Basic Concepts

of
Organic Chemistry

By
Dr. H A Rahim
B. Pharm, MBA, M. Phil, Ph. D, DSOLS

1
 Inductive effect
 Mesomeric effect
 Hyperconjugation
 The Resonance
 Hydrogen bonding
 Steric effect
 Enol-Ketol tautomerism

2
The Inductive Effect
The inductive effect (I.E.) refers to the polarity produced in
a molecule as a result of higher electro negativity of one
atom compared to another. Or
The polarity of a bond INDUCED by adjacent polar bond
is known as the Inductive effect.
 Inductive effect of an atom or functional group is a function
of that group’s
1. Electronegativity
2. Charge
3. Position within a structure.
 Inductive effects refer to those electronic effects of an atom
or functional group that can contribute through single
bonds such as saturated (sp3) carbon atoms. 3
The Inductive Effect
 It involves σ electrons.
 The σ electrons which form a covalent bond are seldom shared
equally between the two atoms.
 This is because different atoms have different electronegativity
values, i.e., different powers of attracting the electrons in the
bond.
 Consequently, electrons are displaced towards the more
electronegative atom introducing a certain degree of polarity in
the bond.
The more electronegative atom acquires a small negative charge
(δ-).
The less electronegative atom acquires a small positive charge (δ+).

4
The Inductive Effect
• Consider the carbon-chlorine bond.
• As chlorine is more electronegative, it will become
negatively charged with respect to the carbon atom.

(1) (2) (3)

Structure (1) indicates the relative charges on the two atoms.

In (2), the arrow head placed in the middle of the bond indicates
the direction in which the electrons are drawn.
In (3), the more heavily shaded part shows the region in which
the electron density is greatest. 5
The Inductive Effect
• The carbon-hydrogen bond is used as a standard. Zero effect is
assumed in this case.
• Atoms or groups which lose electrons toward a carbon atom are
said to have a +I Effect. Such groups will be referred to as
electron-releasing.
• Those atoms or groups which draw electrons away from a
carbon atom are said to have a –I Effect. Such groups will be
referred to as electron-attracting.
• Some common atoms or groups which cause –I Effect Groups
(electron-attracting) are:
-NO2 > -CN > -COOH > -F > -Cl > -Br > -I > -OH > C6H5– &
• Atoms or groups which cause +I Effect Groups (electron-
releasing): (CH3)3C– > (CH3)2CH– > CH3CH2– > CH3–
6
 The Inductive Effect
 Tertiary alkyl groups exert greater +I effect than secondary which
in turn exert a greater effect than primary.
 An inductive effect is not confined to the polarization of one bond.
It is transmitted along a chain of carbon atoms, although it tends to
be insignificant beyond the second carbon.

 The inductive effect of C1 upon C2 is significantly less than the

effect of the chlorine atom on C1. The inductive effect results in a
permanent state of the molecule and can be observed practically

7
 Factors affecting IE

1. Electronegativity:
 Atoms or functional groups that are electronegative
relative to hydrogen such as the halogens, oxygen,
nitrogen, may have a negative inductive effect (-I).
 Thus these atoms withdraw electron density through the
single bond structure of a compound.
 Consider the case of acetic acid, chloroacetic acid and
trichloroacetic acid shown below.
 All three of these compounds can ionize (loss of proton
from the carboxyl OH).

8
 Factors affecting IE

 The only difference between these three structures in

the degree of chloro group substitution.
 Chlorine atoms are electronegative and thus have a -I
effect.
 Thus they can help stabilize a negative charge, and
enhance the ionization of an acid.

