C H 2 Primary

CH 2  CH  CH  R Secondary

CH 2  CH  C R
| Tertiary
R
(iv) Stability of primary, secondary and tertiary allyl carbocations can be compared by (a) Inductive
effect and (b) Hyperconjugation.
Thus, tertiary is more stable than secondary whose isomer is stable than primary allyl
carbocation.
(D) Phenyl Methyl Carbocations :
(i) When positive charge is present on benzyl carbon, carbocation is known as phenyl methyl
carbocation.
(ii) Phenyl methyl carbocations are of three types :
C6H5 – CH2 C6H5 – CH – C6H5 C6H5 – C – C6H5

C6H5
Benzyl carbocation
Diphenyl methyl Triphenyl methyl
or
carbocation carbocation
Phenyl methyl carbocation
(iii) Stability of phenyl methyl carbocations can be explained by resonance.

  
Structure :
C6 H 5  C C6 H 5 C6 H 5  CH  C6 H5 C6 H5  CH 2
|
C6 H 5
No. of Resonating Structures : 10 7 4
—————————————————————————————————
(a) Number of resonating structures in decreasing order
(b) Stability in decreasing order.
(iv) Phenyl methyl carbocations are more stable than allyl carbocations due to the number of
resonating structures
24
(E) Aromatic Carbocations :

(i) Cations in which positive charge is present on carbon of aromatic system is known as
aromatic carbocation.
(ii) Aromatic carbocations are so stable that even their solid states are known. For example
tropolium carbocation as tropolium bromide is a yellow solid. Infact tropolium carbocation is
about 1011 times more stable than triphenyl methyl carbocation.
(iii) Cations obeying Huckel (4n + 2) rule are stable because they are aromatic and there is
complete delocalisation of positive charge.
(F) Cyclopropyl Methyl Carbocations :
(i) These carbocations are very stable carbocations. They are more stable than benzyl
carbocations.
(ii) Stability of cyclopropyl methyl carbocations increases with every cyclopropyl group. Thus
additional cyclopropyl group has cumulative additive effect on the stability. Thus
+ + +
C CH CH2
Stability in decreasing order

(iii) The special stability is a result of conjugation between the bent orbitals of the cyclopropyl
and the vacant-p-orbital of the cationic carbon.
5.2 CHARACTERISTICS OF CARBOCATIONS (EXCEPT VINYL CARBOCATION)

(i) It has three bond pairs with empty p-orbital. Its hybridisation is sp2.
(ii) Shape of carbocation is trigonal planar.
+
Note : Triphenyl methyl carbocation has propeller shape.
(iii) There are six electrons in the outermost of carbocationic carbon hence its octet is incomplete. All
the six electrons are paired.
(iv) It is charged electrophile
(v) It is diamagnetic in character
(vi) It is formed by heterolytic bond fission
(vii) It reacts with nucleophiles.
5.3 CARBANIONS
Anion of carbon is known as carbanion. Carbanion carries three bond pairs and one lone pair, thus

making the carbon atom negatively charged. So carbanion may be represented as  C
|
1. Characteristic of Carbanions :
(i) Hybridisation and geometry : Alkyl carbanion has three bond pairs and one lone pair. Thus
hybridisation of alkyl carbanion is sp3 and geometry is pyramidal.
(ii) There are eight electrons in the outermost orbit of carbanionic carbon hence its octet is complete.
(iii) It behaves as charged nucleophile.
(iv) It is diamagnetic in character because all eight electrons are paired.
(v) It is formed by heterolytic bond fission.
(vi) It reacts with electrophiles.
2. Stability of Carbaions : The stability of carbanion may be explained by
(i) Electronegativity of carbanionic carbon :
Stability  Electronegativity of carbanionic carbon
 % s-character of carbanionic carbon
  
CH 3  C H 2 CH 2  C H CH  C
  
sp 3 sp 2 sp

(i) % s-character in increasing order


(ii) Stability in increasing order
(ii) Inductive Effect :

Stability of carbanions depends on the +I or – I group as follows :
1
(a) Stability 
 I power of the group
   
C H3 R  C H 2 R  C H 2  R R  C  R
|

R

(i) +I power in increasing order


(ii) Stability in decreasing order
(b) Stability of carbaions  -I power of the group.

(c) Delocalisation or Resonance : Allyl and benzyl carbanions are stabilised by delocalisation
of negative charge.
   
CH 2  CH  C H 2 C 6 H5  C H 2  C 6 H 5 2 C H  C 6 H 5 3 C
2 4 7 10

(i) Number of resonating structures is in increasing order


(ii) Stability is in increasing order
(d) Stabilisation by Sulphur and Phosphorous : Attachment of carbanionic carbon of sulphur

and phosphorus atom causes an increase in carbanion stability.
The cause of stability is due to the delocalisation of negative charge of carbanion by vacant
d-orbital  p  d bonding  of phosphorus and sulphur..
26
(e) Stabilisation by >C = O, –NO2 and CN groups present on carbanionic carbon :

These groups stabilise carbanion by resonance effect.
O O
_ _ _
CH2 C R CH2 = C R
Carbanion Enolate ion
(I) (II)
O O
_
CH2 N CH2 = N
O O
(I) (II)
Contribution of structure (II) will be more than (I) because in (II) negative charge is present on
electronegative oxygen.
(f) Stability of Aromatic Carbanions :
(i) Atoms in which negative charge is present on carbon of aromatic system is known as aromatic
carbanions.
(ii) Aromatic carbanions are most stable carbanions.
(iii) Anions obeying Huckel rule are stable because they are aromatic and there is complete delocalisation
of negative charge.
Cyclopentadienyl anion
3. Stability of different types of carbanions in decreasing order : Aromatic carbanion > Benzyl

carbanion > Allyl carbanion > CH  C >

_ R
_ _
CH 2  CH > Alkyl carbanion CH3 > R CH 2 > CH > R C R
R
R
4. Reactions in which product formation take place by formation of carbanion as reaction

intermediate : In the following product formation takes place by the formation of carbanion as
reaction intermediates :
(i) Condensation reactions of carbonyl compounds, i.e., Aldol condensation, Perkin reaction,
Reformatsky reaction etc.
(ii) Condensation reactions of ester ; Claisen condensation.
(iii) Witting reaction.
5.4 CARBON FREE RADICAL

