General organic chemistry I GOGI

Electronic effects

Organic reaction Breaking of old bonds and formation

of new bonds is called reaction

Types of bond dissociation fission for covalent bond

Homolytic bond fission neterolyticbond fission

is Equal partition of shared is unequal partition of

pair of electrons b w shared pair of electrons

constituent atoms Ex Ei Bst A Bt

EB

Ex s Ao t Bo Anion cation

CENA ENB

ENA EAB free radicals

il The process is also

fill The process is also known as Heterolysis

known as Hemolysis

Ciii conditions

Iii Conditions It occurs when there is large

a By heating1hightemp difference in electronegativity and

D

Ex CPI 240 favored in solventphase where

ions formed are stabilised

b By Uv radiationChy

nor hV by solvation

EX Ct I 240
o H

Ex As Bs H2O of SH

C By peroxide
as S
H
St
th tht oy
l

O
R O O R 2 R OO
Alkoxide n's t
se se

H H 1

weakbond due µ

to e e repulsion radical
 H H
O
HlsO Bi t o
H
th ios H
f µ
Note it solvation hydration is always exothermic process
stabilising Lit Higher
iil Extent of solvation Charge charge
Tze densi
Nat

Types of organic reagent

1 Electrophile or electrophilic species
Electro electron
philic loving
e loving species
it e deficient species which can accept a pair
of electrons
Ii Electrophiles are generally Lewis acid
Ex cationic electrophile Et Neutral electrophile E
Ht Clt Brt It Not BHz Bfs Bcb BBB CHz
NOE Itb Ctf E o cuz Incomplete octet
etc 2nd z Feltz feBrz
03 PU
vacant dSorbital

2 Nucleophile or nucleophilic species

nucleo nucleus
Nucleusloving species
philic loving
it erich species having at least one unshared
pair of electron
 Ii Nucleophiles are always Lewis base
Ex Anionic nucleophile Nii Neutral nucleophile Nu
tr Ct Br Nui on R o eh Nig R titty HzO R IH
Ctb H R IH etc

3 Free radicals Electron deficient species having

unpaired electron Codd e
Ex Eng H Clo Bro R Oo et

Ht TN
Note i NtHq Hoot Nat are not electrophiles Wttg Hq
4bond 3bond

iil An electrophile always reacts with forms bond a

nucleophile and a nucleophile always reacts with
forms bond an electrophile
But a free radical reacts with forms bond with
another free radical only

Electronic effects or Electron displacement methods

in organic chemistry
The effects which arises due to electronic distribution
are called electronic effects

Permanent Effects Temporary Effects

it Inductive effect Electromeric effect
in Resonance I Mesomeric effect
in Hyperconjugation

Inductive effect I effect

c c c C No polarity as there is no
difference in electronegativity

c SSE
3
SET
Z I
E EN x END
4 EN s character
Sss s St
c C sss
Caccay EN Y L ENT EN Ct c c
4 3 2 1

Inductive effect can be defined as permanent

shifting of Sigma electrons in a carbon chain
due to a dipole polar bond

add

feted
Toto
 I

Types of Inductive effect

I
St St St s s s S
C C Css C sci C C C C ca

I I EWG I EWG I EDA

EDU Electron withdrawing Electron donating
group group
Nole Hydrogen is taken reference for defining I and
as
I and inductive effect of H is assumed as zero

a I The groups which withdraw electron

effect
clouds EWG are called as I groups and
their effect is called I effect
T
vent
MIT
glint
sp sp

i NEO s R N
O 11 Sp Sp
0
sp2 O
il E
sp2
H DIR
SPL Spz
Eton
I M

iii CECH NH SF CH CHz H

Spa Spa Spa Spz

EN Nsp2 Csp Nsp3 Gp2 Csps

1
Electropositive
b I effect The groups which releases electron clouds
EDA are called as I groups and their effect
is called I effect

zofH3 zo
k Ctb
Ct ectlecttz
la
CHz CHS
No ofSPIT

to I also 9

il o doo
e density is dispersed

ii I T D H
3
H H in
EN H D T
Ip Ipt In Ipt 2N EN
n n C
I CHz C CD L CT
V H
D
V T
S St S St S St
BDE C H C D C T
Max difference in E N

