GOC-intermediate and Application

General Organic Chemistry-II
Applications of electronic effects:

Th1: Reaction intermediates
Reactive, shortlived, high energy, unstable species, those are formed in the course of organic reactions
are called reaction intermediates.
Reaction intermediates generally formed after bond breaking and before bond formation.
A covalent bond can get cleaved by:
(i) Heterolytic cleavage (ii) Homolytic cleavage.
Homolytic fission of covalent bonds:
The bond may break in such a way that each fragment takes away one of the electrons of the bond.
This process is called homolysis, produces fragments with unpaired electron called radicals.
Heterolytic fission of covalent bonds:

The bond breaks in such a way that one fragment takes away both electrons of the bond, leaving the
other fragment with an empty orbital. This kind of cleavage called heterolysis, produces charged
fragments or ions.
Heterolysis of a bond normally requires polarized bond.
Polarisation of a bond usually result from different electronegatives of the atoms joined by the bond.
The greater the difference in electronegativity, the greater the polarisation. In the given instance, atom
B is more electronegative than A.
Section (A) : Carbanions

D1: A carbon intermediate which contain three bond pair and a negative charge on it, is called carbanion.
Hybridisation: Hybridisation of carbanion may be sp3, sp2 or sp.
Hybridisation Example
sp3 , CH3– , , ,
sp2 H2C= , CH2=CH– ,
sp HC
Stability of carbanion: Carbanions are stabilised by electron withdrawing effect as
(i) – I effect (ii) –M effect (iii) Delocalisation of charge
Carbanions are Lewis bases. In their reactions they seek a proton or some other positive centre to
which they can donate their electron pair and thereby neutralize their negative charge.
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Examples of stability order:
Ex. (a) CH3 CH3 CH2 CH3 CH2 CH3 CH3 C CH3 (Stability order: 1>2>3>4)
CH3
1 2 3 4
(b) CH  C .. (Stability order: 1 > 2 > 3)
1
.. .. ..
CH2
(c) (Stability order:1 > 2 > 3)
1 2 3
  
••
(d) CH2  CH – C H2 C6H5 – CH2 (Stability order : 1 < 2 < 3)
(C6H5 )3 C
1 2 3
Rearrangement: Generally carbanions do not undergo rearrangement.
Section (B) : Carbon free radicals

D2: Free radical: An uncharged intermediate which has three bond pair and an unpaired electron on
carbon.
Homolysis of covalent bond results into free radical intermediates possess the unpaired electrons.
It is generated in presence of sun light, peroxides or high temperature
Note: (i) It is neutral species with odd e–.

(ii) It is paramagnetic in nature due to odd e–.
(iii) Rearrangement is not observed generally.
(iv) Carbon atom having odd electron is in sp2 hybridised state
(v) Any reaction if it is carried out in the presence of sunlight, peroxide or high temperature it generally
proceeds via free radical intermediate.
 Stability of free radical: It is stabilised by resonance, hyperconjugation and + I groups.

Ex. (a) < CH3– < CH3– –CH3 < CH3– (Stability order)
(b) CH3– > CH3–CH2– > > (Stability order)
(Due to resultant of inductive effect and hyperconjugation, both operates in same direction)
  
(c) (C6H5 )3 C > (C6H5 )2 CH > C6H5 – CH2 > CH2  CH – C– CH3 (Stability order)
|
CH3
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Section (C) : Carbocations
D3: A carbon intermediate which contain three bond pair & a positive charge on it is called carbocation.
Hybridisation: Carbocation may be sp2 or sp hybridized.
Hybridisation Example
sp2 , , ,
sp H2C= , HC
Carbocations are electron deficient. They have only six electrons in their valence shell, and because of
this, carbocations act as Lewis acids. Most of the carbocations are short-lived and highly reactive, they
occur as intermediates in some organic reactions. Carbocations react with Lewis bases or ions that can
donate the electron pair that they need to achieve a stable octet of electrons (i.e., the electronic
configuration of a noble gas):


Because carbocations are electron seeking reagents, chemists call them electrophiles. All Lewis acids,
including protons, are electrophiles. By accepting an electron pair, a proton achieves the valence shell
configuration of helium; carbocations achieve the valence shell configuration of Neon.
Stability: Carbocations are stabilised by
(i) +M effect (ii) Delocalisation of charge (iii) Hyperconjugation (iv) +I effect
General stability order:
> > > >
> > >
Ex. > >
t-Butyl carbocation has +I effect of three Me–groups and also Hyperconjugation effect which makes it
most stable.
Ex. > >
In Benzyl cation, extensive resonance is seen which stabilises C.

