General organic chemistry

L >

L
Electronic effect is, Effectdue to movements
of electrons in a

molecule.

Electronic effect

Permanenteffect Temporary effect

> Inductive effect (I- effect) >Inductomeric eff

-Resonance (R)/Mesomeric (M) effect Electromeric eff

·Hyper conjugation (U.C)

Inductive effect. -> Partial band electrons to-

*
displacementof a

< >
wards due to this
m o re electronegative atom

displacement of molecule/bond become polar.

called
Resultanteffects
* due to polarity of bond is inductive

effect. 868 88+8 + S-

+

Cul-crh-CH-cH2-ct - c
eg.
↑
<Negligible I effect)
-

C
Note:- ie Electro
↳
negativity by pauling
cl)x Br(=
>S(c(P(y)
f 0> <

(3.01 (2.4) (2.19) (

(2.6) (2.56) (2.55)
(2)(3.5) (3.1)

band
(ii) I- effectapplicable only for a not-bond.

iii) I- effectCL/ distance)

live H atom is
reference atom
for Ieffect.

Types of E-groups is it-I group (iit+5 group

[ >

cit-I groups is These are o-bond electron

withdrawing groups.
L >
Relative strength of -I
groups.
-
F) -
Ry)-sRL -

) -

Non-sOgn-cNY - - - -R

3 -
4-on > - f) -c -Br>-I)-oR>-OU-c=c-4)-N)-Phy-curcM

character
Electronegativity is

sp
* -

>5p>sp?
*sp-N > sp"N) sp?N

1p-N)
* SPIN) SOCSPYN > PC) SPC

cii-+I groups: -
Electron
donating groups.
L ↳
Relative order: -

⑦
crb-> -
⑦
NM >-87 - 2-83 - k- R 3 -
xn ) -

cy
-

R) -

x)D >4
' ,
20 -
38
 A
↑ Cu
(E) 22f 7 I)
as
C
eg > CH +
H ->

I
23 I (y -c -(45( 1)
+
for alkyl group + I effect (no.
of (

↳same
degree

<X-) > 02( -

5) L
-
8*+I)
-
0

No effect)
0
753 -
-
0 -

n( -
1) -
-
0
+I) 26t -

27 (No effect) <6- -

8
-

191 <my-c-CH,<Mgx Corganometallic compound

Li
CIOS cry-crn- Cb +
O

on (-1) H
A

i
(115 42 s
4
-

7 M

r
7

~x 0 Na
200
-

(+ I) ↳+I)

Out compare 1/-5 effect.

+

<- <
-3 c I)
<- cm-cry
+

<1 cr cm (n)
- -
-

- -
Cr

NO2-C-> cl-cm ( -
I)
12 -

133 Noz-cm-cr2-<c1
-
c -
1) <Dist.) No.oc) Power)
r -cr cr
-

cm -

< NO2-(
-

1)
24-
-

I
2 I)
15F
cU-cnz-c-<ce-
-

Cl
I

(6) NOr-cM-<ce-c- ( -

I)
be

L
Resonance: *
>
It is phenomenon of delocalization of conjugated
-election.

When
* a
single structure of compound/ion cannot
explain all

the properties of compound/ion then we use

differentlewis
electronic structures for explanation of all
of comp-
properties
ound/ion.
These
* law's structures are called
resonating structures (R.S)
or comonical structure.
These
~
resonating structures are
hypothetical. However, the

phenomenon is real
* Actual structure of compound/ion is represented by resonance -

hybrid (R.H.)
-
2

S I
2-

Y Bond
length
,
CO
eg. 3 0-

1.21
I
P
L
-> C
C
of c 0
=
-

Il .....
L >
-
/Y
/
o -↳
- To-
B
O

R. S. (R.n.)
 Bond length
is

L S

1.54 [R-1 Ceps-4 1.10 A 1.43

x -c -
x - (7 + C -
0 <

A* 1.09 0)1.23
12
-4 >
22 - C 2
=
> 1.34 25 - Cyp2 16 -
=

1.20 A
23t c = c IS cep-n >106

eg. Benzene (CsUa) Mydrogenation,

Ozonolysis, co
3
ano alyonal

111
I /
I ->
C I a - L ↳
-

- - - 2

ne -
R.S.
(R.U.(
Kekule Dewar R.S.

It of compound/con.
L
Resonance hybrid (R.U) ** is actual structure
R.n.
- has all the properting of R.s.

All R.S contribution in

*
give R.H.

stable contribution
- More R.s. give greated in R.U.

compound
*
gain stability by delocalisation
of electrons (Resonance)
Stability of
* compound/ion < no.
of resonating structures.
Resonance
*
hybrid has least potential energy wort
resonating
structures.

Resonance
energy (R.E.) Energy diffbetween moststable
is the
L -
and
resonating structure resonance

hybride.
R.E =

stable)
ERs (most
-

Ehybrid
R.E. C
stability of compound.

for benzene (C646): -

Isee...
- . . . . . .
Other R.S. --------

- . . . . . Dewal R.S...---

moreticaonamata e

R.E (36 Kal/mole)

Experimental value
/-
101 - - - - - - - - - .
Y

Calculation of RE
for benzene:-

heat
-> On the basis
of of hydrogenation
Metal
ic c
+ heat
of hydrogenation
=
=

m
+
Catalyst
 (Wil Pt
1 +
m ↳ + 28.6 Kcal/mo

11 br
+ - + (3x26.6 85.6) =

kcal/mal
-

R.S. of benzene

<Cyclohexa-1,3,5triene)

32
3
** 19.8
+
K call ma

R. E of Benzene (85.8-19.8)
=
= 36 R cal/ma

/
-------------------- kcal/ma
↑R.E
- N 36
=

E4
- . . . . . . . . . . . . . . . . . .