Q Indicate the direction of Inductive effect

1 Hz CHICHI COOH
I

2 Hz Ct CHE CHE Coo

I
 S St
3 HzcLCHECHzmg.BY
I
Hz t I
u
4 r
u

v
Moz I I

Resonance
conjugation
1 HzC CHz Ethene
Sp2 sp2
Pz Pz
H P P H
ng i Molecule is plainer
ay
plane L n
C
ff
C
ff n plane i a e are localised

PzPz
PzPz
2 Hzf qH gH qHz Butadiene
sp2 sp2 spa sp2

H P P HA B Iz
P P
fBe f
n
n
C C4
rPz n
s
f f H

e e repulsion Pz
H P Pz
C CH
n
W f
ne E
n

f n
 HI I CH OH
2 3
OH
4
HI OH OH Eth
HI CH OH EH

lil A e are delocalised and this type of delocalization

of the is called conjugation

til Delocalization of ae is always stabilizing

phenomenon as it decreases e e repulsion

iii P orbitals participating in conjugation must be

parallel to each other for proper overlapping

Sp3
3 tbc ch Ah OH Chez is Not a conjugated system
Spr Spr SP SP
in a e are localised
1 t

4 sp Ba e s e s conjugated system
S 3
4 d t

Sp3
it Not a conjugated system
l a e are localised
gp

1 I

G
6
L
2
c
G 2 complete cyclic
All C s r 3 5 3 Conjugation
4 4
sp2 it e are delocalised
 it
6 z

S 3
p
4

PzPz PyPy
H Hzc1 c2 Mz 3
Allen
sp2 SP sp2
i Both the T bonds are 1 to each other

iil conjugation is not possible a e are localised

Types of conjugation
a A a conjugation Alternate in bonds with parallel
p orbitals
A five conjugation Alternate Tn bonds and ve

charge with parallel P'orbitals

ex the ch Cha
spa sp2 Osp vacant p orbital

t
HzCI Ch
2
Ith
3 z HII CH CHz
2 3
I l l l
A A
donor acceptor the
charge is delocalised

ex CHEM cuz cuz ve charge is localised

Sp3
 I a Eve conjugation Alternate n bonds and ve

charge with parallel P'orbitals

0
a
ex HzCI OH
2
OH
3 X
complete octet

v
HzC OH oh
3
e HE CH CHz
il 12
a a re charge is delocalised
acceptor donor

4 a lip conjugation Alternate in bonds and lp

with parallel P'orbitals
Complete octet
A
ex HzC
I
OH
I I
EHI HE CH OH
A A
acceptor donor

it odd electron conjugation

freeradical
n N o
ex HzCI OH OH Had CH ICH
2 3

Q No of delocalizing a electrons
Sp
1
localised Gre

a
2 2n e
t
 A v
NtHz
3 Hac CH NHz HI CH Line

Note delocalised lp are considered as delocalising

a electrons

Resonance The phenomenon of delocalization of

A electrons or non bonded electrons in a conjugated
system is called resonance

RS

A 1.59 13 0
pair 39g
6 2 n
Ex 4 a s I
l 1 OR
E 4
D i

Equivalent RS BO I53

Equally contributing Resonance Hybrid

Ex 21
Allyl carbocation
t
them
I 2
OH
3
theI cu
2 gu ni'E cn En
Equivalent RS RH

31 Allyl Carbanion

He I CHEEK
2 3 the a cuz HIE cu HE
Equivalent R S RH

41 vinyl chloride
A o S St
HzC CHIC c HE CH CT Hz CH Cl
Non Equivalent RS RH

S1 Benzyl carbocation

GHz CHz CHz CHz

I
t
c s e s

t a
Non Equivalent RS v
t
St CHz
GHz
I
St s i St
I l
I l
I
St
RH
 2
6 Coz
O O O
C L c c
C z C
O O 0
o o
111
Equivalent Rs z
O3
B 0 1.33
f i
O Z
3 0
RH
7 03
t t
t 0 Oi
t O
n c O i i
0 Ot O LO
2
O I
2
R.H
Equivalent Rrs
8 R Coo
I
70 O OZ
i
c s
I I
C L c C O I
R O R
R O 2
RH
Equivalent Rs