In Ethyl carbocation +I and hyperconjugation of Me–group stabilizes carbocation.
In vinyl carbocation stability decreases rapidly since carbon of (CH2) is sp2 hybridized which is slightly
more electronegative hence acts as – I group which increases (+) charge density.
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Rearrangement of carbocations:
Whenever an Intermediate carbocation is formed in reaction it may rearranges.
Only those carbocation will rearrange which can produce more stable species. It can be done either by
(i) Shifting of H, alkyl, aryl, bond (1, 2 shifting)
(ii) Ring expansion (more strained ring to less strained ring)
(iii) Ring contraction
(i) Shifting of H, alkyl, aryl, (1, 2 shift)
1,2 H
(a) 

Shifting
1,2 Me
(b) 
Shifting
1,2 Ph
(c) 
Shifting
+
CH
– 2 1,2 Bond
(ii) Ring expansion: 

Shifting
1,2 Bond
(iii) Ring contraction: 

Shifting
Note: Cyclopropylmethyl cation: In solvolysis of simple primary cylcopropylmethyl systems the rate is
enhanced because of the participation by the -bonds of the rings. The ion that forms initially is an
unarranged cyclopropylmethyl cation that is symmetrically stabilized, that is, both the 2, 3 and 2, 4-
bonds help stabilize the positive charge. Cyclopropyl group stabilizes on adjacent positive charge even
better than a phenyl group.
3

2 1

4 ~ 48% ~ 47%
 ~ 5%
This special stability, which increases with each additional cyclopropyl group, is a result of conjugation
between the bend orbitals of the cyclopropyl rings's and the vacant P-orbital of cationic carbon.

Q. Rearrange (if applicable) the following carbocations into more stable form:
CH3
(a) (b) (c) CH3 – C – CH – CH3
+
CH3
CH3 CH3
–
–
(d) (e) CH3 (f)

+ +
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Carbon free radical Carbocation Carbanion
Shape trigonal planar trigonal planar Pyramidal

Hybridisation sp2 sp2 sp3
No. of electrons in outermost shell 7 6 8
D4: Carbenes (Divalent Carbon intermediates) :

There is a group of intermediates in which carbon forms only two bonds. These neutral divalent carbon
species are called carbenes. Most carbenes are highly unstable that are capable of only fleeting
existence. Soon after carbenes are formed, they usually react with another molecules.
Methods of preparation of carbene :

–HCl –ZnI2
CHCl3 +  : CCl2 CH2I2 + Zn   : CH2

h or  
CH2N2   N2 + : CH2 CH2 = C = O   : CH2 + CO
Types of carbene Singlet Triplet
Shape Bent Linear
Hybridisation sp2 sp
Nature of reaction stereospecific None
State Excited state Ground state
Magnetic Diamagnetic Paramagnetic
Nature Paired electrons Diradical
D5: Nitrenes: The nitrogen analog of carbenes are nitrenes. They are very much reactive since in them
octet of N is incomplete. In nitrenes only one valencies of N are satisfied.
D6: Benzyne : The benzene ring has one extra C–C  bond in benzyne
Clearly, we can see that the newly formed  bond cannot enter in resonance with other  orbitals of
ring. Since it is in perpendicular plane.
It is also important to note that hybridisation of each carbon involved in 'Benzynic bond' is sp2 since the
overlap between these sp2 hybrid orbitals is not so much effective.
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Section (D) : Basic strength
Th2. Bases
D7: (a) Arhenius base: Base is a substance that can donate (or loose) OH– ions in H2O.
D8: (b) The Bronsted Lowry definition of acids and bases:
An acid is a substance that can donate (or loose) a proton, and a base is a substance that can accept a
proton.
Let us consider, an example of this concept, the reaction that occurs when gaseous hydrogen chloride
dissolves in water :
D9: (c) The Lewis definition of acids and bases:

Lewis proposed that acids are electron pair acceptors and bases are electron pair donors.
For example aluminiumchloride, reacts with ammonia in the same way that a proton donor does.
 Cl¯ + H–

(d) Basicity (Kb):
[NH4 ] [OH ]
Kb =
[NH3 ]
pKb = – log Kb
Basicity order in periodic table:
(1) Basic strength decreases down the group,
(2) Basic strength decreases along the period because electron neagativity increases, so electron
donor tendency decreases.
1.1 Aliphatic bases:
(1) On the basis of +I effect basic strength of amines should be 3º > 2º > 1º > NH3
But this order is applicable only when the amines are in gaseous state or in case of non-polar aprotic
solvent.
(2) Basic strength of nitrogeneous compound depends upon the hybridised state of nitrogen
R–CH2 –CH2 –NH2 > R –CH2 –CH = NH > R–CH = CH–NH2 > R–CN
      
  sp3 (localised) sp2 (localised) sp2 (delocalised) sp
(3) More electronegative atom (–I group) will decrease the basic strength
CH3–CH2–CH2–NH2 > CH2=CH–CH2–NH2 > H–CC–CH2–NH2
(4) Cyclic amines are more basic than acyclic amines of same nature
  >
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(5) Amidines are more basic in nature because their conjugate acid are more stable due to resonance.
   

H
 Nitrogen (X) is more basic than nitrogen (Y).
Th3. Basic strength of aromatic amines and substituted anilines:

(a) Aniline:
Lone pair of aniline lies in conjugation with a multiple bond, it resides in ‘2p’ atomic orbital, so that it can
get resonance stabilisation and hence, basic strength decreases. So, Aniline is a weaker base than
NH3.
(b) Pyridine (C5H5N) : 6-electrons, aromatic

 
H
–H
–
 
S.F. : H N: A.O. Diagram:

N
 
– sp2hybrid orbital
–
H H
(localised lone pair)
Lone pair of N in pyridine is localised so it is more basic than aniline.
(c) Pyrrole (C4H5N:) : 6-electrons, aromatic
 
 (lone pair in 2p A.O.)
S.F. : •• N–H (sp2) A.O. Diagram:
  N–H
—
Complete delocalisation of e
Lone pair of N in pyrrole is delocalised in the aromaticity so it is very less basic than aniline.
> > 

N

–
N
–
:NH2 H

H H H
+ + (4e–)
N N ––– sp
3
–
NH3 – H
–
H H
Aromatic Aromatic Non-aromatic
(d) Ortho substituted anilines :

Electron releasing groups (ERG) +M, HC, + increases the Kb and
Electron withdrawing groups (EWG) –m, – decreases the Kb
Steric effect of ortho-substituent in aniline (ortho effect) :
H
–
+
H2N: H–N–H
–
–
G G
H –
–
  (conjugate acid)
ADVGOC-II - 7
(i) Ortho-substituted anilines are mostly weaker bases than aniline itself.
(ii) Ortho-substituent causes steric hinderance to solvation in the product (conjugate acid i.e. cation).
(iii) The small groups like –NH2 or –OH do not experience (SIR) due to small size.
Ex. (a) G = (–M, –); NO2
NH2
–
(Aniline > m > p > o).
(b) G = (–); CCl3

NH2 NH2
NH2 NH2
–
–
–
–
– CCl3
–
CCl3
–
(Aniline > p > m > o).
CCl3
Only (–) decides the order.
(c) G = (– > + m); Cl
NH2 NH2
NH2 NH2
–
–
–
–
–Cl
–
Cl
–
Cl (Aniline > p > m > o)

Only (–) decides the order.
(d) G = (+, HC); If R = –CH3 (Toluidines)
NH2 NH2 NH2
–
–
–
–
CH3
–
+m CH3
+w
HC  more do min ating
(e) G = (+M > –);
Kb order : p > Aniline > o > m
General basicity order :
Th4. Solvent effect in bases :