20.6
-

- *

3x
- -

a
-

14
-
-

↑ 9.8 K call mal

26.6 KCal/mo
/ 2
--...--------------------
W

D- R.E.
of ↑Y
⑧
=36 Kcal/mal
-

R.E. X 61
=

kcal/ma
125 of ↳K
tds call mat
135 R.E.
of x
=

-I

-R.E. of,/↳I
o
-
o
X
= 92 kalluna

25+ 0 kcal/mal
R.E.
of X 1
=

0
26 R.E
of
=

<1 M =

Rules for resonating structure-

L I

Resonance
* possible only in Planar/nearly planar conjugated system.
Adjacent
* pard orbitals a re presenti n plane
same with parallel

arrangement
* Net charge remain same on each
resonating structure of given
compound.
Only
* -elections of conjugate system can participate in resonance

(Nota electrory).
*
All
resonating structure musthave the same arrangementof
atomic nuclie.

In all
resonating structure paired electrons
of
* no are

also
same.
Similarly no
of unpaired I are
unchanged.
- In all
resonating structure
hybridization of particular atom

remain same.
* In all
resonating structure atom
of 24 period should follow
octate rule

60 3
I
⑦ (May exist)
I

- 0
t 10
-

I
-
c-
I -
C - Ni
/
- N-
I
jo
not
3
I
I
(Does
:
-
⑰ I
-C- E -
⑧ 0
2 + x
exist)
-
- -

/
-
-
I
I I

Df
n

&. . Resonance possible FY -"

eg.
-

-Y

g"..... 8
.... cycloctatetrache
Tub
8....I
shape
No resonance (Nanplanar)
Type of conjugation is cit - ~is - . ciii ④

-
L >
2iV+ - ⑦ -S - ⑧ wie
*

(a- Multiple bond-multiple bond conjugation:-

C X ↳

<(6. or
=
*

CE. 1.) ↑ 1 1111

e

-
-T ↑ 1 4

C
c -c -c
sp*sp sp
-

I- is
* & s e in
conjugation out
of 65 e

sp2
(r c
=

Sp
cb
=

sp2
-

/
C

j Gi,
.......... ---
No
conjugation
be
b2
by by

Cr c
=
cc Pxei n
conjugation out
of be
=

*
N

* - - Since in
conjugation

I
* 6 me in conjugation

-
* I bei n conj. out of lose

Acr
c40,zxe
19 0
=
↳ -
- xe 8xe
I
* ↑ * *
I
k4 -

cne -N c
=

,
* I * I ↑xe* 2 ↳ ~ ↑
-

11 11
I

(b Multiple
+
band-love conjugation
pair - *
C r CH
= -

NU2
L > Sp (not 1p3)
2P
"
21

sp N I ↑

----
in 6.5. 12 ↑
%----
->
N
n ↓ - N in ES ↳ ↑ 14 Th C - -

- ↓-------- D
G-S 11 1 1 Nin n.S-> * 1 I 1

U.S Sp
3 ↑ e
Resonance
1p2
 Resonate

Ap
im
·O
·

H & es
*
CH2
=

cn -

. -

cy C
M
H

conj
H
Axe in

*
Cu = ↑ ein
conjugation * <u 8. No
conjugation
=

C
=

↑
7

* cr cn-cl:4e inconjugation
=

⑦ &--------- n
* Cr cH -c t ↑xe in
conjugation
=

↑ Xc -c - C
0
M

Sp
M
05
H U H
⑦
* Cu I cu No
conjugation -
I

C+ H -
!O n -
I
-
⑦ H 2

#
(r c
=

c H
=

↳a
conjugation in sp ↓ Sp in SP
r >
6e be >e

⑦
:
* - No conjugation 11
C
⑦ *
c :Di
with be
inconjugation
X 11

L conjugation
~

* ↑ e in * r N
-
↑ e in
conj

"II x
/-
*
-↓ - G 8x e in
conj.

-) Multiple bond-vacant orbital

conjugation:-
L >

D
2
-
U
H
* cr cH
=
-

BM
-
B ziei n 3 orbital
U
Dr vacantp-orbital
Cr
*
=

cH -
⑰
cur
& -
- 2 20e
imcarj.
⑧

⑰
* Cr
=
( u -

Nu No orbital
vacant No
ronj.
Sp3
⑰
* Cr
=
CH PRs 25e in
song (P has vacant d-arbital)
D ----
Op D
- - - -

c -
c -

00

cm
* cn-
=
ci:
conjugation occul X c n
=
w lonji
⑰
⑲
*
(r = cu
=

CH conj. Occur *
- no
conje

conjugation
/
* occur
I
2

(d-) Multiple bond and impaired (free radical) conjugation -

C 3

Cn In
c c n 3xein conj. *Cr= X
=

X x c
= =
in w

x
*

vacantorbital
<2-
L
Love pair and
conjugation: -

>

⑦ P -- -
*
<u
-
Bet L B
ze incon. Em -Ev
*

D 00
 ⑰ - ⑦
cm- ie:v * <1
-
: X * C v
*
M
⑰
-
- -

& cm - -

Men ch
* S -

Me -
- ~

Rules resonating structures is

for identification of stability of
C S

it Greater no
of bond containing resonating structures a re more

se able
-

(iit Resonating structures in which all atoms have complete octet,

are
comparitively stable. m o re

viis Neutral
resonating structure are generally more stable the

charged resonating structures.

live for charged resonating structures: -

Lax Negative charge more

is stable
larger size containing
on

atom (If
comparison between atoms of same group)
1b Negative
->

charge more
is stable more electronegative atom
on

and vice-versa (when size of atoms are approx. same.