9 R COOH
70 O o
I
C L C t E
R GH R OH r
C ftH
Non Equivalent RS RH

v
10 Hrc
v
CH CH _CHz a Het CH CH CHI s

Hz OH HzE CH OH EH
THEY
 A Draw all Rs and RH
M 4 Hac CH OH 5

504 21
Hac CH Enz 61 SOE
CHz
7 NOT
3
8 C
10905
9

N'Hz lol
4

soil nm
2 Hac CH Cth the OH OH Hz Ch
Off
Equivalent Rs

jfo
A
eogdgko o gfao so iio.to
Equivalent Rs
 Rules of Resonance
4 For resonance system must be conjugated with all
the p orbitals participating in conjugation parallel
to each other
Ex
Pz Pz Pz Pz
i Hf CH a CH _CH z e s

Pz Pz
Pz
i In cyclic compounds All the atoms
participating in resonance must
Pz
be Coplaner

Pz Pz
All the p orbitals are parallel

o
CHz CHz CHz
iii s
np
Ct and co are
in conjugation
Benzyl Benzyl Benzyl with ring
Carbocation carbanion free radical

H
to
H
Pz Pz sp2
 t o
µ sp2 sp2 SP Ct C and o are

not in conjugation
with ring
Aryl Aryl Aryl
carbocation carbanion free radical

the vacant orbital is L to

the p orbital carrying a electrons
v
sp2hybrid
orbital
Pz
PyPy t
v Hac CH CHz HzC CHIC H
O sp2 Spx
carbocation vinyl carbocation
Allyl ve charge is localised
2 All the Rs must be valid Lewis structure that
means no violation of octet rule for 2nd period
elements

Ex i HzC CHINtHz e s Hz'T CH NHz

v
5bond
complete octet
No vacant orbital

3 In All Rs the relative position of all the atoms

must remains same
 Ex 19 GOH OH
Hsc C H Hac d H Hic Id H
Il NCI CHI
1
Not a R S of II 4 III RS

4 All the RS must have equal no of unpaired e

hence equal no of paired electrons

Ex No of unpaired e

II Hac CH CH CHz O

III Hac CH CH CHI o

NII HzE CH CH Cttz O

HI HE CH CH EHz 2
Not a valid RS contribution is zero

5 All the R S equivalent and if non

Should be

equivalent then difference in P E Should not be

large
Ex HzC CHICHI e s HzCt CH CH O e
I II
v

Highly unstable and HE OH cu o1

u
not considered as valid
Incomplete
Rs contribution not octet
V v
v v v
Note O CIN CEN NEO 5 0
 stability of Rs sequence
11 Generally neutral structures are more stable than
charged structures
Ex 0 O
Ell
R C
f
H
a
R C
I t
OH
I I
I II

2 RS with more no of covalent bonds a bonds

are more stable because energy is released
in formation of covalent bond
Ex A
lil Hac CH CH CHz s x Hed CH CH Ete e x
I II

I IT IT HzE OH OH IHz
HI

ii Oth a He CHIEH
Hse Hye II I
III III
Incomplete octet

3 A Rs in which all the atoms have complete

octet is more stable

Note Generally rule e Coincide with each other

4 A Rs in which re charge is present on more

electropositive atom and ne charge is present

on more electronegative atom is more stable
 Ex o o more stable
S I
i Hz I I H HzC c H II I
III III

Ii H C ETO c CEE II I
III III
Incomplete
octet

5 for charge separated Rs

a separation of opposite charges decreases stability

as energy must be supplied to put the opposite

charges at distance

b separation of similar charges increases stability

Ex 2 4 6
I 3 5
v y s y
v
I III n

x
I IT Ill

HI

Q Arrange stability order for Rs

O O t
N t s 0 O
t N e y
t d t
N s x N
O O
FI II HI O III a
EWG
I II 111 IV
Note it ne charge adjacent to Ewa stability decreases

iil the charge adjacent to Ip or EDG stability

increases

iii ne charge adjacent to Ip or EDG stability

decreases
iv ne charge adjacent to Ewa stability increases

Q Which of the following is least contributing Rs

least stable
X A cry _cm cm cm cry
x ciy cn ou cn.tochg
A B D C

ite ch cu ai ai ay
D aka ch ut est Ochs
attraction

Resonance Energy R E
Delocalization of A e or non bonded electrons always
decreases potential energy of the molecule and increases