The trend is not regular in the aqueous state as evident by their pKb values given in Table.
Name of amine pKb Name of amine pKb
Methanamine 3.38 N,N-Diethylethanamine 3.25
N-Metheylmethanamine 3.27 Phenylmethanamine 4.70
N, N-Dimethylmethanamine 4.22 Aniline 9.38
Ethanamine 3..29 N-Methylaniline 9.30
N-Ethylethanamine 3.00 N,N-Dimethylaniline 8.92
Table : pKb Values of Amines in Aqueous Phase (Ref. NCERT)
ADVGOC-II - 8
In the aqueous phase, the substituted ammonium cations get stabilised not only by electron releasing
effect of the alkyl group (+I) but also by solvation with water molecules. The greater the size of the ion
(Alkyl groups are hydrophobic and inhibits H bonding and solvation.), lesser will be the solvation and
the less stabilised is the ion. The order of solvation of ions are as follows:
R H OH2
+|
|
R |
N +
R N H
| |
OH2
|
> > R H OH2 > |
R
20 30
Greater is the stability of the substituted ammonium cation, stronger should be the corresponding amine
as a base.
On the basis of above two sequences, we can say that the basic strength of amines is the combined
effect of inductive effect, steric hindrance and solvation.
R2NH > RNH2 > R3N > NH3 (if R = CH3) ......... (1)
R2NH > R3NH > RNH2 > NH3 (if R = C2H5) ..........(2)
Th5. Reactions of bases :

(i) Nature of aqueous solution: Amines combine with water to form alkyl ammonium hydroxides. This
gives hydroxide ions in solution, thus the aqueous solution of amines is basic in nature.

RNH2 + HOH RNH3OH– [RNH3]+ + OH–
1º Amine

R2NH + HOH R2 NH2OH– [R2NH2]+ + OH–
2º Amine
The aqueous solution of amines behave like NH4OH and gives the precipitate of ferric hydroxide with
ferric chloride.
3RNH3OH + FeCl3  Fe(OH)3 + 3RNH3Cl
Brown ppt.
(ii) Aliphatic and aromatic amines form salt because of their basic nature:
 –
RNH2 + H2O  RNH3 OH
Alkylammoniumhydroxide
 –
RNH2 + HCI  RNH3 CI
Alkylammoniumchloride

RNH2 + H2SO4  ( RNH3 )2 SO4–2
Similarly we get
 –
C6H5NH2 + H2O  C6H5 NH3 OH
Aniliniumhydroxide
 –
C6H5NH2 + HCI  C6H5 NH3 CI or C6H5NH2 : HCI
Aniliniumchloride Anilinehydrochloride
Salts of amines are ionic compounds and hence water soluble.
ADVGOC-II - 9
Section (E) : Acidic strength
Th6. Acids
D10: (a) Arhenius acid: An acid is a substance that can donate (or loose) a proton in H 2O.
D11: (b) The Bronsted Lowry definition of acids and bases:
An acid is a substance that can donate (or loose) a proton, and a base is a substance that can accept a
proton.
Let us consider, an example of this concept, the reaction that occurs when gaseous hydrogen chloride
dissolves in water :
Hydrogen chloride, a very strong acid, transfers its proton to water. Water acts as a base and accepts
the proton. The products that result from this reaction are a hydronium ion (H 3O+) and a chloride ion
(Cl–).
The molecule or ion that forms when an acid loses its proton is called the conjugate base of that acid.
(The chloride ion is the conjugate base of HCl). The molecule or ion that is formed when a base
accepts a proton is called the conjugate acid of that base.
D12: (c) The Lewis definition of acids and bases
Lewis proposed that acids are electron pair acceptors and bases are electron pair donors.

(d) Acid dissociation constant (Ka) :

RCOOH + H2O RCOO– + H3O+
[RCOO  ] [H3O  ]
Keq =
[RCOOH] [H2O]
[RCOO ] [H3O ]
Ka =
[RCOOH]
pKa = – log Ka
6.1 Relative acidity of hydrocarbons :
Being most electronegative the sp hybridised carbon atom of ethyne polarizes its C–H bond to the
greatest extent causing its H to be most positive therefore ethyne is most acidic hydrocarbon.
HC  CH > H2C = CH2 > H3C – CH3
6.2 Acidity of phenols :
The phenoxide ion is more stabilised by resonance than the unionised phenol.
Groups which are –I, –m increases acidic character of phenol because effectively dispersing the
negative charge of phenoxide ion. Alternatively + I and + m groups decreases acid strength.
Ex. (a)
Ans. Acid strength order : I > II > IV > V > III
ADVGOC-II - 10
Sol. Step-1. III will be least acidic as it has no dispersion of negative charge (No delocalisation of negative
charge).
Step-2. Since –I, –m group will increase acid strength, Nitrophenol will be most acidic followed by
phenol,
Step-3. Amongst cresol and methoxyphenol, methoxyphenol has +M effect of –OCH3 which increases
e– density hence decrease acidic strength
Ex. (b)
Ans. Acid strengh order: I > III > II > IV