i Aromatic resonating structure are

generally more stable
than non aromatic resonating structure.
Ivit-ive charge m o re
is stable on adjacentposition of with -

drawing group, similarly tire

charge is more stable on
adjacentposition of donating group.
[viit conjugated
when
of selections no are same then linear

conjugation containing structure are m o re stable than

crossed
conjugative structures.
⑰ I
+1/2
=
cm
=

=c u
=

cn c >
(
& -cr cr (H c r =>
= - =

- R.U
R. S

=1.5[1 x]
Bond order: bonds
N o.
of
+

- = >

no.
of R.S.
(equally stable)
For band
single B.0 1
=

B.0 Bond
I
double i /I = 2 <
strength
tripple, , I ... 3 2 Bond length
L L ⑦ ⑦
-

Yz -
[Cm cr]
- - - ----

Cm cu-cm
-3 c
Cu cm cn
=
=>
*
=>

Fm
L W.
⑦ -- 8t
*
Cr CH Nr C I
Cu
u
= (cm cu xm)
= =
=

Neutral R.S
charged R. S.
I More stable)
<Less stable)

Cr=cnt im [Cr--- ch]:

·

(
-

* · (n 1
=
=

- R. H
R.S (equally stable)

E 3
Note: ~
for movement
of 2 e
Charge- (Octate/ No ofbond)

for movement
of Iev chargesep.-enage locat?
R.S.)
(stability of
 Bond order= Total noobond involvinc) =
(+ %)
of R.S.
j
Total no.

⑦ ⑰

se
L > L > O W R.S
* ↓ 2 - -.........2A
D

⑰
(a) (b) (C) =
z
y(x
(y<1.52)(x 2) 1.35)
=

a) b c
=

(stability order)
⑰ ⑰ -- It

* C B -Wr =
( < m NUr =
=> [Cm
=

N12] (R.n)
stable
Less stable m o re

s -8-
i I.......
xm]
I ⑰
[cr
~

* Crb-c -
NM < ↳ cr-C NU - -c -

stable Leistabe
-*
More

-o I
&
o-

[Cr
-
4 0 C > c C
Cr
p-B
S ->
- -

*
-
-

- 8

i i--- o 23
-

o
C
-o
o -
L >

- o
-
2

↳
-
3

o
->

I ~
0
/
-
C 11...
-
-
- 2
/ I B.0
5
=

-
43
-
-

11
%i
-

I
C X
* > C ~ L ↳ L -
im
-
⑦
I
/ - ~
- Nrz ⑦ - / st
Cu Ch Ch
I Nah

(a) (b) ()

b) a xc eability
-

order

a.m
-

o
-
op I

n-
Il =>
⑰ .
[ >
-Nur
A >
* ↓
.
-

Na ↳ Nu 0
" n -. H -
⑧
st
H .
⑦
(a) (b) (C)

a) bx -
stability order -

0S-
I
i 0-
I o C

En
S E >

n
C 8-
C
-
*
- ·- N
⑦ ⑦ - -
Ch
Nu Ch
Ct Ch

7
<9-) (b+ 2
-

b) a
(stability order) ENO 0> N>0

so
-

o
or
11
L I
I I ps
* C C L 3 C ⑦ -> L
L S A
Nn 8
s
-

⑦ ⑦ ⑦ --
NM
NH S N
S S
(
-
)
(a I (b-
Stability - 5353N-
b > a) order
stability
..............
sO S-5
S 0 S -
&9
S
11 11 I Il
L S
z
-3 -
*
to
as C (b) f

order
b> >9 ->
stability
⑰ +

113
L > L > - .....
... or ⑰
*
⑰ + a
(a) t

<cyclop renium 2b) 2 Ct

con) a b
= =
c +
Equally stable
⑦ -
5
-

<
I
c0
Y5
........... Y,
-

>
-

2 . >
* I
-3 i Or
-

⑦ -
⑦
-5
-

Y5

cyclopentadien
anion
 ⑦
r ④
X
I
↳ -> < i < L 3 L >
-
-> t
B0 1
=

+
⑰
O
t L
↓
⑰
⑰
Troylium ion
-
0 Y3
-

o
i
r I -

a.
>
L > N
↳
X
D +.....
n
-
Y
* S X I
-
E
I - O
-o

= 8t
S-
L -
=0.
-

c..
-
-

E > -
c C
cm c cm
=
->

m o re stable ↳is stable

(====id]
⑦

* Nr c
=

0.
= < >
* c
= -o- -ru -c 0*
= =

(a) (b) 2)

a)b)c stability order

· * gon
687 ⑦
Go al a

·
2 ...
...

" .....
*
C 7
-

-
L >
L > !----- ~Y
..
/
-p 0
/ -p
o
in I
/ in
"

->

Dianion
of squaric acid
Bond order for 1+1 5
= =
x -c

44
2 0
1 1
2
- = =
, + =

⑲ Cr Cr - Ou S-
Cr

<
8.s
* ⑦
T
I L -
4
L 7 L > > =>
W
- M
(a
⑦ C S
(6t E (d) (C) --
Benzyl arion
E

i 11

/
a e7b
=
d)
=
C 11 (cross conjugat?) (
I
Linear conjugation)
0
t ⑰ 8t
Cr Cr Cr Cr Cr Cr
* I I 4 i

