13 Goc Revision Notes Quizrr

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GENERAL
ORGANIC
CHEMISTRY
2 QUIZRR
C ontents
1. Nomenclature 3
2. Isomerism 33
3. Various Effects 75
4. Reaction Intermediateries 96
5. Acids & Bases 122
GENERAL ORGANIC CHEMISTRY

QUIZRR 3
CL A SSIFICA T I ON OF ORGA N I C COM POU N DS

Depending upon the nature of the carbon skeleton, compounds have been broadly divided into
two categories. These are :
I. Acyclic or Open chain compounds.
II. Cyclic or Closed chain compounds.
I. Open Chain or Acyclic Compounds : Compounds of carbon having open chain of carbon
atoms, branched or unbranched are caled acyclic compounds or aliphatic compounds.
Butane CH3 ă CH2 ă CH2 ă CH3
Isopentane CH3 ă CH ă CH2 ă CH3
|
CH3
Open chain compounds are also known as aliphatic compounds since the earlier compounds of this
class were obtained either from animals or vegetable fats. (Greek, aliphatos  fats).
II. Cyclic or Closed Chain or Ring Compounds : Compounds or carbon having closed chain of
carbon as well as of other atoms are called cyclic compounds. Depending upon the constitution of
the ring, these are further divided into the following categories.
1. Homocyclic or carbocyclic compounds.
2. Heterocylic compounds.
1. Carbocyclic or Homocyclic Compounds : Compounds of carbon having closed chain entirely
made up of carbon atoms are called carbocyclic or homocyclic compounds. These are further
divided into two groups.
(i) Alicyclic Compounds : Closed carbon chains except characteristic benzene ring, resembling
in properties with acyclic compounds.
For example : cycloalkanes, cycloalkenes etc.
Cyclopropane Cyclopentane Cylopenetene Cyclohexene
(ii) Aromatic Compounds : Closed chain of only carbon atoms with alternate single and
double bonds.
For example : Benzene and its derivaties.
Some important examples of monocyclic, bicyclic and triclic compounds are

4 QUIZRR
(a) Monocyclic aromatic compounds :
CH3
Benzene Toluene
(b) Bicyclic and Tricyclic aromatic compounds :
Naphthalene Anthracene
(Bicyclic) (Tricyclic)
2. Heterocyclic compounds : Compounds of carbon having closed chain made up of carbon and
other atoms. The hetero atoms commonly found in these compounds are oxygen, nitrogen and
sulphur but occasionally phosphorus, boron, silicon and some metal atoms like tin, selenium etc.
may also be present, Depending upon the chemical behaviour, these are further classified into the
following two categories.
(i) Alicyclic heterocylic compounds : Aliphatic cyclic compounds containing one or more
heteroatoms in their rings are called alicyclic heterocyclic compounds. For example.
Tetrahydro Furan Pyrrolidine

(THF)
O N
H
(ii) Aromatic heterocyclic compounds : Aromatic cyclic compounds containing one or more
heteroatoms in their molecules are called aromatic heterocyclic compounds. For example :
(ii
Pyridine Furan Pyrrole
N
O N
H

QUIZRR 5
H o m o l o g o u s Se r i e s
Organic compounds can be divided into different groups on the basis of similarity in their structure
and properties. The property by which a number of organic compounds form a homologous series is
termed as homology.
The general characteristics of a homologous series are
Ć All compounds in the series have the same functional group.
Ć All compounds in the series can be represented by the same general formula and can be
prepared by the general methods of preparation.
Ć All the homologues show a gradual gradation in their physical and chemical properties.
Ć Successive members of a homologous series differ by CH2 group and by a mass of 14 units.
Table 1.a : Homologous series of aliphatic organic compounds
Name of the homologous General formula Functional group IUPAC name

Alkanes CnH 2n+2 ă (single bond) Alkanes
Alkenes CnH 2n = (double bond) Alkenes
Alkynes CnH 2nă2  (triple bond) Alkynes
Monohydric alcohols CnH 2n+1 OH ă OH Alkanols
Aldehydes CnH 2nO ă CHO Alkanals
Ketones CnH 2nO C = 0 Alkanones
Monocarboxylic acid CnH 2nO2 ă COOH Alkanoic acids
Ethers CnH2n+2 O CăO-C Alkoxy alkanes
Primary amines CnH2n+1 NH2 ăNH2 Alkanamines
Amides CnH2n+1 CONH2 ă CONH2 Alkanamides
Esters CnH 2nO2 RăCOO ăR Alkyl alkanoate
Cyanides CnH2n+1 CN ăCN Alkane nitriles
O
Nitro compounds CnH2n+1 NO2 N Nitroalkanes

O
Acid chlorides CnH2n+1 COCl ă COCl Alkanoyl chlorides
N o m e n c l a t u r e o f Org a n i c Co m p o u n d s
Nomenclature implies assigning proper name to a particular organic compound on the basis of
certain standard rules so that the study of these compounds may become systematic. In the IUPAC
system, the name of an organic compound consists of three parts.
(i) Word root (ii) Suffix (iii) Prefix

6 QUIZRR
Wo r d Ro o t
The word root denotes the number of carbon atoms present in the chain. For example,
Chain length Word root Chain length Word root

C1 Meth C6 Hex
C2 Eth C7 Hept
C3 Prop C8 Oct
C4 But C9 Non
C5 Pent C10 Dec
Su f f i x
The word root is linked to the suffix, which may be primary, secondary or both.
Pr i m a r y s u f f i x
It indicates the nature of linkages between the carbon atoms. For example,
ane ă for single bonded compounds,
ene ă for one C = C bond
a diene ă for two C = C bonds
a triene ă for three C = C bonds
yne ă for one C  C bond
a diyne ă for two C  C bonds
Se c o n d a r y s u f f i x
It indicates the presence of functional group in the organic compound. For example,
Class of organic compound Functional group Secondary suffix

Alcohols ă OH ăol
Aldehydes ă CHO ă al
Ketones C= O ă one
Carboxylic acids ă COOH ăoic acid
Esters ă COOR alkyl..... oate
Acid amides ă CONH2 ăamide
Nitriles ă C N ănitrile
Amindes ăNH2 ăamine
Thioalcohols R ă SH ăthiol
Amides R ă CONH2 ăamide

QUIZRR 7
Pr e f i x e s
There are many groups, which are not regarded as functional groups in the IUPAC naming of the
compounds. These are regarded as substituents or side chains. These are represented as prefixes and
are placed before the word root while naming a particular compound. For example, if a compound
contains more than one functional group, then one of the functional group is regarded as principal
group and is treated as secondary suffix. The other functional groups are regarded as substituents and
are indicated by prefixes.
Substituent Prefix Substituent Prefix
ăCnH 2n+1 Alkyl ăNH2 Amino
ăF Fluoro ă NO Nitroso
ăCl Chloro ăN=Nă Diazo
ăBr Bromo ăOCH3 Methoxy
ăI ăIodo ăOC2H 5 Ethoxy
ăNO2 Nitro ăOH Hydroxy
ăCN Cyano ăCOOH Carboxy
ăNC Isocyano ăCOOR Carbalkoxy
ăCHO Formyl ăCONH2 Carbamyl
ăSH Mercapto ăCO Cl Chloroformyl
Thus, a complete IUPAC name of an organic compound may be represented as
Prefix + Word root + Primary suffix + Secondary suffix
H o w t o N a m e Org a n i c Co m p o u n d s U s in g t h e I U PA C Ru l e s
In order to name organic compounds you must first memorize a few basic names. These names are
listed within the discussion of naming alkanes. In general, the base part of the name reflects the
number of carbons in what you have assigned to be the parent chain. The suffix of the name
reflects the type(s) of functional group(s) present on (or within) the parent chain. Other groups which
are attached to the parent chain are called substituents.
Sa t u r a t e d H y d r o c a r b o n s
Number of Carbons Name

1 methane
2 ethane
3 propane
4 butane
5 pentane
6 hexane
7 heptane
8 octane
9 nonane
10 decane
11 undecane
12 dodecane

8 QUIZRR
There are a few common branched substituents which you should memorize. These are shown
below.
CH 3 CH 3 CH 3 CH 3
CH 3CH CH 3CH2CH CH 3 C CH 3 CHCH2
CH 3
isopropyl sec-butyl tert-butyl isobutyl
Ru l e s f o r Wr it in g I u p a c N a m e s
1. Identify the longest carbon chain. This chain is called parent chain.
6 4 2 7 5
3 4
1
7 5 8 6
1
3
Chain of seven carbons Chain of eight carbons 2

(wrong) (right)
Note : If more than one sets of longest possible chains are there, the selected longest chain should
have :
(1) Maximum number of side chains or
1 3 1 3 5
2 4 2 4 6
6 atoms chain with two side 6 atoms chain with one side
chains or two unbranched chain or one branched
side chains is selected side chain is rejected

QUIZRR 9
2. If more than one side chain is present, sum of the positions should be minimum while numbering
the carbon chain.
2 4 6 8 8 6 4 2
1 3 5 7 9 9 7 5 3 1
sum of positions : sum of positions :

5 + 5 + 7 = 17 3 + 5 + 5 =13
(wrong) (minimum) (right)
3. If two different substituents are at same position from ends, lowest number is assigned in order
of their alphabets.
Cl Cl
4 1
2 3
3 2
1 4
I I
(Right) (Wrong)
4. If a substituent (such as halogen, or nitro group) and a side chain are at same position from
opposite ends, lowest number is assigned to substituents
CH3 CH3
4 1
2 3
3 2
1 4
Cl Cl
(Wrong) (Right)
5. If more than two substituents and side chains are present, the sum of their number should be
lowest at the first preference irrespective of the nature of Substituents or side chains. This is
referred to as Lowest Sum Rule.

10 QUIZRR
I I
4 2
2 4
3 3
1 5 5 1
Cl CH3 Br Cl CH3 Br
1 + 2 + 3 + 5 = 11 1 + 3 + 4 + 5 = 13
(Right) (Wrong)
Note : In case when starting locant is lower from one side, then lowest sum rule is not obeyed.
CH3 CH3 CH3 CH3
4 6 10 7 5 3 1
2 8 9
7 8
1 3 5 9 6 4
10 2
CH3 CH3
(2 + 7 + 8 = 17 is accepted) (3 + 4 + 9 = 16 is rejected)
(methyl gets lower locant i.e. 2) (methyl gets higher locant i.e. 3)
6. If the same substituent occurs more then once, the location of each point on which the substituent
occurs in given. In addition, the number of times the substituent group occurs is indicated by a
prefix (di, tri, tetra, etc.)
E.g. CH3
CH3 CH CH CH3
H3C C CH3
CH3 CH3
CH3
2-3 Dimethyl butane 2-2 Dimethyl propane
In summary, the name of the compound is written out with the substituents in alphabetical order
followed by the base name (derived from the number of carbons in the parent chain). Commas are
used between numbers and dashes are used between letters and numbers. There are no space in
the name.
Here are some examples :
CH3 CH2 CH3

CH3 CH2 CH3 | |
| | CH3  CH2  CH2  CH  C  CH2  CH3
CH3  CH CH 2  CH  CH2  CH3 |
5 Ethyl  2 methylhexane CH3
4  Ethyl 3,3 dimethylheptane

QUIZRR 11
7 6 5 4 3 2 1
CH3  CH2  CH  CH  CH  CH  CH3
| | | | CH3
CH3 5' CH2 CH3 CH3
|
6'CH2 CH
|
7' CH2 CH 2 CH 2
2,3,5, Trimethyl 4 propylheptane 1-methylcyclopropane
 NOT : 2,3 dimethyl  4 sec  butylheptane 
CH3 CH3
| | 6 5 4 3 2 1
CH3  CH  CH2  CH2  CH  CH2  CH CH2  CH3 CH3  CH2  CH  CH  CH2  CH3
1 2 3 4 5| 6 7 8 9 | |
C H C H 3 CH3 CH2
| |
H3C ă CH2 CH3
2 Ethyl 4  methylhexane
5Sec  butyl 2, 7dimethylnonane
Ru l e s f o r N a m i n g A l k e n e s a n d A l k y n e s – U n s a t u r a t e d H y d ro c a r b o n s
Double bonds in hydrocarbons are indicated by replacing the suffix ăane with ăene. If there is
more than one double bond, the suffix is expanded to include a prefix that indicates the number of
double bonds present (ăadiene, ăatriene, etc.). Triple bonds are named in a similar way using the suffix
ăyne. The position of the multiple bond(s) within ethe parent chain is(are) indicated by placing the
number(s) of the first carbon of the multiple bond(s) directly in front of the base name.
Here is an important list of rules to follow :
1. The parent chain is numbered so that the multiple bonds have the lowest numbers (double
and triple bonds have priority over alkyl and halo substituents)
3 2 4
5
2 3
1
4 5
1
5 carbon chain with (Wrong)
2 unsaturated carbons or
one double bond is selected
2. When both double and triple bonds are present, numbers as low as possible are given to
double and triple bonds even though this may at times give „ăyne‰ a lower number than
„ăene‰. When there is a choice in numbering, the double bonds are given the lowest number.
2 4 6 5 3
1
1 6
3 5 4 2
(Right) (Wrong)

12 QUIZRR
3. When both double and triple bonds are present, the ăen suffix follows the parent chain directly
and the ăyne suffix follows the ăen suffix (notice that the ÂeÊ is left off, ăen instead of ă
ene). The location of the double bond(s) is(are) indicated before the parent name as before, and
the location of the triple bond(s) is(are) indicated between the ăen and ăyne suffixes.
5 4 3 2 1
H C  C CH 2  CHă CH3
2  Penten  4  yne
7 6 5 4 3 2 1
H C  C C CH2  CH2  CH=CH2
1  Hexen  5  yne
4. For a branched unsaturated acyclic hydrocarbon, the parent chain is the longest carbon chain
that contains the maximum number of double and triple bonds. If there are two or more
chains competing for selection as the parent chain (chain with the most multiple bonds), the
choice goes to :
(1) the chain with the greatest number of carbon atoms,
(2) the number of carbon atoms being equal, the chain containing the maximum number of
double bonds.
5. If there is a choice in numbering not previously covered, the parent chain is numbered to give
the substituents the lowest number at the first point of difference.
Here are some examples :
6 5 4 3 2 1 6 5 4 3 2 1 5 4 3 2 1
CH3 CH CH  CH2  CH CH2 CH C  CH CHCH CH2 CH3  CH CH  C  CH
1, 4 Hexadiene 1,3Hexadien 5 yne 3Penten 1 yne
CH2  CH3
CH3 |
6 |5 4 3 2 1 CH2 4
3
CH3  C  CH2  CH2  CH CH2 6 5 4 |3 2 1
| CH C  C  C  CH2 CH2 2
CH3 | 1
5,5Dimethyl 1 hexene CH2 CH2 CH3
3,3  Dipropyl  1,3 hexadien 5 yne 1,4,4-Trimethylcyclobutene
N a m i n g A l i c y c l ic Co m p o u n d s
Aliphatic cyclic compounds are called alicyclic compounds. These compounds are named as follows :
Ć The number of carbon atoms in the ring determines the word root.
Ć The primary suffix cyclo-is added before the word root.
Ć The primary suffix is determined by the nature of the ring (saturated or unsaturated).
For cyclic compounds in which ring contains one double bond
The suffix -ene is added to the word root.
For cyclic compounds in which ring contains a triple bond
The suffix-yne is added to the word root.

QUIZRR 13
When the ring contains two or three double or triple bonds

Suffixes like diene, triene and diyne, triyne are added to the word root.
An appropriate suffix or prefix indicates the relevant functional group or any substituent. The
position of the functional group or substituent is indicated by the serial number of the carbon atom in
the ring to which it is attached.
The lowest number to the functional group/substituent is given while numbering of the carbon
atoms in the ring.
CH2 CH2
H2C CH-CH3
H2C  CH  CH3 H2C CH
| | CH2
H2C  CH2 H2C
methylcyclobutane CH CH2 CH
CH3 cyclopentene
1,3- dimethylcyclohexane
CH 2
H2C C
CH · COOH
H2C C H2 C
cyclobutyne cyclopropanic acid
H a l o a k a n e s (a l k y l h a l id e s )
General formula : CnH2n+1 X or RX
Prefix : Halo
Haloalkanes (or alkyl halides) are monohalogen derivatives of alkanes. They are obtained by
replacing one hydrogen atom of alkane molecule by one halogen (X) atom.
RH ă H + X (= F, Cl, Br I) RX
alkane Haloalkane
In the IUPAC system of nomenclature, monohalogen derivative of alkane is named by adding the
prefix halo (fluoro, chloro or iodo) to the name of the parent alkane.
Halo + Name of parent alkane = Haloalkane
The carbon atoms are numbered, if necessary, to show the position of the halogen atom as follows :
CH3l C2H5Br CH3  CH CH3 CH3ăCH2ăCH2ăBr

|
Br
Common name : methyl iodide ethyl bromide Isopropyl bromide propyl bromide
IUPAC name : iodomethane bromomethane 2-bromopropane 1-bromopropane

14 QUIZRR
Po l y h a l o a l k a n e s
Polyhaloalkanes are those halogen derivatives of alkanes, which contain more than one halogen
atom in their molecule. The compounds containing two halogen atoms are termed dihalo and those
containing three halogen atoms as trihalo, and so on.
The general formula of dihalogen derivatives is CnH2nX2. In the IUPAC system, a dihalo derivative
is named as a dihalogen derivative of the parent alkane, and the positions of halogens atoms are
indicated as usual.
Polyhalo Parent alkane Name
compound Common IUPAC
ClH2CăCH2Cl Ethane (C2H6) Ethylene chloride 1,2-dichloroethane
CH3 ă CHBr2 Ethane (C2H6) Ethylidine bromide 1, 1 dibromoethane
CHl3 Methane (CH4) Iodoform triiodomethane
A l k a n o l s (Sa t u r a t e d M o n o h y d r i c A l c o h o l s )
General Formula : CnH2n+1 OH
Functional Group : OH
Suffix : ol
Alkanols or simply alcohols, are monohydroxy derivatives of alkanes, and are represented by the
general CnH2n+1 OH or simply as R-OH.
Alkanols or monohydric alcohols are further classified as primary, secondary and tertiary alcohols.
The classification is according to the OH group that is attached to a carbon atom, which in turn is
attached to one (or more), two or three carbon atoms respectively. For example,
H CH3
| |
H3C  C  O H H3C  C  OH
CH3CH2OH | |
CH3 CH3
primary alcohol secondary alcohol tertiary alcohol
The IUPAC name of a monohydric alcohol is obtained by replacing the terminal -e from the name
of alkane with -ol.
No. of Molecular Parent Common IUPAC

C- formula alkane name name
Atoms
1 CH3OH CH4 (methane) Methyl alcohol Methanol
2 CH3CH 2OH C2H6 (ethane) Ethyl alcohol Ethanol
3 C3H7OH C3H8 (propane) Propyl alcohol Propanol
4 C4H9OH C4H10 Butyl alcohol Butanol

QUIZRR 15
Name of alkane ă e + ol  Name of the alkanol

For example :
The -OH group can have different positions in alcohols with three or more carbon atoms, leading
to the possibility of more than one kind of alcohol. For example in the case of propyl alcohol, following
two structures are possible.
CH3  C H  CH3
CH3ăCH2ăCH2ăOH |
OH
IUPAC name : 1-propanol 2-propanol
Common : n-propyl alcohol isopropyl alcohol
(a primary alcohol) (a secondary alcohol)
The RO group obtained by removing H atom from the OH group of an alkanol is termed alkoxy
group. For example,
CH3O C2 H 5 O C3 H 7 O C4 H 9 O
Methoxy ethoxy propoxy butoxy
A l k a n e d i o l s (Di h y d r ic A l c o h o l s )
General formula : CnH2 (OH)2
Functional group : OH
Suffix : diol
In the IUPAC system, the name of dihydric alcohol is obtained by adding the suffix diol to the
name of the parent alkane and indicating the positions of the -OH groups.
Polyhalo Parent alkane Name

compound Common IUPAC
2
CH 2OHă1CH 2OH Ethane (C2H6) Ethylene glycol Ethane 1, 2-diol
3 2 1
CH3 ă CHOH CH2OH Propane (C3H8) Propylene glycol Propane 1, 2-diol
A l k o x y a l k a n e s (Et h e r s )
General formula : CnH2n+1-O- CmH2m+1
or R-O-R´
Functional group : O
Prefix : alkoxy
Ethers are alkoxy derivatives of alkanes. These are represented by the general formula R-O-R´,
where R and R´ are alkyl groups. Ether is termed as simple ether when R and R´ are the same. If the
two alkyl groups (R and R´) are different, the ether is termed as a mixed ether.

16 QUIZRR
When one hydrogen of the alkane is replaced by an alkoxy group, alkoxy-alkanes are obtained.
RHăH + OR´ RăOăR´
alkane alkoxy alkoxyalkane
In the IUPAC system of nomenclature, the large alkyl group is considered to be the alkane residue,
while the smaller alkyl group with oxygen atom is considered to be the alkoxy group. Some typical
ethers are named below.
Molecular Common Alkane Alkoxy IUPAC
formula name residue group name
Atoms
CH3OCH3 Dimethyl ether Methane Methoxy Methoxymethane
CH2OC2H 5 Ethyl methyl Ethane Methoxy* Methoxyethane
ether
C2H 5OC2H 5 Diethyl ether Ethane Ethoxy Ethoxyethne
* Here the smaller alkyl groups forms the alkoxy group
A L K A N A L S (A L DEH Y DES)
General formula : CnH2n + 1CHO or
O
R C
H
In IUPAC system of nomenclature, the name of an aldehyde is obtained by replacing the terminal
ăe of the parent alkane by the suffix-al.
IUPAC name of the aldehyde = Name of the parent alkane ă e + al = Alkanal
Names of some individual members
Molecular Acid obtained Parent Name
formula on oxidation alkane Common IUPAC
HCHO HCOOH Methane Formaldehyde Methanal
(formic acid)
CH3CHO CH3CHOOH Ethane Acetaldehyde Ethanal
(acetic acid)
C2H5CHO C2H5COOH Propane Propionaldehyde Propanal
(Propionic
(acid)
Since the ăCHO group is always present at the end of the chain in aldehydes there is no need to
designate its position 1.