1. Carbon free radicals are the species in which carbon atom bears the odd electron.
2. Homolytic bond fission of a covalent single bond gives rise to free radicals.
3. There are seven electrons in the outmost orbit of carbon of carbon free radicals.
4. Owing to the presence of an odd electron; a carbon radical is paramagnetic in nature. Due to this
reason free radicals are highly reactive.
5. The structure of the carbon free radicals are very difficult to predict. They have planar to pyramidal
geometry depending upon the groups and atoms attached to the carbon atom having odd electron.
For example, methyl free radical is planar. On the other hand trifluoro methyl free radicals is
pyramidal. Alkyl free radicals also have pyramidal geometry.
6. Free radicals are neutral electrophiles.
7. Free radicals generally react with free radical.
Stability :
(a) Stability of Alkyl free radicals : Stability of alkyl free radicals can be explained by
hyperconjugation and number of resonating structures due to the hyperconjugation. The decreasing
order of stability of alkyl free radicals is as follows :
tertiary > secondary > primary
Both electron withdrawing groups such as carbonyl, cyano and nitro and electron-donating groups
such as methoxy and dimethyl amino have a stabilising effect on a radical at a adjacent carbon
due to resonance.
(b) Stability of Allyl and Benzyl Free radicals :
(i) Stability of these radicals can be explained by delocalisation or resonance.
Structure :  C 6 H 5 3 C   C 6 H 5  2 C H  C 6H 5  C H 2  C H 2  CH  C H 2
No. of resonating structures : 10 7 4 2
 

(i) Number of resonating structures in decreasing order
(ii) Stability in decreasing order
(ii) Allyl and benzyl radicals are more stable than alkyl radicals. Triphenyl methyl radical and similar
radicals are stable enough to exist in solution at room temperature.
Free Radicals Reactions : Chemical reactions which takes place in the presence of peroxide, heat,
hv, electricity or free radicals is known as free radical reaction.
Characteristics of Free Radical Reactions :
1. Reaction intermediate is free radical.
2. Product formation takes place by formation of most stable free radical.
3. The reaction take place in three steps :
(a) Initiation ; (b) Propagation and (c) Termination
(a) Initiation Step : In this step, homolytic bond fission takes place in the presence of initiator, i.e.,
peroxide, hv, heat etc. The process is always endothermic.
Cl_Cl 
h

Cl  Cl H   ve
(b) Propagation Step : Propagation step is always two or more than two step process and all
propagation steps should be exothermic, otherwise free radical reactions would not
take place.
28
Propagation Step I : In this step, formation of free radical as reaction intermediate takes place.
For example,
. .
CH3 __ H + Cl CH3 + HCl H  negative
Propagation Step II : Reaction intermediate reacts with reagent to give the product.
. __ __ .
CH3 + Cl Cl CH3 Cl + Cl H  negative
(c) Termination Step : In this step, free radical formed in the last propagation step (generally
propagation step II) is destroyed by the addition of free radical or by the addition of some impurities
like CHCl3 or CCl4.
C l + C l 
 Cl2
4. Reaction velocity of free radical reaction is very-very high.
5. Certain compounds, known as inhibitor, retard velocity of free radical reactions.
Common inhibitors are O2, I2, p-benzoquinone and diphenylamine.
6. Amount of energy needed for homolysis of a covalent bond depends upon the stability of resulting
free radical as reaction intermediate (RI)
1
Energy needed 
Stability free radical as RI
Illustration 5 : Write down the correct order of stability of the following carbon free radicals
(I) CH 2  CH  C CH3 (II) CH 2  CH  C H  CH 3

|
CH 3
(III) CH 2  CH  C H 2
Solution : I > II > III
7. Stability of the same type of alkyl free radical  Number of carbons in alkyl free radical
8. Rearrangement takes place in primary free radical in a chemical reaction.
5.5 CARBENES
(i) Carbenes are neutral, divalent, highly reactive carbon intermediates represented by
X
:
C
Y
(ii) Carbenes are related to carbanions through the  -elimination reaction.

alc.KOH/
CHX 3   C X3  H 

C X 2  X

(iii) The simplest carbene is C H 2 which is known as methylene
(iv) Substituted carbenes are simply named as derivative of carbene. For example :
C6 H 5  C H Phenyl carbene
R  C R Dialkyl carbene
CCl2 Dichloro carbene

(v) Hybridisation of the divalent carbon of carbene may be sp2 as well as sp.
(vi) sp2 - hybrid carbene is of two types sp2 -singlet carbene (Fig.–I) and sp2-triplet carbene (Fig-II)
R R
C C
R R
sp2-Singlet carbene Sp2-Triplet carbene

(I) (II)
(vii) sp-hybrid carbene is always triplet carbene.
R_C_R
(viii) Carbenes are neutral electrophiles.

(ix) The decreasing order of stability of different types of singlet carbenes are as follows :
CF2  CCl2  C Br2

(x) Carbenes mainly give two types of reactions
(A) Addition with alkenes
__
:
C=C + CH2 C C
CH2
(B) Insertion reaction between C — H bond
| |
(a)
 C  H  C H 2 
  C  CH 2  H
|  |
O O
|| ||
(b) C  H  C H 2 
  C  CH 2  H

5.6 BENZYNE
1. 1, 2-Didehydrobenzene, C6H4, and its derivatives are called benzyne or arynes and the simplest
member is benzyne.
30
2. It is neutral reaction intermediate derived from benzene right by removing two substitutes, of
ortho positions, one in the form of electrophile and other in the form of nucleophile leaving behind
two electrons to be distributed between two orbitals.
Abnormal
Two sp2 -orbitals

outside the ring
3. Benzyne intermediate is aromatic in character

4. When halobenzene is heated with sodamide formation of benzyne takes place.
Cl
NaNH2
5. (i) It behaves as dienophile and gives Diels-Alder reaction with diene.


(ii) It reacts with strong nucleophilic like N H 2 .
NH2
NH2
H
+ NH2
5.7 NITRENES  R  N 
 .. 
1. The nitrogen analogus of carbenes are called nitrenes.

