Applicationsof Electron migration effect

I. Stability order of carbocations :

+

i) CH, -CH > CH,-CH-CH, >CH,CH, CH,

CH,
CH, CH,
ii) tCH,
(3°+ Reso+ (2°+Reso + (1°)
hyper) hyper)
+

iii)

(3° + Reso) (2° + Reso)

(3°)
 Ex: ix) CHEMISTRY-N
CH, CH, CH
(2°) (1°)
CH,

NO, CI
CH,
iv) (-M) (-I) (+1) OCH,
CH, () (II) (II)
(+M)
(IV)
Stability order : IV > II> II>I
Ex: x)
CHO NO, CH, CH,
CH, CH,
-NO2
() (I) NO
NO,
(I)
(IV)
(on increasing size of ring from 3 - 6 stability
increases) Stability order: IV >I>II>I
CH, CH, CH, Ex: xi)

CH,
vi) CH, ÇH, CH,
3o 2° 1° OH

OH
CH, +
(I) OH (IV)
CH, (II)
Vii)
-CH, > Stability order: II >I>IV>II
Cyclopropylmethylium ion CH,
i) These carbocations are very stable
viii)
NH carbocations. They are more stable than benzyl
carbocations.
nitrogen Oxygen
is better is poor i) Stability of cyclopropyl methyl carbocations
donor donor increases with every cyclopropyl group. Thus
Aromatic carbonium ion additional cyclopropyl group has commulative
additive effect on the stability. Thus
CI
ii) The special stability is a result of conjugation
between the bent orbitals of the cyclopropyl ring
and the vacant - p - orbital of the cationic carbon.
more stable less stable This type of bonding is called as banana bonding
aromatic anti - aromatic or bend bonding.
52 DOCTORS SERIES for Jr. Elite Students
 CHEMISTRY-ID

R R
RN
R
CH, = R RN H HN H
3° amine 2° amine 1° amine
This order is true in vapour phase or non
polar aprotic solvent,
Actual order of basic character is
CH, 2° >1°>3° (ifR is - CH,)
CH-CH,>CH, 2°> 3° >1° (if Ris- C,H,)
thus experimental data of basic strength order will
II. Relative strength of bases: be combined effect of:
Base strength is defined as the tendency to Inductive effect
donate an electron pair for sharing. The +Ieffect Steric effect
increases the electron density while I effect Solvent effect
decreases. So, more is the tendency to donate Basic strength of amines :
electron pair for coordination with proton, the more Basic strength of amine depends upon
is basic nature, i.e., more is the negative charge on hybridized state of nitrogen
nitrogen atom (due to +I effect of alkyl group), the
more is basic in nature. sp (N)>sp (N-localised) > sp (N-delocalised)
CH,CH, -NH, > CH, -CH = NH>
H CH3 ÇH¡ CH¡ H linked to sp'c
H-N: H-G: H-N: H,C+N: CkN: through double bond
H H H, H CH, =CH- NH, > CH, -C=N
linked to spc
Thus, the basicnature order is: through single bond)

(C,H,),NH> C,H,NH, >CH,NH, >NH, -

Aliphatic amines> Ammonia > Aromatic
amines. H

N
R+NH, > -NH, >
On other hand if alkyl part of primary amine (least basic)
is tertiary butyl then ammonia will be more basic
that tert-butyl amine due to steric hinderance in sl NH,
protonation caused by bulky nature of tert-butyl
group

CH, H CH, H
H,C-C-NH, <NH,
CH,
CH,CH,NH, >CH, = CH- NH, »0=
1
On the basic of +I effect basic strength of amine CH- NH, >0=CH- NH-CH=
should be as follows: CH, >0= CH- NH -CH=
GENERAL ORGANIC CHEMISTRY 53
 -NH Basic strength order CHEMISTRY-4D
NH > Basic strength c H° accepting tendency
c lone pair donating tendency
+M, +I
NH -M, -I)
C=0 NH Ex: i)
NH,
Cyclic amines are more basic than -CH,-NH,
amine of same nature due to more compact acyclic I II
structure. l.p is involved in No resonance of l.p
resonance maximum basic
NH -CH,
Amidines are more basic than 20 amine
because its conjugate acid is resonance stabilized. III
1.p is involved in resonance and stabilised
NH H
CH, by +I of CH, group
NH, Basic order: II >III> I
(Amidine)
Ex: ii) NH,
CH, -C NH, ’CH,-C NH, H
NH, NH, III
Guanidines are further more basic than Resonance Localised l.p Localised L.p
amidine because its conjugate acid has more stabilised on more E.N on lessE.N
resonating structure. Basic order : III >II>I
NH Ht
H,N -C
NH, -NH,
(Guanidine) Ex: iii)
H
II

H,N
NH, NH,
I
More resonance of l.p Less resonance of
-NH, H,N-c less basic
NH, Basic character :I<II
1.p more basic