/- ⑰ St
⑰
:
87
I L L
I >I -
↳l >
↳
2
E
L
I L
/
/

⑰ St
(a) (b) (2) (d) (2)
a e
=

-b d)c =
->
stability order

S-

·
-

58
Cr

im
Cr Cr
I
X /
Y
2
C ... I L > 1 >
cm, > ->
:
1

:o
-
- u
0
I
-
o - 1
⑳- Quo-n -
sto - n
↳ ' I I

/ ⑦

. . .s
o 2
#
=I L > 1 2 3 1 ↳ L
I -
S-
2 2 /
⑦
8-
(a) (b) 2 (d) (e)
⑦
-n
,
--
U u v u
-c 0 U- 0 =
0 -
-c
7

r
=
- -
=

C - c
1
* I
/

2
I L ⑰ 1 >
11 L ↳
I
'*, ↳
'
↳

I
87s t
:
2
/

⑰ St

Resonance
*
effectis equally effective on ortho and pala position
for benzene ring. ( Benzylic resonance
group).
H
Y
H H
I I
B is B B
*
⑦ ↳

"
S-
91 L >
< ↳
W c > b) 9
⑦
st
-
/
N ④
↓ E41 ↓(b) i() -
↓
 0 E O -S
11

:
I I 87
* -

9 L >
-
-
st It
in ⑦
N N
in in in
More stable Less stable
o
o
-

0 o
Il I :
b
stability
*
a)
1 I 23 I
⑦
L I - - : 67

a am
8+
Im im 6
29 ) 26-
(-
-

out, Identify no.

of position in resonance hybrid which have so

structures.
Fil
-
for given

⑰ Sest
-

st
-
st ~ St

*I
itt
22 t - I I
⑰
P

I
r
21-
F
(31
sil
-

St ⑰
I
X
W v

St st
St
So
I ↳- /

-W
⑰

(17--
0 of
-
of
-

It

Out Draw neutral

resonating structures for given compounds.
+ Benzene (24 Napthalene 239 Antracers (4-Phenanthaene

sor?
*
21 3 -

N (2-
I 2
< / / / - ↳
I L ↳ I >I stability
↳ / 2 ↳
/
S

(9) b c)
=

(9) (b) 2d)

a have two benzanoid ring
23 +
i.
- ↳ W
↳

,
/

- /
/ / /
>
W -
-I
- /
-

19 -
(b) ( 1 -

(d-S

Stability order (a d))(b c)

= =

-
24- -
- -

I I
/ 2 ↳ ↳
I / /
-
I
2
1
I c
>1 -3
I
I >
L >
I
S - ↳
- -
/ / - ~

29 + (b) (C- 201 2- 1

Stability a d)b e)c

= =
-

<Allwings a re
benzanoids)

Ous Draw possible resonating structures

-
/ ⑰ - ⑰
112
⑰ ↳
I L > I 1 1 I
I Gi c
W - ↳ - 2 ⑨ ↳
2
- 2
(af
<by 2) (d)
⑰ a
C2 l
v

Outof TRS+ 4RS have benzanoid sing. 2 ⑰

I <I d
- - 28/ -
+
 ⑰
22f ~
& -)
- -
2 S
~ / /
-
- ⑦I
2)
- 2
L
·I
Y
⑦ W W ⑰
* I
/ -

(91 26 - 2)
-

(d -

1 x (e)
W
⑰

Out
of 6R.S Only 2 RS have
benzanoid ring. in 159
- -
o I 0 ⑧

(3+
I I 11 i ⑧
I1
- I / ⑦ ~
o ⑦ 2
I -3
&
↑

I L-
L S
/

I -
L
I
2 -(a) ↳ X
- ↳ - - W 2
(b) ⑦ (2) (a)
Arion of a-Naphthal (e)

*
or
o
R 0

i a
I I Il
~ ~ ↳ ⑦ W
1 I L
-I L > I 4-> I I
W - - - - - - E5)
2I
is cas 0 (8) ⑦
(i- E

CK- Anion of B-Naphthal

- &So - -O --- ↑ - o a -
I CI
- 1
L L- >
--
L- >

I - P ⑦
- - - 2 ↳ - ⑦ - -
⑦
(d) (2) 27)
Cas (b - (2) A

I
⑦ ⑦ W

: ↑
↳ 1 - W - -↳ =O
I C
->
I -
L I
/ - - ~ - ~

(i) (h) 28)

Mesomenic effect(M) or Resonance effect(R) it

C 3

*
Effectwhich are
produced by resonance/delocalization of e
in conjugate system.
*
Type of mesomenic
groups:(i) + M groups (ii) -M
groups

C
+ M or +R Groups:
-, i
* edonor in conjugate system.
have love firstatom
*
They pair on
of
conjugate system. -
~ ↳

I
Me
.
+i ine

Relative
strength of +M groups

⑦ ⑦
-

(> -N)-8, -

i)-NMR)-NR3-on>-R -

W 0
⑳
11

<--d-r- in- R
.

c-
Br-c<- f(-c=en <- c cn
=
-

1 - N=c
 for 1: : Br:
halogeny cn <m cn c4
c
=

->
= - =

cm
- -

& P
-

&- -
③ &
G
18
- -

c x
c Br
- -

--
---
0
D--0. - 0
o j ⑧
I
2P 2P 3P 20 20
IP 20 4P

M/-R Groups'sexe withdrawing groups in

conjugate system.
E
-*It have multiple bond on itatom (should be more

electronegative element).
Itmay
* have vacantorbital.