2. There is possibility of two spin states for nitrenes depending on whether the two non-bonding
electrons (the normal nitrogen lone pair remains paired) have their spins paired or parallel.
_
R N These two lone pairs of electrons
These two may be paired or unpaired

3. In general, nitrenes obey Hunds rule and are ground state triplet with two degenerate sp-orbitals
containing a single electron each.
R_N
sp-Triplet nitrene
6. ORGANIC REAGENTS
Organic reagents can be classified in two categories :
1. Electrophile : Electron deficient species or electron acceptor is electrophile.
2. Nucleophile : Electron rich species or electron donor is nucleophile.
6.1 ELECTROPHILES
It can be classified into two categories : (A) Charged electrophile E

  (B) Neutral electrophile (E)
(a) Charged Electrophiles : Positively charged species in which central atom has incomplete octet
is charged electrophile.
O
+ + + +
H , X +, R+ , N N = O, SO3H
:
O
Note : All cations are charged electrophiles except cations of IA, IIA group elements, Al+++

and N H
4
(b) Neutral Electrophiles : These can be classified into three categories :

(i) Neutral covalent compound in which central atom has incomplete octet is neutral electrophile.
BeCl2, BH3, ZnCl2, AlX3, FeX3, C H 3 , CH , CX

2 2
(ii) Neutral covalent compound in which central atom is bonded only with two or more than two
electronegative atoms is neutral electrophile.
SnCl4, SiCl4, PCl5, SF6, IF7
(iii) Neutral covalent compound in which central is bonded only with two or more than two
electronegative atoms is neutral electrophile.
BeCl2, BX3, AlX3, FeX3, SnCl4, PCl3
PCl5, NF3, CX , CO2, SO3, CS2, CX4

2
Note : (i) Cl2, Br2 and I2 also behave as neutral electrophiles.

(ii) Electrophiles are Lewis acids.
6.2 NUCLEOPHILES
Nucelophiles can be classified into three categories :
(a) Charged nucleophiles : Negatively charged species are charged nucleophiles.
      
H,O H, R  O, C H3 , X , SH, R  S
(b) Neutral Nucleophiles : It can be classified into two categories :
(i) Neutral covalent compound, in which central atom has complete octet, has at least one lone
pair of electrons and all atoms present on central atom should not be electronegative, is
neutral nucleophile.
N H 3 , R  N H 2 , R 2 N H, R 3 N, N H 2  NH 2 (Nitrogen nucleophile)
32
H  O  H, R  O  H, R  O  R (Oxygen nucleophiles)
H  S H, R  S H, R  S R (Sulphur nucleophiles
P H 3 , R P H 2 , R 2 P H, R 3 P (Phosphorus nucleophiles)
(ii) Organic compound containing carbon, carbon multiple bond/bonds behaves as nucleophile.
Alkenes, Alkynes, Benzene, CH2 = CH – CH = CH2, CH2 = CH – C  CH
(c) Ambident nucleophiles : Species having two nucleophilic centres, one is neutral (complete
octet and has at least one lone pair of electrons) and other is charged (negative charge) behaves
as ambident nucleophile.
O
  
C  N, O  N  O, O S OH

O
Note : 1. Organometallic compounds are nucleophiles.

2. Nucleophiles and Lewis base.
Organic compounds which behave as electrophile as well as nucleophile : Organic compound

in which carbon is bonded with electronegative atoms (O, N, S) by multiple bond/bonds behaves as
electrophile as well as nucleophile :
O O O O
|| || || ||
R  C  H, R  C  R, R  C  OH, R  C  Cl
O O
|| ||  
R  C  OR, R  C  NH 2 , R  C  N, R  N  C
Note : During the course of chemical reaction electrophile reacts with nucleophile.
EXERCISE – 4
1. Compare the stabilities of phenyl (C6H5 ) and cyclohexyl (a) cations and (B) anions.
2. Of the ethanol and trifluoro ethanol, which is mroe acidic?
3. Arrange the following compounds in the increasing order of basicity?
O
N N N
N
H H H
(I) (II) (III) (IV)
7. ISOMERISM
Different compounds with the same molecular formula are known as isomers.
Subdivisions of Isomers : Isomers can be divided into two categories :
(i) Constitutional isomers or structural isomers
(ii) Stereoisomers or configurational isomers
7.1. CONSTITUTIONAL ISOMERS OR STRUCTURAL ISOMERS

Isomers whose atoms have a different connectivity is known as structural or constitutional isomers and
the isomerism among them is known as structural isomerism.
(a) Chain isomerism : Isomeric substance that differ only in the arrangement of carbon atoms
forming the base chain are known as chain isomers and isomerism between them is known as
chain isomerism.
Examples :
CH 3
|
C5H12 : CH3  CH 2  CH 2  CH 2  CH 3 , CH3  CH  CH 2  CH 3 , CH3  C  CH3
n-Pentane | |
CH 3 CH 3
Isopentane Neopentane
C4H10O : CH 3  CH 2  CH 2  CH 2  OH and CH3  CH  CH 2  OH

1-Butanol |
CH 3
2-Methyl-1-butanol
C4H8 : CH 3  CH 2  CH  CH 2 CH3  C  CH 2
1-Butene |
CH 3
2-Methylpropene
(b) Position Isomerism : If compounds with the same molecular formula but differ in the position
of the same functional group or substituent on the identical base chain the compounds are called
position isomers. Isomerism between position isomers is called position isomerism.
Cl CH 2  CH 2
C2H4Cl2 : CH3 _ CH | |
Cl Cl Cl
1,1-Dichloroethane 1,2-Dichloroethane
CH3 CH3 CH3

CH3
C8H10 :
CH3
CH3
o-xylene m-xylene p-xylene
O O
|| ||
C5H10 : CH 3  CH 2  CH 2  C  CH 3 CH 3  CH 2  C  CH 2  CH 3
2-Pentanone 3-Pentanone
34
(c) Functional Isomerism : Compounds with the same molecular formula but differing in the type
of functional group they possess are classed as functional isomers and isomerism between them
is known as functional isomerism.
For Examples :
1. Aldehydes, ketones and unsaturated alcohols, (C nH2nO)
O
||
C4H8O : CH3 — CH2 — CH2 — CHO CH3 - CH2 - C - CH3
CH2 = CH — CH2 — CH2OH

2. Acids and ester, (CnH2nO2 )
C4H8O2 : CH3 — CH2 – CH2 – COOH CH3 – CH2 – COCH3
(d) Ring Chain Isomerism : If one isomer has open chain structure and the other has cyclic structure
then isomers are known as ring-chain isomers and isomerism between them is known as ring-
chain isomerism.
For examples :
1. Alkene and cycloalkane, (CnH2n)
CH3 — CH = CH2 CH2 __ CH2

CH2
2. Alkenols and cyclic ethers, (CnH2nO)
C3H6O : CH2 = CH — CH2OH CH2 - CH2

| |
CH2 - O
Note : Ring-chain isomers are always functional isomers.
Illustration 6 : How many structural isomers are possible for C4H8.