stability
The difference in P E of most stable RS and
R H is called as resonance energy CRE
 s RS

pE Resonance energy of benzene

RH
152 KI Moy
v

al RE is not stored in the molecule It is the energy

which is released because of resonance

Greater the R E means more stabilization due to

resonance

R E depends on extent of resonance Greater the

extent of resonance higher the R E

Extent of resonance

1 CII u
e s
t t

II e s
ya V

RE I I

or More the no of Rs higher the extent of

resonance In similar type of molecule
2 Size and electronegativity of donor atom
is IT cnj cnZp N.kz e s Hic OH DHe

AI
2 Af
CHEM EH Hic OH EH
RE I II

2p 2p
In same period variation in size are small and
electronegativity is the dominating factor

Nitz is better a donor than OH

n
ii I Check un H e s Hic ch_EH
Zp Zp RE I II

Il
n f FH
cuz Ch IH s HIC est
Zp 3p
In same group variation in size are large and
dominates over electronegativity
EH group is better a donor than EH

Equivalent Resonance when all

the R s are equivalent
Resonance
Nonequivalent Resonance when
are Rs are not equivalent
o
Il Rf If R Leo RE I 11
Equivalent Rs
 o
I R I H r c o less stable and
and less likely to
Non equivalent Rs form
is Equivalent resonance is more effective than
non equivalent resonance
cit R E in equivalent resonance is higher than
non equivalent resonance
 4 Extent of resonance in linear conjugation is
higher than cross aryugation
El un v v linear conjugation

E w crossed conjugation
G when two groups are in
RE I 11 Conjugation with a third
a bond group but not in
Equal no of
conjugation with eachother
Q Compare R E
1
linear cross
III nfe.ssg.rs III

II III I
0 0
Of
2
f Il 111 1
linear cross
I III
III
Moreno of Rs

Calculation of R E Using heat of hydrogenation data

c C t n n Ni e C
1
s t Heat
t r r
T T H H
bonds breaking bonds forming
 i Hydrogenation is exothermic
process
a Heat of hydrogenation Energy liberated when
HOH
1 more of a compound undergo hydrogenation
Ex
H
Cal Ni
t Hz DH 120KIMM
H

7
t 2Hz
Ni DHtheoritical
b
Jr 240 KJ1m01
BHexp 232 KJIMM
RE AH µ Dµe p
RE 240 C 232 8KJIMA or 8 KJIMA

C t 3 Hz
Ni DH th 360KJIMA
DHexp 208 KJIMA
Benzene
µ RE 3 Go C 208 152 KJ1m01
Aromaticity or 36kcal Imd

Mesomeric effect Resonance effect

1
key atom
1
G or CHEM G
t
A donor in acceptor
The group a may increase or decrease a e density
on the ring by resonance
 The permanent shifting of a e density due to
resonance1conjugation is known as Mesomeric effect
or Resonance effect

Types of mesmeric effect

1 M HR effect the effect of a donor groups
is called Mlt R effect
Cil H the key atom of group a hare lp then
it act as a donor
H OH OH
µ t a donor
l l y
f El
G 5
1 I 1
acceptor bn 9
OH Stoy
i
t
s s
I E l
i
l

These groups increases e density on the ring at

ortho 4 para position

ex CH CHINH HE CH NtHz
acceptor a donor
fuse on nite
121 MI R effect the effect of a acceptor groups
is called MI R effect
i If the key atom of group G have a bond
then it can act as a acceptor

H c fo
O O
H µ µ C O
g f ta acceptor C

I a donor I I e
1

0
s t
H c
l µ C O
st
EI I
St

These groups decreases e density on the ring at

ortho 4 para position

How to identify c MIM groups

Attach the givers group to or cH CHz

Group effect
cu Wii di R
A
Cheech
v
int E R MI R

a
it
v
e CHEMIE M HR
 r

I OR Hatch a
di ER MI R
O
Il og
4 S OH Hzc CHa s OH MI R
Il 11
O O
O O
D u
o s R cm cn Q s R M HR
H H
O O

a
feel CH Hs M ITR

MITR group A good a donor groups shows

higher
M effect

Enz WH o ivHz ivHR NR's

ion ER inn I R DIR

f s E Ei Bir i S no

is Enz Nh O charge density

high ne

more electronegative
ii o H
W L n H R
R
Oz Oz H 104.5 07104.5
O
O Oz R R
O 1100
 Sp3 sp2 Sp
S 25 33 3 l 501 EN L t S character O
O 109.50 1200 1800