9
 Factors affecting IE

2. Bonding order and charge:

•As mentioned above, it is important to consider both
the electronegativity and bonding order when analyzing
the inductive potential of an atom.
•For example, oxygen in a hydroxyl group (OH) is
electron withdrawing by induction (-I) because the
oxygen atom is relatively more electronegative and is
uncharged in that bonding arrangement. However,
oxygen in an "alkoxide" (O¯) structure is electron
donating (+I) by induction because in this bonding
order (a single bond to oxygen) it has an "excess" of
electron density.
10
 Factors affecting IE
The strength of the inductive effect produced by a
particular atom or functional group is dependent on it's
position within a structure. For example, the further
from the site of ionization, the lower the inductive effect.
This is illustrated in the example below where the acid
with the chlorine atom positioned on a carbon atom
nearer the reaction site (OH) is more acidic that the acid
where the chlorine atom is positioned further away.

11
 Applications of inductive effect
1. Strength of an acid
Commonly the strength of an acid cab be calculated for the pKa
value. Greater the pKa less the strong will be the acid. The pKa is
related to the electron donating and electron drawing group. For
example
Formic acid Acetic acid

The formic acid is more strong than acetic acid. Because in acetic
acid, with carbonyl carbon EDG (CH3) is attached. In case of
electron donation by methyl their will be abundance of electron (-
ve charge) on carbonyl carbon. For the stability of carbonyl
carbon EWG is required but CH3 is EDG. Due to electron
abundance on carbonyl carbon it will not easily give H+ ions. Less
the potential of releasing H+ ions less strong will be the acid. 12
 Strength of an acid
 In case of FORMIC ACID there is attached EWG (H) with carbonyl
carbon. In case of EWG their will be electron deficiency on the next
carbon.
 This electron deficient carbon (+ve charge) will stabilize by sharing
of electron from oxygen and so H ions will be easily released.
Other examples
 Acetic acid (CH3 is EDG)
 Chloroacetic acid (Cl is EWG)
 Di-chloroacetic acid (2 Cl are EWG)
 Tri chloroacetic acid (3 Cl are EWG)

ALL chloro acetic acids are stronger than acetic acid.

13
 Substitution of electrophile in Benzene
 Electrophile are electron loving groups it will easily
move toward nucleophile (+ve charge).
 In case of reaction between nitro group and Toluene, due
to the presence of methyl with benzene ring, which is
electron releasing group will increase the electronic
density on ortho and para position.

14
 The Mesomeric Effect
The Mesomeric effect (M effect) refers to the polarity
produced in a molecule as a result of interaction between
two π bonds or a π bond and lone pair of electrons. The
effect is transmitted along a chain in a similar way as are
inductive effects.
 It involves π electrons of double and triple bonds.
 The Mesomeric effect is of great importance in conjugated
compounds (in which the carbon atoms are linked alternately
by single and double bonds).
 In such systems, the π electrons get delocalized as a
consequence of mesomeric effect, giving a number of
resonance structures of the molecule.

15
 The Mesomeric Effect
Consider a carbonyl group (>C=O). The oxygen atom is more
electronegative than the carbon atom. As a result, the π electrons of
the carbon-oxygen double bond get displaced toward the oxygen
atom. This gives the following resonance structures:

The mesomeric effect is represented by a curved arrow. The head

of the arrow indicates the movement of a pair of π electrons. If the
carbonyl group is conjugated with a carbon-carbon double bond,
the above polarization will be transmitted further via the π
electrons.

16
 The Mesomeric Effect
 In a system involving resonance the distribution of electron density is
different from the system that does not involve resonance.
 For example, in ammonia where resonance is absent, the unshared pair
of electrons is located on the nitrogen atom, however if one of the H
atom is replaced by benzene ring the electron pain of N is delocalized
over the ring and resulting the decrease of electron density on the N
atom and the corresponding increase of electron density on the ring.