Solution : Five.
CH3 – CH2 – CH = CH2 , CH3 – CH = CH – CH3,
_
CH
CH
CH
3 CC=C=CH= 2
, , CH3
CH3
(e) Metamerism : This type of isomerism is due to the difference in the nature of alkyl groups
attached to the polyvalent atom or functional group. Metamers belong to the same homologous
series. Compounds like ether, thio ethers, ketones, secondary amines, etc. Show metamerism.
CH3  CH 2  CH 2  O  CH 3 CH 3  CH 2  O  CH 2  CH3
1-Methoxypropane Ethoxyethane
CH 3  CH 2  CH 2  NH  CH 3 CH 3  CH  NH  CH 3
|
CH 3
(e) Tautomer ism : Migration of acidic hydrogen from   carbon to electronegative atom which is
bonded with multiple bond is the cause of tautomers and this phenomenon is known as tautomerism.
O OH
H CH2 C CH3 H2C C CH3

(i) (ii)
1. Both (I) and (II) are isomers known as tautomers.

2. Tautomers are always in equilibrium state.
3. Number of sigma, pi and lone pair of electrons in both tautomers are always same.
4. Tautomerism is a chemical phenomenon which takes place only in liquid state.
5. Tautomerism are always functional isomers.
1,3-keto-enol system :
In this tautomerism one tautomer exists as ketone (known as keto form) while the other exists as an
enol (known as enol form)
O OH
|| |
CH3  C  CH3 CH 2  C  CH3
keto form enol form
1,3-keto-enol tautomerism
In most of the cases; content of the keto form is always more than that of the enol form. i.e., Keto form
is more stable than the enol form. But in some cases enol form is more stable than the keto form.
Percentage of enolic contents of some common compounds in decreasing order is given below :
O
> C6H5COCH2COCH3 > CH3—CO—CH2—COCH3 > CH3COCH2COOC2H5 > CH3COCH3
Percentage composition of tautomeric mixture :

Percentage of enol contents of some compounds is given below in the table :
Table : Enol Content of some compounds
Compound Enol percentage
CH3 – CO – CH3 0.00025

CH3 COCOCH3 0.0056
CH3COCH2 COOCH3 4.8
CH3COCH2 COOC 2 H 5 31.00
CH3  CO  CH  COOCH 3 80.4

|
CH 3
CH3 — CO — CH2 — COCH3 89.0

O
99.999
36
The conversion of a keto form into an enol form is known as enolisation and the enolisation of a
compound has been found to depend upon various factors such as structural factor, temperature and
nature of solvent. However, the most important is the structural factor (resonance and hydrogen bonding).
(i) Ketonic form predominates in simple monocarbonyl compounds like acetaldehyde, acetone and
cyclohexanone. This is due to the greater bond strength of C = O bond ( >C = O, 364 kJ/mole)
present in keto form than the carbon-carbon double bond ( C = C, 250 kJ/mole) present in enolic
form.
(ii) Enolic form predominates in  -diketones due to intramolecular hydrogen bonding and resonance.
Intramolecular hydrogen bonding stabilizes enol form by 7 kcal/mole and resonance stabilises enol
form by 15 Kcal/mole. Thus enol form is more stable than keto form by 22 kcal/mole in 1,3-
diketones. H
: :
O O O O

CH 2  C  CH 2  C  CH 3 
 CH  C _
3 C CH3
CH
H
O O
_ _
CH3 C C CH3
CH
H
H O O
O
:
O _ _
CH3 C C CH3
CH3 _ C C
_
CH3 CH
CH
H H
O O O O
CH3 _ C C _ CH
_
CH3 C _
3 C CH3
CH CH
The polar protic solvent (H2O, alcohol and acid) which tends to stabilise thick to form relative to
the enol form will reduce the enol content. On the other hand, non polar solvents (benzene,
hexane, toluene, xylene etc. ) which do not form hydrogen bonds, tend to increase the enol content.
(iii) Nitro-acinitro system : In this system one tautomer exists as nitroalkane (nitroform) while the
other tautomer exists as an acinitro.
O OH
CH 3  N CH 2  N
O O
Nitro form Acinitro form
Illustration 8 : Write the tautomer of CH3CH2CH = NH

Solution : CH3CH2CH = NH  CH3CH = CH NH2
imine Enamine
7.2 STEREOISOMERS OR CONFIGURATIONAL ISOMERS

Isomers that have the same molecular formula, same Connectivity (i.e., structure) but differ in the
arrangement of their atoms in space are known as stereoisomers and the isomerism among them is
known as stereoisomerism.
Configurational isomers
Geometrical isomers Optical isomers

These differ in the way their atoms are arranged in space.
(1) Geometrical Isomerism
Hindered rotation about carbon-carbon bond : A double bond consists of a -bond and a -
bond. A -bond prevents free rotation of the carbon atoms of the double bond with respect to
each other. Due to this hindered rotation, the relative positions of atoms or groups attached to the
carbon atoms of the double bond get fixed. For example, Ha and Hb cannot exchange their positions
by rotations of C1 with respect to C2 without breaking the -bonds.
Ha Ha
C C
Hb Hb
 Definition : Compounds having same molecular formula and structural formula but the
arrangement of atoms or group of atoms are different due to hindered rotation around doubly
bonded atoms (C=C, C=N, N=N) or cyclic compounds such compounds are geometrical isomers.
Cis-trans isomerism : Alkenes can exist in two distinct isomers, which differ from each other
only in the relative positions of atoms or groups in space around the bond. For example, but-2-ene
can exist in the following two forms (I and II).
H3C CH3 H3C H

C C C C
H H H CH3
cis-But-2-ene (I) trans-But-2-ene (II)
Both these isomers have the same structural formulae but differ in the relative spatial arrangement
of hydrogen atoms and methyl groups around the double bond. The isomer I, in which the similar
atoms or groups lie on the same side of the double bond is called the cis-isomer whereas the
isomer II, in which the similar atoms or groups lie on the opposite sides of the double bond is called
the trans-isomer. It is because of this reason that geometrical isomerism is also called cis-trans
isomerism.
38
Geometrical isomerism is also shown by compounds which contains C N OH, –N=N–
structural units. Cyclic compound also exhibit geometrical isomeris.
Compounds containing C N OH units are commonly called oximes. Oxime of formaldehyde
H
is incapable of showing geometrical isomerism C N OH while oxime of any other aldehyde
H
(other than formaldehyde) will exhibit geometrical isomerism.
R H R H
C C
N N
OH
OH
(syn isomer) (anti isomer)
The nomenclature for aldoximes is syn (when H and OH are present on same side of the double
bond) and anti (when H and OH are present on opposite sides of the double bond).
R
Oximes of symmetrical ketones C N OH do not show geometrical isomerism but
R
R
oximes of unsymmetrical ketones C N OH are capable of showing geometrical
R
isomerism.
R R' R R'
C C
N N
OH
OH
Syn (R') or Syn (R') or
anti (R) anti (R)
Diazobenzene also exhibit geometrical isomerism.