WH if HR N'Rz same concept

9 g
Ciii ivied R DIR
internal resonance the availbity of lp
Due to
on donor atom decreases hence 1M also decreases

Civ can act as M as well as m

due to a bond
b I o f Ci Br I Based on E N

m E Ei BI I Due to lp
CEz i cBigg
pp
If size
factor

MI R group A good a acceptor groups shows

higher
M effect

Noz CEN I H DIR

group

I o E R
do
or E on E NHz di p
group61
 cis group

TO v og og
µ
Nyo CEN d H da
o SP TI
Gil group z

I o
r E R
do
or E on E N'Hz E o

o
11 u I
I C L H c L
M

al M effect of DIE decreases due to internal

resonance M effect of i

b As 1M effect of Li increases M effect of

I L group decreases

0
M O d R OR C on C WHK o

Note The groups which can show both MI M effects

x ch _cha CECH NINH NIO etc

Inductive effect involves partial polarization of r

bond electrons Distance dependent

Resonancelmesomeric effect involve complete

transfer of the 1mmbonded e hence distance
independent
3 Resonancelmesomeric effect dominates over
inductive effect Except for halogens 4 NO

4 for halogens and No group

X i s I I
e i
m 1M
Net electron
x F Ci Br I
withdrawing
n i s I Net electron
m 3 donating
a Arrange e density on ring
M
Abt i
El't I tM CHOT M N024 Mmax
1

Cal b c d
a b c d TM
O
M
Ht firing'd R if P I tm CN t M
g

Cal b c d
a b c d

CHzOH CHzOH
3
OH OCHz
M TM
 steric Inhibitation of Resonance SER
Ho O Ho Pz O
C
T M C
for resonance the
Pz pz
B Pz Pz Coon group must
Wpfane
p Pz Pz Pz be Coplaner with
Pz Pz the ring
Ho o ryStdfance
To minimize this sterichindrance
a
1 G Coon group go out of the
plane of ring by rotation
about Ca Ca bond rotation
is free about a bond
Ho O
C µ
G G
Note p
NO SIR NO SIR
G

The phenomenon in which resonance is restricted

or inhibited due to steric hindrance of a group at
ortho position is called SIR

The group at ortho position may be an Ewa

or EDG C electronic effects are not important
in SIR
 2 The groups which are affected by SIR

Koon Eo Er n
infer
A more bulkier group at ortho position causes
more SIR hence lesser extent of resonance

Em
9ft jook E7a
extent of SIR

Application of resonance
G Bond length and bond order Resonance modifies
band length and bond order
Bond length Bfd order
for equivalent resonance
R COO or RCOI
o
ride r c r EEE
Equivalent R S
in All C 0 bonds are identical and have equal
bond length
Bond order is given by average PEO
BO 2tzL_
 ORI It of bonds in
no
BO
If a r
conjugation zone
i
i e
I cIl o BO I 11 1.5
R i
2

Total no of bonds around e A

od BO
No of surrounding atom

B0 3 I

1.39 1.3g.no
2 c s

Equivalent Rrs
Cil AU C C bonds are identical 4 have
equal bond length
BO 2 1.5
fig or Bo I
f LI
3 032
O O o
Il
f To to to
2
Equivalent Rrs 03
l
C
bonds are
cis All C 0
identical
of o
E E
4
Cit B O It b 3 132
Q 1 Compare O_0 bond length in Oz 03,4202