17
 The Mesomeric Effect
 This decrease in electron density at one position and the
corresponding increase elsewhere is called the RESONACE
EFFECT OR MESOMERIC EFFECT. Thus –NH2 group in
aniline donated electrons to the ring by the resonance effect or
mesomeric effect.
The M effect like the I effect may be positive or negative.
Atoms or groups which lose electrons toward a carbon atom are
said to have a +M Effect.
Atoms or groups which draw electrons away from a carbon atom
are said to have a –M Effect
Some common atoms or groups which cause
(a) +M Effect are: Cl, Br, I, NH2, NR2, OH, OCH3 &
(b) –M Effect are: NO2, CN, >C=O
18
 The Mesomeric Effect
The +M effect of the bromine atom is:

The -M effect of the Nitro group is:

19
 Significance of Mesomeric Effects
The mesomeric effect has an appreciable influence on the
physical properties and the chemical reactivity of the organic
compounds. For example compare the acidity if phenol with
that of ethanol, the acidity of both is the result of the
dissociation of O-H bond yet phenol (pKa = 10) is more acidic
that ethanol (pKa =17).

 CH3CH2OH + H2O CH3CH2O- + H3O+

 Ph-OH + H2O Ph-O- + H3O+
The enhanced acidity of phenol can be attributed to the –ve
charge distribution which is not possible in ethoxide ion.
Phenol therefore has much tendency to lose proton and
behave as an acid.
20
 Significance of Mesomeric Effects
 Nitro group further enhances the acidity of phenol particularly
in the ortho and para position because it further delocalizes the
negative charge over to the nitro group and increasing the
number of contributing structures.

21
 Significance of Mesomeric Effects

Nitro groups stabilize the phenolate ion by resonance

electron withdrawal that allows the negative charge to be moved to
an electronegative oxygen atom in the nitro group when the nitro
group is ortho- or para- to the -OH group. The more nitro groups
there are in these positions, the greater the stabilization of the
phenolate and the more acidic the phenol.
22
 Significance of Mesomeric Effects
 The basicity of anime is very sensitive to resonance effect. For
example aniline is a weaker base than aliphatic amines because
the electron pair on the N atom which is responsible for the basic
strength of the amines is delocalized over the aromatic ring in
aniline and is not available for protonation to the same extent as
in the case of aliphatic amines where such delocalization is not
possible.

23
Hyperconjugation
The relative stability of various classes of carbonium ions
may be explained by the number of no-bond resonance
structures that can be written for them. Such structures are
arrived at by shifting the bonding electrons from an adjacent
C–H bond to the electron-deficient carbon. In this way, the
positive charge originally on carbon is dispersed to the
hydrogen. This manner of electron release by assuming no-
bond character in the adjacent C–H bond is called
Hyperconjugation or No-Bond Resonance.
H H
H H

H
H H
H
H H
ethyl carbocation 24
Hyperconjugation
The more hyperconjugation structures (no-bond resonance
structures) that can be written for a species, the more stable is the
species. For example,
1.Ethyl carbonium ion is stabilized by three hyperconjugation
structures:

2. Isopropyl carbonium ion is stabilized by six hyperconjugation

structures.
25
Hyperconjugation
3. t-Butyl carbonium ion is stabilized by nine hyperconjugation
structures
Thus, the following order of stability holds:

In general, resonance effects (mesomeric effects) are more

important than hyperconjugation effects.

The allyl and benzyl carbonium ions are more stable than most
alkyl carbonium ions because the former are stabilized by
resonance while the latter are stabilized by hyperconjugation.

26
Conjugation
A diene is said to be conjugated when its double bonds are not
directly next to each other, but rather separated by a single bond
in between them (CH2=CH-CH=CH2).
Conjugated dienes are particularly stable due to the
delocalization of the pi electrons along sp2 hybridized orbitals,
and they also tend to undergo reactions atypical of double bond
chemistry. For instance, chlorine can add to 1,3-butadiene
(CH2=CH-CH=CH2) to yield a mixture of 3,4-dichloro-1-butene
(ClCH2-CHCl-CH=CH2) and 1,4-dichloro-2-butene (ClCH2-
CH=CH-CH2Cl). These are known as 1,2 addition and 1,4
addition, respectively. 1,2-addition is favored in mild reaction
(irreversible) conditions (the kinetically preferred product) and
1,4-addition is favored in harsher reaction (reversible) conditions
(which results in the thermodynamically preferred product).
27
The Resonance
A number of organic compounds cannot be accurately
represented by one structure. For example, benzene is ordinarily
represented as :