Ph Ph
N N
N N
Ph
Ph
(Syn or cis) (Anti or trans)
Cyclic compounds too have restricted rotation because of the impossibility of rotation around C–
C single bond as the conformation of cyclic compound would twist on rotation. Appropriaetly
placed substituents on cycloalkanes would be capable of showing geometrical isomerism.
X X X X
X X X X X
X X
X
1, 2-cis 1, 2-trans 1, 3-cis 1, 2-trans 1, 4-cis 1, 2-cis
E & Z nomenclature : In the case of cis-trans nomenclature, the atoms or groups attached to
the C-atoms should be similar but if all the four groups are different, then E, Z nomenclature
comes into picture. According to this nomenclature, if the atoms or groups of higher priority are on
the same side of the double bond, the isomer is designated as Z (zusammen, in German means
together) and if the two atoms or groups of hgher priority are on the opposite sides, the isomer is
designated as E (Entegegan, in German means opposite). The priority of a group or atom is based
on the given below rules.
Rule 1 : The atom of higher atomic number gets higher priority. If the two atoms attached to the
double bond are isotopes, the isotope of higher mass number gets the higher priority. For example,
in 1-bromo-2-chloro-2-iodo ethene, C1 has two atoms viz. Br and I. Since I (Z = 53) has higher
atomic number than Br (Z = 35), therefore I is assigned priority I wile Br is assigned priority 2.
Similarly, Cl is assigned priority 1 while F ia assigned priority 2 on C2.
Br CH2 Cl
2 1
C C
I CH2 OH
1
2
Rule 2 : If two atoms directly attached to the doubly bonded carbon have the same atomic
number, then the relative priority of the group is determined by a similar comparison of the atomic
numbers of the next element in the group. (and so on, if necessary, work outwards till the first
point of difference is reached). For example, in the following compound,
H3 C CH2 Cl
2 1
C C
H2 CH3 C CH2 OH
1 2
one of the carbon atoms of the double bond carries CH3 and CH3CH2 groups, since the first atom
(i.e. C) attached to the carbon atom of the double bond is the same in CH3 and CH3CH2 groups,
compare the atomic number of the atoms attached to each of these first atoms.
40
Rule 3 : Double bond and triple bonds are treated as if they have duplicate or triplicate single
bonds. For example,
–CH=CH– is treated as CH CH and C O is treated as C O
C C O C
C C
H CH
is treated as C C
C C C and –C=C is treated as C C
C C C C
H H
For example, consider the following compound,
H3C CHO
(2) (1)
C C
H5 C 6 CH2 OH
(1) (2)
one of the atoms of the double bond carries CH3 and C6H5 group. Since, in C6H5 group, the first
carbon is attached to two other carbons by a double bond and the other by a single bond. Therefore,
phenyl gets higher priority than CH3 group. Similarly, CHO gets higher priority than CH3OH.
Thus, the given isomer is ‘E’.
Necessary and sufficient conditions for geometrical isomerism : All compounds containing
double bond necessarily do not show geometrical isomerism.
The necessary conditions for a molecule to exhibit geometrical isomerism are
(i) The molecule must have restricted rotation due to the presence of a C=C, C=N, N=N and cyclic
structure.
(ii) Each of the two atoms have restricted rotation must have different substituents attached to it,
which may be same or different. Thus, alkenes of the type abC=Cab and abC=Cde show
geometrical isomerism.
a a a b
C C C C
b b b a
cis-isomer trans-isomer
a d a c
C C C C
b e b d
Z-isomer E-isomer
(If groups 'a' and 'd' have (If groups 'a' and 'd' have
higher priority) higher priority)
However, geometrical isomerism is not possible, if one or both the doubly bonded carbon atoms
carry two similar substituents. This is because in such cases, the two possible configurations are,
identical as shown below.
a d a e
C C C C
b e a d
It is because of this reason that terminal alkenes such as propene, but-1-ene, 2-methyl prop-1-ene
and alkenes carrying identical substituents on one of the doubly bonded carbon atoms such as
2-methyl but-2-ene and 2, 3-dimethyl but-2-ene etc. do not show geometrical isomerism.
(2) Optical Isomerism
Optical activity : Plane-polarised light possess certain properties that are best understood by
considering it to be a wave phenomenon in which the vibration occur at right angles to the direction
in which the light travels. There are an infinite number of planes passing through the line of
propagation, the ordinary light is vibrating in all these planes.
Ordinary Light is turned into plane-polarised light by passing it through a lens made of the material
known as Polaroid or more traditionally through pieces of calcite (a particular crystalline form of
CaCO3) so arranged as to constitute a “Nicol prism”.
Plane-polarised light is light whose vibration take place in only one plane
or
(a) Ordinary Light (b) Plane-Polarized Light
An optically active substance is one that rotates the plane of polarized light.
When plane polarised light, vibrating in a certain plane is passed through an optically active
substance, it emerges vibrating in a different plane.
If the substance does not affect the plane of polarization light transmission is still at a maximum
and the substitution is said to be optically inactive.
The measurement of rotation of plane of polarised light can be done by polarimeter.
α
α
eye
Light source
If the rotation of the plane, is to the right (clockwise), the substance is dextrorotatory (Latin :
dexter-right), if the rotation is to the left (anticlockwise), the substance is leavo rotatory (Latin :
Leavus : left)
42
(3) Optical Activity and Chirality

Any material that rotates the plane of polarized is said to be optically active. If a pure compound
is optically active, the molecule is non superimposable on its mirror image. If a compound is super-
imposable on its mirror image, the compound does not rotate the plane of polarised light, it is
optically inactive.
The property of non superimposability of an object on its mirror image is called chirality. If a
molecule is not superimposable on its mirror image it is achiral. The relationship between optical
activity and chirality is absolute.
In each case of optical activity of pure compound there are two and only two isomers, called
enantiomers.
Enantiomers rotate the plane of polarized light in opposite directions, though in equal amount. The
isomer that rotate the plane to the left (counter clockwise) is called the leavo isomer and is
designated (–), while the one that rotates the plane to the right (clockwise) is called the dextro
isomer and is designated (+). Because they differ in this property they are often called optical
antipodes.
Enantiomers may differ in solubilities in an optically active solvent they may have different index
of refraction or absorption spectra when examined with circular polarized light.
A mixture of equal amount of enantiomers are optically inactive since the equal and opposite
rotations cancel.
Such mixtures are called racemic mixture or racemates.
A molecule that contains just one chiral carbon atom (defined as a carbon atom connected to four
different groups : also called as asymmetric carbon atom) is always chiral hence optically active.
Such molecule cannot have a plane of symmetry (also called a mirror plane passing through an
object such that the part on one side of the plane is the exact reflection of the part on the other
side.)
Compound possessing chiral carbon
H OH
| | *
CH 3 CH 2 CH 2  C  OH , CH3  C  COOH , CH3 CH 2 CH  CH3
| | |
D H Br
1-butanol-1-d latic acid 2-bromo butane
Example :
Lactic acid exists in two forms, one is the mirror image of the other and the two forms are non-
superimposable.
CH3 CH3
OH H
H HO
COOH COOH
Mirror
(4) Specific Rotation : Specific rotation is the number of degree of rotation observed if a 1-dm (10
cm) tube is used, and the compound being examined is present to the extent of 1 g/mL.
This is usually calculated from observations with tubes of other lengths and the different
concentration by means of the question:

[ ] 
ld
observed rotation (deg rees)
sp.rotation 
length(dm)  g / mL
[  ] = the specific rotation

 = the observed rotation
c = concentration of the solution in grams per milliliter of solution or density in g/mL of pure liquid.
l = the length of the tube in decimeters (1 dm = 10 cm)
The specific rotation also depends on the temperature and the wavelength of light that is employed.
Specific rotations are reported so as to incorporate these quantities as well.
25
A specific rotation weight be given as follows :  0  5.910
This means that the D line of a sodium lamp    589.6 nm  was used for the light, that a temperature
of 250 was maintained and that a sample containing 1 gmL-1 of the optically active substance in a
1 dm tube, produced a rotation of 5.910 in a clockwise direction.
Molecules Display Optical Activity :
Although the ultimate criterion is, of course, nonsuperimposability on the mirror image (chirality),
other tests may be used that are simpler to apply but not always accurate. One such test is the
presence of a plane of symmetry. A plane of symmetry (also called a mirror plane) is a plane
passing through an object such that the part on one side of the plane is the exact reflection of the
part on the other side ( the plane acting as a mirror). Compounds possessing such a plane are
always optically inactive, but there are a few cases known in which compounds lack a plane of
symmetry and are nevertheless inactive. Such compounds possess a centre of symmetry, such as
in  -truxillic acid, or an alternating axis of symmetry as in figure shown.
Ph COOH
H H H
H
COOH Ph
A centre of symmetry is a point within an object such that a straight line drawn from any part or
element of the object to the centre and extended an equal distance on the other side encounters an
equal part or element. An alternating axis of symmetry of order n is an axis such that when an
object containing such an axis is rotated by 360o/n about the axis and then reflection is effected
across a plane at right angles to the axis, a new object is obtained that is distinguishable from the
original one. Compounds that lack an alternating axis of symmetry are always chiral.
44
Optically active compounds may be classified into several categories.

(i) Compounds with a chiral carbon atom : If there is only one such atom the molecule must be
optically active. This is so no matter how slight the differences are among the four groups. For
example, optical activity is present in
H
|
CH 3CH 2 CH 2  C  OH
|
CH 3
However, the amount of rotation is greatly dependent on the nature of the four groups, in general
increasing with increasing differences in polarizabilities among the groups. Alkyl groups have very
similar polarizabilities.
(ii) Restricted rotation giving rise to perpendicular dissymmetric planes :Certain compounds
that do not contain symmetric atoms are nevertheless chiral because they contain a structure that
can be schematically represented as in figure.
A
A
B B
For these compounds we can draw two perpendicular planes neither of which can be bisected by
a plane of symmetry. If either plane could be so bisected, the molecule would be superimposable
on its mirror image, since such a plane would be a plane of symmetry. These points will be
illustrated by examples.
Biphenyls containing four large groups in the ortho positions cannot freely rotate about the central
bond because of steric hindrance. In such compounds the two rings are in the perpendicular
planes. If either ring is symmetrically susbtituted, the molecule has a plane of symmetry. For
example, consider :
Cl NO2 B O2 N Cl
HOOC COOH
A
HOOC COOH O N
2
NO2
Mirror
Ring B is symmetrically substituted. A plane drawn perpendicular to ring B contains all the atoms
and groups in ring A; hence it is a plane of symmetry and the compound is achiral. On the other
hand, consider :
NO2 NO2
HOOC COOH
COOH NO2 O2 N HOOC
Mirror
There is no plane of symmetry and the molecule is chiral ; many such compounds have been
resolved. Note that groups in the para position cannot cause lack of symmetry. Isomers that can
be separated only because about single bonds is prevented or greatly slowed are called
atropisomers.
In allenes the central carbon is sp bonded. The remaining two p orbitals are prependicular to each
other and each overlaps with the p orbital of one adjacent carbon atom, forcing the two remaining
bonds of each carbon into perpendicular planes. Thus allenes fall into the category represented by
figure
A A A A
C=C=C C=C=C
B B B B
Mirror
Like biphenyls, allenes are called only if both sides are unsymmetrically substituted. For example
CH 3 H CH 3 H CH 3 H
C=C=C C=C=C C=C=C
H H H H CH 3
CH 3
Inactive Inactive Active
These cases are completely different from the cis-trans isomerism of compounds with one double
bond. In the later cases the four groups are all in one plane, the isomers are not enantiomers, and
neither are chiral, while in allenes the groups are in two perpendicular planes and the isomers are
a pair of optically active enantiomers.
These- 3- dimensional projections of lactic acid can be representd on 2-dimension by Fischer
Projection Formula’s.
(5) Fischer Projection : Chemists sometimes represent structures for chiral molecules with two
dimensional formula called fischer Projection formulas.
By convention fischer projections are written with the main carbon chain extending from top to
bottom with all group eclipsed. Vertical lines represent bonds that project behind the plane of the
paper (or that lie in it). Horizontal lines represent bonds that project out of the plane of the paper.
The intersection of vertical and horizontal lines represents a carbon atom usually, one that is a
chiral centre.
46
COOH COOH
H2N H
H2N H
CH3 CH3
In order to obtain proper result with these formula, it should be remembered that they are projections
and must be treated differently from the models in testing for super-imposability.
Every plane is superimposable on its mirror image, hence with these formulas there must be
added the restriction that they may not be taken out of the plane of paper. We are permitted to
rotate the structure in the plane of the paper by 1800 but by no other angle. We are not allowed
to them over.
COOH CH3 NH2
H2 N H H NH2 CH3 COOH
CH3 COOH H
It is also permissible to keep any one group fixed and to rotate the other three clockwise or
counter clockwise (because this can be done with models).
COOH COOH NH2
H2 N H H2 N CH 3 HOOC CH3
CH3 H H
However, the interchange of any two groups results in the conversion of an enantiomer into its
mirror image. With these restrictions fischer projection may be used instead of models to test
whether a molecule containing asymmetric carbons is superimposable on its mirror image.
7.3 NAME OF OPTICAL ISOMERS