QUIZRR 17
While counting the carbon atoms in the parent chain, the carbon of the ăCHO group is also
counted.
For example, the parent chain in CH3CH2CH2CHO consists of four C atoms and not three. Hence,
CH3CH2CH2CHO should be named as butanal and not 1-butanal as -CHO is always at the end of the
chain (i.e., -CHO carbon is always at position 1).
A L K A N ON ES ( K ET ON ES)
General formula : (CnH2n+1 . CO . Cm H2m+1)
Functional group : CO

or R-CO-R´
Suffix : one
The following general formula describes Ketones (or alkanones)
R
C = O where, R and R´ are alkyl groups.
R
The two alkyl groups (R and R´) may be same or different. When the two alkyl groups (R and R´)
are same, the ketone is a simple ketone. If the two are different the ketone is called a mixed ketone.
The IUPAC name of an alkanone is obtained by replacing the last -e from the name of the parent
hydrocarbon with the suffix - one. The position of the carbonyl group is indicated by a numeral
referring to the serial number of the carbon atom bearing the carbonyl group in the chain. The
numbering is done so as to give the carbonyl group the lowest number.
IUPAC name of ketone = Name of parent alkane ăe + one = Alknone
No. of Molecular Alkyl groups Parent Common IUPAC

C- formula attached to name name
Atoms the > CO group
3 CH3ă CO ă CH3 Methyl, Methyl Propane Dimethly ketone Propanone
4 CH 3ă CO ă CH 2CH 3 Methyl, Ethyl Butane Ethyl methyl Butanone-2
ketone
5 CH3CH 2ăCOăCH2CH 3 Ethyl, Ethyl Pentane Diethyl ketone Pentanone-3
Alk onic Ac ids or sat urat ed m onoc arbox ylic ac id

General formula : CnH2n COOH
+ 1
O
Functional group : R  C
OH
Suffix : oic acid

18 QUIZRR
On replacing one H atom of an alkane by one carboxylic (- COOH) group a saturated monocarboxylic
acid or alkanoic acid is obtained. Higher members of this family are generally, known as fatty acids
(obtained by the hydrolysis of fats).
In IUPAC system, the name of an alkanoic acid is obtained by replacing the last ÂeÊ from the name
of the parent alkane with -oic acid.
Name of monocarboxylic acid = Name of the parent alkane -e + oic acid
= Alkanoic acid
Typical members are named below :

C- formula alkane name name
Atoms
1 HCOOH Methane Formic acid Methanoic acid
2 CH3COOH Ethane Acetic acid Ethanoic acid
3 CH3CH 2COOH Propane Propionic acid Propanoic acid
4 CH3CH2CH 2COOH Butane Butyric acid Butanoic acid
5 CH3(CH 2)3COOH Pentane Valeric acid Pentanoic acid
A l k a n e d i o i c a c i d s (Sa t u r a t e d d i c a r b o x y l i c a c i d s )
General formula : Cn H2n+2 (COOH)
O
Functional grooup : C
OH
Suffix : dioic acid
A dicarboxylic acid contains two carboxylic groups linked to the same or different carbon atoms.
In the IUPAC system, the name of alkanedioic acid is obtained by adding the suffix, -dioic acid to the
name of the parent alkane.
Name of the dicarboxylic acid = Name of the parent alkane + dioic acid = Alkanedioic acid
For example : Ethanedioic acid (oxalic acid, parent alkane is ethane)
COOH
|
COOH
Propanedioic acid (Malonic acid, parent alkane is propane)
COOH
HC
2
COOH

QUIZRR 19
Butanedioic acid (Succinic acid, parent alkane is butane)
H2 C COOH
H2 C COOH
A l k a n a m i d e s (A c i d A m i d e s )
General formula : CnH2n CONH2
+ 1
where n = 0, 1, 2 ...
Functional group
O O
C R C
NH2 or NH2
Suffix : amide
In IUPAC system, the amides are named by replacing the letter e of the parent alkane by the word
amide.
IUPAC name of acid amide = Name of the parent alkane - e + amide = Alkanamide
Typical amides are named below :
Molecular Parent acid Parent alkane Common name IUPAC name
HCONH2 HCOOH (formic acid)* Methane Formamide Methanamide
CH3CONH2 CH3COOH (acetic acid)* Ethane Acetamide Ethanamide
CH3CH2CONH2 C2H5COOH Propane Propanamide Propanamide
(propionic acid)*
* Common names of the acid.
A l k a n e n i t r il e s (A l k y l Cy a n i d e s )
General formula : R-C  N
Functional group : C  N
Suffix : nitrile
The IUPAC name of an alkyl cyanide is obtained by adding the suffix - nitrile to the name of the
parent alkane. Thus, an alkyl cyanide is alkanenitrile in the IUPAC system.
Some common alkane nitriles are :
Molecular Acid formed Parent Common IUPAC

formula on hydrolysis alkane name name
HăC  N HCOOH (formic Methane Hydrogen Methanenitrile
acid) cyanide
H3ă C  N CH3COOH Ethane Methyl Ethanenitrile
(acetic acid) cyanide

20 QUIZRR
A l k a n o y l c h l o r id e s (A c i d Ch l o r id e s )
General formula : CnH2n+1COCl
where n = 0, 1, 2 ...
Functional group :
O O
C R C
Cl or Cl
Suffix : oyl chloride
Acid chlorides contain the functional group ăCOCl. This functional group is obtained by replacing
the ăOH group of a carboxyl group with a chloride atom.
The IUPAC name of an acid chloride is obtained from the IUPAC name of the parent acid by
replacing the terminal e of the parent alkane by oyl chloride.
IUPAC name of the acid chloride = Name of the parent alkane - e + oyl chloride
= Alkanoyl chloride
Some acid chlorides are named below,
Methanoyl chloride : (formyl chloride, parent acid is Methanoic acid) HCOCI
Ethanoyl chloride : (acetyl chloride, parent acid is Ethanoic acid) CH3COCI
A l k a n o i c a n h y d r id e s (a c i d a n h y d r id e s )
O O
|| ||
General formula : R  C O  C R
O O
|| ||
Functional group :  C O  C 
Suffix : oic anhydride

An acid anhydride may be considered as the condensation product of two molecule of a
monocarboxylic acid obtained by losing one molecule of water.
RCOOH RCO
- H2 O O
RCOOH RCO
IUPAC name of an acid anhydride = IUPAC name of acid parent acid-acid + anhydride = Alkanoic
anhydride
H3 C CO
O
H3 C CO
For example, Ethanoic anhydride (acetic anhydride, parent acid is ethanoic acid)

QUIZRR 21
A l k y l a k a n o a t e s (e s t e r s )
O
||
General formula : R  C OR '
O
||
Functional group :  C  OR'
Suffix : oate
An ester contains the group COOR where R is an alkyl group. The hydrolysis of the ester gives
the parent acid and so its name is based on the name of the acid.
Name of an ester = Alkyl group from the alcohol + Name of the parent acid - oic cid + oate
The names of some typical esters are
Molecular Common system IUPAC system

formula Parent acid Name of ester Parent acid Name of ester
HCOOCH3 Formic acid Methyl formate Methanoic acid Methyl methanoate
CH3COOCH3 Acetic acid Methyl acetate Ethanoic acid Methyl Ethanoate
N i t r o a l k a n e s a n d A l k y l N i t r it e s
O
General formula : R · N
O
O
Functional group : · N
O
Prefix : nitro

C- Atoms formula alkane name name
1 CH3NO2 Methane Nitromethane Nitromethane
2 CH3CH2NO2 Ethane Nitroethane Nitroethane
3 CH3CH2CH2NO2 Propane n-Nitropropane 1-Nitropropane
CH3 CHCH3
4 | Propane iso-Nitropropane 2-Nitropropane
NO2
Nitro compounds are named as the nitro derivatives of the parent alkane in both the systems of
nomenclature. This is done by adding the prefix nitro to the word root of the parent alkane.

22 QUIZRR
Alkyl nitrites
General formul : R-O-N=O
Functional group : ăO-N=O
Alkyl nitrites are named by adding the suffix nitrite to the alkyl group. For example
CH3-O-N=O is Methyl nitrite.
C2H5-O-N=O is Ethyl nitrite.
A l k a n a m i n e s (A m i n e s )
Amines are formed by replacing one or more hydrogen atoms of ammonia (NH3) with alkyl groups.
These are further classified as primary, secondary and teritary amines according to one, two or three
hydrogen atoms of ammonia being replaced by alkyl groups. For example,
Primary (amino, NH2) RăNH2
Secondary (imino, NH)
R
NH
R
Tertiary (nitrile,N)
R
R N
R
In IUPAC system, primary aliphatic amines are named as alkanamine. This is done by replacing
the ÂeÊ of the parent alkane by the suffix amine.
The secondary and tertiary amines are named as alkyl derivatives of the primary amine.
The higher alkyl group is considered as the residue of the parent alkane.
Examples of the amines :
No. of Molecular Parent Common name IUPAC name
C- Atoms formula alkane
H3C
NH
1* Methane Dimethylamine N-methylmethanamine
H3C
H5C2
NH
2* Ethane Ethymethylamine N-methylethanamine
H3C
H3C
H3C N
Methane Trimethylamine N,N-dimethylethamine
C2H5
* This indicates the number of C-atoms in the chain : the other groups are considered as the
substituent.

QUIZRR 23
Primary amines
C- Atoms formula alkane name name
1 CH3NH2 Methane Methylamine Methanamine

2 C2H5NH 2 Ethane Ethylamine Ethanamine
3 C3H7NH 2 Propane Propylamine Propanamine
4 C4H9NH 2 Butane Butylamine Butanamine
For primary amines containing three or more carbon atoms, there can be more than one isomers
of the concerned amine. For example, there are two propylamines.
H3C  CH  CH3
H3C  CH2  CH2  NH2 |
1propanamine
NH2
2 propanamine
A l k a n e n i t r il e s (A l k y l Cy a n i d e s )
Geneal formula : R-N-C  N
Functional group : C  N
Suffix : nitrile
The IUPAC name of an alkyl cyanide is obtained by adding the suffix - nitrile to the name of the
parent alkane. Thus, an alkyl cyanide is alkanentrile in the IUPAC system.
Some common alkane nitriles are :
Acid formed Parent Common IUPAC name
Molecular on alkane name
formula hydrolysis
HăC  N HCOOH (formic Methane Hydrogen Methanenitrile

acid) cyanide
H3CăC  N CH3COOH Ethane Methyl Ethanenitrile

(acetic acid) cyanide
A l k y l c a r b y l a m i n e s (A l k y l I s o c y a n i d e s )
General formula : R · N C
Functional group : · N C
Suffix : Carbylamine
In the IUPAC system, these compounds are named as carbylamines of alkyl groups attached to
the ăNC group.

24 QUIZRR
Molecular Acid formed on Common IUPAC name

formula hydrolysis name
CH3ăNC CH3COOH Methyl Methyl

(acetic acid) isocyanide carbylamine
C2H5ăNC C2H5COOH Ethyl Ethyl
(propionic acid) isocyanide carbylamine
Ru l e s f o r N a m i n g Org a n i c Co m p o u n d s Co n t a i n i n g On e o r M o re Fu n c t io n a l Gro u p s
The rules for naming an organic compound containing functional groups are exactly same as
discussed already for compounds containing double and triple bonds. In this case, the preference of
lowest number is given to carbon atom bearing the functional group. The rules are summarized
below :
(i) Select the longest continuous chain containing the carbon atom having functional group(s).
(ii) The numbering of atoms in the parent chain is done in such a way that carbon atom bearing
the functional group gets the lowest number.
(iii) If two or more same functional groups are present, these are indicated by using di, tri, tetra
as prefixed to the name of the functional group.
(iv) If the organic compound contains a functional group, multiple bonds, side chain or substituents,
the following order of preference must be followed,
Functional group > Double bond > Triple bond > Side chain.
(v) When an organic compound contains two or more functional groups, one group is regarded as
the principal functional group and the other group is treated as the secondary functional
group, which may be treated as substituent(s). The following order of preference is used for
selecting the principal functional group,
Carboxylic acids > sulphonic acids > acid anhydrides > esters > acid chlorides > amides >
nitriles > aldehydes > ketones > alcohols > amines > imines > ethers > alkenes > alkynes.
Different classes of functional groups including multiple bonded compounds and the suffix or prefix
required to name these compounds are given in the preferential decreasing order in the following table.
Class of compounds Functional group or Suffix Prefix

substituent
1. Carboxylic acids C= O Carboxylic acid/oic acid Carboxy

HO
O
||
2. Sulphonic acids  S  OH Sulphonic acid sulfo
||
O

QUIZRR 25
O O
|| ||
3. Acid anhydrides  C O  C oic anhydride ·
4. Esters C =O (R) ... carboxylate alkoxy carbonyl

RO
/(R) ... oate
5. Acid halides C= O Carbonyl halide/oyl halo carbonyl

X
halide
6. Amides C= O Carboxamide/amide carbamoyl

NH2
7. Cyanides ă CN Carbonitrile/nitrile cyano
8. Aldehydes C= O Carbaldehyde/al formyl/oxo

H
9. Ketones C= O one keto/oxo
10. Alcohols ăOH ol hydroxy
11. Amines ăNH2 amine amino
12. Imines = NH imine imino
13. Ethers ă C ă O ă C ă ă alkoxy
14. Alkenes = (double bond) ene ·
15. Alkynes  (triple bond) yne ·
For those functionalities, which have two prefixes and/or suffixes, the first one is used when carbon
atom of the functional group is not a part of the longest continuous chain and the second one is used,
when carbon atom is counted in the longest chain.

26 QUIZRR
Some Examples
(1) (HOCH2CH2O)2CHăCO2H Bis(2ăhydroxyethoxy) ethnaoic acid
C2H5
1
2
3
(2) 4 1ăEthylă4ămethylcyclohexane
CH3
F F
CH3CHăCH CH2CH3
(3) CH3(CH2)4CH2CHCH2CH(CH2)3CH3 7 ă (1, 2 ă Difluorobutyl) ă 5 ă ethyldecane
O
||
(4) CH3 CH2 C H2  C  CH2Cl 1ăchloropentană2ăone
5 4 3 2 1
2 1
(5) CH3 CH2  O  CH2 CH 2Cl 1ăChloroă2ăethoxyethane
(6) OHCCH2 CH2 CH  CH2 CHO 3ă(Formylmethyl)hexanediă1, 6ăal

|
CH2CHO
4 3 2 1
(7) OHCCH2CH2 CH  CH2 CHO Butaneă1,2,4ătricarbaldehyde
|
CHO
(8) CH3 CH2 CH  OCH2CH3 1, 1ăDiethoxypropane

|
OCH2CH3
(9) HO2CCH2 CH2 CH C H2 CH2 CO2 H Pentaneă1,3,5ătricarboxylic acid

|
CO2H
(10) NCCH2CH2CH2 CH CH2 CH2 CN Hexaneă1,3,6ătricarbonitrile

|
CN
(11) CH3CSăOăCOCH2CH 3 Propionic thioacetic anhydride
O
||
(12) CH3  C CH2 CH2CH2CO2 H 5ăOxohexanoic acid
6 5 4 3 2 1
O O
|| ||
(13) CH3CH2  C  CH2  C  CH3 Hexaneă2,4ădione
6 5 4 3 2 1
(14) CH2=CHCH2CH(OH)CH3 Pentă4ăenă2ăol
QUIZRR 27
N a m i n g A l i c y c l ic & A r o m a t i c Co m o p o u n d
Ć If alcicyclic group is attached to the long chain, the chain is numbered from the side
of the alcicyclic group.
7 5 3 1
8
6 4 2
Ć Cycloalknes with only one ring are named by attaching prefix cyclo-to the names of
the alkanes possessing the same number of carbon atoms.
cylopropane cyclopentane
Ć If only one substitutent is present, it is not necessary to designate its position.

OH Cl
cyclohexanol chlorocyclohexane
isopropylcyclohexane
Ć When two substituents are present, we number the ring beginning with the substituent
first in the alphabet. When three or more substituents are present, we begin with the
substituent that leads to the lowest set of locants.
CH3 CH3
CH2 CH3
1
2
3
4
CH2 CH3
Cl
1-ethyl-3-methylcyclohexane 1-ethy 1-3 methylcyclohexane
not 1-ethy l-5 cyclohexane not 1-ethy l-5 cyclohexane

28 QUIZRR
Ć When a single ring system is attached to a single chain with a greater number of
carbon atoms, or when more than one ring system is attached to a single chain, then
they are named as cyclocalkanes.
1-cyclobutylpentane 1,3 dicyclohexylpropane
Ć Cycloalkanes consisting of two rings only and having two or atoms in common are
named by taking the prefix bicyclo followed by the name of the alkane. In between
bicyclo and alkane, number of carbon atoms representing the bridge (except bridge
head positions) are written with in bracket. Brid ge head positions are those which
join two rings.
7 C1 and C4 are joined
4 to bride of one carbon atoms
3 5
{ 2 6
{
C1 and C2 are joined C1 and C4 are joined
to bride of two carbon atoms to bride of two carbon atoms
It is alicyclic compund with seven carbon atoms, hence it is bicycloheptane. The two rings
have two C-atoms in common, (numbered 1 and 4) in structural formula. These positions
are called the bridgehead positions. Carbon atoms 1 and 4 are tied together by three
bridges of two, two and one carbon atoms. Hence, it is bicyclo [2, 2, 1] heptane (norbornane).
7
4
1
5
3
2 6
bicyclo [2, 2, 1] hept-2-ene bicyclo [2, 2, 0] hexane bicyclo [4, 4, 0] decane

QUIZRR 29
9 2
1 3
H3C 8
4
6
7 5
bicyclo [2, 1, 1] hexane bicyclo [1, 1, 1] pentane 8-methy bicylo [4, 3, 0] nonane
1
7
8 CH3 3
6
5
4
8 methyl bicyclo [3, 2, 1] octane
Ć Spiranes are polycyclics that share only one C. Spiro is written before the alkane.
spiro [4, 3] octane spiro [5, 2] octane
Ć For naming aromatic compounds, no special rules are needed to name them, but they
are named as substituted benzene.
CH3 CH3CHCH3 CH CH2
methylbenzene ispropylbenzene vinylbenzene Cyclopropyl

(toluene) (cumene) (styrene) (benzene)

30 QUIZRR
Ć When large and complex groups are attached to the benzene ring it is common practice
to name the molecule as an alkane, alkene, etc., and benzene as side chain derivative
written as pheny 1 (C 6 H 5 , ·,Ph).
CH3CHCHO
·C CH  ·CH2 · 
phenylbenzene
or
phenylethyne 2-phenylpropanal diphenylmethane biphenyl
Fo r A r o m a t ic r i n g
X
(1)
(6) (2)
(3)
(5)
(4)
Let there is an element on position 1. We do numbering of other positions, after defining the no.
1 position.
There are specific name for different positions.
position 1, 2 and 6  Ortho (o)
position 3 and 5  meta (m)
position 4  para (p)
NO2
NO2
Cl
Cl
m-choro nitro benzene Oăcholro nitro benzene
NO2
Cl
(p-chloro-nitrobenzene)

QUIZRR 31
Ex a m p l e s
1. Phenol
CH2 CH3
2. EthylBenzene
Cl
3. Chlorobenzene
OH
4. Phenol
OH
5. 3-Chlorophenol
Cl
OH
CH2 CH CH2 CH3
6. 1-phenylButană2ăol
7. H3 C CH CH2 CH3 2-ButylBenzene
8. CH2 C CH3 1-phenylpropană2ăone

32 QUIZRR
CHO
9. Benzaldehyde
COOH
10. Benzoic acid
CHO
11. 4-aminobenzaldehyde
NH2
C OO H
12. OH 3-hydroxy benzoic acid
CO NH2
13. Benzanamide
14. N H Năphenylbenzenamine
O
15. C NH CH 3 N-methylbenzenamide
O
NH C CH2 CH3
16. N-phenylpropoanamide

QUIZRR 33
I SOM ERI SM
In the study of organic chemistry we come across many cases when two or more compounds are made
of equal number of like atoms. A molecular formula does not tell the nature of organic compound;
sometimes several organic compounds may have same molecular formula. These compounds possess the
same molecular formula but differ from each other in physical or chemical properties, are called isomers
and the phenomenon is termed isomerism (Greek, iso = equal; meros = parts). Since isomers have the
same molecular formula, the difference in their properties must be due to different modes of the combination
or arrangement of atoms within the molecule. Broadly speaking, isomerism is of two types :
I. Structural isomerism : When the isomerism is simply due to difference in the arrangement
of atoms within the molecule without any reference to space, the phenomenon is termed
structural isomerism. In other words, while they have same molecular formula they possess
different structural formulas. This type of isomerism which arises from difference in the
structure of molecules, includes :
(i) Chain or Nuclear Isomerism;
(ii) Positional Isomerism
(iii) Functional Isomerism
(iv) Metamerism and
(v) Tautomerism
II. Stereoisomerism : When isomerism is caused by the different arrangements of atoms or
groups in space, the phenomenon is called Stereoisomerism (Greek, Stereos = occupying
space). The stereoisomers have the same structural formula but differ in the spatial
arrangement of atoms or groups in the molecule. In other words, stereoisomerism is exhibited
by such compounds which have identical molecular structure but different configurations.
Stereoisomerism is of three types :
(a) Geometrical or cis-trans isomerism; and
(b) Optical Isomerism
(c) Conformational isomerism
Thus various types of isomerism could be summaried as follows :
ISOMERISM
STRUCTURAL
ISOMERISM
GEOMETRICAL OPTICAL CONFORMER

ISOMERISM ISOMERISM ISOMERISM

34 QUIZRR
CH A I N I SOM ERI SM
This type of isomerism arises from the difference in the nature, structure of the carbon chain. For
example, for butane (C4H10), the following arrangements are possible.
(a) Butane (C4H10)
H3 C  CH  CH3
|
H3 C  CH2  CH2  CH3 CH3
n-butane (butane) iso-butane  2-methylpropane 
(straight chain) (branched chain)
(b) Pentane (C5H12)
CH3
H3CHCCH2 CH3 |
| H3C  C  CH3
H3 C  CH2  CH2  CH2  CH3 CH3 |
CH3
n-pentane iso-pentane (neo-pentane
(2-methylbutane) (2,2-dimethylpropane)
(c) Butanol (butyl alcohol)
H3CHCCH2OH
|
CH3
H3CăCH2ăCH2ăCH2ăOH isobutyl alcohol
(butan-1-ol) (2-methylpropanol-1)
POSI T I ON I SOM ER I SM
This isomerism arises due to the difference in the position of the same functional group or the same
substituent while the arrangement of carbon atoms remains same. For example,
(a) Chloropropane (C3H7Cl)
H3 C  C H  CH3
H3 C  CH 2  CH2  Cl |
(n-propyl chloride) Cl
(iso-propyl chloride)
(1-chloropropane) (2-chloropropane)
(b) Butene (C4H8)
H2 C  CH  CH2  CH3 H3 C CH  CH  CH3

1 2 4 1 2 3 4
(butane-1) (butene-2)

QUIZRR 35
(c) Propanol (C3H7OH)

H3 C  CH  CH3
H3 C CH 2  C H2  O H |
n-propyl alcohol OH
iso-propyl alcohol
(propanol-1)
(propanol-2)
FU N C T I ON A L I SOM ERI SM
The compounds having the same molecular but different functional groups are said to exhibit
functional isomerism. Such compounds are termed functional isomers. For example,
(a) For C2H6O
Ether Alcohol
H3C · O · CH3 H3C · CH2 · OH
(methoxymethane) dimethyl ether (ethanol) ethyl alcohol
(b) The molecular formula C3H6O represents two functional isomers.