This structure has three carbon-carbon single bonds and three

carbon-carbon double bonds. However, it has been determined
experimentally that all carbon-carbon bonds in benzene are
identical and have the same bond length (1 .42Å). Furthermore,
the carbon-carbon bond length of (1.42 Å) is intermediate
between the normal carbon-carbon double-bond length (1.33 Å)
and the normal carbon-carbon single-bond length (1.52 Å).
Actually two alternative structures (1 and 2) can be written for
benzene :

1 2 28
These two structures differ only in the position of electrons.
Neither (1) nor (2) is a correct representation of benzene. The
actual structure of benzene lies somewhere between these two
structures.
This phenomenon in which two or more structures can be
written for a compound which involve identical positions of
atoms is called Resonance.

29
The Resonance
 The actual structure of the molecule is said to be a Resonance
Hybrid of various possible alternative structures. The alternative
structures are referred to as the Resonance Structures or Canonical
Forms. A double headed arrow (↔) between the resonance
structures is used to represent the resonance hybrid. Thus in the
case of benzene, (1) and (2) represent the resonance structures.
Actual structure of the molecule may be represented as hybrid of
these two resonance structures, or by the single structural formula
(3).
 It should be clearly understood that the resonance structures (1)
and (2) are not actual structures of the benzene molecule. They
exist only in theory. None of these structures adequately
represents the molecule. In resonance theory, we view the benzene
molecule (which is of course a real entity) as being hybrid of these
two hypothetical resonance structures. 30
30
The Resonance Energy
The resonance hybrid is more stable than any one of the various
resonance structures. The difference in energy between the hybrid and the
most stable resonance structure is known as the Resonance Energy.
Resonance energy can be determined by the difference between the
calculated and experimental heats of combustion (energy given off as
heat when one mole of compound is burned) of the compound.
For example, it has been calculated that the hypothetical structure (1) or
(2) would have a heat of combustion of 797 Kcal/mole. The measured
value for the heat of combustion of benzene is 759 Kcal/mole. Therefore,
the resonance energy of benzene is (797–759) Kcal/mol. The benzene is
said to be "stabilized" by a resonance energy of 38 Kcal/mole

31
The Resonance
Another species that is not correctly represented by a single
structure is the acetate ion. As in the case of benzene, acetate
ion is a hybrid of two resonance structures. Both carbon-
oxygen bonds in the acetate ion are identical and have the same
bond length (1.26 Å). The carbon-oxygen bond length of 1.26
Å is intermediate between the normal carbon-oxygen double-
bond length (1.20 Å) and the normal carbon-oxygen single-
bond length (1.43 Å).

32
The Resonance (Governing Rules)
1. Resonance occurs whenever a molecule can be represented by two or more
structures differing only in the arrangement of electrons, without shifting
any atoms. Resonance only involves the delocalization of electrons.
2. Resonance structures are not actual structures for the molecule. They are
nonexistent and hypothetical.
3. Resonance structures are interconvertible by one or a series of short
electron-shifts. For example,

33
The Resonance (Governing Rules)
4. Resonance hybrid represents the actual structure of the
molecule. The structure of the resonance hybrid is intermediate
between the various resonance structures and is not a mixture
of them.
5. Resonance hybrid is represented by a double headed arrow
(↔). This should not be confused with the two arrows ( )
used to denote equilibrium between two different compounds.
6. Resonance hybrid is more stable than any of its contributing
forms (resonance structures).
7. Resonance always increases the stability of a molecule and
lessens its reactivity.

34
The Hydrogen Bonding
• Hydrogen bonding is an attractive force which occurs in any
compound whose molecules contain O–H or N–H bonds (as in
water, alcohols, acids, amines, and amides) or any EN atom.
• A bond formed between a functional group (H–A) and an other
atom (B) or group within the same molecule or different molecule
is called Hydrogen bonding.
• The O–H bond, for example, is a highly polar bond. Oxygen is
more electronegative than hydrogen and pulls the bonding
electrons closer to it. As a result of this displacement, the oxygen
atom acquires a small negative charge (δ–) and the hydrogen atom
a small positive charge (δ+).