2 Compare c 0 bond length in CO2 co cost

3 Compare P o bond length in Pof HPOE.H.PE
1 0 0 Bo 2

H O O H BO L Hz0z 037oz
t t
0
ok to do BO 11 1
2
1.5

2 0 5 0 BO 2

CEO BO 3 COz2 C0z

BO 133
o Mo
i
3 poof HPO HaPOI
O O O
H H Il
Pyo
O
n
fO o
Hy o

4cg Rs 3egR.SI 12cg R.SI

B0 I 11 1 25 1 1 1 33 1 1 15
4 3 2

For non equivalent resonance

Q NHz GNHz GNHz Compare C N
a b k
f f band length

I I
a b C pqµ NHz
I 1 Greater
Extent of
G c
resonance

H M
I I
N a N b
a 1 sp life a b
µ
compare c N bond length
Q compare C a bond length
a C b a
HzC OHz B0 2
b
HzC Chl HzE
q qqHz om ch OH

the
Iq N
t
O
the OH OH N
1
o
o

M
NOz
Q ya
compare c N bond length
b C
02N NEO
to
I SIR b c a
Hypercoryugation
special type of resonance which
A
involve delocalization of r bond pair of electrons
of C H bond or c c bond which is directly
attached to an unsaturated system or an atom
having vacant partially filled p orbital

ex is Hjelm 1ha propene

Sp3 Sp2 Sp2

H
v
V
HzC H
SP
ca se c s r p overlapping
H H

H ret
x
v
µ E ch cha e H C ch Eth e
sp3 µ H

H H
Hst
Ht date ate H dem est
ns.t oh off H Ht
Hst Hypercoryugative structures
No bond R H or No bond RS
 H H H H
Cil H 4 H v H d ut n d ut n d ut
v
e e Je
G y
HSt v

STH C
i
Hst further
i
i
s i r S
i t
I
8

Note oh group is behaving like M and increases

e density at ortholpara position on the
ring
vacant P'orbital
µ
t
Liii µ C CHz
H

H Ht H
t
N C T CHz e H C Ctf e H C Ctf
H H Ht

v
Hst
St t St H
H C CHz Ht c
i ctlz
Mst H
 HI HO H
Iv H Th Enz e i n C CHz e s no c cHz
H H H
A

H H
H cuz H C CHz
H Ho

Nok Hypercoryugation operates in alkyne alkene

benzene carbocation and free radical only
H
ex
µ d ith
µ No vacant orbital

Condition for hyperoryugation

Presence at least one
of hydrogen on a Sps
carbon which is x adjacent wit Alkenefalkyne
benzene carbocationfree radical
ex Lil HzC Mz NO 2 hydrogen
Hypercoryugation is not possible
2
Cii Chs Ch _Mz 32 H
No of no bond RS 3
 cry
Ciii Hye dtcM Mz No L H
dB No hyperconjugation
I
Hs sbtm9m
sp
Yp
ctsp.ly
thscp oshp

Not in proper
in a orientation
CHz ont Mz 6L H
L o X
vi Hye Mz Ctb 8dm
g
acts
Ctb LCHzCHz LCH CH3 z CCH3 3
Cii

3L H LL H 0TH
22M
No hyperconjugation

some important points

1 Hyperconjugation is also known as Baker Nathan
effect or No bond resonance or r a congregation
or T bond resonance

2 In hyperconjugation the overlapping is r P

overlapping or r a overlapping
VBT MOT
 Extent of hypercoryugation a noof alpha
hydrogen
stability a extent of hyperconjugation

Hyperconjugation is more effective than inductive

effect because it involve delocalization of
electrons but it is less effective than mesmeric
effect resonance as r electrons are strongly bonded
compared to the or lp
Mesomeric effect Inductive
Hypercoryugation
or resonance effect

the group is
alkyl e donating due to
hypercorujugation
H37z
I e Ctb CtlzCHz CHzo

cCOH37 3 ooinomYtni
9 L 59.1
c
gn.s
99.1
a Arrange e density on ring
32kHz 2MHzCH ILMCH Hdz odHC CHS
4

Cal b c d
 a b c d hyperconjugation is dominating
2 M CH f ICH TH Incl I TM CN T M

al b c d
a b c d

Applications of hyperconjugation

Bond length order hyperconjugation

and bond
also modifies bond length and bond order
H Ht
Tv 2 A3 y I 2 3
ex µ c oh Chze H C CH cha e
H H
HS1
I s
HE gI c
2
cuz
3
i Bond is elongated
Bond is Hst
v
elongated Bond is shortened

Q Compare Ch bond length

a d b c
Cheech cha HIS Ury ch ch H
Hz ay Wh H
IS Sp3 Sp3 Sp2 IS
t
participating in strong
b a c bond
hyperconjugation
Q compare C C bond length
a b c
HzC cuz Ctb oH Chz City CHICK CH
B0 2 32M 62M
C b a