Aldehyde Ketone
H3C · CH2 · CHO O
(propionaldehude) propanal ||
H3C · C · CH3
(acetone) propanone
(c) Carboxylic acids and esters

CH 3 CH 2 COOH CH 3 COOCH 3
Propanoic acid Methyl ethanoate
Only Methanoic acid cannot have its isomeric ester.
(d) Dienes, allenes and alkynes

CH 2 = CHăCH = CH 2 CH 2 = C = CHăCH 3 CH 3 CH 2 C   CH
Buta ă 1, 3 ă diene Buta ă 1, 2, ă diene But ă 1 ă yne
(An allene)
(e) Cyanides and Isocyanides

RăCN RăN C
Alkyl cyanide Alkyl isocyanide
(f) Nitro alkanes and alkyl nitrites
O
R N
RăOăN=O
O Alkyl niytites
Nitroalkanes

36 QUIZRR
(g) 1Ĉ , 2Ĉ and 3Ĉ amines
CH3
CH 3 CH 2 CH 2 NH 2 CH 3 CH 2 NHCH 3 |
H3C  N  CH3
propan ă 1 ă amine N ă methyl ethanamine N, N ă Dimethyl methanamine

(1Ĉ amine) (2Ĉ amine) (3Ĉ amine)
(h) Aromatic alcohols, phenols and ethers
CH2 OH OCH3 OH
CH3
Benzyl Alcohol Anisole Oă(cresol)
Met am erism
This type of isomerism arises from the unequal distribution of carbon atoms on either side of the
functional group in the molecule of compounds belonging to the same homologous series. For example,
(a) diethyl ether and methylpropyl ether are metamers.
H5C2ăOăC 2H 5 H3CăOăC3H 7
(diethylether methylpropyl ether
(eethoxyethane) (methoxypropane)
(b) A k et on i c com pou n d h av i n g t h e m ol ecu l ar f or m u l a C 5H10O
O O
|| ||
H5C2  C  C2 H5 H3C  C  C3H7
diethyl ketone methyl propyl ketone
(pentan-3-one) (pentan-2-one)
Taut om erism
It is a special type of functional isomerism in which an -hydrogen atom is shifted from one
position (atom-1) to another (atom-3). This is referred as 1, 3-shift. Such shfits are common between
a carbonyl compound containing an -hydrogen atom and its enol form.
R' R'
| |
 R 1 C 2 C  R''
R 1 C 2 C  R'' 
| || |
H 3O 3
Keto form OH
Enol form

QUIZRR 37
H = (CăH + CăC + C=0) ă (C=C + CăO + OăH) = 359 ă 347 = 12 kcal/mol

Thus, generally keto form is more stable than enol form by 12 kcal. So, in most cases, the
equilibrium lies towards the left.
Mostly the keto form is more stable than enol form but in certain cases, enol form can become the
predominant form. The enol form is predominant in following cases :
1. Molecules in which the enolic double bond is in conjugation with another double bond/phenyl
ring. In such cases, sometimes interamolecular hydrogen bonding also stabilizes the enol.
R R
C C R´ C C R´
H O O
Keto form H
Enol form
(crossăconjujation)
CH
CH3 C CH2 C OEt CH3 C C OEt
O O O O
H
Keto form Enol form
(Crossăconjugation and
intramolecular hydrogen bonding)
CH
CH3 C CH2 C CH3 CH3 C C CH3
O O O O
H
Keto form Enol form
(Crossăconjugation and intramolecular
hydrogen bonding)
2. Molecules, which contain two bulkyl aryl groups.
Me
Ar Ar
C C H C C H where Ar = Me
Ar Ar
H O H O Me
keto form (5%) Enol form (95%)
In the keto form of 2,2ădimesitylenthanal, the ArăCăAr bond angle is 109Ĉ, whereby the
bulky aryl groups experience greater steric repulsion. This steric repulsion eases off when the
keto form transforms to enol form, where the ArăCăAr bond angle widens to 120Ĉ.

38 QUIZRR
3. When the enol is aromatic stabilized.
O OH
H
H
Keto from Enol from
The extent of enolization is also affected by the solvent, concentration and temperature. Thus,
acetoacetic ester has an enol content of 0.4% in water and 19.8% in toluene. This is because water
reduces the enol content by hydrogen bonding with the carbonyl group, making this group less available
for intramolecular hydrogen bonding. The effectiveness of intramolecular hydrogen-bonding in stabilizing
the enol, with respect to the keto form is seen on varying the solvent and particularly on transfer to
a hydroxylic solvent with MeCOCH2COMe.
Solvent % Enol Thus, the proportion of enol in the non-polar solvent (hexane) is
Gas phase 92 the same as in the gas phase and higher than in the liquid itself,
the latter acting as a polar auto-solvent. The proportion drops
Hexane 92 again in the more polar MeCN and more dramatically in water.
Liquid 76 What is happening is the increasing relative stabilization of the
keto form by solvation, this being particularly marked in water
MeCN 58 where intramolelcular hydrogen bonding of the keto formÊs C=O
H 2O 15 groups can now take place as an alternative to its enolization.
Also, the enol content of pentană2,4ădione (CH3COCH2COCH3) is found to be 95% and 45% at
27.5Ĉ and 275.5ĈC respectively.
When a strong base is added to a solution of a ketone with -hydrogen atom, both the enol and
ketone form can lose a proton. The resulting anion is same in both the cases as they differ only in the
placement of electrons. They are not tautomers but canonical forms.
R R
C C·R C C·R
R R
O O
H
H
+ ă + +
+H ăH +H ăH
ă
O
R R
ă
C C·R C C·R
R R
O
{Canonical form} {Canonical form}

QUIZRR 39
Mec hanism :
In basic medium
O H O
OH ă ă
CH3 · C · CH2 CH3 · C · CH2
OH
ă
OH + CH3 ă C = CH2 CH3 · C = CH2
H2O
ă
O
In acidic medium
+
O H O·H
+
H
CH3 · C · CH3 CH3 · C · CH2
H
+
ăH
OH
CH3 · C = CH2
Ot h e r t y p e s o f t a u t o m e r i s m
(i) PhenolăKeto tautomerism
O OH
H
Cyclohedxadienone Phenol
In this case, enol form is more stable than keto form because of the aromatic stabilization.

40 QUIZRR
(ii) NitrosoăOxime tautomerism :
R R
C N C N
R R
H O OH
Nitroso form Oxime form
This equilibrium lies far to the right and as a rule nitroso compounds are stable only when
there is no -hydrogen atom.
(iii) Nitro-Aci tautomerism
Aliphatic nitro compounds are in equilibrium with the aci forms.
R O R  O R  O
C N C N C N
R  R O R
H O OH
H
Nitro form Aci form
The nitro form is much more stable than the aci form because nitro group has resonance. Aci
form of nitro compounds is also called nitronic acids.
(iv) ImineăEnamine tautomerism/cyanideăeminine tautomerism:
R R
C C R C C R
R R
H N R NH R
Imine form Enamine form
Imine form predominates generally. Enamines are stable only when there is no hydrogen
atom attached to nitrogen.
R R
C C C C
R R
H N
.. N H
O
||
Note : Keto-enol tautomerism occurs in those compounds in which  C  bond is attached through
the carbon of CăH bond when C is saturated.

QUIZRR 41
Ex a m p l e
Which will not show tautomerism :
O
||
(a) CH 3  C  H (b) O O
CH3 O O
| || ||
(c) H3C  C  C  H (d) CH 2  CH  C  H
|
CH3
Solution :
(b), (c) & (d) will not show tautomerism.
O
||
In (b) & (d)  C  is not attached to saturated carbon or we can say that the carbon attached to
O
||
the  C  group is not sp3 hybridized.
O
||
In (c),  C  is attached to carbon which does no have any hydrogen bonded to itself.
Therefore tautomerism is not possible in this case.
Ex a m p l e
Which will have more enol : Write the order of increasing enol content.
O O
|| ||
(1) CH 3  C  CH 2  C  O CH 3
..
O O
|| ||
(2) CH 3  C  CH 2  C  CH 3
O O
(3) || ||
C· CH 2 · C· CH 3

42 QUIZRR
Solution :
(1) O H O (2) H O
O
CH3 · C · CH · C · O · CH3 CH3 · C · CH · C · CH3
OH O OH O
CH3 · C = CH · C · OCH3 CH3 · C = CH · C · CH3
(enol form) (enol form)
(3) O H O
· C · CH · C · CH3
OH O
· C = CH · C · CH3
(enol form)
..
Due to presence of lone pair in (1) on  OCH , power of carbon to withdraw electron decreases,
3
therefore its enol content is least.
In enol form of (3) extended conjugation is obtained. Thus its most stable
 order is
1< 2< 3
Ex a m p l e
Which will have more enol content ?
O
O O
|| || O
(a) CH 3  C  C  CH 3 (b)

QUIZRR 43
Solution :
enol forms are
(a)
H O O OH O
CH2 · C · C · CH3 CH2 = C · C · CH3

(enol form)
O O·H
(b)
H O O
In (a) due to repulsion between 2 O atoms, rotation occurs & hydrogen bonding gets weaker.
Rotation is not possible in (b) due to five membered ring.
 (a) > (b) {enol content}
Ex a m p l e
Write all possible structural isomers of the compound with molecular formula C5H12O.
Solution :
Total number of structural isomers = 7
(i) CH3ăCH 2CH 2CH 2ăOH (ii) CH3  CH CH2 OH

|
CH3
CH3
|
(iii) CH3  CH  CH2 CH3 (iv) H3C  C  OH
|
| CH3
OH
(v) CH3CH 2ăOăCH2CH 3 (vi) CH3ăOăCH2ăCH2ăCH 3
(vii) CH3  O  CH  CH 3
|
CH3

44 QUIZRR
Ex a m p l e
C4H8 can have so many isomers. Write their structures.
Solution :
C4H8 can have following structures :
(a) CH3ăCH2ăCH=CH2 1-butene
(b) CH3ăCH=CHăCH3 2-butene, (cis and trans)
(c) CH3  C  CH2 2-methyl-1-propene

|
CH3
(d)
CH3
(e)
ST EREOI SOM ERI SM

When isomerÊs have the same structural formula but differ in relative arrangements of atoms or groups
in space within the molecule, these are known as stereoisomers and the phenomenon as
stereoisomerism.
Stereo isomers can be configurational isomers or conformation isomers.
A particular orientation (or arrangement) of atoms in a molecule, differing from other possible
orientations by rotation around single bonds is known as conformation.
Configurational isomerÊs can be geometrical isomers (or) optical isomers.
We d g e -d a s h d i a g r a m s
Usually drawn with two bonds in the plane of the page, one infront, and one behind to give the
molecule perspective. When drawing wedge-dadh it is a good idea to visualise the tetrahedral arrangement
of the groups and try to make the diagram „fit‰ this. As a suggestion, they seem to be most effective
when the „similar‰ pairs of bonds (2-in-plane, 2-out-of-plane) are next to each other, see below :
comes forwards out of the plane of the page  infront

goes backwards out of the plane of the page  behind

QUIZRR 45
Sa w h o r s e
Sawhorse diagrams are similar to wedge-dash diagrams, but without trying to
HH CH3
use „shading‰ to denote the perspective. The representation to the right of propane
has been drawn so that we are looking at the molecule which is below us and to H HH
our left.
N e w m a n Pr o j e c t i o n s H
H CH3
These projections are drawn by looking directly along a particular bond in the
system (here a C-C bond) and arranging the substituents symmetrically around the H H
H
atoms at end of the bond. The protocol requires that the atoms within the central bond
are defined as shown below :
H
The „circle‰ defines the back H CH3 The „dot‰ defines the front
carbon atom and the groups carbon atom and the groups
attached to it. H H attached to it.
H
In order to draw a Newman projection from a wedge-dash diagram, it is useful to imagine putting
your „eye‰ in line with the central bond in order to look along it.
LetÊs work through an example, consider drawing a Newman projection by looking at the following
wedge-dash diagram of propane from the left hand side.
Ć First draw the dot and circle to represent the front and back C respectively
Ć Since the front carbon atom has an H atom in the plane of the page pointing up we can add
that first
Ć The back carbon atom has an H atom in the plane of the page pointing down
Ć Now add the other bonds to each C so that it is symmetrical
Ć The groups / bonds that were forward of the plane of the page in the original wedge-dash
diagram are now to our right
Ć Those behind the plane are now to our left
H H
CH3
H H
H
H H
H CH3 CH3 H
H H H H
H H

46 QUIZRR
Co n f o r m e rs o f c y c l o h e x a n e
The cyclohexone ring can assume many shapes due to rotation around carbon-carbon bonds.
The chair form and the boat form are the extreme cases.
1 4 1
3 2 3 2
5 6 5 6
4 Boat (less stable)
Chair (more stable)
Ć Each Carbon atom of Cyclohexane is bonded to two Hydrogens. The bond to one of
these hydrogen lies in the plane of the ring; this is called equatorial hydrogen. The
bond to the other hydrogen atom is parallel to the axis, this hydrogen atom is called
Axial Hydrogen.
Ć I n Chai r f or ms, C – H f l agpol es at C 1 and C 4 are in trans side thus minimising strain
and thus increasing stability.
Ć In boat form, there is some repulsion between C ă H flagpoles at C 1 and C 4 being on
same side and thus steric hindrance is increased and stability decreased.
N e w m a n Pr o j e c t i o n
These projections are obtained by viewing the molecule along the bond joining the two
carbon atoms. H H H
H H
H
H H
H H
H
H
Eclipsed Staggard
The various other conformers of ethane are :
Ha Hb Ha Ha H
60Ĉ
H Hb
120Ĉ
60Ĉ 60Ĉ
rotation rotation
H H
H H H
H H H
H Hb
H
Eclipsed (I) Skew or gauche (II) Eclipsed (III)

QUIZRR 47
Ha Ha H Ha
H H Hb H
180Ĉ
60Ĉ 60Ĉ
rotation rotation
Hb
H H H
H H H
H
Hb H
Staggard (IV) Eclipsed (V) Skew or gauche (VI)
1 7 .1 Co n f o r m a t i o n a l I s o m e r i s m
Conformational isomers (or conformers) are isomers formed by the rotation of bond.
(a) Conformations of Ethane
In ethane, the two carbon atoms are connected by a -bond. If one of the methyl group
in ethane molecule is kept fixed and the other is rotated about the CăC bond, infinite
number of conformers of ethane result. The conformations can be represented by
sawhorse or Newman projections.
(i) Sawhorse Projection
The sawhorse projections are represented as show in the figure. The two extreme
conformers are termed as staggered and eclipsed and the conformations lying between
them are termed as gauche or skew conformations.
H H
H H H
H H
H
H H
H H
(eclipsed) (eclipsed)
There are 2 types of strain among conformers :

(i) Torsional strain - strain due to repulsion between the bonded electron pair of CăH or
CăC bonds or other types of bonds.
(ii) Vander WaalÊs StrainăStrain due to repulsion or crowding when atoms or groups are
too close to each other due to electrostatic repulsion of the electrons.
Eclipsed form of ethane has both these strains more than in the skew form. Skew and
staggered from have similar strains, so they are equally stable

48 QUIZRR
Po t e n t i a l En e r g y Pro f i l e f o r Et h a n e Co n f o r m e r s
Energy Profile for Ethane Conformers
(I) eclipsed (III) (V) (VII)
eclipsed
PE
staggered staggered
(II) (IV) (VI)
60
120
180
240
300
360
0Ĉ
Dihedral Angle (degrees)
(b) năButane Conformations

H H
·
1 2 3 4
CH3 · C · C · CH3
·
H H
If we consider rotation about C 2 ă C 3 bonds, we get the following conformers. There Anti
and Gauche conformations are represented by prefix A and C. These conformers represent
staggered conformations.
CH3
H3 C H 3 H
2 H H
3 CH3 Anti
A C C
CH3 H H Conformation
CH3 2 H
H CH3
H HCH3
H3 C 3
2 partially eclipsed
B C C H3C H CH3 3
2 Conformation
H CH3
CH3 H
2 H H
H
CH3
CH3
H3 C CH3
2 3 CH3 CH3 CH3
Gauche
C C C 3
2 Conformation
CH3
3 H3 CCH3
H3 C CH3
3 3
C C Eclipsed
D 2 Conformation
2

QUIZRR 49
D D
B B
C C
Dihedral Angle (degrees)
Out of the four conformations listed above, anti-conformation is the most stable since in
this conformations the two non-bonded methyl groups and the four hydrogen atoms are as far
apart as possible. The next in order of higher energy come the gauche conformations in which
the two non-bonded methyl groups are only 60Ĉ apart and hence causing crowding or steric
strain them eclipsed forms.
Next in order of higher energy fall the partially eclipsed conformations.
The fully eclipsed conformation is however, the least stable. This is due to the reason that
in this conformation, there is one methyl-methyl eclipsing interaction and two weak hydrogen-
hydrogen eclipsing interactions. Thus, the order can be sumarised as :
Anti > Gauge or skew > Partially eclipsed > fully eclipsed.
Ex a m p l e
Increasing order of stability among the three main conformations (i.e. Eclipse, Anti, Gauche)
of 2-fluoroethanol is
(a) Gauche < Eclipse < Anti (b) Eclipse < Anti < Gauche
(c) Anti < Gauche < Eclipse (d) Eclipse < Gauche < Anti
Solution :
Eclipsed form of 2-fluoroethanol is least stable due to repulsion between the F and OH groups as
well as due to torsional strain. Gauche form is most stable as the torsional as well as vander WaalÊs
strain both are considerably reduced and the intramolelcular H-bond further increases the stability.
Therefore, the increasing order of stability is Eclipse < Anti < Gauche.
 (b)

50 QUIZRR
Ge o m e t r i c a l I s o m e r i s m
Isomers which posses the same molecular and structural formula but differ in arrangement of
atoms or groups in space around the double bonds, are known as geometrical isomers and the phenomenon
is known as geometrical isomerism.
Condition for the presence of Geometrical isomerism :
(1) Rotation about C ă C bond must be hindered
C=C ăCă
ăCă (ring)
(2) On some carbon two different groups should be attached
(i) Cisătrans isomerism : When similar groups are on the same side it is cis and if same groups
are on the opposite side it is trans isomerism.
HOOC COOH
C=C HOOC H
C=C
H H H COOH
(Maleic acid)
Fumeric acid
(cis form)
(trans form)
(ii) Syn-anti isomerism :
Compounds conteining C = N ă OH units are commonly called oximes. Apart from
H
oxime of formaldehyde C = N ă OH , Oximes of any other aldehyde exibits
H
geometrical isomerism. The nomeclature of aldoximes is Syn (when H and OH present
on same side) and anti (when H and OH on opposite sides).
CH3 CH3
H H
C C
N N
OH (aldoxime) OH
(Syn) (anti)
C6 H5 N C6 H5 N
C6 H5 N N C6 H5
(Syn) (anti)

QUIZRR 51
R
Also in case of oximes of un symmetrical ketons C = N ă OH show geometrical
R'
isomerism.
R R' R R'
C C
N N
OH OH
Syn (R') anti (R')
or or
anti (R) Syn (R)
(iii) In cyclic compounds: Because of the impossibility of rotation around CăC single bond
as the conformation of cyclic compound would twist on rotation, they show isomerism.
ï ï ï
1, 2 ă cis 1, 2 ă trans 1, 3 ă cis
ï ï ï
ï ï
1, 3 ă trans 1, 4 ă cis 1, 4 ă trans
Di f f e r e n t i a t in g p r o p e r t i e s o f c i s -t r a n s i s o m e r i s m
(i) Dipole moment : Usually dipole moment of cis is larger than the trans-isomer.
Cl H Cl
H
C C
C C
H Cl Cl H
ø = 1.84D ø = 0.8D

52 QUIZRR
(ii) Melting point : The steric repulsion of the group (same) makes the cis isomer less stable than
the trans isomers hence trans form has higher melting point than cis.
E a n d Z n o m e n c l a t u r e o f g e o m e t ri c a l i s o m e r is m
If all the four groups / atoms attached to C = C doube bond are different, then Cis and trans
nomenclature fails in such cases and a new nomenclature called E and Z system of nomenclature
replace it.
H I higher priority
H II
C C
C C
Br Cl Cl Br
higher priority
higher priority
E Z
The group / atom attached to carbon-carbon double bond is given to higher rank, whose atomic
weight is higher. If the two higher ranked group are across, it is called E form (E stands for the German
word entgegen meanin thereby opposite) and if the two higher ranked groups are on the same side,
they are called Z-form (Z stands for German word Zusammen meaning thereby on the same side).
Ru l e s f o r d e c i d i n g p r i o ri t i e s a r e :
(1) Higher the atomic number of the atom attached to the double bond carbon, higher will be the
priority.
(2) If same priority group are on same side  Z
If same priority group are on different side  E
CH3 CH3
(2)
(1)
CH CH
C CH3 C
(2)
CH3 (1)
C C
H D H D
(2) (1) (2) (1)
(3) If the atom attached to the double bonded carbon are same, then priorities are decided by
next atoms attached to that atom.
(4) If the isotopes are attached to double bonded carbon atom then higher the (2) (1)
atomic mass, higher will be priority. CH3
Note : Higher priority is marked by (1) and lower by (2)
C
C
Br OH
(1) (2)

QUIZRR 53
(5) If the atom attached to the double bonded carbon continues double or triple bond then the
priorities are decided by considering the same atom twice or thrice.
(2) (1)
H3C CH2CH3
C
C
Br H
(1) (2)
N u m b e r o f Ge o m e t r i c a l I s o m e r s
(i) The number of isomers when there is only one double bond  2
(ii) If there are n alternate double bonds and their ends are not identical  2 n
For Example
CH 3 ă CH = CH ă CH = CH ă CH 2 CH 3
The isomers are

(1) (2)
H H H
CH2 CH3
CH3 C=C CH3 C=C
C=C CH2 CH3 C=C H
H H H H
cis ă cis cis ă trans
(3) (4)
H H H
CH2 CH3
H C=C H C=C
C=C H C=C CH2 CH3
CH3 CH3
H H
trans ă trans trans ă cis
Hence the compound has 2 2 = 4 isomers

54 QUIZRR
(iii) If the ends are identical, then
isomers = 2 nă1 + 2 pă1
n
where p = if (n is even)
2
n 1
p = if (n is odd)
2
For example
CH 3 ă CH = CH ă CH = CH ă CH 3
The isomers are :
(1) H H
CH3 C=C
C=C CH3
H H
cis ă cis
(2) H
CH3
CH3 C=C
C=C H
H H
cis ă trans
(3) H
CH3
H C=C
C=C H
CH3
H
trans ă trans
So, total isomers = 2 1 + 2 0 = 3

QUIZRR 55
Some students night be wondering that a trans ă cis isomer should also be considered as
done in the earlier case, but please note that here cis-trans and trans - cis isomers are identical,
hence we can write them as only one isomer :
Ex a m p l e
Find the total number of isomers of the following compounds and draw them.
(a) CH 3 ă CH = CH ă CH = C = CH CH 3
(b) CH 3 ă CH = CH ă CH = C = C = CH CH 3
CH3
C = C = C = CH · CH3
(c)
CH3
Solution :
(a) This part is an exception to the formulae used for calculating the number of isomers
with a alternate double bonds.
(i) CH C = C = CHCH3
3
C=C
H H
cis
(ii)
H CH = C = CHCH3
C=C
CH3
H
trans isomer
Note: For an isomer to exist, all the groups must be in the same plane, whether or
not the whole structure is in same plane.
Hence, for compounds like
R ă CH = C = CH ă R´, isomers do not exist because R and R´ are in perpendicular plane.
R R
C C C
H
H
[we can see that R is in the plane of paper and R´ is into the plane of paper (H is coming out
of plance)].

56 QUIZRR
(b) The isomers are :
(i) H H
CH3 C=C=C=C
C=C CH3
H H
cis ă cis
(ii) H CH3
CH3 C=C=C=C
C=C H
H H
trans ă cis
(iii) H CH3
H C=C=C=C
C=C H
CH3
H
trans ă trans
(iv) H
H
H C=C=C=C
C=C CH3
CH3
H
trans ă cis
Hence, there are 4 isomers because now the groups attached to the first and last carbon
atom are in the same plane.