35
 Adjacent molecules of the compound containing an O–H bond will
be attracted to each other by means of these opposite charges. This
force of attraction is known as the Hydrogen Bond. Usually a
hydrogen bond is represented by a dotted line.

 Consider the following HB

 H2O – H2O
 NH3 - H2O
 In all the above examples we saw that in all cases the two
electronegative atoms are linked due to H atoms.
36
The Hydrogen Bonding
 Besides this the strength of H-Bond will depend on the value of
electronegativity for examples in H-F the H-Bond is most stronger
as compared to HCl, HBr and HI. This is only due to EN. The order
of Hydrogen bond strength in halogens atoms will be decreased
from TOP to the BOTTOM.
 H----F
 H----Cl
 H-----Br
 H-----I
 Types of Hydrogen bonding

There are two type of Hydrogen bonding

1. Intermolecular HB
2. Intramolecular BH
37
The Hydrogen Bonding
1. INTERMOLECULAR HB
Intermolecular HB exist between two SAME molecules or
DIFFERENT molecules.
Examples
HF-HF

CH -O-CH (Dimethyl ether) and H O

3 3 2

2. INTRAMOLECULAR HB
Intramolecular HB occurs WITHIN THE SAME molecule and
sometime it is called as INTERNAL HB.
For example SALICYLIC ACID

38
The Hydrogen Bonding
Some times the intramolecular HB results in the formation of a
2nd pseudo ring like in salicylaldehyde. The formation of an extra
ring is know as CHELATION (holding of a H atom between two
atoms of the same molecule). In case of chelation the H atom
finds itself a member of a six member ring.
Energy of HB

The HB is much weaker than ordinary covalent bond. The strength

of the HB are in the range of 8 – 42 kj/mol. In general the strength
of HB increases with the acidity of hydrogen in H-A and the
basicity of B. For example the HB energy for HF-HF, H2O- H2O,
NH3-NH3 is 41.84, 29.29 and 8.37 kj/mol respectively. In case of
Fluorine (strong base) a very low polarization occur because of its
electrons being close to and tightly held by the nucleus, form a
stronger HB.
39
The Hydrogen Bonding
 If the H atom (present in strong acid) is too strong acidic and
the acceptor atom is too strong basic, the H atom will shift as a
proton to form a covalent bond with the acceptor atom in a
simple acid base reaction.
 The strengths of hydrogen bonds (5-10 Kcal/bond) are much
less than the strengths of ordinary covalent bonds. However,
they have a very significant effect on the physical properties
(boiling points, solubility) of organic compounds.

40
The Hydrogen Bonding
Effect on Boiling Points:
It is understandable that substances having nearly the same
molecular weights, have the same boiling point. The BP of alkanes
and ethers of comparable molecular weights are not far apart, but
the boiling points of alcohols having almost equal molecular
weights are considerably higher.
CH3--CH2---CH3 CH3—O—­­CH3 CH3—CH2—OH
Propane Dimethyl ether Ethanol
(MW 44 ; bp –45°C) (MW 46 ; bp –25°C) (MW 46 ; bp +78°C)
This can be explained on the basis of hydrogen bonding. Ethanol
forms hydrogen bonds. Extra energy in the form of heat is required to
break the hydrogen bonds holding the molecules together before it
can be volatilized. Propane and dimethyl ether do not form hydrogen
bonds and, therefore, have low boiling points. 41
41
The Hydrogen Bonding
Effect on Water Solubility:
A hydrogen-bonded substance is usually soluble in another hydrogen-bonded
substance. For example, alcohols are soluble in water but alkanes are not.
This is because a nonpolar alkane molecule cannot break into the hydrogen-
bonded sequence in water. It cannot replace the hydrogen bonds that would
have to be broken to let it in.