C
Relative
strength of -M
group it
S

o
0

4
-

>O
- c N)
=

jo - -

n) -
-
R) - 4 -

·V
0 - 4-

) 4- -rm(-- oR 11

am=aX < -c c -n -

--R --
D

-
11
-
n 3 -
i -
e 7 R
-
- M

o
& ↑ 24 -
"-
of -

R xm)
- C > - - -
-

-
=
c > -

Hyperconjugation/Baker-Nathan effect / No-band resonance -

L ↳

When
*
min one c-U/C-D (obond) of sp carbon is/are present
on

adjacent position of c-c multiple band/+ivecharge/carbon free

radical, then these c-n/c-D o bond orbitals is/are overlap with

adjacentp/a/** orbital, special

this delocalisation called
hyper
conjugation.
U.C.
* possible in
following structure: -

(x) spr ~
M/D
sr
<xD)
4 -
S - - c c
=
- (21 - -
c = -

23I -
-
=Y
↳
-

I I I

:
WD
I *
21 -
-
C -

c- 255 -

I Spr
S sp2

H
n
12
- ⑦
cm 21 cm <
n. 2 in alkene is (n <1 c -

as Cit H-
-
--
=
=

L 3
in In
It W
1

"I
H
I ⑦
8- I ⑦ Cu
8t ut C CH2
-
-

c=cu-2t
-

<
c-cr_-_Cm H -

i
. - .
. .

i *2
se
n+

Bond , 1.5
length y< Z ,
x 31.10 y z

2> 1.34 A
 vacant,*
->

H
9o D C u cr
I

III
L
-

R
- ·D
(b- H i s in carbocation/carbonium ions it
< ↳

it s
H n H H

I ⑰ I
H C Ch <
In -

2 ct
=
L 3
H
⑰
c cm<
=

-n - k c
=
->
...

is t
-

i ↳ in n

It Hyperconjugation in free radicale: -

< >

⑭
n-zer
③
↳
↑
8 M H H
:

d 1
H -C L
⑧

4 em
=
n -

a
=

u....
=

↓
M

he i

CdS
<
typerconjugation in Tolere
(Ph-c
H
H H H
H ↳St
c
+ I I

!--- C.... St
f I t I
n -
n
+ 4 c H H c H r c H
-

H
-

H
- -

c
-

I I I "
/
if wo
E
--

A
④
- -
Er --
-
3 x 3 5
=

Total hyper conjugation: 9 +2=11

L
Note
it (it stability of alkene and alkyne < No
of hyper song. Struct

ciit Is 3 Carbocations 2 ' -1 3

iiis 1 , "Free radicals C -

> -

Live Hyperconjugation electron

is
donating effect
Effectivity, Resonance effect) Hyperconjugation) Inductive effect
donating nature M) ) I
+ +4
I + +

Me
C Me
eg. Gins CUS Me
-
-

S- S- -- S-
6
x --

So So So

IV. On aromatic effect is applicable ortho and para polit

ring r.c on

tion (equal effect).

[vis -u > c -
D(n.c. effect) because c-n bond is weaker

the c-D bond.

Application
L
of Hyperconjugation,
cit stability of alkene: (2No.of d-n)

Cm ac

12 d-H 9a -
H
6d -
H 3x -
H
NO d -
H
 (ii)~

<
Stability of carbocation: (CNo.od-H)
-

⑰ ⑦
> ⑦> 0 > Cub

9d -4 6d -n 2aH Nodn

free radicals in (CNo. of a-h)

<iiit
<
stability of >

⑳
5

> · > X Cub

9d -4 6dt 2 an Nodn

Live Electron
density on aromatic
ring it

L -
C <H
Cu -cub -
an-c I
(-c
I CB
-

I I I

0 0 D 0

3d Ian -d
2an

E -

(m) ) -cu(CB) - ) -

cur- > -
cu effect
+ I order
3
[V-> Bond length of C = c in alkenes < no.
of U.C

L >

C1 <1
=

d-H 3 -d-H an d r

E. 1.34A
-

0
2 -

1 - dN 0

A RA
↳

1.39 1.3 1.35°A 1.3

u.clit
L
Reverse
hyperconjugation (-ive
-

X XO
X X
I ⑰
I ⑰ I ⑰
c Cn cm < ⑦
x I c- cn-cU2 [->
=

x
-

/
W C
cn-cU2 <> X -- Cn-CU2
↓ ↓
-

Y
↓ xO

X -
-
x
r
XS-
SSt
+ -- i St

X C
(n-CU2
.....
....

S-
X

If

Application of electronic effects: -

L b

[ItBayer's angle strain/Ring strain it

< >

Itis represented difference between ideal bond angle and

*
by
actual bond
ring.
angle in

Ideal 109°5 109.5* 109.5 109.50

[Acterature)
angle 90 106 120
60

Actual 49.50 19.50 1.50 10.58

angee
 Angle strain -
cyclopropane) cyclobutane) cyclopentare) cyclohexane
stability -
cyclopropane (cyclobutane (cyclopentare<cyclohexane

Note's cyclopropane can show addition reaction.

m+
3
Ni/Pt/Pd
X
Bu Bu
Be > - ~

Heat combustion & cators

of is Heat
of combustion no.
of
2 I
for so.

6 5 ↑C 3 stability

>
creatof combustion
>

< L [
Heat combustion
of per c >

↳ <
Que
Angle Strain order

<1 3
-

[11- - ciiit <ive

ic sp
- e

SP
so so
-

< sol, Angle strain i < ii< iii <iv

Note's up atom is notpossible in small ring (up to 2 men-

bered
ring)
11
strain)
==(Angle
11

[2-) BRADT's Rule:- this rule conditions

plenarity
< 3
According to
of
a re possible
not bridge on head atom
of
Amal (Upt> membered ring) bicyclic compound (due to
sing strain).
This
* rule is not
applicable for fixed ring containing bicyclic
compound. (eg. 3
I

eg. 06 -
y

5 3
[Norborname) -
Bycylo (2,2,1) heptane
↑
C,4-bridge head)
- sp - sp - e
0
ji sp I -
-

-
L
is
Osb If there no resonance
sp
Unstable
# ② ③ -

(x)
⑦ ->
stable (Exist in nature) Unstable

-
 Stable (v) Unstable (X)
U
ep2
in 3 sp
⑫ X ⑮
SP
⑰
-
(6- ( -

yyewi
26 -
2105
-
~

Qu
(1 - s
3 3
,
D

(B-
compare

(ii) Delocalized
stability

Bond
love pail

ciis =0
length
Live CNBondlength (V) edenity on (vi) Basic
strength
·h
L
sale (it
ciit
A)
A ~
B

C
(A
delocalization
show resonance)
of er in is not occur
3
ziiis A > B LIVE B>A CUS BSA CU BSA
*.2

3 Gunstable)
(27
I <stability) ⑦L ⑦

s
S
<Stability)
Hrce
No
2 H.C Hydrogen
No resonance

Steric inhibition in (SER) effect

135
it
resonance
4

<Steric hindrance - It is the repulsion between

bulky groups)
In compounds disturbed
*
some
planarity of conjugated system are

also
by teric hindrance, due to resonance
this is disturbed

This effectis called SIR effect.