2 Stability of alkene 4 Alkyne

stability of Alkene alkyne x No of L H
L L x
HzC oHz q BC Ctb
Cly oHz C C
OL H 32 H µ cis H 62M
L d
X
Bc H BC BC
c c C Mz C CH EHz
H Trans Lb BE 6dm BCx 92N
6TH
x x
BC Ctb
C C
BcL 122 H 1B

is Generally more substituted alkenes are more stable

steric hindrance
Cil Bc Forb Bc H BC
C C C C C Mz
µ cis H H trans Ctb BC Isobutene
H µt
HE AC Ctb HE
C e c Entre 6 No bond
H H H 20 TI RS
cisltrans
 H Ht
M 7 HE
6 No bond
C Ork i c oHz
RS
BC Hye Lo
more stable
Greater extent of hyperconjugation

Compare stability and HoH order

q L
L L L
L
L X
L L
Gd H 3L H
III 10TH III III
I II HI II I
stability NOH HI

Note cis HOH No of a bond Except aromaticity

1 bond
dit Hoy x Equal no of a
Stability
compare mom
L L L A
CHEM Uz Cry cu ch ay CHEM CHICK
I 32M III GL H III
HOH HI 1711

stability and HoH order

Q compare

x 9 x 9 a
x a

x J x j
7LH 32 H 7 LN a 34M
III III CHI II
 Bicycle compound µ
too
a Sp3
Spa Sp2

Bridge
head C
L Sp3
H X 1

Bridge head atom can never be spz hybridise

due to rigidity of molecule
 I II II II II HI II I
stability HOH

Reverse1 Negative hypercoryugation

Xr X
H t
ch cuz a c Ch cuz
g I I
X F CI Br I

ex n F F F
F C F F C F F C F

c s e s
y
CF is
strong e withdrawing due
group
to reverse hypercoryugation behaves like M

Electromeric effect E effect temporary effect

complete transfer of a electrons of a multiple bond
to one or other atom under an attacking reagent
ex Nt

1 U
1 electrophile Y K
H
te effect

H
H I
ex EEE c o
U Nucleophile E effect
Aromaticity or Aromatic character

Benzene

RE 8 KJ IMM RE 152KJ1m01

This unusually high R E of benzene is due to a

special property known as aromaticity or aromatic
character
Note is
Highly unstable and do not
exist at room temp
Cyclobutadiene

Cii Exist but not that stable

cyclooctatetraene

Hackel's Rule Based on mot and applicable for

monocyclic compounds
41 Compound must be cyclic
There should be complete cyclic conjugation in
close loop conjugated system and ring must
be planer
 2 G 10 The
3 It in cyclic conjugation
a
can 12 a e are
then compound is called Aromatic
where n 0 I 2 3
cis Aromatic compound have high RE and highly
stable

Cii stability y

Gate
Aromatic compounds are more stable than their
acyclic analogue
Aromaticity is a stabilizing factor

4 8,12 the
b If 4h it e are in cyclic conjugation then
compound is called anti aronnatic
Where n 1 2 3

is Anti aromatic compound have 0 RE and

highly
unstable do not exist at room temp

stability C
Hae
 Anti aromatic compounds are less stable than
their acyclic analogue
Ciii Anti aromaticity is a destabilizing factor
A thicket's rule fails means either no
complete conjugation or ring is non
planer
then compound is called Non aromatic

ex lo 1207
Angle strain
_gsP
y Actually exist in non planer
tub shape
Ste in
111

I AU p orbitals are not

parallel hence no
Complete conjugation

Non planet Non aromatic

Non aromatic compound have comparable

stability with their acyclic analogue

stability

Stability Aromatic Non aromatic Anti aromatic

Note a Aromatic compounds have characterstic smell and
bums with sooty flame more carbon content

Anti aromatic compounds are highly unstable

because they contains some unpaired e in
anti bonding or non bonding MO's
o
ex
Diradical

Due to unpaired electron anti aromatic compounds

are paramagnetic and have tendency to get
dimerite
o o

o 0

Anti aromatic non aromatic

Annulenes cyclic hydrocarbons containing alternate

c C and c C bonds

41

Annulene ft AnnuleneCG Annulene 8

the Gate 8Ae
planet peaner Non Planer
Anti aromatic Aromatic Non aromatic
2 Annulenello