QUIZRR 57
(c) CH3 H
C=C=C=C
CH3 CH3
This compound has no isomers, as the groups are not proper (two CH 3 on the same carbon
atom).
ST EREOCH EM I ST R Y T ER M I N OL OGY
Stereochemistry is all about the 3D spatial aspects of chemistry.
Stereoisomers are molecules that differ only in the arrangement of bonds in 3D space.
Superimposable Many objects (including molecules) are indistinguishable from their mirror images,
so they are superimposable.
Non-superimposable Other objects, such as your left and right hands, can be distinguished, they
are non-superimposable.
Chiral An object that has a non-superimposable mirror image is said to be „chiral‰
(Greek = „handedness”) and one that has a superimposable mirror image is „achiral‰.
If we restrict our thoughts to 2D for a second, and think about letters of the alphabet, some are
chiral while others are not. To appreciate this, print some words on a piece of paper, then look at them
in a mirror. Do they still look the same (superimposable) or are they different (non-superimposable) ?
Words like „MOM‰ are the same as the mirror image but „DAD‰ is not. ThatÊs why the word
„AMBULANCE‰ on the front hood of the vehicle looks „odd‰ unless you are looking at it in your rear
view mirror.
The most common type of „chirality‰ is observed when a carbon atom has four different groups
attached to it (so it must be sp3 hybridised). This carbon atom is them described as achirality center.
En a t i o m e r s
Ć If a pair of stereoisomers are non-superimposable mirror images of each other, then they are
enantiomers.
Ć If you donÊt know what is meant by non-superimposable mirror images then note that your
left and right hands are a pair of enantiomers.
If objects are superimposable, it means you can not tell them apart. If they are non-
superimposable, then you can always distinguish them.
Ć For example, if you look at your hands, you will see that while they are very similar, they
are essentially mirror images. They are not identical, because you can always tell which one
is which!
Me Me
H Cl H
Et Cl
(R)-2-chlorobutane Et
(S)-2-chlorobutane

58 QUIZRR
A molecule that can exist as a pair of enantiomers has the property of chirality or is described
as chiral. A molecule that lacks this property is achiral.
You should be a ble to draw the two mirror ima ges of a n a chira l molec ule a nd then see
if you rota te one of the ima ges the two molec ules a re a ctua lly the same (i.e. tha t they a re
superimposable). For exa mple, compa re 2-chloropropa ne a nd 2-chlorobuta ne systems :
CH3 CH3 CH3

b a
H CH3 H3 C H H CH3
Cl a Cl Cl b
though C a and C b are different they are indistingushable

from each other
Because the 2 alkyl groups are indistinguishable, the original molecule and itsÊ mirror image are
superimposable.
CH3 CH3 120Ĉ CH2 CH3
H CH2 CH3 H3CH2 C H H CH3

Cl Cl Cl
mirror
plane
non-superimposable structures
Because the 2 alkyl groups are distinguishable, the original molecule and itsÊ mirror image are
non-superimposable.
I m p o r t a n t p r o p e r t i e s o f e n a n t io m e r s t h a t y o u s h o u l d k n o w :
Ć They have different physical properties
Ć They have different chemical/biological properties
A mixture that contains equal quantities of enantiomers is called a racemate or a racemic
mixture.
DI A ST EREOM ER S
There are a couple of ways we can use to define diastereomers :
Ć Stereoiosmers that are not mirror images are diastereomers
Ć Stereoiosmers that are not enantiomers are diastereomers.

QUIZRR 59
Chiral molecules that possess two (or more) chirality centers (we will define this soon) have
stereoisomers that may be either enantiomers or diastereomers. Diastereomers are stereoisomers that
are not mirror images.
Br CH3
H
H
H3C Cl (S,R) - 2- bromo-3-chlorobutane
H CH3
Br
H
H3C Cl
(R,R)-2-bromo-3-chlorobutane
Diastereomers can have quite different physical and chemical properties from one another. This
is important as it allows them to be separated.
OPT I CA L I SOM ERI SM

A compound, in which an atom (say carbon) has all the four groups different, is said to have
chirality and this centre (carbon) is said to be Chiral (asymmetric) centre or stereogenic centre.
a a
x C b x C x
y y
Chiral centre achiral centre
(as all groups are different) (2 same x on the carbon atom)
A better way to determine whether a molecule is chiral is to examine its symmetry (called as
plane of symmetry). If an imagniary plane passes through the centre of the object and divides
the object so that the one half is the mirror image of the other half is having of plane of symmetry.
Any molecule that has a plane of symmetry is not chiral.
CH3 O CH3
H C H
Cl
Plane of symmetry not a plane of symmetry

(achiral) (chiral)

60 QUIZRR
OPT I CA L A CT I V IT Y
Ordinary light has vibrations in all possible planes. The ordinary light can be converted
into plane polarized light by making it pass through a nicolprism. The plane polarized light has
vibrations only in one plane. When this plane polarized light is passed through a compound,
and it turns the plane of the polarized light, then it is said to be optically active.
compound A
nicol prism Plane polarized (A is optically

light active)
Dextrorotatory ă If the compound A (isomer) rotates the plane of the polarized light to
the right, it is dextrorotatory (d)
Leavorotatory ă If the compound A (isomer) rotates the plane of polarized light to the
left, it is Laevorotatory (l)
Co n d i t i o n s f o r Op t i c a l A c t i v i t y
(1) The compound should be chiral (asymmetrical). The compound should be devoid of any
element of symmetry like plane of symmetry, centre (point) of symmetry etc.
(2) The mirror image of the compound should be non-super imposable on it.
Plane of symmetry (  ) : A plane which when passed through a molecule divides in into
two identical parts (mirror image)
b
O
a b

a b
H H
(plane of symmetry) b
Such an isomer is called meso isomer, which is optically inative due to the presence of
plane of symmetry. The optical rotation of one half of the molecule is exactly cancelled by the
other half. This is called internal compensation.
Centre of Symmetry : It is an imaginary point within the molecule and is present when
all the joining similar groups pass through a common point. This common point is called as
centre of symmetry.

QUIZRR 61
c
a b
b
i (centre of symmetry)
c
For ringed structures
Ph COOH
H H
H H
HOOC Ph
It must be noted that only even membered rings possess a centre of symmetry. It is not
found in odd-membered rings. Centre of symmetry will never exist in a molecule having only
the chiral centre.
FISH ER PROJ ECT I ON FORM U L A

Steps for drawing fisher projection :
(1) Draw horizontal cross equal to the number of a symmetric carbon atom.
(2) Carbon atoms are arranged on vertical line, C 1 being at the top or most oxidized form
at the top. E.g. CH 3 CH (OH) COOH
COOH COOH
HO H HO H
CH3 CH3

62 QUIZRR
(3) Groups present on vertical line are behind the plane and groups on horizontal are
above the plane.
COOH COOH
HO C H H C HO
CH3 CH3
This is a general method used for representation of compound in a 3-Dimentional space.
This shows that veritcal bonds are extending behind the plane whereas the horizontal bonds
project in front of the plane of page.
(a) Relative Configration : This method for designating configuration of enantiomers
uses the descriptors D and L. As we have already done, D stands for dextrorotatory and
L for leavorotatory.
Note: atoms other than C and H are called hedro atoms.
Now, for assigning the compound as D and L, we draw an arrow from H to hedro atom
through topmost element i.e. most oxidised from.
COOH COOH
H HO HO H
(dextro) (leavo)
CH3 CH3
If the arrow goes in a clockwise manner, it is called dextro rotatory and if the arrow
goes in anti clockwise, it is leavorotatory.
When the molecule contains more than one a symmetric atom, there can be differnt
configuration at different chiral carbon.
COOH COOH
L D
HO H H HO
D L
H HO HO H
COOH COOH

QUIZRR 63
COOH
L
HO H
D
H HO
COOH
(b) Absolute Configuration: optical isomers in this configuration are now written in
terms of R (rectus) and S (sinister).
Ć This is based on the actual 3-dimensional formula of the compound and not upon
its projection on a 2-dimenstional surface (as done in relative configuration).
Ć If a, b, c and d are the groups attached to the chiral atom, there on arranging
these groups in a priority sequence, configuration,
R is given to the isomer if sequence is left to right
S is given to the isomer if sequences is right to left.
Pr i o r i t y Cl a s s i f i c a t io n :
(1) Higher the atomic number, higher the priority.
Cl
H C F
Br
Br  Cl  F  H
For this sequences will be (35) (17) 9 (1)
(2) If the first atom fails to assign the priority then check for second corresponding atom
For example, while deciding priority amongst the following groups, they can be
considered as
H H
(a) H C O < > C O
O C

64 QUIZRR
N
(b) C N < > C N
N C
O O C
(c) C NH2 < > C NH2
So, while deciding the next atom in all these compounds, the structure is droken into the
structure as shown on the right hand side.
IMPORTANT NOTE : For assigning the configuration, the enantiomer is viewed along
the axis of the bond connecting the chiral centre to the group of lowest priority and from the
side of the mulecule opposite to this atom.
a
C Here d has the lowest priority

b c
Now,
Here the sequence is a  b  c  d and we can see that it is anti clock wise hence its
configuration is S.
c c
C C
a b b a
d d
(S) (R)

QUIZRR 65
Illust rat io n
Find the R & S configuration.
CHO
H3C C CH2 CH3
H
Solution :
For this case priority order is
CHO CHO
O
||
· C· H (a) Carbon attached to oxygen C C
CH2 CH3 CH3
CH3 CH3 CH2
· CH 2 CH 3 (b) Carbon to carbon
· CH 3 (c) Carbon to hydrogen. H H
(R) (S)
When the molecule contains more than one chiral centre, configuration of each centre is
determined seperately following same sequence rule.
Simplest way is to take group of lowest priority at the bottom side (we shall call it viewing
side). In this process, we always carry out even number of changes. If we take odd number of
changes, if alters its configuration).
2
COOH COOH
1 one interchange
4 H OH H3C OH
3 H
CH3 OH
second
interchange
H3C COOH

66 QUIZRR
Hence, we have here even number of changes, thus it is an R configuration.
Let us have another example,
H CHO
HO CHO H2N H
NH2 OH
NH2
OHC OH
H
(S)
An example with two chiral carbons
4
COOH
3
H OH
2
HO H
1
COOH
Here, we determine configuration of each carbon separately.

QUIZRR 67
For C 2
CH(OH)COOH OH
2 2
HO H HOOC(OH)HC COOH
COOH H
( R at C2 )
For C 3
COOH OH
3 3
H OH COOH(OH)HC COOH
CH(OH)COOH H
( R at C3 )
Thus,
4
COOH
3
H OH
is (2R, 3R) ă tartaric acid.
2
HO H
1
COOH
Meso c om pounds
In the simplest case, a compound with two chirality centers where there is the same set of four
groups at each chirality center, the combination where the four groups are arranged such that the
centers are mirror images of each other (i.e. where the molecule has an internal mirror plane) is a meso
compound.

68 QUIZRR
For example consider 2, 3-dichlorobutane. There are two chirality centers (C2 and C3), each with
ăH, ăCl, ăCH3 and the other ăCHClCH3 groups attached. Since there are two chirality centers, then,
at least in principle, there are 4 possible permutations (R, R), (R, S), (S, R) and (S, S).
H Cl H H Cl Cl Cl H
Cl Cl Cl H H H Cl
H
H3C CH3 H3C CH3 H3C CH3 H3C CH3
(R, R) (R, S) (S, R) (S, S)
If we look at the (R, S) and (S, R) as drawn above, it should be reasonably easy to recognise that
these two structures are actually the same thing because they are superimposable. This structure is the
meso isomer.
H H ClCl H H Cl Cl
Cl Cl H H Cl Cl H H
=
H3C CH3 H3C CH3 H3C CH3 H3C CH3
(R, S) (S, R)
rotate the whole
(S, R) -2, 3-dichlorobutane molecule 180Ĉ
(R, S)-2, 3- dichlorobutane (S, R)-2, 3- dichlorobutane
In the conformation shown, the mirror plane is obvious. However, lets look at other conformations
of the meso isomer and make sure we recognise why it is the meso isomer.
Important properties of meso compounds that you should know :
For simple meso compounds with 2 chirality centers :
Ć they are optically inactive
Ć they must be (R, S) configuration
Ć they are diastereomers of the (R, R) and (S, S) isomer.
Isom er t ypes
Compounds that have the same molecular formula but different chemical structures are called
isomers. Remember isomerism is a property between a pair (or more) of molecules, i.e. a molecule is an
isomer of another molecule. A similar relationship is that of brother or sister... you can only be a brother
or sister to someone else.
Depending on the nature of the difference between the structures, it is possible to classify isomers
into various sub-types. The following tree diagram should help you recognise the difference based on
a simple YES/NO question.
Isomers are compounds with the same molecular formulae but that are structurally different in
some way. It is important to be able to recognise isomers because they can have different Chemical,
Physical and biological properties.

QUIZRR 69
Do the compounds'
have the same molecular
formulae?
NO
Not isomers
YES
lsomers
Do the compounds have

the same connectivity?
NO YES
Constitutional Stereoisomers
O
OH Can the compounds be
interconverted by rotation
about single bonds ?
NO YES
Configurational Conformational
H3C H H H
Is there isomerism at a H H H
double bond ?
YES H
NO H CH3 H3C CH3
Geometric Optical
Are the compoundss

non-superimposable
mirror images?
NO YES
Diastereomers Enantiomers
Cl H Cl Cl
H3C H H3C Cl
CH 3 CH2 H H CH2 CH3
H H CH3
H3C
H3C Br H3C Br

70 QUIZRR
N u m b e r o f o p t ic a l i s o m e r s
Number of possible optical isomers in compounds containing different no. of asymmetric atoms.
1. The molecule has no symmetry
The no. of d and l ă forms a = 2n
n = no. of asymmetric atoms
The no. of meso l-forms m = 0
Total no. of optical isomers = a + m = 2n
2. The molecule has symmetry and n is even
The no. of d and l forms a = 2nă1
n
Meso forms m = 1
22
n
= 2n 1  2 2 1
Tartaric acid
COOH
·
H · C · OH
· ·
H · C · OH Plane of symmetry n = 2
COOH
a = 2nă1 = 22ă1
n
m = 1 = 21ă1 = 20 = 1
22
Total = 2 + 1 = 3
COOH COOH COOH

·
H · C · OH HO · C · H H · C · OH
·
HO · C · H H · C · OH H · C · OH
·
COOH COOH COOH

I II III
(meso forms)
One of asymmetric centre is rotating plane polarised light towards right other towards left so
total optical rotation is zero.
I & III or II & III which are not mirror image to each other are called diastereomers.

QUIZRR 71
3. The molecule has symmetry & n is odd
 n  1
n 1
The no. of d and l forms a  2 2 2
 n1 
Meso forms m  2 2
Total = a + m
= 2(nă1)
e.g. Lactic acid
CH3
|
H  C  OH
|
COOH
n = 1 no symmetry
d & l forms = 2n = 2
meso form = 0
total = 2
CH3 CH3
| |
H  C  OH OH  C  OH Mirror images are also called as enantiomers
| |
COOH COOH
Op t ic a l ly a c t iv e c o m p o u n d s h a v i n g n o c h i ra l c a r b o n
The presence of chiral carbon is neither a necessary nor a sufficient condition for optical activity,
since optical activity may be present in molecules with no chiral atom and since molecules with two or
more chiral carbon atoms are superimposable on their mirror images and hence inactive.
(i) Any molecule containing an atom that has four bonds pointing to the corners of a tertahedron
will be optically active if the four groups are different.
16
O
CH2 S CH2
1 8O
(ii) Atoms with pyramidal bonding might be expected to give rise to optical activity if the atom
is connected to three different groups, since the unshared pair of electron is analgous to a
fourth group.
Z
N
X Y

72 QUIZRR
Many attempts have been made to resolve such compounds, but until recently all failed
because of umbrella effect, also called pyramidal inversion. The umbrella effect is rapid
oscillation of the unshared pair from one side of XYZ plane to the other.
(iii) Allenes, with even number of adjacent double bonds are optically active if both sides are
dissymmetric.
H3C H H CH3
C=C=C C=C=C
H3C H H3C H
Inactive Active
Explanation :
H3C CH3
SP 2 SP
C=C=C SP 2
H3 C 1 2 3
CH3
Central carbon is sp. Therefore both the double bonds are in perpendicular direction thus in
different plane. If carbon (1) is in plane of paper then the group attached to carbon (3) are
in plane perpendicular to plane of paper. Thus no plane of symmetry exists. Thus the structure
is chiral.
CH2 CH2
(iv) CH2 is optically active.

CH2
Because both the benzene rings are in different plane, therefore structure is non-
superimposable over its image. Thus it is optically active.
(v) Biphenyls
H H
H H
It is opically inactive because the mole cule is symmetrical and plannar.

QUIZRR 73
So m e i m p o r t a n t p o i n t s :
Ć If bulky groups are present at ortho positions of both the rings, then rotation about the
CăC bond takes place, to reduce the extra energy due to repulsion and stabalize the
molecule, now the two phenyl molecules are not in same plane, hence optically active.
NO2 NO2 below plane
of paper
outside the
COOH COOH plane of paper
Ć Despite the molecule is non planar, it is optically inactive because of the presence of
plane of summetry. (plane through A & B cutting their molecules into halves and on
the other phenyl both groups are same)
A D
B D
(vi) SPYRO
In these type of compounds, the alternate molecules are in same plane.
(1) a a
b b
(optically active because of the absence of plane of symmetry)
(2)
a a
Plane of
Symmetry
b b
(Optically inactive)

74 QUIZRR
Ex a m p l e
Find whether the following compounds are optically active or not.
D
T C H
R1 R3 R1 R3
(i) (ii) R2 R4
R2 R4
CH3 Cl
(iii) H H H
H
Cl CH3
Solution :
Compound (i) is optically active because there is no plane of symmetry, which can cut the molecule
into two equal halves. Compound (ii) also does not have plane of symmetry so, it is optically active.
Compound (iii) is optically inactive because of the presence of centre of symmetry.
Ex a m p l e
Find out whether the given compounds are optically active or not.
H C H
SO3 H SO3 H 2 5
(i) (ii)
I H I CH3
CH3 C3 H7
(iii) C= C=C=C
C2 H5 CH3
Sol u t i on :
In compounds (i) and (iii), there is plane of symmetry passing through the compounds (molecular
plane). Therefore, they are optically inactive. Compound (ii) does not have any plane of symmetry as
the two phenyl rings are not in the same plane. One of the ring rotates about C-C bond axis because
of bulky substituents at O, O´ positions of two adjacent phenyl rings and the two rings are perpendicular
to each other. So, (ii) is optically active.
Op t i c a l Pu r i t y
The optical purity or the enantiomeric excess (ee%) of a sample can be determined as follows :
Optical purity = % enantiomeric excess = % enantiomer1 - % enantiomer2
= 100 []mixture / []pure sample
ee% = 100 ([major enantiomer] - [minor enantiomer]) / ([major enantiomer] + [minor enantiomer])
QUIZRR 75
where [major enantiomer] = concentration of the major enantiomer

[minor enantiomer] = concentration of the minor enantiomer
Diasteromeric substances can have different rotations both in sign and in magnitude.
Ex a m p l e
The specific rotation of Ră2ăbromooctane is ă 36Ĉ. What is percentage composition of a
mixture of enantiomers of 2-bromooctane where rotation is + 18Ĉ.
Solution : Let X = mole fraction of R,
 (1 ă X) = mole fraction S.
X (ă 36Ĉ) + (1 ă X) 36Ĉ = 18Ĉ
1
or, X
4
The mixture has 25% R and 75% S, it is 50% racemic and 50% S.
T H E B REA K I N G A N D FORM I N G OF B ON DS
Organic reactions usually involve the fission and formation of covalent bonds. The covalent bond is
often represented as a dash (·) and the movement of a pair of electrons is shown by a curved arrow,
( ), where as the movement of a single electron is a shown by fish hook arrow .
There are two ways in which a covalent bond may be broken.
H o m o l y t i c Fi s s i o n
Suppose the atoms X and Y are bonded through a covalent bond. When a bond breaks such that each
of the atoms retains one of the bonding electrons, the process is called homolytic bond cleavage (or)
homolysis. Homolytic fission results in the formation of free radicals.
XăY X+Y
Free radicals
H e t e r o l y t ic Fi s s i o n
When more electronegative atom remainÊs attached with less electronegative atom, then the bonded
pair of electrons moves towards more electronegative atom, thereby more electronegative atom gets
negative charge and less electronegative atom gets + ve charge such type of fission is known as
heterolytic fission i.e. this fission occurs by a shifting of bonded pair of electrons from less
electronegative atom to more electronegative atom.
The ions of carbon, known as carbanions and carbonium ions, are of special importance in organic
chemistry.
Homolytic chemistry is the chemistry of the odd electron; Heterolytic chemistry is the chemistry of
the electron pair. Where homolytic chemistry deals with the neutral particles called free radicals,
heterolytic chemistry deals with positive and negative charges, with cations and anions. Homolytic
reations are typically carried out in the gas phase; or in solvents whose principal function is to provide
an inert medium in which the reacting molecules can move about. Heterolytic reactions are typically

76 QUIZRR
carried out in solution in polar solvents, because of the greater ease of separation of charges therein
and very often because of the stabilization of the resultant ion pairs through solvation.
X+ Y
ă
XăY
Carbanion
Carbocation
EL ECT ROPH I LES A N D N U CL EOPH I LES
Di s c u s s i o n :
Consider the reaction of hydroxide ion (a Bronsted base) with hydrogen chloride (a Bronsted acid).
ă ă
H O H Cl H O H + Cl
The oxygen of hydroxide ion bears a formal charge of ă 1. The hydrogen of hydrogen chloride
bears a + charge because chlorine is more electronegative than hydrogen and thus the H-Cl bonding
electron pair is unequally shared. We can envision the start of the acid-base reaction between hydroxide
ion and hydrogen chloride as an electrostatic attraction between the opposite charges. As the reaction
proceeds, the oxygen atom of hydroxide ion shares a lone electron pair with the hydrogen atom of
hydrogen chloride, as shown with the curved arrow in the reaction above. This simple reaction shares
one feature in common with the majority of reactions that you will encounter in your study of elementary
organic chemistry. One species in the reaction shares an electron pair (a Lewis base) with another
species (a Lewis acid) to make a new covalent bond. Application of this electron sharing idea to any
reaction gives you an excellent chance at starting to figure out the mechanism for most common organic
reactions.
Because of the ubiquity of electron pair shares and acceptors in organic reactions, we assign special
and distinct terms to these species. A molecule or ion that accepts a pair of electrons to make a new
covalent bond is called an electrophile (from the Greek for „electron loving‰). An electrophile is the
same thing as a Lewis acid. Any molecule, ion or atom that is electron deficient in some way can
behave as an electrophile. Electron deficiency would include a formal positive change (methyl carbocation),
a partial positive charge (+), usually in conjunction with a polar bond (such as H-Cl) or an open octet
(borane). „E‰ or „E+‰ are common abbreviations for generic electrophiles.
Typical electrophiles :
H H
+ ă
H C H B H Cl
H H
methyl carbocation borane hydrogen chloride
carbon has a formal boron has an hydrogen bears
positive charge open octet a + charge

QUIZRR 77
A molecule or ion that donates a pair of electrons to form a new covalent bond is called a nuclephile
(from the Greek „nucleus loving‰). A nucleophile is the same thing as a Lewis base. Any molecule, ion
or atom that has electrons that can be shared can be a nucleophile. The most common indications that
electrons are available to be shared are formal negative charge (iodide ion), a partial negative charge
(ă), usually in conjunction with a polar bond (methyl magnesium bromide), a  bond (isobutylene) or
lone pairs (ammonia). „Nuc‰ or „Nu‰ are common abbreviations for generic nucleophiles.
Typical nucleophiles :
ă ă + H3C H
I
H3C MgBr
iodide ion C CH2 H N
carbon bears a ă charge
iodine has a formal methyl magnesium
negative charge H3C H
bromide
isobutylene ammonia
C = C  bond nitrogen lone pair
Electrophiles (Lewis Acid)
Soft Acids Hard Acids