H,G-cNH,
NH,
Aniline is less basicthan ammonia because
i.p. of e- present at N atomn in aniline will conjugate Ex : iv)
H
with es of benzene ring as a result e density at
n atomn is decreased and basic strength is also l.p on more E.N, More - I of oxygen
decreased.
minimum basic
54
DOCTORS SERIES for Jr. Elite Students
CHEMISTRY-ID

NH, NH,

H
III H CH, IV
IV
II
+I Less - I of N +R and +I
Basicorder : II > IV > II>I
Basic strength order: III > [V > II>I
NH, NH, NH,
NH,
MeN Me Me N Me Me N Me
Ex: v)
Me Me Me
NO, CI
CH, OCH,
-M III IV SIR
-I -I -I, +M
+ 1, HC
lone pair localised due to lone pair
Basic strength order : IV >II> I>I steric inhibition of resonance delocalised
NH, IL. Acidic strength of substituted benzoic acid:
NO. NH,
It depends upon
Ex: vi)
1) Inductive Effect : Operative at all positions
II
NO, 2) Mesomeric effect :Operative at ortho and
SIP -I para position
- M and -I
3) Hyperconjugation :Operative at ortho and
NH, para position
NH,
Ortho effect : Ortho effect occurs when a
group present in the ortho position with respect to
NO, IV
carboxylic group creates steric strain resulting in
III rotation of the carboxylic group and shifting it out
- M and -I
of plane of the benzene ring. Thus the carboxylic
group can no longer participate in ring resonance
Basic strength order: IV > II> III>I
and thereby the acidity increases as delocalisation
NH, of negative charge on the conjugate base of the
NH, acid is improved. It is called Ortho effect.
NO, CH, Note:SIR means steric inhibition of resonance
Ex: vii) 4) Steric Effect:Operative at ortho position.
SIP II Larger the ortho substituents, greater will be
-M and -I +1 (SIP) ortho effect and more acidic will be
(SIP- steric inhibition of protonation) compound
GENERAL ORGANIC CHEMISTRY
55
e.g.
COOH COOH
COOH
CHEMISTRY-4D
COOH
C(CH)3 CH(CH;),

COOH COOH NO, IV

1) III
CH,CH3 CH,
-Iand -M
Acidicorder : I > III> II> IV
COOH COOH COOH COOH
COOH COOH COOH
Br C

COOH COOH COOH COOH Ex: ix) NO, CI

o)E
CCl, -M II
-I -I

CCl, CCls COOH COOH

Considering reverse hyperconjugation for
above example
4) COOH COOH COOH COOH COOH
CH, OH
IV V
+I +M
+ H.C
NO, CI H CH, OCH,
-I

5) COOH COOH COOH

Acidic order : I >I> II> IV>V

COOH COOH
OCH,
NO2 OCH3 Ex: x)
COOH COOH
OCH,
Ortho effect
H CH, COOH
COOH
COOH COOH

NO,
Ex : viii) OCH,
III IV
NO, -Iand + M
Ortho effect -I Acidic order : I> II> IV> II
56 DOCTORS SERIES for Jr. Elite Students
CHEMISTRY-ID
a) OH OH OH OH OH
Ex :xi)
COOH
COOH
CH3
NO, CI H CH, OCH,
CH3
OH OH
OH
Ortho effect +1

COOH b
COOH
NO2 Ci OCH3
OH OH

H3
II
IV
H CH,
+I and +R Acidic character:
OH
Acidic order :I > IV> II> III OH
NO,
Ex: xii) Ex: xiii) NO, NO,
COOH COOH
COOH COOH
NO, NO,
I II
Maximum -M and
X
II III IV -Ieffect, more acidic
Ortho effect - I(more) -I(less) OH
OH
Acidicorder :I >II > III>IV
IV. Halo Substituted Phenol: Chlorine group NO:
attached to benzene ring as well as trichloromethyl
group attached to benzene ring will show -I effect III IV
only. Acidic order : I> II> Il>IV
Acidicstrength : Stability of carboanions :
Ex : xiv)
OH CL OH OH OH

CI II II

OH OH OH Resonance More resonance Localised

OH
CCl, stable stable -ve charge
Stability order : II > I> II
CCl,
CCl,
Acidic stength of phenol having different &H,-NO, CH, -CH, - NO,
II
substituents at para and mneta phenol. Resonance stabilised No resonance

GENERAL ORGANIC CHEMISTRY 57

 CH,-H-NO,
III
Resonance stabilised but +I of CH,
Stability order: I >II>II

CH,

Resonance stabilised Resonance stabilised

and + IE

CH,
III
Resonance stabilised and more +I
Stability order: II>>II
Stability orders of ions :
R-C-OH > R-C=0-H>R-C-OH

Complete octet Complete octet Incomplete

non polar polar Octet

R-C-OH > R-- OH

Less EN atom with More EN atom with

incomplete octet incomplete octet
R- =Ô: < R-C=9
incomplete octet Complete octet
CH, =CH-0 > CH, -CH =0
-ve charge on more EN -ve chargeon less EN
Tautomerism :