* SIR effect is applicable for bulky groups like -NR2,-coon,
-

NOr, -Br, -Ie tc.

Me Me
Me
Me in -
eg. ~I
B B
C
B-
sterically active group
B
(S[R) H, D, F,
=
0-, 0n, NM, CN,

<NO SIR) ⑦ ④
m
-

a, ah,
(is (ii
B =
ce B, I, NO2, coon,

Resonance
* A
> B Nh-Me, -NCMe)2.- CONB,
energy
-> -

⑦
C-
* N bond length - A < B -

LOOR, -

I(Me)-, -clMe32,
I
* density on
aromaticing -> ATB -
((Me) ,
-

<Cy,
-

2Br, -
53

* 'I I x -> ALB

-

AL B
Basic strength
->
*

④ ⑰
Me Me Ma - -
Me Me - Me
eg. c

I
Me Me ↑

↳stability order)
 Me
Me
eg.
z
x y

Me Me

(a- )
267 <-

Resonance c>97b
energy
-

Bond length
I
2) a > y

C4- Dipole moment (l) It bond

↳
it
7
is a
degree of polarity of on

q -
q differentatom
eg. H > c
u qxd
=

unit->col-m(S.I.1

e,7
esu.Cm(CGS) or
Debye (D)
Met e
h,+l2+24, b, c0s0
IO2
=
*

*
(A t B) 3
Mmiy.= MAXA +MBNB
MA MB
XA *B

* Non polar compounds (r 0) =

al
Fr I
Lu 0)
it0- Ic i( 0) clie of (Mnet=0) (iiit
=
=
= = C
B

C
f le 'ce
F
I
ce -c
(ive & 0) (ViT OF3Cl2 MEO
- 0
C P u =

c P =

CV
-

-
-

- c

a I

Dipole
* momentin
organic compounds
cie Cu + NO2 cr-CN) cr-on) cry-cr(r
0),
> cr-cUo> =

<Dipole momenton the basis

of -

effect)
I

sp
2
Sp sp3 sp SP 16 S P

ciit Cl-CH
-

Cy cub-cH c
=

Cr ch
-c =
(EN -
1P >103 164)

E U.

ciiis <B-cm
-
ce Cm c 4 - c
=
H - c =
c -
c

-> pr 103
Sp

Live n - F ) u -
c > n -
Br > 4 - I

[V+ <-c ) <B -

f) <B- Br ) <B -
I (Exception) (r q.d)
=

(215 -

f)(,45 -

x)(215 -

Br) c45 -
5 (No exception)
c C C NOW (+M)
N
c 0k 0 Now
(wie e
=

I I I I q ↑ 1 14
-c -
⑧ 0 ⑧ Eviit ⑧ 0
X
(iit ⑧ ⑧ 0 0

e
↳ ↑b rot im* 3 Mre(M)

v
C
mo
- ~

sixt
L
(x- -
- 7
-
A
C

[xiT (xiif
in i
\4> 5]
or >Or n+ +

H
n
D D U ad
 .I .4
(xiit N N

H I e
F ↓ f

G
Note G
E - I M G
-
~
or Or
⑧
= C

M
G
'
d
Pala trans Anti

(1) IfG = -

x, -

c,
-

xxx,
-

NO2, -c00,-cNetc. then b=0 in all

above case

Clie If G =
-OU,-OR,-SH,-SR, -coon,-cooR,-coce, -ch-d, -cuchete

then MEO in all above care.

n Or,-*
8 -

8 a c
eg. I ↳-
R 911,I ↑
0
0)
0 0
<enet 0)
0)
=

Eleint
=

+U net 0) =
O (net =

oor-o ↓

H
Eit oxt-o
- n
Cl
I↳ 11197

Ch
a

e
o
I

0 (Mat =0) 0 c-cm-cm -

c
(Mnt =0)
EUnet =
0) C

·an
"1111 C
H C C
C C C n -
-
c

H n
n -
-
un I

na"( 0) Eu =0)
=
H

* 0 0
<Due to bulky group)
H U H Cu
CB (B

*
cr- c
Ct C2 NC3 <Cp (Due to
bulky group)
I
LAM
So-Me
I I
c A
I
*

E 3
O O ⑧ - I
(a) a)b 0 Me + M,
- -

(a) (b)
dominate
↓

dow
on Now

151 stability of alkene it

< S

Stability of alkene C delocalization of se

< No
of hyperconjugation

it cit, <M cM
- -

1/
=

"
-
Delocalization of i (Resonance) (No.of -

n)

-
Liiit/ - (Resonance dominate over
hyper conjugation)
Resonance v Res. =
X

u.c - X n.c. x
=

divy / W 2
I I I
I
(V-> 1 I I I b a)d>
2 -
~ ~ > c

I I
(a) (b) () (at (61 (C- (d)
X R x
R
=

R V R 2
=
=

b
=

(a) dH 2an 10 dU
2 au
1
 (vit ~(a) / / (b) - (2) (d) -)b)a>d
6a, R-
RV, oan RV, san RX, 3an

is branched
Note:- * When no
of den same then alkens are m o re

Stable than umbranched alkeny.

eg.
-
Stability)
6dN 6dV

* Branched alkane isomers are m o re stable than umbranched

alkane.