An alcohol molecule is capable of hydrogen bonding. It can slip into the

hydrogen bonded sequence in water. It can replace the hydrogen bonds that
must be broken to let it in.

42
The Hydrogen Bonding
Effect on Water Solubility:
Thus alcohols of low molecular weight are water soluble. However,
when the alkyl group (R–) is four or more carbons in length the
alkane nature of the molecule predominates, and water solubility
falls off sharply. Alcohols containing more than seven carbons are
insoluble in water.

43
The Hydrogen Bonding
 Effect on volatility
Volatility increase by increasing intramolecular HB. In case of
chelation in salicylaldehyde the BP is lower expectedly because
in this case the molecule behaves as monomer and is therefore
easy to volatilize. The chelated salicylaldehyde boils at 196 oC and
can easily vaporize while its para or mata isomer boils above
240oC and not vaporize through steam distillation.
In case of o-nitrophenol
The solubility of o-nitrophenol is water is lower as compared to its
para and mata isomer because in case of ortho isomer the
volatility increases and solubility decreased. While in case of para
isomer the volatility decreases and solubility in water increases
due to formation of intermolecular HB.

44
The Hydrogen Bonding
 Effect on acidity
O-Hydroxybenzoic acid (salicylic acid) is more acidic than para
position. Because in ortho isomer the OH group is in a better
position to stabilize the carboxylate ion, formed after ionization, by
chelation.

45
 The Steric Effect
• The effect of the structure of molecules on the STABILITY and REACTION
of the compound is called steric effect.
• Steric effects arise from the fact that each atom within a molecule occupies a
certain amount of space.
• If atoms are brought too close together, there is an associated cost in energy
due to overlapping electron clouds (Pauli or Born repulsion), and this may
affect the molecule's preferred shape (conformation) and reactivity.
• The size as well as the electronic properties (i.e. inductive and mesomeric
effects) of the surrounding groups affects the stability of carbocations,
carbanions and radicals.
• When bulky substituents surround a cation the reactivity of the cation to
nucleophilic attack is reduced by steric effects.
• This is because the bulky groups hinder the approach of a nucleophile.

46
The Steric Effect
• When the size of groups is responsible for reducing the
reactivity at a site within a molecule, this is attributed to
steric hindrance.
• When the size of groups is responsible for increasing the
reactivity at a site within a molecule, this is attributed to
steric acceleration.
• Steric hindrance or steric resistance occurs when the size of
groups within a molecule prevents chemical reactions that
are observed in related smaller molecules.
• Although steric hindrance is sometimes a problem, it can
also be a very useful tool, and is often exploited by chemists
to change the reactivity pattern of a molecule by stopping
unwanted side-reactions (steric protection).

47
The Steric Hindrance

 Nucleophile approaches from the back side.

 It must overlap the back lobe of the C-X sp3 orbital.

48
Examples
1. The methylation of 2,6-Ditertiary butyl pyridine under high
pressure is not possible as compare to the methylation of 2,6-
Dimethyl pyridine. Because the possibility of the 2nd reaction
is that methyl groups are less bulkier than tertiary butyl. in
case of SN2 reaction the rate of reaction is inversely
proportional to bulkiness of the attached groups.
2. Penicillin
Penicillin is an antibiotic with the following chemical formula,

49
In the above structure R is related to the chemical activity of
penicillin. If in place of R there is Benzyl group so this penicillin
will be called benzyl penicillin. Now Benzyl group is not bulky
so the enzyme produced by the bacteria know as beta lactam or
penicillinase will attack on this penicillin and will rupture the
beta lactam ring.

50
In case of Cloxacillin,
the R1 has been
replaced by the bulky
group and due to steric
hindrance the beta
lactamase enzyme can’t
rupture the beta lactam
ring.