Following nomenclatures are used for optically active compounds :
(a) D. L. System of Nomenclature: This nomenclature is mainly used in sugar chemistry or optically
active polyhydroxy carbonyl compounds. This nomenclature was given by Emil Fischer to designate
the configurations of various sugars relative to the enantiomeric (+) and (-) glucose as reference.
All sugars whose Fischer projection formula shows the OH group on the chiral carbon atom
adjacent to the terminal CH2OH group on the right hand side belong to the D-series.
H C OH
CH2OH
D-series
Similarly if OH is on the left hand side, then the sugars belong to the L-series.
HO C H
CH2 OH
L-series
Examples : CHO CHO
H C OH HO C H
CH 2OH CH2OH
D(d)-glyceraldehyde L(l)-glyceraldehyde
or or
D(+) glyceraldehyde L(-) glyceraldehyde
— It must be noted that there is no relation between the sign of rotation (+, -or d, l) and the
configuration (D and L) of an enantiomer.
— Any compound that can be prepared from, or converted into D(+) glyceraldehyde will belong
to D-series and similarly any compound that can be prepared from, or converted into L(-)
glyceraldehyde will belong to the L-series.
(b) R, S Nomenclature (Absolute configuration)
The order of arrangement of four groups around a chiral carbon (stereocentre) atom is called the
absolute configuration around that atom. System which indicates the absolute configuration was
given by three chemists R.S. Cahn, C.K. Ingold and V. Prelog. This system in known as (R) and
(S) system or the Cahn-Ingold Prelog system. The letter (R) comes from the Latin rectus (mean
right) while (S) comes from the Latin sininster (mean left). Any chiral carbon atom has either an
(R), configuration or an (S) configuration. Therefore, one enantiomer is (R) and other is (S). A
racemic mixture may be designated (R) (S), meaning a mixture of the two.
(R) (S) nomenclature is assigned as follows :
Step I : By a set of sequence rules given below the atoms or groups connected to the chiral
carbon are assigned a priority sequence.
(c) Sequence Rules for Order of Priority
Rule- 1 : If all four atoms directly attached to the chiral carbon are different, priority depends on
their atomic number. The atom having highest atomic number gets the highest priority i.e. (1).
The atom with the lowest atomic number is given the lowest priority, i.e. (4), the group with next
higher atomic number is given the next higher priority (3) and so on. Thus.
Cl 2
F C I 4 C 1
Br 3
F Cl Br I
Increasing atomic number
48
4 3 2 1
Increasing priority
COOH 4
H 2N C Br 3 C 1
OH 2
C N O Br
Increasing priority
Rule 2 : If two or more than two isotopes of the same element is present, the isotope of higher
mass receives the higher priority.
1 H1 1H 2 1H 3
Increasing priority
3 2 1
Rule 3 : If two or more of the atoms directly bonded to the chiral carbon are identical, the atomic
number of the next atoms are used for priority assignment. If these atoms also have identical
atoms attached to them, priority is determined at the first point of difference along the chain. The
atom that has attached to it an atom of higher priority has the higher priority.
I 2H and Br
1
I _ H C _ H C _ C _ CH _ Br
2 2 2
3 2
2H and C
CH _ CH __ CH
2 2 3
2H and C
4
Rule 4 : If a double or a triple bond is linked to chiral centre the involved atoms are duplicated or
triplicated respectively.
O N
C O C O; C N C N
N
The molecule is then visualised so that the group of lowest priority (4) is directed away from the
observer (at this position the lowest priority is at the bottom of the plane). The remaining three
groups are in a plane facing the observer. If the eye travels clockwise as we look from the group
of highest priority to the groups of second and third priority (i.e. 1  2  3 with respect to 4)
the configuration is designated R. If arrangement of groups is in anticlockwise direction, the
configuration is designated S.
Example : Glyceraldehyde has one asymmetric carbon, hence it has two configurational isomers
(I) and (II).
CHO CHO
H C OH HO C H
CH2OH CH2OH
(R) glyceraldehyde (S) glyceraldehyde
(I) (II)
Stereoisomers can be subdivided into two general categories

(a) Enantiomers; (b) Diastereomers.
(a) Enantiomers : As already discussed, are stereoismers where molecules are non-
superimposable and mirror images of each other.
(b) Diastereomers : Are the stereoisomers whose molecules are not mirror images of each
other.
7.4 CALCULATION OF NUMBER OF OPTICAL ISOMERS

1. If molecule is divisible into two identical halves, then number of optical isomers depends on the
number of asymmetric carbon atoms. (When compound has even number of carbon atoms)
(i) Number of optically active forms = a = 2n-1 (where n is number of chiral carbon atoms)
(ii) Number of enantiomeric pairs = a/2 (number of racemic mixture)
(iii) Number of meso forms = m = 2(n/2 -1)
(iv) Total optical isomers = a + m
COOH COOH COOH
H OH HO H H OH
HO H H OH H OH
COOH COOH COOH

(a) (b) (c)
Optically inactive isomers
Optically active isomers
(meso form)
(a)& (b) - enantiomers.
(b) & (c) - diastereomers.
(a) & (c) - diastereomers.
2. Molecule is not divisible into identical halves and molecules
(i) Number of optically active forms = a = 2n (where n is number of chiral carbon atoms)
(ii) Number of enantiomeric pairs = a/2 (number of racemic mixture)
(iii) Number of meso forms = m = 0
(iv) Total optical isomers = a + m
50
* * * *
Example : HOH 2 C  C H  CH  C H  CH  CHO
| | | |
OH OH OH OH
Number of Isomers = 24 = 16.
EXERCISE – 5
1. (a) Draw all the stereoisomers of 3–chloro–2–pentanol, CH3CH(OH)CHClCH2CH3.
(b) Give the stereochemical relationships of the stereoisomers.
2. Draw all the stereoisomers of 1, 2– and 1, 3– dimethylcyclopentanes.
7.5 FREE ROTATION ABOUT T HE CARBON-CARBON SINGLE BOND:

CONFORMATIONS
1. The stereo isomers which are interconvertible without breaking a bond are called Conformational
isomers or Conformers.
Br
H2C – CH2 CH2 – CH2
Br Br Br
2. For the same reason of free rotation about a single bond the number of conformers is always
infinte. However the number of important conformers will be always limited.
3. All conformers exist in a state of rapid equilibrium. Therefore they can’t be separated. Also for
the reason that stability difference among conformers is less.
At equilibrium however’ the population of most stable conformers will be more.
4. Conformers have different physical and chemical properties.
5. Dihedral angle : The angle between two planes is called dihedral angle.
A
C
B
180º A B
C
D D
D ABC dihedral angle is 180
A B
DABC dihedral angle = Oº