2
(Hg 2 , Fe2  , Ag  , etc.) (Fe3  , H , Li  , Na  , C etc.)
Metals of low oxidation state Metals of relatively higher oxidation state
They have low positive charge density They have high positive charge density
Nucleophiles (Lewis bases)
Soft bases Hard bases

       
(HSO3 , HS , Cl , Br , I  etc.) (NH2 , F , H , OH etc.)
less electronegative elements having More electronegative elements having
low negative charge density high negative charge density
The study of reaction mechanisms is central to the study of organic chemistry at any level.
Therefore identification of electrophiles and nucleophiles is a critical organic chemistry survival skill.
Examination of a structure for the features discussed above is one way to identify how a molecule or

78 QUIZRR
ion might behave in a reaction. Another way is by considering the curved arrows. Because electrons
flow from an electron source to a place of electron deficiency, a curved arrow points away from a
nucleophile and to an electrophile.
Elec trons a lwa ys flow from nucleophile to elec trophile : Nucleophile : Electrophile
Ex a m p l e
Decide if each molecule or ion shown below will react as a nucleophile or electrophie, or
both.
ă 
(a) Br (b) NH2 (c) H2O
Solution :
Examine each structure for the charge distribution and electronic features discussed above.
(a) Bromide ion : This atom has four lone pairs and a formal negative charge, suggesting it is
electron-rich and can therefore function as a nucleophile. It has none of the features that
would suggest it might behave as an electrophile.
(b) Ammonium ion : This ion has a formal positive charge, suggesting it is electron-poor and can
therefore function as an electrophile. It has no lone pairs or areas of negative charges,
suggesting it will not function as a nucleophile.
(c) Water : The oxygen atom of water has two lone pairs and a -charge (oxygen is more
electronegative than hydrogen). This suggests that water can behave an a nucleophile. Each
hydrogen atom bears a + charge, so the molecule can behave as an electrophile as well.
Many molecules can be both nucleophiles and electrophiles. How they behave depends upon
what they react with. For example, if water is reacted with an electrophile, the water will
behave as a nucleophile.
Ex a m p l e :
Identify the nucleophiles and electrophiles in each mehanism step shown below.
ă CH3 CH3 CH2 CHo

CH3 S CH3 CH2 ă
C C + I
(a) S CH3
I H H
H
H  ă
CH2 + Br
(b)
Br
H OH
ă
+ H2 O + Cl
(c)
Cl

QUIZRR 79
NO2
O H NO2 
OH2
(d) N + H3O

O
Decide if each molecule or ion shown below will react as a nucleophile or electrophile or both.
CH3 H
H3 C C C O
(e) (i)
CH3 H
H
ă H C Cl
(f) H O (j)
H
O
Cl H H
C
(g) Al Cl (k) C N
Cl H H
H
(h) H·C C·H
So l u t i o n :
(a) The curved arrow that starts at the sulfur lone pairs and ends at the carbon bearing the
iodine atom indicates that the sulfur is donating a pair of electrons to form a new S-C bond.
This means CH3S- (methanethiolate) is a nucleophile in this reaction. As there are only two
reactants, the other reactants must by default be a electrophile. We can verify this by noting
that the iodoalkane is accepting a pair of electrons from the sulfur atom to form a new
covalent bond. (This is an example of the SN2 reaction).
ă CHo CHo CH2 CHo

CH3 S CHaSCH2 ă
C C + I
l H H SCHo
nuclephile electrophile
(b) In the ionization of the bromoalkane to form a carbocation and bromide ion no new bonds are
formed. Therefore this ionization process does not involve a nucleophile or electrophile. The
reverse process, reaction of the carbocation with bromide ion to form a bromoalkane, does
result in a new bond. The curved arrow that starts at the bromide ion indicates a bromine
lone pair is shared with the carbon bearing the formal positive charge resulting in a new
80 QUIZRR
C-Br bond. Therefore bromide ion is a nucleophile. The carbocation is accepting an electron
pair to make a new C-Br bond, so it is an electrophile.
H
H  ă
CH2 Br
Br
not nucleophile electrophile nucleophile
not electrophile
(c) The hydroxide ion is sharing a lone pair with the hydrogen atom, resulting in a new O-H
bond. Therefore the hydroxide ion is a nucleophile. We might also notice that hydroxide ion
bears a formal negative charge, and that ions bearing a full negative charge are electron rich
and therefore rarely act as electron acceptors (i.e., electrophiles). Because there are only two
reactants and one of these is clearly the nucleophile, the chloroalkane must therefore be the
electrophile. (This is an example of the E2 reaction).
nucleophile
ă
H OH
ă
+ H2 O + Cl
Cl
electrophile
(d) In the first step of the reaction, a  bond of benzene (C6H6) is shared with the nitronium ion
is the electrophile. The product of this electrophilic attack on the benzene ring is called an
arenium ion. In the second step, a lone pair from a water molecule is used to make a new
O-H bond with a hydrogen that is plucked from the arenium ion. Because the water is
donating the lone pair, it is the nucleophile. This means the arenium ion is the electrophile
in the second step. (This is an example of electrophilic aromatic substitution.)
nucleophile
electrophile
NO2
O H NO2 
OH2
N + H3O

O
nucleophile electrophile
(e) Tert-butyl carbocation : The central carbon of this ion bears a formal positive charge and has an
open octet. Both of these features suggest this cation will behave primarily as an electrophile.

QUIZRR 81
(f) Hydroxide ion : The oxygen atom has three lone pairs and a formal negative charge. These
features suggest this anion will behave principally as a nucleophile.
(g) Aluminium chloride : The aluminium atom has an open octet, suggesting the molecule will
behave as an electrophile. Each chlorine has three lone pairs, suggesting a possibility for
nucleophilic properties as well. Neutral halogen atoms do not share electrons very often,
however, because it would give them a formal positive charge. Because of their high
electronegativity, halogen atoms do not tolerate a positive formal charge very well. The main
exception to this rule is when a halogen can share a lone pair with a neighboring carbocation
resulting in a structure in which all atoms have complete octets.
(h) Acetylene : We predict this alkyne will behave primarily as a nucleophile because it has
two  bonds to share. A C-H bond is almost nonpolar because of the small difference in
electronegativity of carbon and hydrogen. Thus the molecule has no obviously electrophilic
sites.
(i) Formaldehyde : The lone pairs on oxygen and the C-O  bond suggest this molecule might
behave an a nucleophile. Because carbon is less electronegative than oxygen, the C=O bond
is polarized with a + charge on carbon and a - charge on oxygen. This observation gives
another reason why the molecule is a nucleophile, and also suggest it can be an electrophile.
Thus formaldehyde could be a nucleophile or electroophile, depending upon what else was in
the reaction. This dual reactivity is a common feature of many more complex molecules.
Because this dual reactivity is due to the carbonyl group (C = O), any molecule containing
this feature is expected to behave as both a nucleophile and electrophile.
(j) Methyl chloride : The lone pairs on chlorine suggest this molecule could be a nucleophile
(see answer g above for more discussion). Carbon is less electronegative than chlorine, so the
C-Cl bond is polar, with a + charge on the carbon and a - charge on chlorine. That the
carbon bears a partial positive charge suggests that the carbon atom is electrophilic. Thus this
molecule could be a nucleophile (low probability) or electrophile.
(k) Acetamide : This molecule contains a carbonyl group (C=O). As mention in answer (i) above,
this means it can be both nucleophilic and electrophilic. The nitrogen lone pair is an addition
nucleophilic site.
I n d u c t iv e e f f e c t :
Inductive effect may be defined as the permanent displacement of electrons forming a covalent
bond towards the more electronegative element or group.
The inductive effect is represented by the symbol, the arrow pointing towards the more electronegative
element or group of elements. Thus in case of n-butyl chloride inductive effect may be represented as
below.
' ' ' ' '

CH3 CH2 CH2 CH2 Cl

82 QUIZRR
Any atom or group, if attracts electrons more srongly than hydrogen, it is said to have a -I effect
(electroattracting or electron-withdrawing), viz NO2, Cl, Br, I, F, COOH OHC3, etc. while if atom or
group attracts electrons less strongly than hydrogen it is said to have + I effect (electron repelling or
electron releasing) viz,
CH3, C2H5, Me2CH and Me3C groups. The important atoms or groups which cause negative or
positive
inductive effect are arranged below in the order of decreasing effect. -I (Electron-
attracting) groups :
+
N  CH 3 3  NO2  CN > F > COOH > Cl > Br > I > CF3  OH  OCH 3  C6 H 5  H
Always remember this order.

+ I (Electron-attracting) groups :
(CH3)3 C > (CH3)2CH > CH3CH2CH2 > CH3CH2 > CH3 > H
A c i d i c s t r e n g t h o f Ca r b o x y l ic a c i d
Compound which easily donates H+ to other are good acids. So carboxylic acids which relase H+
ion more easily are better acids.
Rule
Ć ăI effect increases acidic nature
Ć +I effect reduces acidic nature
For Ex.
Ć HCOOH > CH3 COOH > CH3 CH2 COOH
(formic acid)
Formic acid is strongest among the above 3 acids because of least +I effect.
Ć Now taking another example to show ă I effect over acidic nature of acids
Cl3 C COOH > Cl2 CHCOOH > Cl CH2 COOH > HCOOH > CH3COOH
More the Cl, more is the ăI effect & hence more the acidic nature.
Ć In the case of Cl, what if Cl atoms are attached for from COOH group.
Cl CH2 COOH > Cl CH2CH2COOH > Cl CH2 CH2 CH2 COOH
The closer the ăI group more is the acidic nature. This is also known as proximity effect.
Ć As ÂsÊ character increases, the acidic nature increases as electronegativity of atom increases
i.e. sp > sp2 > sp3
(50% S (66.31) (25%)
character)
CH  C ă CH2 ă COOH > CH2 = CHCH2 COOH > CH3CH2CH2COOH
The explanation follows from the above explanation.

QUIZRR 83
Ć More the electronegativity to an atom, more the acidic nature. We will explain this with the
help of various examples
HClO4 > HClO3 > HClO2 > HO Cl
(+7) (+5) (+3) (+1)
In this case the electronegativities of Cl are in decreasing order & hence the acidic nature.
Same reasoning applies to the following
HClO4 > H2SO4 > HNO3
(+7) (+6) (+5)
We will deal with these kind of examples later.
Re a c t iv i t y o f a l k y l h a l id e s
It can be deduced by reacting substance with Ag salt (AgNO3).
RX + AgNO3  AgX
fast
NaCl + AgNO3   AgCl (Ionic reactions)
Always keep in mind
More stable is the intermediate of a chemical reaction higher is the reactivity of the initial
compound.
CH3
|
CH3  C  Cl  CH3  CH  Cl  CH3  CH  Cl  C2 H5Cl  CH3 Cl
| | |
CH3 C2H5 CH3
CH3
|
Here CH3  C would be intermediate which is most stable among other intermediates.
|
CH3
 i.e. 3Ĉ > 2Ĉ > 1Ĉ > CH3 (If R groups are differen, reactivity order)
RI > RBr > RCI is the reactivity order of halogens.
On the basis of bond dissociation energy RI is maximum reactive due to largest size of I atom and
minimum bond dissociation energy.
RESON A NCE
Whenever a molecule can be represented by two or more structures that differ only in the arrangement
of atomic nuclei ă there is resonance. The molecule is hybrid of all these structures, and cannot be
represented satisfactory any one of them. Each of these structure is said to contribute to the hybrid.

84 QUIZRR
Localized Versus Delocalized Electrons
CH3 NH2 CH3 CH CH2
localized localized
electrons electrons

Oă
CH3C delocalized
electrons

Oă
Re s o n a n c e Co n t ri b u t o r s a n d t h e Re s o n a n c e H y b ri d
1 1
2 2
resonance contributor resonance contributor
resonance hybrid
Resonance contributors are imaginary, but the resonance hybrid is real.

The resonance hybrid is more stable than any of the contributing structures.
Ru l e s f o r Dr a w in g Re s o n a n c e Co n t ri b u t o rs
1. Only electrons move
2. Only  electrons and lone-pair electrons move
3. The total number of electrons in the molecule does not change
4. The numbers of paired and unpaired electrons do not change
The electrons can be moved in one of the following ways :
1. Move  electrons toward a positive charge or toward a  bond
2. Move lone pair electrons toward a  bond
3. Move a single nonbonding electron toward a  bond
Resonance contributors are obtained by moving  electrons toward a positive charge.
 
(a) CH3CH CH CHCH3 CH3CH CH CHCH3
+ +
CH3CH CH CHCH3
  
(b) CH3CH CH CH CH CH2 CH3CH CH CH CH CH2 CH3CH CH CH CH CH2

QUIZRR 85
+ + +
CH3CH CH CH CH CH2 resonance bybrid
 
CH2 CH2 CH2 CH2 CH2
 
(c)

+
CH2
+ +
+
Moving  electrons toward a  bond
resonance contributors
resonance hybrid
ă + + ă
CH2 CH CH CH2 H 2C CH CH CH2 CH2 CH CH CH2
CH2 CH CH CH2
resonance hybrid
Moving a nonbonding pair of electrons toward a  bond
ă ă ă
O O O O O
R C R C ă C ă C ă ă C
O O O O O O
NH2 NH2
+
resonance contributors resonance contributors
ă ă
O O
R C ă C ă
O O
NH2
+
resonance hybrid resonance hybrid

86 QUIZRR
Re s o n a n c e St r u c t u r e s f o r t h e A l l yl ic Ra d i c a l a n d f o r t h e B e n zy l Ra d i c a l
CH3 CH CH CH2 CH3 CH CH=CH2

 
CH3 CH CH CH2
resonance hybrid
CH2 CH2 CH2 CH2 CH2

CH2
 

resonance hybrid
Im po rt an t po int s
Ć Electrons move toward an sp2 carbon but never toward an sp3 carbon
Ć Electrons are neither added to nor removed from the molecule when resonance contributors
are drawn
Ć Radicals can also have delocalized electrons if the unpaired electron is on a carbon adjacent
to an sp2 atom
Ć Resonance contributors with separated charges are less stable
O Oă
O Oă
+
R C OH R C OH ă
R C O R C O
Electron always move toward the more electronegative atom
+O ă
O O
+
CH3C CH CH2 CH3C CH CH2 CH3C CH CH2
E F G
resonance contributor obtained resonance contributor obtained
by moving  electrons away by moving  electrons toward
from the more electronegative atom the more electronegative atom

QUIZRR 87
When there is only one way to move the electrons,

CH 2 CH OCH2 CH 2 CH OCH 2
movement of the electrons away from the more electronegative atom is better than no movement
at all becauase electron delocalization makes a molecule more stable.
Features that decrease the predicted stability of a contributing resonance structure...
1. An atom with an incomplete octet
2. A negative charge that is not on the most electronegative atom
3. A positive charge that is not on the most electropositive atom
4. Charge separation
Re s o n a n c e En e r g y
Ć A measure of the extra stability a compound gains from having delocalized electrons
+ H2 HĈ = ă28.6 kcal/mol (ă120kj/mol)

experimental
cyclohexene
+ 3 H2 HĈ = ă85.8 kcal/mol (ă339 kj/mol)

calculated
cyclohexene
hypothetical
+ 3 H2 HĈ = ă49.8 kcal/mol (ă208 kj/mol)

experimental
benzene
Benzene is stabilized by electron delocalization
Su m m a r y
Ć The greater the predicted stability of a resonance contributor, the more it contributes to the
resonance hybrid.
Ć The greater the number of relatively stable resonance contributors, the greater is the resonance
energy.
Ć The more nearly equivalent the resonance contributors, the greater is the resonance energy.

88 QUIZRR
Re s o n a n c e -St a b i li ze d Ca t io n s
+ +
CH2  CHCHR CH2  CHCH2
an allylic cation the allyl cation
+ +
CHR CH 2
a benzylic cation the benzyl cation
Relative Stability of Resonating structures

All the resonating structure donÊt contribute equally to the resonance hybrid. More the stability
of resonating structure, more will be its contribution.
Stability of resonating structure (in preference order)

(1) More the no. of covalent bond in a molecule, more will be its stability.
 
CH2 = CH ă CH = CH2  CH  CH  CH  CH
2 2
first structure is more stable than second.
(2) The resonating structure in which all the atoms have complete octet will be more stable than
the resonating structure in which all the atoms have not complete octet.
 ..  ..
CH2  O  CH3  CH2 =O  CH3
(a) (b)
(b) is more stable than (a), as octet of carbon is not complete in (a)
(3) The structure in which negative charge lies on electronegative element are more stable.
ă
O O O O O
(a) (b) (c) (d) (e)
(a) & (e) are most stable as ăve charge is present on oxygen, more electronegative than carbon.

QUIZRR 89
M e s o m e r i c Ef f e c t :
Special properties are associated with systems in which a  bond is conjugated either with a second
-bond (or) with an atom which possesses a pair of electrons in a p-orbital. These are : stabilization
energy, single bond lengths which are shorter than those in non-conjugated compounds, and (in some
cases) the modification of dipolar properties.
(a) -bond- bond conjugation : The simplest example is butadiene, CH2=CHăCH=CH2. This
is symmetrical molecule and conjugation does not lead to the appearance of a dipole. In
+ 
valence bond language, contributions from the ionic structures CH2  CH  CH  CH2 and
 
CH2  CH  CH  CH2 are necessarily equal and their dipoles therefore, nullify each other.
This is not true, however, when -bonds of different types are in conjugation. For example
in an ,  unsaturated carbonyl compound such as butenal the contribution of structure (A)
is greater than that of (B) because oxygen significantly more electronegative than carbon the
carbonyl group thus polarizes the C = C bond.


H3 C O H3 C O
(A) (B)
A group such as carbonyl which withdraws electrons from an adjacent group via the -
bonding frame work is described as having a ă M effect, the ăve sign indicating electron
withdrawal and M standing for mesomeric. Other groups of ă M type include ester, nitrile and
nitro etc., and the curved arrows in the representation denote the direction of the mesomeric
effect.
C C C
+
O N N O
O
(b) -bond-p-orbital conjugation : In vinyl chloride (chloroethene) the p-orbital on the

carbon which is attached to chlorine can overlap with both the p-orbital on the second
carbon atom and one of the filled p-orbitals on chlorine thus three delocalized MOÊs are
established of which the two of lowest energy are occupied. Since the p-orbital on chlorine
is initially filled, its participation in the delocalized  system leads to the partial removal of
electrons from chlorine and the appearance of a dipole moment directed from chlorine
towards carbon. This is opposed to the dipole establishment in C ă Cl  bond as a result
of the ăI effect of chlorine, with the overall result that the dipole moment of vinyl chloride

90 QUIZRR
(1.44D) is considerably smaller than that of ethyl chloride (2.0D) in which the ă I effect is
operative. The capacity of chlorine for donating electrons into a molecular -system is
described as a + M effect.
H
H
H H
C
H Cl H2C
ă +
Cl H2C Cl
(A) (B) (C)
In VB terminology, vinyl chloride is described as a hybrid of the structures (B) and (C), the latter
symbolizing the + M effect of chlorine. Both descriptions also indicate that CăCl bond should be shorter
than in a saturated alkyl chloride, as is found.
Other elements with unshared p-electrons which take part in forming delocalized -systems include
other halogens, oxygen and nitrogen, e.g.,
CH2 = CH = OCH2 CH 2 = CH ă N (CH3)2
In each case the substituent has a + M effect.

Two further points should be noted. First, bond strength is dependent on the extent of the overlap
of the combining atomic orbitals, so that in these conjugated systems the more nearly equal in size the
p-orbitals are, the more effective is the -orbital overlap. Hence fluorine is more effective than chlorine
in conjugating with carbon, and oxygen is more effective than sulphur. Secondly, as the nuclear charge
in an atom is increased, so also is the hold of the nucleus on the surrounding electrons so that, for
comparably sized atoms, the ability to conjugate decreases as the atomic number increases. Hence the
order of + M effect is
ă NR2 > ă OR > ă F
+ M effect possessing groups are :
.. .. .. .. .. .. ..
 OH,
..   OR
.. ,  NH 2 ,  NHR,  NR 2 ,  SR
.. ,  X
.. etc.
ă M effect possessing groups are :

ă CHO, = CO, ă CN, ă NO2, ă SO3H etc.
The low reactivity of halogens bonded to unsaturated carbon is due to the + M effect of the
halogen. The CăBr bond in vinyl bromide has a partial double-bond character due to the + M effect
of bromine with consequent low reactivity of bromine.

CH 2 = CH Br CH 2 CH = Br

QUIZRR 91
The acidity of phenol is due to the + M effect of OH group. The mesomeric transfer of the lone pair
on the oxygen atom of phenol to the  electrons of the benzene ring results in several resonance
structures with positive charge on the oxygen atom. This aids the hydrogen atom of OH group to leave
as proton.
  
OH OH OH OH O
H 2O
+ H3 O+
The ionization is specially aided due to the formation of the relatively more stable phenoxide ion.
The charge delocalization in phenoxide ion affords greater stability over phenol in which charge
separation occurs in the canonical forms.

O O O O
Hence, phenol prefers to ionize, i.e. it is acidic.
Relative Stabilities of Allylic and Benzylic Cations
+
CH2  CH C R + +
| > CH2 =CHCHR > CH2 =CH CH2
R
tertiary allylic cation secondary allylic cation allyl cation
+ + +
CR > CHR > CH2
tertiary benzylic cation secondary benzylic action benzyl cation
increasing stability

92 QUIZRR
Hyperc onjugat ion :
The alkyl groups with at least one hydrogen atom on the -carbon atom, attached to an unsaturated
carbon atom, are able to release electrons by a mechanism similar to that of the electronic effect.
H
H+
ăC ă C = C ăC = C ă C
Note that the delocalization involves s and p bond orbitals (or p orbitas in case of free radicals);
thus it is also known as s-p conjugation. This type of electron release due to the presence of the system
H-C-C=C is known as hyperconjugation
H H+ H H
| | |

H  C  CH  CH2  H  C  CH  CH 2  H C  CH  CH 2  H  C  CH  CH2
| | |
H H H H+
Ex a m p l e
Which is more stable
+
(a) CH3  CH2
+
(b) CH3  CH2  CH3
Solution :
(b) is more stable than (a) as (b) has 6  hydrogen while (a) has only 3.
Ex a m p l e
Ć
How many hyperconjugative structure of CH3ăCHăCH3 are possible ?
Solution :
As there are 6  hydrogen therefore 6 hyperconjugative structures are possible.
Ex a m p l e
CH3ăCH=CH2
How many hyperconjugative structure of given molecule possible ?
Solution :
H
H
H C CH = C
H
H
As 3  hydrogen are possible, therefore 3 structures are possible.
QUIZRR 93
Note :  hydrogen is hydrogen of C-H bond where C is attached through carbon with one positive
charge/through carbon with unpaired eă/through carbon forming multiple bonds.
Note : Stability due to different effect is generally in the order.
Resonance > hyperconjugation > Inductive effect
This will help in comparing the stability of structures.
Carbocation : All three effects are considered.
Radical : Resonance & hyperconjugation predicts the stability.
Carbanion : Resonance & inductive effects predicts stability.
Note : If in resonance, nonplanar orbitals or orbitals of different energy are involved, then
inductive effect will be more dominating than resonance.
Ex a m p l e
Compare stability of :
Cl
Cl
&
NO2
NO2
(a) (b)
Here inductive effect of Cl is dominating as C (2p) and Cl (3p) have orbitals of different energies.
Therefore (b) containing NO2 at meta position will be more stable.
Ex a m p l e :
Arrange in the order of increasing stability.
   