Sol. Step-1: Notice that CH3 have +I effect so all methylphenols (cresols) are less acidic than phenol (I).
Step-2: Now amongst cresols p- and o-CH3 are increasing the e– density due to their hyper conjugation
but ortho isomer has viable +I effect also, which will help in destabilising phenoxide ion therefore o- is
least acidic. Since at meta position only +I works it as least e– density amongst the cresol.
Ex. (c)
Ans. Acid strength order: II > IV > III > I

Sol. Step-1 : In nitrophenols –I effect of NO2 will help to increase acidic strength hence phenol is least acidic
amongst all nitrophenols
Step-2 : Only –I effect is applicable in meta nitrophenol it will be number three. Now –o, –p have both –I
and –m effect of NO2 group over OH and in this particular case para isomer is more acidic than ortho
since
H is trapped by NO2 group.
Table : pKa values of some phenols and Ethanol. (Ref. NCERT)

Compound Formula pKa Compound Formula pKa
o-Nitrophenol o–O2N–C6H4–OH 7.2 o-Cresol o-CH3–C6H4–OH 10.2
m-Nitrophenol m–O2N–C6H4–OH 8.3 m-Cresol m-CH3C6H4–OH 10.1
p-Nitrophenol p-O2N–C6H4–OH 7.1 p-Cresol p-CH3–C6H4–OH 10.2
Phenol C6H5–OH 10 Ethanol C2H5OH 15.9
From the above data, you will note that phenol is million times more acidic than ethanol.
6.3 Acidity of carboxylic acids :

Conjugate base of carboxylic acid exists as two equivalent cannonical structures (A) and (B). This ion is
resonance stablised and resonance hybrid structure is (C).
Electron withdrawing group (–M, –I effect) increases acidic nature.

Electron releasing group (+M, +I effect) decreases acidic nature.
ADVGOC-II - 11
Ex. (a) F–CH2–COOH > Cl–CH2COOH > Br–CH2COOH > I–CH2COOH
Cl Cl
(b) Cl – C – COOH > Cl – CH – COOH > Cl–CH2COOH > CH3COOH
Cl
(c) HCOOH > CH3COOH > CH3–CH2–COOH
COOH
(d) COOH > CH2 > CH2 – COOH
COOH CH – COOH
COOH 2
The effect of the following groups in increasing acidicty order is [Ref. NCERT]
Ph < I < Br < Cl < F < CN < NO2 < CF3
Thus, the following acids are arranged in order of decreasing acidity (based on pK a values) :
CF3COOH > CCl3COOH > CHCl2COOH > NO2CH2COOH > NC–CH2COOH > FCH2COOH >
ClCH2COOH > BrCH2COOH > HCOOH > ClCH2CH2COOH > C6H5COOH > C6H5CH2COOH >
CH3COOH > CH3CH2COOH
6.4 Comparison between two geometrical isomers :
Maleic acid :
Fumaric acid :
Now K1m > K1f

Since the conjugate base is stabilised by intramolecular H bonding.
But K2f > K2m Since in maleate ion, after donation of H two –COO groups faces each other and
makes system unstable. In fumarate ion this repulsion is minimised.
6.5 Acidic strength of substituted benzoic acids :

Formic acid is more acidic than benzoic acid while phenyl acetic acid is more acidic than acetic acid.
HCOOH > PhCOOH > >
Electron withdrawing group attached to benzene ring will increase the acidic strength while electron
releasing group decreases acidic strength.
If electron donating group present at para position than it is always less acidic than benzoic acid.
> > > >
Also it is less acidic then meta substituted benzoic acid.
> >
ADVGOC-II - 12
On the other hand if e– withdrawing group is present at meta position then it is more acidic than benzoic
acid.
> > > >
Th7. Ortho effect :