Stability of alkane
Branching
Because have greater Ic-l bonds which
isomers
of no. a re

stronger than 2 c-n&3°c-n bonds.

El
Cr - <B +
4
Cr
CH
I
n Es 1.
C - 4: Ez
E,>
-

C
-

a
-

dus dus
Ic-u> 2°c-n) 3°
strength
c-h
Bond
* -

eg.
six 1° c-n Nine IC-l bond

Heat
*
of formation (Enthalpy of formation) (No. of atomy in one molecule

C
Stability (for isomers)
Heat
*
of Combustion a No. of catoms

al/stability) for isomer

Heat
*
of hydrogenation & of in-bonds
n o.

<Cystability) for isomers

e.g. CUp<<2Ms<<N0 creat

of form. & Heat
of comb)

for geometrical
steric
isomery &
* ->
Stability hindrance)
H Ch
- -n
(viis c C
=
C =C
-
<Stability)
C C Cr

Ci Trans
Cub Ch 245
-
c
-
-
(viiig C - CI
H
<Stability)
U
C2H5 Cr

(ix- -
-
I <Ring strain) (Stability)
↑&H ↳an ↑ dN

(x+
11 (xis -
xiis
can
-
-

↑d 5 d rai
7d loan

xiiif
↳Higuain)
strain decreases in 5
sing
(Ring
want
7 dr
 Note:- When no
of conjugated me are same then linear
conjugated
isomers a re m o re stable than crowed conjugated struct.
⑰
eg. - ~ ④ /
i
* -
Linear conj Cross-conj
Lineal sonj. cross
conj.
11 il
-X
A
- - 7 X /
I
I I
1 I -
/

Lineal Cros

Bond order:
16- length Bond
length C
/Multiplicity of bond)
-

L S

Lis Ch= Ct < <c bond

length)
-

I c
- -
=

(iit ncmcu u -
B
24
y
= Ch nIc cr
bond order
c-a
length -> x >8>2
- -
k H 1/ / (a) B) 8

↳iiis - Cu cu
civt - E x ) y
Fyr
-

- A
x
y > x y
ze
X
<Ve
yA
I
- I
-I
0 0
-I
=

"I
->
-- x <y
/ -
- --

stable
-

most

⑦ O ⑧
⑧
11 1 11
! 20
bond)
C 4.
(c
C 2 . C
(vis
-
0
N
=

H A 2 ↳H u NM CN

191 (b) ( (a) d)) b> a

⑧ -
E
s
11E 11 11 8

(wiit
C
bond 2
LY
length
C C -
-- -
Cr 0 (t
0 a
-

4
L

Cu I
ch I a 2 -
0 bond
length - d) B
B0> 1.5 ↓
↓
P
=
c- b
y 3 0 1.5
[viiit c E
=

cry- k <
-

-n
--
a
↑ x < (a =

b) <
y (Bord length)
o
--
V W

Cu
E x -
y) Ch c
-

=-
n - 8

(a b)
=

Me
Me
x
y
cixt ↓ ↓ x< y

Me Me

(Mare Resonance occur cheures occur

fr ol y
ok,
↓

no
P c 0
OKN 0
0 0
- -c
2
=
= = =
c
I
* I xy I
9
~CU
I L
- -

1 b

SIR effect)
↑

/ /
(xiit
/
xcy(X13 xcy /
I I I I
(x- acb -

8)
- -

-
↳
Me C
-

y A
(x >

x
, Aromaticity's
-

>

conditions of aromaticity:- (it compound should be

cyclic
C >
lit Ring should be
planar, unsaturated
and
completely conjugated.
Liiit Each atom
of ring should sphybridized (in some cases sp is
also
accepted.)
 ins Ring have
must (4n+25e (Huckle's rule)
n 0,
=

1, 2, 3, . . .
.

(In + 2)x 2e
=
6x2, 10x2, 14xe, 18x2-...-

* Aromatic compound gives electrophilic substitution reaction.

condition
for antianomaticity compound (Highly unstable)
L >

(i), (ii) it conditions are lame as aromatic compound.

(iv-s must
h ave Inxe- >
Ring Mae, 8xe, 12x2 . . . . . .

order Aromatic cork.) Non-alomatic comb.) Antiaronatic

Stability
* ->

Antiaromatic
* compound does notexist
atro o m temp. (highly estable).

Ou- Identify aromatic (Ar) non-aromatic (NA), Antiaromatic (A) compound.

sp ⑰
a
⑦

cit- NA
2
+
11 -

Argitt - A sing-scein (reI NA (visI I lovea

④
1b
⑰ ⑦

(viis I NA [viiis I
④
Ar
(ix) I ONNEAcx+1 ⑦
Ar
xi 1 I N. A

⑦ ⑰ -

wivl
GaveA r / / -
I dare, A I Ar Ar = Ar
(xiis
1 I xiis 1
cars. xriy I
1 ↳
↓
+16 * Au
YNA
NAS
C↳s
-

12 - *i)
62
1 sxe
48- C 151 I W see
(22- 65
-

I Ar E I
+
1 Ar
e 1 Ar I I I
N 65 W Ar
spe ⑦
- - -

Trop ylium

Nonbe
I

e
-

I I -
22311 I (24) 6x
& ~
N Ar
⑦ ⑦ in

10x Ar

se
in
se (255
[24- I I I 2261 / - 6e
(Ar) j
(ArS (Ar)
-

S 0
-
-
I
Thiophene Furan

I
in
(225 (201
&, [299 / I
--
8
F (AA)
L
=> s
f) B
- (A i
in ↑ Me

Sp ⑦

cos
⑦

6 1311 6 652 8xe (A)