CH2 CH2 CH2 CH2
OCH3
CH3 O ă CH3 NO2
(a) (b) (c) (d)

94 QUIZRR
Solution : (c) < (d) < (a) < (b)

CH2
Writing resonant structure of
 
CH2 CH2 CH2 CH2

..
O CH3 stabiliser +ve charge on ortho position by resonance thus most stable.
NO2 withdraws ă ve charge, thus increasing +ve charge density decreasing its stability.
CH3 donates eă by inductive effect.
..
OCH3 at meta position increases + ve charge through inductive effect and resonance is not
possible at this position. Thus

(c) < (d) < (a) < (b)
El e c t r o m e r i c Ef f e c t
This is a temporary effect and takes place between two atoms joined by a multiple bond i.e. a
double or triple bond, in the presence of an attaching reagent.
It is temporary because the molecules acquire their original electronic condition once the attacking
reagent is removed.
It also occurs as +E and ăE effect, similar to inductive effect.
Ć ăE effect ă When the transfer of electrons take place away from attacking reagent.
ă ă
C O + CN C O
(away from agent) CN

QUIZRR 95
Ć +E effect : When the transfer takes place towards the attacking agent.
+ +
C C + H C C
(towards the agent)
Interesting case
CH3 H has 2 options
(1) H can go to C(1)
C C (2) H can go to C(2)
2 1 +
H
H H
For case 1
H
CH3 H CH3
+
C C C C H
+
H
H H H
ăE effect H
(2Ĉ carbocation)
For case 2
CH3 H CH3
+
C C H C CH2
+
H
H H
+E effect H
(1Ĉ carbocation)
Case 1 will be the result, because it produces 2Ĉ carbocation which is more stable.
Note : It is a misconception that adding a nucleophile will cause ăE effect & electrophile causes
+E effect. You can see from the above question that electrophile caused ă E effect.

96 QUIZRR
FREE RA DI CA L S
There are two possible structures for simple alkyl radicals. Either a free radical may be a planar
species (A) in which the carbon atom bearing the odd electron is sp2 hybridized (as in carbocations) and
the odd electron remains in the p-orbital, or it could have a shape resembling a shallow pyramid (B)
which is neither planar nor tetrahedral and the orbital containing unpaired electron is some sort of a
hybrid between a p and an sp3 orbital.
R' R" R R
fast
C or R' C C R'
R" R"
R
(A) (B)
The question as to whether free radicals exist in a planar configuration or in a rapid equilibrium
between the two pyramidal forms (B) is difficult to answer with certainty. However, available evidence
indicates that the unpaired electron is in a p orbital stabilized free radicals certainly exist in planar
configuration.
Formation : Free radicals are often produced when a molecule is supplied with sufficient energyă
thermal or photochemicalăto cause homolysis of a covalent bond. In addition oxidation-reduction reactions
involving the gain or loss of a single electron can also generate radicals. Some typical reactions producing
free radicals are given below :

(CH3)4 Pb   4 CH3 + Pb

CH3 ă N = N ă CH3   2CH3 + N2

C6H5CO ă O ă OCOC6H5   2C6H5COO  2C6H5 + 2CO2
h
CH3COCH3   CH3 + COCH3  CH3 + CO
O O
|| anode ||
R  C O    R  C O  R  CO2
e
Stability : In general, it has been found that the stability of alkyl radicals is in the order
tertiary > secondary > primary. The reason for the stabilizing influence of alkyl groups is not far to seek
if we consider that in going from methyl to t-butyl, there is increasing tendency for electron release due
to hyperconjugation. As we have seen that the carbon atom carrying an unpaired electron has half-
filled orbital that gives the radical its characteristic unstability; the hyperconjugative mechanism tends
to fill this orbital and thus stabilizes the radical to some extent. Various hyperconjugative contributing
forms of tert-butyl radical are given below :

QUIZRR 97
CH3 CH2 H CH3 CH3
C C C H C
H3 C CH3 H3 C CH3 H3C CH2 H CH3
CH2
Allyl and benzyl radicals are particularly stable because of resonance involving  electrons of the
double bond or aromatic ring.
. .
CH2  CH  CH2  CH2  CH  CH2
CH2 CH2 CH2
Another factor that is responsible for the increased stability of tertiary radicals may be steric.
Formation of a tert-butyl radical by the removal of a hydrogen atom from isobutane, (CH3)3 CH, is
favoured as the steric repulsion between the methyl groups is relieved to a certain extent by an increase
in bond angles from 109.5Ĉ to about 120Ĉ. Clearly this steric relief should be the greatest in the
formation of a tertiary radical.
St a b i li t y o r d e r o f f r e e r a d i c a l s
CH3 CH3
CH3 < CH3 · CH2 < CH3 C < CH3 C
H CH3
< CH2 = CH · CH2 CH2
The stability can be explained on the basis of hyperconjugation and inductive effect.
C A RB OC A T I ON S
Introduction
A carbocation is molecule in which a carbon atom bears three bonds and a positive charge.
Carbocations are generally unstable because they do not have eight electrons to satisfy the octet
rule.

98 QUIZRR
H
H C +
open octet on carbon
Ca r b o c a t i o n Cl a s s i f i c a t i o n
In order to understand carbocations, we need to learn some basic carbocation momenclature. A
primary carbocation is one in which there is one carbon group attached to the carbon bearing the
positive charge. A secondary carbocation is one in which there are two carbons attached to the carbon
bearing the positive charge. Likewise, a tertiary carbocation is one in which there are three carbons
attached to the carbon bearing the positive charge.
H H
Methyl carbocations H C CH3O C
+
no C-C bonds
H H
H H
Primary (1o) carbocations CH3 C C
one C-C+ bond H H
H 
Secondary (2o) carbocations CH3 C
two C-C+ bonds CH3
CH3
Tertiary (3o) carbocations CH3 C 
three C-C+ bonds CH3
If the carbon bearing the positive charge is immediately adjacent to a carbon-carbon double bond,
the carbocation is termed an allylic carbocation. The simplest case is called the allyl carbocation.
R  R 
H2C CH2
R R
Generic allylic carbocation The allyl carbocation

QUIZRR 99
If the carbon bearing the positive charge is immediately adjacent to a benzene ring, the carbocation
is termed a benzylic carbocation. The simplest case is called the benzyl carbocation.
R H
 
R H
Generic benzylic carbocation The benzyl carbocation
If the carbon bearing the positive charge is part of an alkene, the carbocation is termed a vinylic
carbocation. The simplest case is called the vinyl carbocation. Note that the carbon bearing the
positive charge has two attachments and thus adopts sp hybridization and linear geometry.
R H
 
C C R C C H
R H
vinylic carbocation vinyl carbocation
If the carbon bearing the positive charge is part of a benzene ring, the carbocation is termed an
aryl carbocation. The simplest case is called the phenyl carbocation.
R R
R  
R R
Generic phenylic carbocation The phenyl carbocation
Ca r b o c a t i o n St a b i l i t y
The stability of carbocations is dependent on a few factors. The first factor of look at when deciding
the stability of a carbocation is resonance. Resonance is a stabilizing feature to a carbocation because
it delocalizes the positive charge and creates additional bonding between adjacent atoms. Dereasing the
electron deficiency increases the stability.

100 QUIZRR
Consider the following :
H H H

CH3 C CH3O C CH3O C
H H H
No resonance Resonance
The structure on the left does not have any resonance contributors in which electrons are donated
to the carbon with the open octet. Compare this with the carbocation that has resonance and a
delocalized positive charge. Charge delocalization imparts stability, so the structure with resonance is
lower in energy.
In the example shown above, an oxygen atom lone pair is involved in resonance that stabilizes a
carbocation. In general, any adjacent lone pair or  bond can also be involved in resonance delocalization
of a carbocation positive charge. Allylic and benzylic carbocations enjoy resonance stabilization by
delocalization of the positive charge to the adjacent  bond(s). Vinylic and aryl carbocations do not enjoy
resonance stabilization because their  electron clouds are perpendicular to the vacant p orbital of the
carbocation. (Recall that resonance requires the interacting orbitals to be parallel so they can overlap.
Without overlap there can be no resonance.)
Note the influence of inductive effect versus resonance on the energies of these molecules. The
oxygen atom that is bonded to the carbocation on the right is more electronegative than the corresponding
hydrogen atom in the left-hand structure. We would think that the inductive effect would pull electron
density away from the carbocation, making it higher in energy. In actuality, resonance usually
(but not always) outweighs other factors. In this case, carbocation stabilization by resonance
electron-donation is a more significant factor than carbocation destabilization by inductive electron
withdrawal.
Methyl and primary carbocations without resonance are very unstable, and should never be
involved in a reaction mechanism unless no other pathway is possible. More stable carbocations (secondary
or tertiary with resonance, or any carbocation with resonance) is sufficiently stable to be formed in a
mechanism under reasonable conditions.
Ex e r c i s e
Draw all significant resonance contributors for the following carbocations.

(a) (c) CH2

 OCH3 
(b) (d)

QUIZRR 101
The second factor that should be considered when thinking about carbocation stability is the
number of carbons attached to the carbon carrying the positive charge. We look at the number of
bonding electrons that are attached to the carbocation because those bonding electrons will help in
alleviating the positive charge. Bonding electrons from adjacent  bonds may overlap with the unoccupied
p orbital of the carbocation.
Hyperconjugative overlap
Adjacent H Empty pz orbital

C-H bond of carbocation
R R
R R
This phenomenon is termed hyperconjugation. Since the overlap supplies electron density to the
electron-deficient carbocation carbon, we predict that increasing the number of hyperconjugative
interactions increases carbocation stability or increasing the number of bonds adjacent to the carbocation
by increasing the number of alkyl groups attached to the carbocation carbon results in an increase in
carbocation stability. For example, a tertiary carbocation should be more stable than a secondary
carbocation.
Our simple prediction suggests that any adjacent bonding electron pair will participate in carbocation
hyperconjugation. However, only C-H and C-C bonds provide a significant level of increased stability.
When considering the importance of hyperconjugation versus resonance as the more important
stabilizing feature, resonance usually wins out. For example, a primary carbocation with resonance is
more stable than a secondary carbocation without resonance. A secondary carbocation with resonance
is usually more stable than a tertiary carbocation without resonance.
The general rules for carbocation stability can be summarized as follows :
(a) Increases substitution increases stability
+ o + o o
CH3 (methyl; least stable) < RCH2 (1 ) < R2CH (2 ) < R3C+ (3 ; most stable)
(b) Resonance is more important than substitution. For example, a secondary carbocation without
resonance is generally less stable than a primary carbocation with resonance.
Ex e r c i s e
Rank the relative stability of the three carbocations in each set.
+ 
H2 C  C  CH2 , H3C  C  CH3 
(a) | | and  CH3  C
3
H H
 
(b)


102 QUIZRR
In vinylic carbocations, the positive charge is assigned to a carbon with sp hybridization. How does
this influence the carbocationÊs stability? An sp orbital has more s character than an sp2 orbital.
Electrons in an s orbital are closer to the nucleus and therefore more tightly held than electrons in a
p orbital. This can be taken to mean that the electronegativity of carbon increases with increasing s
character. Thus : sp carbon (most s character, most electronegative) > sp2 > sp3 (least s character; least
electronegative). Electronegativity is a measure of electron attraction. So the stability of a cation is
influenced by the electronegativity of the atom bearing the positive charge. The more electronegative
the atom the less stable the cation. A vinylic carbocation carries the positive charge on an sp carbon,
which is more electronegative than an sp2 carbon of an alkyl carbocation. Therefore a primary vinylic
carbocation is less stable than a primary alkyl carbocation.
Similar reasoning explains why an aryl carbocation is less stable than a typical secondary alkyl
carbocation such as cyclohexyl carbocation.
Because of their reduced stability; vinyl and aryl carbocations are not often encountered.
The stability order of carbocations is as follows :
+ + + +
R C CH2 CH2 = CH · CH2 CH
R +
1Ĉ CH3
Ca r b o c a t i o n Fo r m a t i o n
Even though carbocation can be found in many organic reaction mechanisms, most carbocations
are formed by one of only two basic mechanism steps, ionization of a carbonăleaving group bond or
electrophilic addition to a  bond.
Ionization of a Carbon-Leaving Group Bond.
When a bond between a carbon atom and a leaving group ionizes, the leaving group accepts the
pair of electrons that used to be shared in the covalent bond. This may leave the carbon atom with an
open octet, resulting in a carbocation. The ionization is indicated with a curved arrow starting at the
bond and pointing to the leaving group atom that accepts the electron pair. Better leaving groups or
formation of a more stable carbocation result in lower activation energy and faster ionization. Carbonă
leaving group bonding ionization is illustrated using an oxonium ion.
 
(CH3)CăOH2 (CH3)3 C + OH2
Carbocation formation by ionization of a leaving group occurs in many organic reactions such as
the SN and E1 mechanisms which we will cover in later chapters.
1

QUIZRR 103
Electrophilic Addition to a  bond.

When an electrophile attacks a  bond, the  electron pair may form a new  bond to the electron-
deficient atom of the electrophile. (Not all additions to  bonds involve electrophiles or carbocations.)
This addition is indicated with a curved arrow starting at the  bond and ending at the electron
deficient atom of the electrophile. More powerful electrophiles or the formation of more stable carbocations
result in lower activation energy and faster addition. Electrophilic addition to a  bond is illustrated by
the reaction of HBr (an electrophie) wit styrene (PhCH=CH2). Note that the more stable carbocation
(secondary with resonance) is formed. This is a key mechanistic feature of MarkovnikovÊs Rule.
H Br

+ Br
Electrophilic addition to a  bond occurs in many reactions of alkenes, alkynes and benzene rings.
Note every addition reaction forms a carbocation, for example, catalytic hydrogenation or ozonolysis.
Pr o p e r t i e s o f Ca r b o c a t io n s
(i) Rearrangement
The bonding electrons of a carbocation may shift between adjacent atoms to form a more stable
carbocation. For example rearrangement will occur if a secondary carbocation can be formed from
a primary carbocation because a secondary carbocation is more stable than a primary carbocation
for e.g.
+ hydride +
CH3 CH CH2 CH3 CH CH3
shift
H more stable
2Ĉ carbocation
1Ĉ carbocation
CH3 CH3
+ methyl
CH3 C CH2 CH3 C CH2
shift +
CH3 CH3
more stable
3Ĉ carbocation
Phenyl shifts are preferable as they increase the stability by resonance effect
The migration aptitude of various groups is
(a) H ă > 3Ĉ > 2Ĉ > 1Ĉ alkyl > CH3
(b) Phă > CH3

104 QUIZRR
However a migration in reverse direction can also take place if the migration leads to formation
of benzylic compound which is highly stable.
H CH3
+ hydride +
Ph CH C CH3 Ph CH CH
shift
CH3 CH3
3Ĉ carbocation 2Ĉ carbocation
(benzylic form)
The result is highly stable due to delocalization of electrons due to resonance.

Another such example is
CH3 CH3 CH3
hydride +
CH3 C C CH3 CH3 C C CH3
+ shift
OH OH CH3
(3Ĉ carbocation)
resonating
structures
CH3
CH3 C C CH3
+ OH CH3
1. SPECIAL CASES :
Given, CH3
+ now here there 2 options, methide shift

Ph C CH2
& the other being phenyl shift
Ph

QUIZRR 105
CH3 CH3
+ yl +
meth
Ph C CH2 Ph C CH2
shift
Ph Ph (A)
phenyl shift
CH3
Here both are benzylic compounds

and are almost equally stable.
(B) Ph C CH2
+
Ph
So for major product in such cases, we go by migratory aptitude, and phenyl shift is preferable over
methide shift. So compound B will be major product.
2. Ring expansion
Rearrangement may lead to a change in ring size or formation of a ring causing greater stability
for example
+ intermediate + +
CH2 CH2
form
ă
+ +
or
(2Ĉ carbocation)
The ring stability increases as number of carbon atoms in the ring increases.
3<4<5<6
increasing order of stability

106 QUIZRR
Generally ring carrying more than 6 carbon atoms are less stable.
+ +
(1Ĉ carbocation) (2Ĉ carbocation

+ ring expansion)
+
+
methyl
shift
(3Ĉ carbocation)
(3)
+
+
H
OH
lone pair at Oxygen will react with hydrogen to complete its octet & leave the compound giving
us a 2Ĉ carbocation.
Now compound (A) has 2 option
+
ring expansion (favourable)

l
hy
et
m ift
sh
+
+
or
(3Ĉ carbocation)

QUIZRR 107
deprotonation
deprotonation
(B) (C) (D) (E) (F)

(major) (major)
(c) & (f) are the major products as more substituted alkenes are more stable.
(4) Deprotonation
Carbocations are very reactive species and are very strongly driven to dispose of the positive
charge. Even a weak base such a water can accomplish this deprotonation.
CH3 CH3
H2O
H3C C CH2 H3C C CH2
+
H H OH2
Vinylic carbocations generally do not rearrange, even if they can become more stable. For example,
the rearrangement shown below does not occur, even though a secondary carbocation would rearrange
to become more stable allylic carbocation (primary with resonance).
H H
 
H2C C CH2 X H2C C CH2
This resistance to rearrangement is probably due to orbital alignment restrictions during the
rearrangement transition state.

108 QUIZRR
Ex a m p l e
Provide a carbocation to complete each reaction. Draw the curved arrows.

H2O OH2
(a) ???
(b) H2O 
??? + H3O
1,2-alkyl shift
(c) ???

Solution :

OH2
OH2
(a)

H OH2

(b) + H3O

 1,2-alkyl shift
(c)

Ex a m p l e
Illustrate the three carbocation fates using any molecules you want. Use curved arrows and give the
products.
Solution :
Any carbocation and any other reactants are acceptable as long as the carbocation fates are
accurately illustrated.
Capture nucleophile :

H H O CH3

C CH2 + HOCH3 C CH2
H H

QUIZRR 109
Lose proton, form  bond :

H H
 
C CH2 C CH2 + H2OCH3
H HOCH3
Rearrange :
H H

C CH2 C CH3

H
CARBANIONS
Carbanions are units that contain a negative charge on a carbon atom. The negative charge gives
good nucleophilic properties to the unit that can be used in the formation of new carbon bonds.
Carbanions thus act as nucleophiles in substitution reactions, in carbonyl addition and substitution
reactions, and in 1, 4-addition (Michael) reactions.

R  C R
|
R
a carbanion
Carbanions may bear substituents that can affect the structure and reactivity of the carbanion,
and can affect the acidity of a parent C-H precursor. Halogens stabilize carbanions in the order of
Br > Cl > F. A prominent - repulsion between the F and Carbanionic centre causes some destabilization
in apha-fluorinated carbanions. The magnitude of the destabilization depends on the carbanion structure.
The destabilization maximizes as the carbanion structure approaches a planar configuration. Thus,
fluorinated carbanions possess pyramidal structures with high barriers to inversion.
Ca r b a n i o n St r u c t u r e
Carbanions are trivalent with sp3 hybridization. The lone pare of electrons occupies one of the sp3
orbitals. The geometry is thus tetrahedral. The tetrahedron can undergo inversion or retain its
stereochemistry depending on the attached substituents. A methy carbanions has a barrier to inversion
of about 2 kcal/mole.
R R
inversion
C R
C R
R R
tetrahedral carbanion

110 QUIZRR
Fo r m a t i o n :
As there is little difference between the electro negativities of carbon and hydrogen (2.5 and 2.1,
respectively) the polarity of the C-H bond is very small. The heterolytic fission of this covalent bond
to form an anion and a proton should then be a very difficult process. In other words, a hydrogen atom
bound to an sp3 carbon atom shows negligibe acidity. However, the presence of electron attracting
substituents such as nitro, cyano or carbonyl groups on the same carbon renders the hydrogen relatively
acidic. The increase in acidity is not only due to the electron-withdrawing ability of these substituents,
but also due to their ability to delocalize the negative charge of the anion. Thus hydrogens on the
carbon atom alpha to nitro, cyano or carbonyl groups have acidic character and can be removed as
protons leaving resonance stabilized anions.
ă
O O O
+ ăH
ă + +
H3C N H2C N H2C N
ă ă ă
O O O
ă ă
ăH
CH3 CN CH2 CN CH2 = C = N
ă
O O O
ă
ăH H2C C H
H3C C H H2C C H
Carboanions are also formed when a nucleophie adds to a carbon-carbon double bond.
ă
C2H5OCH2 CH CN
ă
C2 H5 O + CH2 = CH CN
ă
C2H5OCH2 C= C= N
H
St a b i l i t y :
As we have already seen, carboanions are stabilized by electron-withdrawing substituents. Generally
speaking, a carbanion is stabilized by resonance if a double bond is located  to to the anionic carbon.
This explains the stability of the allyic and benzylic carbanion.
R CH = CH CH2 R CH CH = CH2
CH2 CH2 CH2 CH2

QUIZRR 111
Ready conversion of triphenylmethane to the triphenlymethyl carbanion can be similarly explained.
Na
 C6 H5 3 CH   C6 H5 3 C 
: Na 
(C6 H5 )2 C (C6 H5 )2 C etc
The order of stability of the simple carbanion is :

methyl > primary > secondary > tertiary
Anot her fact or t hat cont r ibut es t o t he st abilit y of car banions is t he extent of s-character of the
bonding orbitals of the carboanionic carbon. Carbanion stability, thus, has been found to be in the
order : RC  CHă > R3C ă CH2ă. We have already seen that the carbon atom in acetylene is sp
hybridized (50% s character) and hence hydrogen atom attached to it should be more acidic than that
of ethylene where the carbon is sp2 hybridized (33% s character).
An interesting example is cyclopentadiene which readiy loses a proton to form the cyclolpentadienyl
anion.
CH2 Oă

H H H H
The unusual stability of cyclopentadienyl anion is explained by the fact that although it has only
four  electorns, two more electrons become available to it by the heterolysis of the C-H bond thus
forming a system of six electrons. These electrons are spread over all the five carbon atoms like the
delocalized aromatic system of benzene ring, thus conferring on it stability so characteristic of the
aromatic compounds.
Re a r r a n g e m e n t
Rearrangement does not takes place in case of carboanions.
It is due to poor migrating ability and poor leaving tendency of carboanions. Further more only
primary carboanions are stable
Exception
Ph Ph
ă
Ph C CH2 Ph C CH3
ă
(resonance stabalized)
H
Carboanion as a nucleophile will be discussed in details later on.