D13. It is common observation that generally ortho substituted benzoic acids are more acidic as compared to
their isomers and benzoic acids itself. This is called ortho effect (which is combined effect of steric
hindrance, crowding & electronic effect) in benzoic acid. However exceptions are seen.
Ex. (a) > > >
(b) > > >
COOH
COOH
(c) > > >

NO2
NO2
(d) > > > >
(e) > > >
(f) >
OH OH OH
NO2 NO2 NO2
(g) > >
O2N O2N NO2
NO2 NO2 NO2
(picric acid)
ADVGOC-II - 13
Section (F) : Feasible reactions of acids and bases
Th8. Reaction of acid with salt:
(1) NaX + HY   NaY + HX
Salt of Weak acid Strong Acid
Remark: A stronger acid displaces the weaker acid from weak acid metal salt. The weaker acid is
released out as a gas or liquid or precipitates out as a solid. The weaker acid cannot displace the
stronger acid from the salt.
1. 2 NaCl + H2SO4  Na2SO4 + 2HCl
2. Na2SO4 + 2HCl  No reaction
3. CH3COONa + CH3SO3H  CH3COOH + CH3SO3Na (feasible)
4. CH3COONa + PhOH  PhONa + CH3COOH (not feasible)
Section (G) : Tautomerism

Th9. Tautomerism
D14: Definition :
Tautomerism is a phenomenon by which a single compound exists in two or more readily
interconvertible structures that differ in the relative positions of at least one atomic nucleus, generally
hydrogen.
These two isomers remain in dynamic equilibrium and can be isolated also give different lab test.
Conditions :
1. Usually present in the following functional groups
2. Basic need for its existence is attachment of these groups with the sp 3 hybridised C-atom having
atleast one hydrogen atom as –
To get tautomer of above structures -hydrogen atom is shifting to more electronegative atom attached
to double bond (i.e. hydrogen atom from 1st atom to 3rd atom) and double bond is developed between
1,2-atom from 2,3-atom. This can be represented as:
These two forms (remain in equilibrium) are called tautomers of each other. The interconvertibility of
tautomers is a chemical reaction which involves making and breaking of bonds.
O OH
|| |
Ex. (a) CH3  C  CH3 CH2  C  CH3 (b)
( I) ( II)
(c) (d)
ADVGOC-II - 14
Th10. Keto-enol tautomerisation :
10.1 (A) Base-catalyzed enolization :
Protonation of the carbanion by water on the -carbon gives back the carbonyl compound. Protonation
on oxygen gives the enol. Notice that the enolate ion is the conjugate base of both the carbonyl
compound and the enol.
(B) Acid-catalyzed enolization :

Involves the conjugate acid of the carbonyl compound. Recall that this ion has carbocation
characteristics. Loss of the proton from oxygen gives back the starting carbonyl compound; loss of the
proton from the -carbon gives the enol. Notice that an enol and its carbonyl isomer have the same
conjugate acid.
10.2 % Enol content in the carbonyl compounds :

(a) For monocarbonyl % Enol is very less
(b) Enol content increases with increase in the stability of enol by resonance, hyperconjugation,
hydrogen bonding etc.
Decreasing order of enol content for above carbonyl compounds is : 3 > 2 > 1.
(c) For a carbonyl compound having active methylene group percentage of enol content will be more
because enolic form has intramolecular H-bonding and also it will be stabilised by resonance.
ADVGOC-II - 15
(d) If active methylene group is more acidic then enol content will be more.
For example in acetyl acetone enolic content is 75–76% while it is 7–8% in

acetoacetic ester because ester group shows less electron withdrawing nature than keto group.
(e) Percentage of enol content is more in non-polar media while % of keto form is more in polar media.
Th11. Racemisation and D-exchange :