Q tone Can 12
Non aromatic

Non planer

is Annulene1103 and higher annulene contains some

H atoms inside the
ring which are called
cavity hydrogen
fit Due to repulsion b w these cavity hydrogens
annullhl 103 annullhl 121 annullhl 114 and
annulenefto are non planer hence Non
Aromatic

Hµ
I

Annulene 1123 Annulene1143 Annulenell'D

Non aromatic Non aromatic Non aromatic

iii Annulene118 and higher annulenes containing

an 12 a e are aromatic as repulsion b w cavity
hydrogen become insignificant
 Cations
sp2
at cyclic conjugation planes
sp2 sp2
2n e
Aromatic
cyclopropenyl
carbocation
t
3ML
3 3
or
t
z f ta i L 1I
3 3
3 equivalent R s
t
2 cyclic conjugation Planer
4n e
Anti aromatic
cyclopentadienyl unstable
carbocation highly

cyclic conjugation planes

bite
Aromatic
Tropyliumion
ti v
Z t t
e i e i e
3 b t

4 5 t

e n e i e i E
t
t r
A equivalent Rs
 sp2
sp t cyclic conjugation planer
4 2 a e
spa Aromatic
sp2
z v 3
t t t
t
e i V e i e g
i t 1
t t r
l
a equivalent Rs
21

Anions

CH cyclic conjugation Planer

4 a e
cyclopropenyl
Anti Aromatic
carbanion

H
cyclic conjugation Planer
6 a e
Aromatic
L v

5 v
Z e sn c s e s
j
2
4 3 n
5 equivalent Rs
U

s
 cyclic conjugation Planer
3 6 a e
Aromatic
z L 3 L
r
e i r e i e y
v
is a a
111
a equivalent Rs
2

Heterocyclic compounds
cyclic conjugation Maner
L 6 a e
N Sp2 Aromatic
Pyridine
Lp of N is localised
in a Lp is present in sp2 hybrid
SP2 orbital
which is 1 to the
p orbitals carrying a bond
Note When tp and a bond both are present then a bond

participate in conjugation

2 cyclic conjugation Planer

6 a e
w
sp2 Aromatic
pyrrole n
 Z 3 v

s e s
1 A 4 e s
j wt C wt r

H
III III INI
H H
v

e s s non equivalent Rs
t t
µ N
III II
H n
i stability I HI II II
Electron density order _ ii Cz 44794 G

3 cyclic conjugation planes

6 a e
Aromatic
furan

only one lp participate in conjugation at a time

Z 3 v

s h e s
4 s
i n
O O C O r
v
II t II t
III

e s s non equivalent Rs
O O
III t II
it stability I HI II II
Electron density order ii Cz 44794 G
 4 cyclic conjugation planes
6 a e
Aromatic
Thiophene
OS Os
Note St Os E St
St

v v v
O O O
t t
t

2n e
Cine
Gre Aromatic
Anti aromatic
Aromatic
C J Break the a bond then check

Q How many of the following compounds are aromatic

sp3 1 sp

1 2 3
N sp2

Gite Gite
Aromatic Non aromatic Aromatic

µ SP µ spa
4
Gite
Aromatic t
w o o
µ
H H
 5 b t

Sp3
sp3 Gte
Gte r Aromatic
Aromatic Not part of
cyclic conjugation

Polyclic Compounds Hackel's rule can be extended

for polycyclic compounds if conjugation is possible at
the periphery

1
tone
Aromatic

Naphthalene

2 14 A e
Aromatic
Anthracene

3
Kite
Aromatic

phenanthrene
 4 tone
Aromatic
Azulene Isomer of naphthalene

Reactions
o
1 2K 2kt 2e
Gate
o
the Anti aromatic Aromatic

2
2Nd 2Nat 2e
tone
Non aromatic Aromatic
Sae
Anti aromatic and non aromatic compounds reacts
with metals to form aromatic compounds

Cl
3 2Sbcls 2 Cls
C
Gte
Non aromatic Aromatic
Sbcls Lewis acid Sbcls Csbcld

t
4 Ce AgNog
t t Agcl t
2A e
Aromatic