D C
6. Newman’s Projection Formula : This formula is written along a bond. One C-atom of the bond
is represented as and other is represented as , overlapping the two on each other gives
Newmann formula of the compound and is obtained as
Newman formula is of two type (i) Staggered and (ii) Eclipsed
Staggered Eclipsed
7. Conformational Analysis of Butane : The study of the relative energies of conformational

isomers can be done nicely taking butane as an example. Let us have a Newmann projection by
looking down the C(2) – C(3) bond of butane.
H CH3
1 2 3 4 H
CH3 – CH2 – CH2 – CH3 C C
H
CH3
H
Let us assume that relatively large methyl groups will best be kept as far from each other as
possible then we have the conformation called the anti form shown in the figure (A). 120º clockwise
rotation passes over a transition state to a new minimum energy conformation of butane shown in
the figure (B).
CH3
H H
H H
CH3
Fig. (A)
Conformation of (B) will be less stable then (A) because in (B) the two methyl groups are closer
than they are in (A). Conformation (B) is called ‘gauche’ form. Gauche form of butane (B) is about
0.6 kcal mol–1 higher in energy than the anti form (A). There was an eclipsed transition state for the
interconversion of (A) of (B) which lies about 3.4 kcal mol–1 higher than (A).
CH3
H3C H
H H
CH3
Fig. (B)
Another 120º clockwise rotation brings us to a second gauche form of butane (B'). The transition
state for the conversion of (B) to (B’) involves an eclipsed state of two C–CH3 bonds shown in
fig. (C) and lies 3.8 kcal mol–1 above (B) and (B’), a total of about 4.4 kcal mol–1 above (A). Final
120º clockwise rotation return us to (A).
52
CH3 H3C
CH3
H CH3
H
H H H HH
H
Fig. (B’) Fig. (C)
The angle versus energy plot for butane can be shown as
H3C
CH3
H3C
H3C H H
H H
H C H
H
CH3 H3C H
H 3.8 kcal/ H H3C
H H H H –1
mol
Potential energy
3.4 kcal/ 3.4 kcal/

H H –1 B B' –1
mol mol
CH3 CH3 CH3
H3C H CH3
H
H H H H
H H
0º 60º 120º 180º 240º 300º 360º
Rotation about the Central C2 – C3 bond
Conformations are of three types as

(i) Eclisped (with highest energy, hence least stable)
(ii) Staggered (with lowest energy, hence most stable) and
(iii) Intermediate conformations are called Skew conformation
To represent such conformations we often use two kinds of three dimensional formulae; and
Sawhorse formulae and Newman projections. The energy required to rotate the ethane molecule
about carbon-carbon bond is called torsional energy.
H H
H H
H H
H H
H
H H
H Sawhorse Representation
Eclipsed Staggered II
H
H H
H H
Newman
Projection
H H
H H
H H
H
Eclipsed I Staggered II
54

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Chemistry : General Organic Chemistry & Isomerism

Concepts of hybridisation of carbon, sigma, pi bonds, resonance, homologous series, structural,

2. INTRODUCTION TO ORGANIC COMPOUNDS

2.1 CLASSIFICATION OF ORGANIC COMPOUNDS

Aliphatic, or Open-chain compounds e.g. n-butane and Iso-butane etc.

Cyclic or closed-chain compound e.g. Benzene, cyclohexane etc.

Aromatic compound e.g. Benzene, Naphthalene etc.

2.2 NOMENCLATURE OF THE ORGANIC COMPOUNDS

2.3 SYSTEMATIC NAME OF AN ALKANE IS OBTAINED USING THE FOLLOWING

Number of Carbon Name (Prefix)

Two Different way to draw 3-methyl hexane

2.4 LIST SUBSTITUENTS IN ALPHABETICAL ORDER

2.5 IUPAC RULES WE FOLLOWED IN NAMING ALKENES

H3C CH2 CH2 C CHCH2 CH CH3 CH 3CH  CH  C  CH 2 CH 3

2.6 NAMING OF ALKYNE

Illustration 2 : Name each of the following compounds :

(i) CH 2  CH 2 C  CH (ii) CH3CH 2CH  C  CH

Solution : (i) 1-pentyne (ii) 3-ethyl-1-hexyne

2.7 NOMENCLATURE OF CYCLOALKANES:

propylcyclopentane 1-cyclopropyl pentane

not 1-ethyl-3-methyl-4-propyl cyclohexane

2.8 NOMENCLATURE OF SUBSTITUED HYDROCARBONS (HAVING SECONDARY

2.9 ETHERS (ALKOXY ALKANE)

(b) Cyclic ether :

Illustration 3 : Name the following compounds

3.1 NOMENCLATURE OF COMPOUND HAVING SECONDARY SUFFIX

Functional Group Prefix Secondary Suffix

O isopropyl cyclopentyl methanoate

IUPAC name : cyclopentylmethanoyl chloride

CN Cyclopentyl methannitrile

e.g. : (i)  no. of conjugated e–s (6) 

(ii)  no. of conjugated e–s (6) 

e.g. (i)  no. of conjugated e–s (4) 

(ii)  no. of conjugated e–s (4) 

3.2 NOMENCLATURE OF AROMATIC COMPOUNDS

COOH COOH HOOC

Benzenesulphonic 4-toluenesulphonic acid

Illustration 4 : Name the compound

Solution : 3-tert-butyl-4-methyl benzolychloride

2. Which of the following is anit-aromatic species?

3. Which of the following is non-aromatic?

4. Which of the following is non-aromatic?

5. Which is the most aromatic in character?

4.1 HOMOLYTIC FISSION OR HOMOLYSIS

4.2 HETEROLYTIC BOND FISSION OR HETEROLYSIS

4.3 VARIOUS EFFECTS

Inductive effect is thus

less stable more stable

(ii)  (C–H), positive charge conjugation : It occurs in alkyl carbocations

Explanation of Acidity and basicity of different compounds on the basis of

(ii) Electron-withdrawing group (–I-effect) increases acidity of acid.

II. Acidity of Phenols and alcohols

(More acidic) (Least acidic)

I. Basicity of Aliphatic Amines

II. Basicity of aromatic amines

Me2CH - CO2 H Me - CH - CO2 H CH2 - CH2 CO2 H

(a) 2>5>3>6>1>4 (b) 5 > 3 > 2 > 1 > 6 > 4

(a) CH2  NH2 CH2  NH2