51
Keto Enol Tautomerism
(As a general rule enols are unstable)
ol
O H ENOLS :
( have -OH attached to a double bond)
Think of this combination as unstable.
C C
ene
OH
NOTE :
Phenols are not “enols” and they are
very stable (benzene resonance).
52
Keto Enol Tautomerism
Nature of tautomerism:
1. Carbonyl compounds with hydrogen's bonded to their α carbons
equilibrate with their corresponding enols.
2. This rapid equilibration is called tautomerism, and the individual
isomers are tautomers.
3. Unlike resonance forms, tautomers are isomers.
4. Despite the fact that very little of the enol isomer is present at room
temperature, enols are very important because they are reactive. For
example, ethyl acetoacetate is an equilibrium mixture of the keto
and enol form. At room temperature, the mixture contains 93% of
keto-form plus 6% of the enol-form.

53
Mechanism of tautomerism:
1. In acid-catalyzed enolization, the carbonyl α carbon is
protonated to form an intermediate that can lose a hydrogen
from its carbon to yield a neutral enol.

2. In base-catalyzed enol formation, an acid-base reaction occurs

between a base and an α hydrogen.

i. The resultant enolate is protonated to yield an enol.

ii. Protonation can occur either on carbon or on oxygen.
iii. Only hydrogen on the α positions of carbonyl compounds
are acidic.

54
Keto Enol Tautomerism
H
O O
K
C C C C

H
keto enol

For most ketones, the keto form

predominates in the equilibrium

55
Acid-catalyzed Enol Formation
:O H—A Acid-catalyzed enol formation.
: The protonated intermediate can lose H +, either from the
C H
C oxygen atom to regenerate keto tautomer or from the α
Keto tautomer carbon atom to yield an enol.

Protonation of the carbonyl oxygen

atom by an acid catalyst HA yield a
H : H cation that can be represented by two
+
:O :O resonance structures.
C H C
+ H :A-
C C
Loss of H+ from the α position by
reaction with a base A- then yields the
enol tautomer and regenerates HA
catalyst.
H
:

:O
+ HA
C
C

Enol tautomer 56
Base-catalyzed Enol Formation
:O Base-catalyzed enol formation.

: :
: :OH
-

C H The intermediate enolate ion, a resonance hybrid of

C two forms, can be protonated either on carbon to
Keto tautomer regenerate the starting keto tautomer or on oxygen
to give an enol.
Base removes an acidic hydrogen from
the α position of the carbonyl
:
H—O—H compound, yielding an enolate anion

: :
:O :O:-
: that has two resonance structures.
C C
I:

C C
Protonation of the enolate anion on the
oxygen atom yields an enol and
regenerates the base catalyst.
H
:

:O + OH-
C
C
Enol tautomer
57
Carbocations
 Carbocation:
• a species in which a carbon atom has only six electrons in its
valence shell and bears positive charge
 Carbocations are:
• classified as 1°, 2°, or 3° depending on the number of carbons
bonded to the carbon bearing the positive charge
• electrophiles; that is, they are electron-loving
• Lewis acids

58
Carbocation Stability
• relative stability
H H CH3 CH3
H C+ CH3 C+ CH3 C+ CH3 C+
H H H CH3
Methyl Ethyl Isopropyl tert-Butyl
cation cation cation cation
(methyl) (1°) (2°) (3°)
Increasing carbocation stability

• methyl and primary carbocations are so unstable that they are

never observed in solution

59
Carbocation Stability

• we can account for the relative stability of carbocations if we

assume that alkyl groups bonded to the positively charged
carbon are electron releasing and thereby delocalize the positive
charge of the cation

• we account for this electron-releasing ability of alkyl groups by

(1) the inductive effect, and (2) hyperconjugation

60
 LEAST MOST
STABLE STABLE

H CH3 CH3 CH3

C C C C
H H H H H3C H H3C CH3

Methyl Primary Secondary Tertiary

Carbocation Carbocation Carbocation Carbocation
Carbon atom is electron deficient (only has 6
electrons in its outer valence). CH3
The methyl groups have +I inductive effects.
Thus, extra electron density is ‘pushed’ onto the
carbocation, which stabilises the carbocation. C
H3C CH
61 3