112 QUIZRR
C A RB EN E
A reaction in which both the groups or atoms are lost from the same carbon is called -elimination
reaction and results in the formation of carbenes.
Carbenes can be defined as neutral, divalent carbon intermediates in which a carbon is covalently
bonded to two atoms and has two non-bonded orbitals containing two electrons between them. There
are two kinds of carbenes, singlet and triplet. In the singlet state, a carbon atom is presumed to be
sp2 hybridized. Two of the three sp2 hybrid orbitals are utilized in forming two covalent bonds whereas
the third hybrid orbital contains the unshared pair of electrons. The remaining p-orbital remains
vacant. Thus, singlet carbene resembles a carbonium ion very closely. On the other hand, carbon atom
of a triplet carbene is sp hybridized and it is a linear species. These two hybrid orbitals are involved
in the bond formation with two groups and the remaining two electrons are placed, one each, in the
equivalent, mutually perpendicular py and pz orbitals. These electrons have parallel spins and a
carbene with this structure is said to be in a triplet state.
R
R
C C
R R
(singlet carbene) (triplet carbene)
At first sight, it appears that a singlet carbene has lower energy as the unshared electron pair is
in a sp2 hybrid orbital but the consideration of the electron repulsion energy that must be overcome
to pair two electrons in a single orbital places it at a higher energy level than a triplet structure. Thus,
the triplet state of a carbene is more stable than the singlet state. Triplet carbenes are not linear but
have a bond angle of 140Ĉ to 150Ĉ.
Among dihalocarbenes, the order of stability is
  CCl
Singlet carbenes : CF  
 CBr 
 CI
2 2 2 2
  CCl
  
Triplet carbenes : CF2 2  CBr2  CI2
Carbenes
CH2 CH2
triplet singlet
sp sp2
(only this one acts as a lone pair)

QUIZRR 113
Generation
1. From chloroform
Cl Cl
ă
OH ă
H C Cl ă C Cl + H2O
Or B
Cl Cl
(chloro form)
ă
CCl2 + H2O + Cl
(carbene)
2. From diazo-methane
h
CH2N2 CH2 + N2

(carbene)
Though the method is
+
CH2 N N CH2 + N ·
·N
Here N will break bond with C as it cant be pentavalent.

3. From Ketenes (Keto + alkene)
 ă +
CH2 C O CH2 + C ·
·O
4. By removal of CO2
O
ă
Cl3 C C  ă ă Cl
ă CCl3 CCl2
CO2
(carbene)
Oă

114 QUIZRR
Generally in such kind of reactions CO2 is liberated as gas, as it is stabalized due to resonance.
another example, +
N· N
O O
·
·
·
·

R · C · CH ă ă
R · C · CH
N2 CO2
ă (acyl carbene)
C·O
·
·
O
Re a c t io n s o f c a r b e n e
1. Addition :
The addition of carbenes lead to formation of cyclo compounds. Also it can be used to distinguish
singlet carbene with triplet carbene.
Generally
CH2
C C C C
CH2
Now let us see the stereochemistry behind this and how it is useful to distinguish singlet & triplet
carbene.
CH3 CH3 CH3 CH3
C C C C
CH2
H H H H
(cis product)
CH2
(assuming that this
(but sometimes due to is a triplet carbene)
collision, spin gets reversed
CH3 CH3 CH3 CH3
C C C C
H H H H
CH2 CH2
now rotation along C ăC bond will take

place, as a bond can only be formed
between e ă of opposite spins.

QUIZRR 115
CH3 CH3 CH3 CH3
C C C C
H CH2 H H3 C CH2 H
cis-1-2 dimethyl cyclopropane
CH3 CH3
C C
H3C CH2 H
trans-1-2-dimethyl cyclopropane
So with triplet we get 2 answers in the form of cis & trans forms
whereas,
in case of singlet we get only one answer for cis (we get cis) and trans (we get trans)
CH3 CH3 CH3 CH3
CH2
C C C C
H H H H
(cis )
CH2
CH3 CH3
C C
H CH2 H
2. Insertion (cis )
Carbenes can be added / inserted into a CăH bond, to increase the length of carbon chain for
example H
·
·C·H + CH2 ·C·C·H

·
H
CH2
CH2 · CH · CH3 Here 2 products are produced
·
H H
116 QUIZRR
1. CH2 · CH2 · CH3 CH2 · CH2 · CH3

·
·
H CH2
CH2
·
H
2. CH2 · CH · CH3 CH2 · CH · CH3

·
·
H H H CH2
CH2
·
H
3. Rearrangement
Alkylated and phenylated carbenes also undergo ready rearrangement to gives alkenes
R · CH
R can be alkyl, acyl, alkenyl
Note : Rearrangement in carbenes is similar to that of carbocations.
1. CH3 · CH · CH CH3 · CH ·
· CH2
·
This can have 2 products

2.
CH a. A double bond with cyclopropane
b. Ring Expansion
(a) CH CH
(b) CH
Or

QUIZRR 117
Sp e c i a l Ca s e :
H H
OH ă
+ CHCl 3
 here OH is a base which abstract H from the ring
to form carbanion and CHCl3 (chloroform) produces
carbene (:CCl2)
ă ă
Cl now since Here is a lp (lone

CCl2
C pair) it will form a double bond
Cl & simutaneous spring
ă expansion will take place as
Cl being more electronegative
can pull the electrons
Cl
C
Cl Cl
N I T REN ES
Nitrenes are electron-deficient monovalent nitrogen species in which the nitrogen atom has a
sextet of electron in its outer shell. There are two possible forms in which a nitrene can exist, the singlet
and triplet states.
R N R N
singlet triplet
Ge n e r a t i o n
1. Such compounds are formed by the elimination of a proton and a leaving group.
H
·
Br2
R · C · NH2 R · C · NH · Br
ăHBr
·
·
O O ă
R·C·N R · C · NH · Br
·
·
·
·
O O
(acyl nitrene)

118 QUIZRR
2. From isocynate
/
R·N· ·O
·C· R · N + CO
h
+ ă
·N·
·N 
R·N· R · N + N2
Nitrenes have properties like carbenes and undergo reactions like that of carbenes.
a case of rearrangement in nitrenes
+ ă
R ·C·N C·N ·C·
R·N· ·O
·
·
·
·
·
O O R (allcyl isocynate)
This reaction is also useful in generation of isocynates
ARYN ES
Arynes may be defined as aromatic compounds containing a formal carbon-carbon triple bond. The
best known aryne is benzyne which may be regarded as the aromatic counterpart of acetylene or in
other words, it is benzene minus two ortho hydrogens and can also be called as dehydrobenzene.
The benzyne bond is not like the triple bond of acetylene where the two carbons form a  bond
using sp orbitals and the remaining p orbitals are used to form  bonds. Such a structure is not possible
in benzyne because of the hexagonal geometry associated with the benzene ring. Most probably the
new bond of benzyne is formed by the overlap of sp2 orbitals to two neighbouring carbon atoms. These
sp2 orbitals are orthogonal to the  moleculr orbital of the benzene ring.
B e n zy n e
These intermediates are generated by the elimination of -proton and a leaving group (generally
halogen) from the adjacent carbons from a benzene ring system. For example,
Cl ă Cl
NH2 ăCl
ăNH3
ă
H Benzyne

QUIZRR 119
+
N2 Nă
ăN
NaNO2 /HCl decomposes
Nă
ăN + O ă C ă O +
0ă5Ĉ C ă
CO2 H C·O
·
O
Br MgBr
Mg (1 equiv.)
MgBrCl +
THF
Cl Cl
Benzynes are very reactive. Neither benzyne nor any other aryne (substituted benzyne) has yet
been isolated under ordinary conditions. The triple bond in benzynes is not identical with the formal
triple bond of alkynes because here the two -bonds are formed by the overlapping of PzăPz and
sp2 ă sp2 orbitals whereas in alkynes, they are formed by the overlap of Pz ă Pz and PyăPy orbitals.
It should be noted that the -bond (resulted from sp2 ă sp2 overlap) is a very weak bond, which
can be easily ruptured by the attack of a nucleophile (they cannot be attacked by electrophiles), thus
making benzynes very reactive. Another feature to be noted is that the extra pair of electrons does not
affect the aromaticity of benzene nucleus. The original sextet still functions as a closed ring and the
two additional electrons are merely located in a -orbital that covers only two carbons. In a reaction
where benzyne is formed, if the solution does not have sufficient nucleophile, they undergo dimerization
to give biphenylene.
Dimerization
Biphenylene
Stability : The new bond of benzyne, formed by the overlap of sp2 orbitals belonging to two
neighbouring carbon atoms in unstable, and therefore benzynes are extremely reactive chemical
species.
AROM ATI CI TY
Many cyclic, conjugated compounds possess markedly different physical and chemical properties
from those expected by comparison of their structures with acylic analogues. The simplest example is
benzene, which may be regarded as the parent compound of the aromatic series. Benzene is a planar,
cyclic compound with a cyclic cloud of delocalized  electrons above and below the plane of the ring.
Because its  electrons are delocalized, all the carbon-carbon bonds have the same length-partway
between the length of a typical single and a typical double bond. We also saw that benzene is a
particularly stable compound because it has an un-usually large resonance energy (36 kcal/mol or 15

120 QUIZRR
kJ/mol). Most compounds with delocalized electrons have much smaller resonance energies. Compounds
such as benzene with unusually large resonance energies are called aromatic compounds.
(a) (b) (c)
(a) Each carbon of benzene has a p orbital. (b) The overlap of the p orbitals forms a
cloud of  electrons above and below the plane of the benzene ring. (c) the electrostatic
potential map for benzene shows that all the carbon-carbon bonds have the same electron
density.
For a compound to be classified as aromatic, it must fulfill both of the following criteria :
1. It must have an uninterrupted cyclic cloud  electrons above and below the plane of the
moleculle (often called a  cloud). LetÊs look at what this means a little more closely.
For the  cloud to be cyclic, the molecule must be cyclic.
For the  cloud to be uninterrupted, every atom in the ring must have a p orbital.
For the  cloud to form, each p orbital must be able to overlap with the p orbitals on either
side of it. Therefore, the molecule must be planar.
2. The  cloud must contain an odd number of pairs of  electrons.
Benzene is an aromatic compound because it is cyclic and planar, every carbon in the ring has a
p orbital, and the  cloud contains three pairs of  electrons.
The German chemist Erich Huckel was the first to recognize that an aromatic compound must
have an odd number of pairs of  electrons. In 1931 he described this requirement by what was has
come to be known as HuckelÊs rule, or the 4n + 2 rule. The rule states that for a planar, cyclic compound
to be aromatic, its uninterrupted  coud must containt (4n + 2)  electrons, where n is any whole
number. According to HuckelÊs rule, then, an aromatic compound must have 2 (n =0), (n = 1), 10
(n = 2), 14 (n = 3), 18 (n = 4), etc., electrons. Because there are two electrons in a pair, HuckelÊs rule
requires that an aromatic compound must have 1, 3, 5, 7, 9, etc. pairs of electron. Thus, HuckelÊs rule
is just a mathematical way of saying that an aromatic compound must have an odd number of pairs
of  electrons.
Cyclobutadiene has two pairs of  electrons and cyclooctatetraene has four pairs of  electrons.
Therefore, these compounds are not aromatic because they have an even number of pairs of electrons.
There is an additional reason why cyclooctatraene is not aromaticăit is not planar, it is tub-shaped. We
saw that for an eight-membered ring to be planar, it must have bond angles of 135Ĉ, nd we know that
sp2 carbons have 120Ĉ bond angles. Therefore, if cyclooctatetraene were planar, it would have considerable

QUIZRR 121
angle strain. Because cyclobutadiene and cyclooctatetrene are not aromatic, they do not have the
unusual stability of aromatic compounds.
cyclobutadience benzene cycloctatetraene

[4]-annulene [6]-annulene [8]-annulene
Monocyclic hydrocarbons with alternating single and double bonds are called an-nulenes. A prefix
in brackets denotes the number of carbons in the ring.
Which of the following three-membered ring structures is aromatic? Cyclopropene is not aromatic
because it does not have an uninterrupted ring of p orbtial-bearing atoms. One of its ring atoms is sp3
hybridized, and only sp2 and sp hybridized carbons have p orbitals. Therefore, cyclopropene does not
fulfill the first criterion for aromaticity.
+ ă
cyclopropene cyclopropenyl cyclopropenly
cation anion
The cyclopropenyl cation is aromatic because it does have an uninterrupted ring of p orbital-
bearing atoms and the cloud contains one pair of delocalized electrons. The cyclopropenyl anion is
not aromatic because its  clouds has two (an even number) pairs of  electrons.
+ +
+
resonance contributors for the cyclopropenly cation
+ +
+
resonance hybrid
Cycloheptariene is not aromatic. Although it has the correct number of pairs of electrons to be
aromatic (three pairs), it does not have an uninterrupted ring of p-orbital-bearing atoms because one
of the ring atoms is sp3 hybridized. Cyclopentadiene is also not aromatic. It has an even number of
pairs of electrons (two pairs) and it does not have an uninterrupted ring of p orbital-bearing atoms.
cycloheptatriene cyclopentadiene

122 QUIZRR
The criteria for determining whether a monocyclic hydrocarbon compound is aromatic can also be
used to determine whether a polycyclic hydrocarbon compound is aromatic. Naphthalene (five pairs
of electrons), phenanthrene (seven pairs of electrons), and chrysene (nine pairs of electrons) are
aromatic.
naphthalene phenanthrene chrysene
In cyclic compounds, when an element other than carbon is present in the ring, they are called
heterocyclic compounds. They are aromatic in nature because of fulfilling both the conditions.
N N O S
H
Pyridine Pyrrole Furan Thiophene
In pyrrole, furan and thiosphene, the lone pairs are actually in sp3 hybrid orbitals to form the
aromatic sextet (4n + 2) -electrons. In pyridine, the lone pair is in sp2 hybrid orbital, which is not
involved in delocalization thus, pyridine also has 6 -electrons and is aromatic in nature.
A CI DS & B A SES
The conversion of carboxylic acids and phenols to carboxylate or phenolate ions is common because
the proton is acidic, thus the proton is easily removed to form the anion in weakly basic medium. Most
organic compounds are much less acidic than carboxylic acids, and thus need stronger basic medium
to ionize a carbon-hydrogen bond. Because of the high electronegativity of a fluorine atom, fluorinated
compounds are always more acidic than non-fluorinated compounds.
Strength of an Acid : The strength of an acid HA in water may be determined by considering
the equilibrium :

  
 H3O  A
H2 O + HA 
The equilibrium constant, in water is given by :
 H3O    A  
Ka    
HA 

QUIZRR 123
It should be emphasized that Ka, the acidity constant of the acid in water, is only approximate (as
above) if concentrations are used instead of the more correct activities. The smaller the numerical value
of pKa, the stronger the acid to which it refers.
The origin of ac idit y in organic c om pounds

Among the factors that may influence the acidity of an organic compound, HA, are :
(a) The strength of the H-A bonds.
(b) The electronegativity of A.
(c) Factors stabilising Aă compared with HA.
(d) The nature of the solvent.
Of these (a) is not normally found to be a limiting factor, but the effect of (b) is reflected in the
fact that the pKa of methanol, CH3O-H, is = 16 while that of methane, CH4 is = 43, oxygen being
considerably more electronegative than carbon. Much more important is (c) : the stabilisation is possible
in the methanoate anion compared with the undissociated methanoic acid molecule results in the pKa
of formic acid being 3.77.
O O
HC HC
ă
OăH O

+ H2O + H3O
O O
HC HC
OăH O

This is extremely effective delocalisation, with consequent stabilisation, in the methanoate anion
involving as it does two canonical structures of identical energy.
With alcohols there is no such factor ă
O O O
stabilising the alkoxide anion ROă, relative to
the ROH itself and alcohols are thus very much ă
less acidic than caroxylic acids. With phenols,
however, there is again the possibility of relatvie
stabilisation of the anion by delocalisation of its ă
negative charge through interaction with the 

orbital of the aromatic nucleus.
O

124 QUIZRR
Phenols are indeed found to be stronger acids than alcohols (the pKa of phenol itself is 9.95) but
considerably weaker than carboxylic acids. This is due to the fact that in carboxylic acids, delocalisation
of the negative charge in the carboxylate anion involves structures of identical energy and the atoms
holding the negetive charge are the highly electronegative oxygen atoms; whereas in the phenoxide
anion, the structures involving negative charge on the carbon atoms are likely to be higher energy
content than the one in which it is on oxygen and, in addition, of the centres carrying negetive charge,
only one structure is carrying highly electronegative oxygen atom.
Influenc e of t he solvent :
The prime requirement of the solvent is that it should be capable of functioning as a base; the
weaker the base, the smaller the dissociation of the acid. Thus we find that in, for example, methylbenzene
(toluene) HCl occurs as such, i.e., it is almost fully undissociated.
Fa c t o r s a f f e c t in g t h e s t r e n g t h o f a c i d s a n d b a s e s
[A] Effect of structure :
1. Field effect (ăI effect and +I effect)
2. Resonance effect
3. Periodic Table correlations
4. Steric hinderance
5. Hybridisation
6. Statistical Effects : In a symmetrical diprotic acid, the first dissocation constant is twice as
large as expected, since there are two equivalent ionizable hydrogens, while the second constant
is only half as large as expected because the conjugate base can accept a proton at two
equivalent sit es. So k1/k2 should be 4. Similar arguments hold good for basic groups.
7. Hydrogen Bonding :
p-hydroxy benzoic acid > o ă hydroxy benzoic acid
pka = 4.58 pkn = 2.98
ă5
(ka = 10 ) (kn = 10ă3)
Intra molecular hydrogen bonding between the OH and COOă groups of the conjugate base
of the ortho isomer stablizes it and results in an increased activity.
[B] The Effect of Medium or Solvent

(a) If a base is more solvated than its conjugate acid, its stability is increased relative to the
conjugate acid. e.g.
MeNH2 > NH3.
(b) Aniline in the gaseous phase is a stronger base than NH3 but its much lower basicity in
aqueous solution is caused by similar solvation effects and not by resonance and field electron
with drawing effect of a phenyl group.

QUIZRR 125
Similarly,
Pyridine and pyrrole < NH3 (In aqueous solution)
Pyridine and pyrrole > NH3 (In aqueous phase)
(c) For simple alcohols, following order of acidity is due to solvation effect.
H2O > MeCH2OH > Me2CHOH > Me3COH (in solution)
H2O > MeCH2OH < MeCHOH > Me3COH (in gaseous phases)
(d) A change from a protic to an aprotic solvent can also effect the acidity or basicity because there
is a difference in solvation of anions by a protic solvent and an aprotic one e.g.
In DMF : Picric acid is stronger than HBr
In water : HBr is stronger than picric acid
Re l a t i v e St r e n g t h o f Org a n i c A c i d s
1. % S-character
(a) Hydro carbons
Hydrogen atom attached to sp-hybridised carbon is more acidic than that on sp2 hybridised carbon
which in turn is more acidic than that on sp3.
In other words, acidity increases with percentage (%) s-character. This is because, higher the s-
character closer the electrons to the nucleus of C and farther the electrons go from H, and easily
can H be removed as H+.
Thus,
HC  CH  H2C  CH2  H3C · CH3

sp sp2 sp3
The factors responsible for influencing the acidity of an organic compound, HăX are
(a) the strength of the HăX bond
(b) the electronegativity of X
(c) factors stabilizing Xă as compared to HX and
(d) the nature of the solvent.
The most important factors among all is (c). More stable (less basic) the conjugate base is, more
acidic the compound will be. On comparing the acidic strength of two compounds, the compound having
greater acidity will have higher value of Ka and lower pKa value.
Now let us see using any of these factors, how we can predict the order of acidic strength for
organic acids.
(i) Alcohols : If we were to predict the order of acidic strength of ethanol, iso-propanol and
tertiary butanol, we can proceed as
Me Me
ă 2 ă 3 ă
Me CH2 O H CH O H C O H
Me Me

126 QUIZRR
As alkyl groups (methyl group) have a +I effect, the electron density at the oxygen atom will
increase. More the number of alkyl groups, more will be the intensity of negative charge on oxygen.
Greater the negative charge on the oxygen atom, the closer is the electron pair in the OăH bond driven
to the hydrogen atom and consequently separation of a proton becomes increasingly difficult. Thus, the
acidic strength of given alcohols will be in the order
Ethanol > iso-propanol > t-butanol
In general, electron releasing groups decreases the acidity while electron withdrawing
group increases the acidity of a compound.
Su b s t it u t e d Ph e n o l s
The effect of a ring substituent on the acid strength depends on :
(1) Substitued group is electron attracting or releasing : electron withdrawing groups increases its
acidity and vice-versa.
(2) Ability of the group to enter into resonance with the hydroxyl group and its position.
(3) Steric effect and hydrogen bonding due to the substituted group.
Illust rat io n
Compare acidity of
OH OH OH OH
CH3
, , ,
CH3
Solution : CH3
The methyl group is electron releasing and so release of a lone pair from oxygen (of the OH group
in the unionized phenol or from the Oă phenoxide ion) into the ring is opposed. This results in
diminished resonance in the contributing structures and consequently the phenoxide ion is more resonance
stabilized with respect to phenol than is the methyl phenoxide ion with respect to methylphenol. Hence,
phenol is stronger acid than all methyl phenols. Thus, the order of acidity is
OH OH OH OH
CH3
> > >
CH3
CH3

QUIZRR 127
Now among o, p, m methyl phenols, meta methyl phenol is most acidic
O O O
ă ă ă ă ă ă
CH 3
ă CH 3 ă ă
CH3
Now it is clear that meta methyl phenol are more acidic than ortho and para after the above
structure. Now in case of o-methyl phenol, methyl group is closer to O of OH group in phenol than
compared to p-methyl phenol. As a result it show more +I effect, hence decreasing the acidic character.
Illust rat io n
Compare the acidic strength of
OH OH OH OH
NO2
, , ,
NO2
Solution : NO2
The corresponding phenoxide ions obtained from the three nitrophenols would be stabilized by
delocalization as
ă
(1) O O
NO2 NO2
ă
ă
O O O O O O
N O ă N O N O
ă
ă
O
O
N O

128 QUIZRR
(2) ă
O O O
NO2 NO2 ă NO2
ă
O O
NO2 NO2
(3) ă
O O O
NO2 NO2 N
O O
ă
O O O
NO2 NO2 N
ă
O O
We can clearly see that oăand pănitrophenoxides are more extensively stabilized with respect to
m-nitrophenoxide and hence they are more acidic.
Now, m-nitrophenol is more acidic than phenol because of the ăI effect of the nitro group.
Out of oăand pănitrophenols, p-nitrophenol is slightly stronger than o-isomer as o-isomer involves
intramolecular hydrogen bonding, thus having less tendency to release the Hydrogen atom.

QUIZRR 129
O H
O
N
O
Thus the order of acidity is
OH OH OH OH
NO2
> > >
NO2
NO2
Note : The cumulative effect of the three nitro groups 2, 4, 6 positions results in a very strong
acid {2, 4, 6-trinitrophenols or picric acid}
OH
O2 N NO2
NO2
Illust rat io n
Compare the acidity of the following :
OH OH OH OH
Cl
, , &
Cl
Cl
Solution :
Since all halogens show ăI effect, it increases the acidic nature of phenols. Therefore all halophenols
are more acidic than phenols. Now, halogens cam show both +R & ăI effect. But there, ăI effect
dominates. The reasons is that for resonance to occur, there should be sufficient overlapping between
the molecules & since the size of halogens and carbon are very different, resonance does not occur
properly.
 All Halogens are weakly deactivating

130 QUIZRR
Since we are considering ăI effect, and we know that I effect decreases with distance
 Order becomes
OH OH OH OH
Cl
Cl
Cl
Illust rat io n
Arrange the following in decreasing acidic order
OH OH OH OH
OCH3
OCH3
OCH3
Solution :
Here in this question OCH3 shows ăI effect which increases the acidic nature of phenols
But, methoxy group at para position and orthoposition can show electron repelling nature. but at
ortho position we have ortho effect which makes it most acidic. And at p position methyoxy shows
repelling nature, which contradicts its ăI effect and hence making it even less acidic than phenols.
OH OH OH
now this will repel
the lone pair of OH
& hence will not
facilitate the release
OCH3 OCH3 of H.
+ OCH3 +
Hence the order becomes
OH OH OH OH
OCH3
OCH3
OCH3
A l i p h a t ic c a r b o x y l ic a c i d s :
The aliphatic carboxylic acids are much stronger acids than phenols and alcohols. This is attributed
to the fact that the carboxylate ion (obtained by the loss of proton from carboxylic acid) is relatively

QUIZRR 131
more stabilized by delocalization than the phenoxide and alkoxide ions with respect to their undissociated
molecules.