Exchange of -hydrogen from deuterium as well as racemization at the -carbon are catalyzed not only
by bases but also by acids due to the phenomenon of tautomerisation.
1. (D-exchange)
2.
3.
Th12. Other examples of tautomers (not to be done in class only for the
reference of students)
(a) Imine-Enamine system :
R2CH – CR = NR
Imine
Among these two tautomers, enamines are stable only when there is no hydrogen on the nitrogen,
otherwise the imine form predominates.
(b) Nitroso-oxime system:
Like primary and secondary nitro compounds, primary and secondary nitroso compounds also exhibit
tautomerism with their more stable isonitroso or oxime form.
NO
|
CH3 – C – CH3
; CH3 – CH – CH3 ||
2-Nitrosopropane
NOH
Acetoneoxime
(c) Nitro-Acinitro system:
The acidic nature of the nitro compounds gives rise to the belief that the nitro compounds exist in two
forms, a more stable or normal nitro form and the less stable acinitro form.
ADVGOC-II - 16
R – CH2 R – CH
| ||
N N
O O HO O
Nitroform Acinitroform
The stability of the nitro form is more as compared to the acinitro form because it is stabilised by
resonance.
O OH
C6H5 – CH2 – N C6H5 – CH = N
Nitroform O Acinitroform O
(d) Lactam-Lactim system :

O OH
|| |
O O C C
; NH N
N O N OH SO2 SO2
|
H
CHECK LIST
Definitions (D) Theories (Th)
D1 : Carbanion 
Th1 : Reaction intermediates 
D2 : Free radicals  Th2 : Bases 
D3 : Carbocation  Th3 : Basic strength of aromatic amines and
D4 : Carbenes (Divalent carbon intermediates)  substituted anilines 
D5 : Nitrenes  Th4 : Solvent effect in bases 
D6 : Benzyne  Th5 : Reactions of bases 
D7 : Arhenius base  Th6 : Acids 
D8 : Bronsted base  Th7 : Ortho effect 
D9 : Lewis definition of acids and bases  Th8 : Reactions of acids with salts 
D10 : Arhenius acid  Th9 : Tautomerism 
D11 : Bronsted acid  Th10 : Keto-enol tautomerisation 
D12 : Lewis definition of acids and bases  Th11 : Racemisation and D-exchange 
D13 : Ortho effect  Th12 : Other examples of tautomers 
D14 : Tautomerism 
ADVGOC-II - 17

GOC-intermediate and Application

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General Organic Chemistry-II

Applications of electronic effects:

Heterolytic fission of covalent bonds:

Heterolysis of a bond normally requires polarized bond.

Section (A) : Carbanions

sp2 H2C= , CH2=CH– ,

Examples of stability order:

Section (B) : Carbon free radicals

It is generated in presence of sun light, peroxides or high temperature

Note: (i) It is neutral species with odd e–.

 Stability of free radical: It is stabilised by resonance, hyperconjugation and + I groups.

(b) CH3– > CH3–CH2– > > (Stability order)

> > >

Ex. > >

Ex. > >

In Benzyl cation, extensive resonance is seen which stabilises C.

(d) (e) CH3 (f)

Shape trigonal planar trigonal planar Pyramidal

D4: Carbenes (Divalent Carbon intermediates) :

Methods of preparation of carbene :

Types of carbene Singlet Triplet

Shape Bent Linear

Nature of reaction stereospecific None

State Excited state Ground state

Magnetic Diamagnetic Paramagnetic

Nature Paired electrons Diradical

D9: (c) The Lewis definition of acids and bases:

(d) Basicity (Kb):

 Nitrogen (X) is more basic than nitrogen (Y).

Th3. Basic strength of aromatic amines and substituted anilines:

(b) Pyridine (C5H5N) : 6-electrons, aromatic

> > 

(d) Ortho substituted anilines :

  (conjugate acid)

(b) G = (–); CCl3

Cl (Aniline > p > m > o)

Kb order : p > Aniline > o > m

General basicity order :

Th4. Solvent effect in bases :

Th5. Reactions of bases :

(d) Acid dissociation constant (Ka) :

Ans. Acid strength order : I > II > IV > V > III

Ans. Acid strengh order: I > III > II > IV

Ans. Acid strength order: II > IV > III > I

H is trapped by NO2 group.

Table : pKa values of some phenols and Ethanol. (Ref. NCERT)

6.3 Acidity of carboxylic acids :

Electron withdrawing group (–M, –I effect) increases acidic nature.

6.4 Comparison between two geometrical isomers :

Now K1m > K1f

6.5 Acidic strength of substituted benzoic acids :

> > > >

Also it is less acidic then meta substituted benzoic acid.

> > > >

Th7. Ortho effect :

Ex. (a) > > >

(b) > > >

(c) > > >