 ă +
R  C OH  R  C O  H
|| ||
0 0
The delocalization of the negative charge in the carboxylate anion involves structures of identical
energy content (as the negative charge resides on more electronegative atom, oxygen) while in phenoxide
anion, the negative charge also resides on the less electronegative atom (carbon) making these structures
of high energy content with respect to those structures in which the negative charge is on oxygen.
The presence of electron-withdrawing substitutents in simple aliphatic acids increases their acidity
while the electron-releasing substituents have reverse effect. For instance, let us compare the acidic
strength of fluoroacetic acid and acetic acid.

 ă +
CH3  C OH  CH3 ă C ă O  H
|| ||
0 0

 ă +
FăCH2  C OH  F ă CH2 ă C ă O  H
|| ||
0 0
The fluoro acetate ion is stabilized more due to strongăI effect of fluorine, with respect to acetate
ion. Hence, fluoro acetate ion is less basic than acetate ion, thereby making fluoroacetic acid stronger
than acetic acid.
Now, we can also compare the acidic strength of -and -halosubstituted acids i.e.
  
F · CH2 · CH2 · C· OH , F · CH2 · C· OH
|| ||
C C
Here the -substituted compound will have less ă I effect as compared to -substituted acid and
thus will be less acidic than b-substituted acid. Hence, the acidic strength is
F · CH2 · COOH > F · CH2 · CH2 · COOH > CH3 · COOH
If there is a doubly bonded carbon atom adjacent to the carboxyl group, the acid strength is
increased. This will be evident if we compare the acid strength of propanoic acid and propenoic (acrylic)
acid.
 O


CH2  CH ă CO2H  CH2  CH ă C  H
ă
O
 O
CH3 ă CH2 ă CO2 H 

 CH3 ă CH2 ă C  H
ă
O

132 QUIZRR
As we know that unsaturated -carbon atom in propenoate ion is sp2 hybridised, which means that
electrons are drawn closer to the carbon nucleus than in a saturated, sp3 hybridised -carbon atom,
due to greater s-contribution in the sp2 hybrid orbital. The result is that sp2 hybridised carbon atoms
are less electron-donating than saturated hybridised ones, thus, propanoate ion will be comparatively
less stabilized than propenoate ion, thereby making propenoic acid stronger than propanoic acid (but
propanoic will still be weaker than methanoic acid).
It there is a triple bonded carbon atom adjacent to carboxyl group, the acid strength is more with
respect to the presence of a doubly bonded carbon atom adjacent to ăCO2H group. This is attributed
to the fact that sp hybridized carbon atoms are less electron-releasing than sp2 hybridized carbon
atoms.
Some other trends of acidity are :
HCO2H > CH3CO2H > CH3CH2CO2H > ................
HO2CăCO2H > HO2CăCH2ăCO2H > HO2CăCH2CH2ăCO2H > ...........
These trends reflect that in any homologous series, when we move from lower members to higher
members, the acidity decreases.
A r o m a t i c c a r b o x y l ic a c i d s
It has been pointed out that replacement of the hydrogen atom in formic acid by an alkyl group
weakens the strength of the acid and the greater the +I effect of the R group, the weaker is the acid.
Phenylacetic acid, PhCH2CO2H is stronger than acetic acid and therefore the phenyl group has an
overall-I effect. On the other hand, benzoic acid is weaker than formic acid. In this case, the phenyl
group has an overall releasing effect (which is smaller than that of methyl group). These apparently
contradictory results may be explained as follows. When the carboxyl group is directly attached to the
nucleus, the resonance effect (+R) overcomes the ăI effect (in phenylacetic acid, the phenyl group is
insulated from the carboxyl group by a CH2 group and so the +R effect is not possible) :
ă
O + O O
C C + C
OH OH OH
ăI +R +R
This prevents to a large extent, the lone pair on the O atom of the OH group from entering into
resonance with the CO group. The result is a smaller positive charge on the O atom of the OH group
and so proton release is more difficult than in formic acid. The fact that benzoic acid is stronger than
acetic acid means that [ăI+(+R)] < [+I+(+R)] of the methyl group.
The same arguments may be applied to ionized benzoic acid.
O O + O
+
C + H2O H3O + C C
OH O O
ăI ăI ăR

QUIZRR 133
The orthoăeffect. This is a steric effect that is shown by o-substituents. Nearly all o-substituted
benzoic acids are stronger than benzoic acid due to this ortho effect irrespective of the polar nature of
the o-substituent.
As we have seen that benzoic acid is a resonance hybrid and so the carboxyl group is coplanar with
the ring. An o-substituent tends to prevent this coplanarity. Thus, resonance is diminished (or prevented)
and so the O atom of the OH group has a greater positive charge, resulting in increased acid strength.
It follows from this that greater the steric inhibition of resonance, the stronger is the acid. Support for
this is the following order of strengths of substituted benzoic acids.
2, 6-diăMe > 2-t-Bu > 2-Me
Here again, if we consider the stability of the anion, steric inhibition of resonance prevents the +R
effect of the ring coming into operation and since this weakens acid strength, its absence results in
increased acid strength.
OăHydroxybenzoic acid (salicylic acid) is far stronger than the corresponding m-and p-isomers.
Steric inhibition of resonance cannot explain this very large increase, since the corresponding
methoxybenzoic acids all have almost similar strengths. The carboxylate ions of o-hydroxybenzoic acid
is stabilised by intramolecular hydrogen bonding while such hydrogen bonding is not feassible in o-
methoxy benzoic acid and support for this is given by the following order of acid strength,
2, 6 ă di ă OH > 2 ă OH > benzoic acid
It can be seen that two hydrogen bonds would be expected to bring about more stabilization than
one hydrogen bonds.
ăó ăó ăó ăó ăó ăó
O O O O O O
C C H H C H
O O O
Illust rat io n
Compare acidic strength of :
COOH COOH COOH COOH

CH3
, , ,
CH3
CH3

134 QUIZRR
Solution :
Due to the ortho-effect as explained above,
COOH COOH
CH3
>
Now let us consider the effect of substituents from m-and p-positions. First let us take methyl
substituted benzoic acids. As the methyl group has +I effect, so the net result will be to increase the
+R effect in the mă or pătolyl group. Since, the inductive effect decreases with distance, so the +I effect
of CH3 from para position would be less than the +I effect of CH3 group from meta position. Thus, the
electronădensity in the OăH bond of m-methyl benzoic acid would be greater than that in p-methyl
benzoic acid. Accordingly, the p-isomer should be more acidic than the m-siomer. But in real practice,
the order is reverse. Actually, we have ignored the hyperconjugation effect of CH3 group. Due to
hyperconjugation effect of CH3 in p-isomer, the electron density in the OăH bond would be increased
greatly with respect to that in m-isomer.
O O·H O O·H O O·H

C C C
H + +
H H etc.
C·H C·H C·H
H H H

C C C
etc.
+ +
H·C·H H·C H H·C H
H H H
Thus, the release of proton is facilitated easily in m-isomer than in p-isomer.

Thus, the final order of acidity COOH COOH COOH COOH
CH3
> > >
CH3
CH3

QUIZRR 135
Illust rat io n
Compare the acidity of
COOH COOH COOH COOH

NO2
, , ,
NO2
NO2
Solution :
It is clearly observed that due to the ortho effect, o-nitrobenzoic acid will be most acidic. As the ă
NO2 group exerts ăI and ăR effect (both reinforcing each other), the electron-density from the OăH
bond would be withdrawn, thus destabilizing the OăH bond and making mă and pă nitro benzoic acids
stronger than benzoic acid.
O O·H O O·H
C C
NO2 NO2
N+
ă
O O
As it is clear that ăNO2 group exerts its electron withdrawing resonance effect from the p-position
and not from m-position, thus withdrawal of electron density from the OăH bond is greater in p-nitro
benzoic acid than m-nitro benzoic acid. Thus, p-isomer is stronger acid than m-nitro benzoic acid.
Hence the order of acidity is :
COOH COOH COOH COOH

NO2
> > >
NO2
NO2
Illust rat io n
Compare the acidity of
COOH COOH COOH COOH
OCH3
, , ,
OCH3
OCH3

136 QUIZRR
Solution :
O-methoxy benzoic acid will be most acidic due to ortho effect.
Now, we compare the acid strength of mă and pă methoxy benzoic acid. OMe group exerts ăI and
+R effects. The electron-releasing resonance effect (+R) is operative in p-methoxy benzoic acid and not
in m-methoxy benzoic acid while ăI effect is operative in both the isomers. Thus, the electron density
is greatly increased in the OăH bond in p-isomer than in m-isomer, thereby making m-isomer stronger
acid than p-isomer.
O O·H
C
OMe

C C C
etc.
+ +
OMe OMe OMe
As we see here that there exists high electron density on the OăH bond in the p-substituted isomer,
thus benzoic acid will also be more acidic (but less acidic-than m-isomer) than p-isomer.
Thus, the acidic strength is as follows,
COOH COOH COOH COOH

OCH3
> > >
OCH3
OCH3
Illust rat io n
Explain why acrylic (propenoic) acid is weaker acid than propynoic acid ?
Solution :
O O
CH2 = CH · C · O · H CH = C · C · O · H
sp 2 sp
Acrylic acid Propynoic acid

QUIZRR 137
If we look at these two acids, electron withdrawing effect of sp2 carbon adjacent to carbonyl group
in acrylic acid is less than the electron withdrawing effect of sp hybridized carbon. Thus, OH bond of
propynoic acid has greater polarization than the OH group of propenoic acid. Hence, propynoic acid is
a stronger acid than propenoic acid.
Note : A CH2 group flanked between two electron. withdrawing groups has acidic hydrogen.
Aldehydic group isomer is more electron withdrawing than ketonic group, which is more electron
attracting than ester groups. Thus, order of acidity of carbon acids is
H ă Că CH2 ă C ăH  CH3 ă Că CH2 ă Că CH3  CH3 O ă Că CH2 ă Că OCH3

|| || || || || ||
O O O O O O
Cl
|
ă
: C ă Cl
CHCl3 is more acidic than CHF3 because the conjugate base of CHCl3 i.e. |
Cl
ă
stabilised by ăI effect of ClÊs as well as by p-d delocalization (which is absent in :CF3 due to
the absence of d-orbital in F).
B A SI C ST REN GT H OF ORGA N I C B A SES

Strength of bases is related to the ease of accepting a proton, which in turn depends on the
availability of electron pair on the nitrogen atom (or some other basic atom). More is the availability
of electron pair, more easily the proton will be accepted and more will be the basic strength.
If we compare the basicities of NH3, MeNH 2, Me2NH and Me3N, then at a glance it would
seem like NH3 < MeNH 2 < Me2NH < Me2NH < Me3N is the basicity order but the result is quite
different in aqueous media. The correct order is Me2NH > MeNH 2 > Me3N > NH 3. This order can be
explained considering the solvation effect of the protonated amines. But in absence of a polar
protic solvent i.e. in the presence of non-polar solvent or gaseous phase, the order of basicity is
Me 3N > Me2NH > MeNH 2 > NH 3.
The effect of introducing electron withdrawing groups like Cl, NO2, RCO group close to a basic
centre decreases the basicity, due to their electron withdrawing inductive effect.
In aniline, owing to resonance, the lone pair of electrons on the nitrogen atom is less available for
co-ordinating with a proton and at the same time, small positive charge on the nitrogen atom would
tend to repel a proton. Alternatively, since there are more resonating structures possible for aniline

itself than for the cation C6 H5 NH3 , the former will be stablized with respect to the latter.
+ + +
:
:
NH 2 NH 2 NH 2 NH 2 NH 2
:
:

138 QUIZRR
Aniline is a weaker base than ammonia or cyclohexylamine. It is because of the fact that the
electron pair on nitrogen in involved in delocalization, making it less available for donation.
:
NH 2
:
NH 3
cyclohexylamine ammonia
Diphenylamine is even a weaker base than aniline due to the presence of another phenyl group
:
NH
and triphenylamine (Ph3N) is not basic at all by any means.

Introduction of alkyl group (like Me) on the nitrogen atom of aniline results in small increase in
the basic strength.
C6H5NH2 < C6H5NH2Me < C6H5NMe2
Unlike such introduction in aliphatic amines, this small increase in basic strength is progressive,
indicating that cation stabilization through hydrogenăbonded solvation, here as less influence on the
overall effect.
The effect of a ring substitutent on basicity depends on whether the substituent is electron attracting
or releasing, its ability to enter into resonance with the amino-group and its position. All the nitroanilines
are weaker bases than aniline. The nitroăgroup has a strong ăR effect and oăand pănitroaniline are
therefore, more resonance stabilised than aniline itself.
Oă Oă
+ + +
N NH2 N NH2
ă
O O
A m-nitro group cannot enter into resonance with the amino-group, but nevertheless m-nitroaniline
is a much weaker base than aniline. In this case, nitro-group has a strong-I effect. This ăI effect tends
to draw into the ring the lone pair of N, thus decreasing its basicity. Thus, the order of basicity of
nitroanilines is C6H5NH2 > m-NO2C6H4NH2 > p-NO2C6H4NH2 > o-NO2C6H4NH2.
+ +
:
O NH 2 O NH 2 O NH 2
ă
O=N O=N OăN
so on

QUIZRR 139
+ + +
:
NH 2 NH 2 NH 2 NH 2
so on
N N N N
O O O O O O O O
Tetraalkylammonium salts, e.g. R4N+Iă on treatment with moist silver oxide (AgOH) yield basic
solutions comparable in strength with the mineral alkalis. This is readily understandable as R4N+ ăOH
formed is completely ionized to give R4N+ and free OHă.
the amine Tris (trifluoro methyl) amine is found to be virtually non-basic due to the presence of
three powerful electron-withdrawing CF3 groups.
F3C
F3C N:
F3C
The amides are also found to be only very weakly basic in water because of the ăI and ăR effect
of RCO group which makes the electron pair very slightly available on nitrogen atom.
O Oă
+
R ă C · NH 2 R ă C = NH2
If two C=O groups are present, the resultant imides often become suficiently acidic to form alkali
metal salts. For example, benzeneă1, 2-dicarboximide is not basic but is acidic in nature because of the
presence of two electron-withdrawing C = O groups.
O O ă
ă
OH
N·H N ă
ăH2O
O O ă
When the ring contains an electron-releasing group, this reduces resonance of the NH2 group with
the ring and consequently should increase basicity. The methyl group raises the electron density more
at the oă and păpositions than at the măposition. Thus, the carbon atom para to the methyl group has
a high electron density and the lone pair on the nitrogen atom is therefore prevented to some extent
from entering into resonance with the ring. A methyl group raises the electron density at the m-position
is prevented less than for the p-position. Consequently, a methyl group in the ring increases the
basicity of the aniline, more so from the p-position than from the m-position.

140 QUIZRR
First drawing structure of
+ + +
NH 2 NH 2 NH 2 NH 2
CH3 CH3 CH3 CH3
+ +
NH 2 NH 2 NH 2
CH3 CH3 CH3

Now here a 3Ĉ carboanion is formed which is highly unstable and thus prevents there resonating
structures. So at para position, methyl group discourages detocalization & hence increases the basicity.
And we know that p & m methyl aniline are more basic than aniline. Now only o position is left.
At ortho position, there is ortho effect which increases the acidity and it is even weather base than
aniline.
 Order becomes
NH 2 NH 2 NH 2 NH 2
CH 3
CH 3
CH 3
Illust rat io n
Arrange the following in increasing order of basicity
NH 2 NH 2 NH 2 NH 2
OCH3
, , ,
OCH3
OCH3
Solution :
Let us see how to solve this case. Methoxy group can show both +R & ăI effect. +R effect will
increase the basicity whereas ăI effect reduces basicity.

QUIZRR 141
NH 2 NH 2 NH 2
here lp of NH2 & lp of C atom of

benzene repel each other, hence lp
of NH 2 is not delocalized, which
increases the basic nature.
OCH3 OCH3 OCH3
+ +
NH 2 NH 2 NH 2 NH 2
OCH3 OCH3 OCH3 OCH3

+ + +
In this case ăI effect of OCH3 is stronger & ăI effect reduces the basicity
NH 2
OMe
NH 2 NH 2
OCH3 OCH3
+
Here OCH3 produces the same effect as methoxy

group at para position produced, But, Ortho effect
will also be here, which reduces the basic nature. hence the order is
NH 2 NH 2 NH 2 NH 2
OCH 3
OCH 3
OCH 3
Some Important trends :

(a) Among hydrocarbons, acidity increases with the percentage of s-character. This is because
higher the s-character, closer will be the electrons to the nucleus of carbon and the electrons
further more away from H and it can be easily removed as H+. Therefore, the increasing
order of acidity is, CH3-CH3 < CH2=CH2 < CHCH
(b) Alcohols are more acidic than alkanes because oxygen is more electronegative than carbon
and consequently O-H bond will break easily to give H+ ions than C-H bond.

142 QUIZRR
(c) Carboxylic acids are more acidic than alcohols because carboxylate anion is more resonance
stabilised as compared to alkoxide ion.
(d) Phenols are more acidic than alcohols because phenoxide ion is more resonance stabilised as
compared to alkoxide ion.
(e) Phenols are less acidic than carboxylic acids. This is because in phenoxide ion some of the
resonance structures are of higher energy and this makes phenoxide ion not very stable.
O
 H5C6OH < H
OH
(f) CH3COOH > CH3CH2COOH (greater the number of CH3 added, less is the acidity due to +
I effect of CH3).
(g) Increase in electron withdrawing substituents in simple aliphatic acids increases acidity.
CH3COOH < I-CH2COOH < Br-CH2COOH < F-CH2 COOH
Cl
Cl
Cl < Cl COOH
COOH
Cl
(h) As the distance between chloro group and COOH group increases, acidity decreases.
Cl
H3C COOH H3C
COOH < < H3C < COOH
COOH Cl
Cl
(i) Benzoic acid is more acidic than carboxylic acid because benzoate anion is more resonance
stabilised.
(j) Aniline is less basic than NH3. This is because in aniline the nitrogen atom is bonded to an
sp2 hybridized carbon atom but the unshared pair on nitrogen interacts with the delocalized
orbital.
(k) Introduction of an alkyl group on the nitrogen of aniline results in small increase in pKa
value due to + I effect of alkyl groups. Therefore order of acidity is C6H5NH2 > C6H5 NHMe
> C6H5NMe2.
(l) Introduction of phenyl groups on N lowers basicity because the substituted amine becomes
more stable than the ion.

QUIZRR 143
Ex a m p l e
Compare the basic strength :
H3C CH3 H3C CH3 (x)

NH2 N N
H3C CH3 (y)
(a) (b) (c)
Solution :
In (c) due to repulsion between bulky CH3 groups, rotation occurs, thus resonance does not occur.
Therefore order of basic strength is :
(a) < (b) < (c)
Ex a m p l e
Write the order of basic strength :
NH2 O
N N N H
H
(a) (b) (c) (d) (e)
Solution :
Delocalisation of electron present on N is possible in (a) therefore (a) is least basic. N in (b) is sp2
hybridised, therefore it is less basic than (c), (d) and (e).
Oxygen in (e) withdraws electrons from N through inductive effect and in (d) CH2 groups increases
ă
e density.
Thus, the order will be :
(a) < (b) < (e) < (c) < (d)

144 QUIZRR
Ex a m p l e
Compare the basic strength :
NH2
N
N
H
(a) (b) (c)
Solution :
eă will be delocalised through resonance in (a). In (b) N is sp2 hybridised. Therefore, basic strength
is :
(a) < (b) < (c)
Points to Remember :
(1) The more stable Aă is, more stronger acid HA will be.
(2) Easier a compound is ready to give electron, more will be it basic in nature.

13 Goc Revision Notes Quizrr

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5. Acids & Bases 122

GENERAL ORGANIC CHEMISTRY

CL A SSIFICA T I ON OF ORGA N I C COM POU N DS

Cyclopropane Cyclopentane Cylopenetene Cyclohexene

GENERAL ORGANIC CHEMISTRY

(b) Bicyclic and Tricyclic aromatic compounds :

Tetrahydro Furan Pyrrolidine

Pyridine Furan Pyrrole

GENERAL ORGANIC CHEMISTRY

Table 1.a : Homologous series of aliphatic organic compounds

Name of the homologous General formula Functional group IUPAC name

Nitro compounds CnH2n+1 NO2 N Nitroalkanes

GENERAL ORGANIC CHEMISTRY

Chain length Word root Chain length Word root

Class of organic compound Functional group Secondary suffix

GENERAL ORGANIC CHEMISTRY

Number of Carbons Name

GENERAL ORGANIC CHEMISTRY

Chain of seven carbons Chain of eight carbons 2

(1) Maximum number of side chains or

GENERAL ORGANIC CHEMISTRY

sum of positions : sum of positions :

GENERAL ORGANIC CHEMISTRY

CH3 CH2 CH3

GENERAL ORGANIC CHEMISTRY

GENERAL ORGANIC CHEMISTRY

GENERAL ORGANIC CHEMISTRY

When the ring contains two or three double or triple bonds

Halo + Name of parent alkane = Haloalkane

CH3l C2H5Br CH3  CH CH3 CH3ăCH2ăCH2ăBr

GENERAL ORGANIC CHEMISTRY

No. of Molecular Parent Common IUPAC

GENERAL ORGANIC CHEMISTRY

Name of alkane ă e + ol  Name of the alkanol

Polyhalo Parent alkane Name

GENERAL ORGANIC CHEMISTRY

GENERAL ORGANIC CHEMISTRY

Functional group : CO

No. of Molecular Alkyl groups Parent Common IUPAC

Alk onic Ac ids or sat urat ed m onoc arbox ylic ac id

Suffix : oic acid

GENERAL ORGANIC CHEMISTRY

No. of Molecular Parent Common IUPAC

Propanedioic acid (Malonic acid, parent alkane is propane)

GENERAL ORGANIC CHEMISTRY

Butanedioic acid (Succinic acid, parent alkane is butane)

Molecular Acid formed Parent Common IUPAC

GENERAL ORGANIC CHEMISTRY

Suffix : oic anhydride

GENERAL ORGANIC CHEMISTRY

Molecular Common system IUPAC system

No. of Molecular Parent Common IUPAC

GENERAL ORGANIC CHEMISTRY

GENERAL ORGANIC CHEMISTRY

1 CH3NH2 Methane Methylamine Methanamine

HăC  N HCOOH (formic Methane Hydrogen Methanenitrile

H3CăC  N CH3COOH Ethane Methyl Ethanenitrile

GENERAL ORGANIC CHEMISTRY

Molecular Acid formed on Common IUPAC name

CH3ăNC CH3COOH Methyl Methyl

Class of compounds Functional group or Suffix Prefix