/ 1 I (312 11 (339 1 I
(Aw) (NVA) cArs
- & -
Be j j
~
j

-
- 105 e
-

[341 12x2 (359

=

- Ar
I ~
/
-
(AA)
zuhene
A

important
↑

aromatic comp.
<
3D structure
of >

Pyridine -888
unrybrid
↑

Sit de
& -

parbital
-i

888 hybrid
rL
sp arbite
(1b)
 88
P
"
it Pyrvols 88- (is Frame
I I - n
1.2
I 1.
-
·spr
-i ~
↳-

88/0 ↑

88/0
in

parent U

Bb

"Deb
bond weaken than sybord. (localized)
sploverlabbing
[ivs Benzyne <1, / S
-up L

↓Reaction ... Je (Ar)

Intermediate) I
n

(v) Borazole/Borazine/Inorganic benzere ->

Ny By Us

n
I

iS zi
-"
1 -
n
-

/ 6x A r.

82 -"
&
11
-

...........~......
B
-H
....... B

8
- D
n -
i
T

B
-
i S

N
n 0
i
Iti s
* m o re reactive than benzene
*Lesser stable than benzen (due to polarity

[vit Annulers it complete conjugated monocyclic polyene

↳5 11 -
24] Annulare -> AA (ii) ->
[6] Annulere - Se
I
W
(Ar)

(iis
-, [8] (Non-klamar
2 Annulere - Now A r.

I
->
/I
-

sins in
(V-) 12 All is

I
(10]Annulars I
(10) Annulers
r ci, cis, Trans,
↳
-
W I Now. Ar. (Non planer)
dis, trans

Non-Ar. (Non-planar

[vi-

⑰,
123 mee [14] Annulere
I
-> Non planal wiie Va partial
=>
aromatic

->
Non Aromatic I M
-n
I
-

L
Example of polar aromatic
compound,
o so
P u-high
102x(Ar)
t

cit L I

8
-

o
⑧
11 I I

(ii-
I
&
[Trobon) <>
, 652

(Ar)
t
re
high
- -

↑or d
-....
O ---
⑧

(iii- 7
<

I I
t
10 I'........
10
-

I I [M-high)
-
 ↓
(M high)
live
=
-

↳
L ↳ C > ⑦
O
20 6se (Ar)

(V- t

Gr=high)
-

[ > C 3 ⑦ ⑰
I
[AwS
6
6
⑰

Wie I ↳ 2
I ↳
O
· (M-high/water
S

soluble)
-

L
-
-
⑦
6
Azulene 65 -

↑
D O -
(vii- I L >
I
I

->
-
+

Y -
t
O --
25
CAr)
on
&vilis ↑ E on
of on
O
- ↑
I (squaric acid) ->
<
I ->
-

*
-

+t

on I ⑦
.... ⑦
on - / -
CAr)
On
2x
-

- in ⑰

(ixy A ⑦
-

I G
L > I > - -

/ ⑧*, ⑰

18- Electron
density on aromatic
rings/Reactivityof aromatic compounds is

L >

E
I

-1 E* SE t

↳Electrophilia substitutionron)
↳
(Electrophile) >
8
-> H

reactant
=
Reactivity of aromatic compound (edensity on aromatic
ring of
Reactivity increase in presence
of donating group (Activating groups (
=>

( + M,+4, I)
+

I decreases 11
"
"I withdrawing groups)-M,-1)

Identify aromatic
Put order
of electron
density on
ring.
Ch
I u ins
(i
⑨
O 0 0
⑨ O (ab<xd)
⑥ ② -
Cr /S
-
C
UC 3 d ~dr dN
id
[B
·
-
I

(ii 0
(b)
0
2)
⑧
CdS
O 0 (b)xd> e)a)
(a) (e)
⑧

-M)
M)
(N7M)
(No
+ I ( -
C-
+

NO2
cs
N
-

c -
- c
I I I

ciiiy as 0(b) 0
x-
⑧
(d)
O 0
(f)
0 0
(e)

[Note:- In vitroso & halogem-I effect m o re dominate than til effect

d)b))a)e)g)f
 it
Other applications of electronic effect
C 7

(It Type of reaction intermediates

(ii) Acidic & Basic strength

(iii)Acid-Base reactions
(iv Tantomerism

Types Intermediates -
of isolable
L S
van
f
In general reaction -> Reactants
↳
transition
or state)
Intermediates
-> Products

<Isolable
type of Intermediates.-

is carbocation (it carbanion (iit free radicals (iv) Carbene (VI Nitrene

vie Benzyne

(i) carbonionion or carbocation is

< >

30 20+ 15 10 25
+

De t

120° ( C &+ >E

notexist)
Isvacant
arbital
C
<does
8
ep" igonal Planar) so
=> (Lineal

*Incomplete octet

* Electrophile
Lewis
* acid

Carbanions -
-
1
C >
A complete octate

6e's
* in bonded pair +2e in non-bonded (love pair)
Nucleophile
*

30 20 + 1x 10 2x
+

(in]
-

[ [cc=]-
-

-
=
I so (stable)
162
sp"Trigonal (bent)
Pyramidal)

is free radicals in * Incomplete octet

[ >
*Tecontaining (be in a bond + I n ow banded unpaired ef
Paramagnetic
*

30 20 15
+ 10 297
+

I D (Westable)
IC =
C
=

I
sb (line)
No trigonal
plamal)
(iv) Carbeneit :
C -

Incomplete
* octet

bee
* in bonds + 2 non-bonded et
there
a re two types of carbency

cas, singlet Carbere L Om):

S

vacantporbital
A-
*** sbarbital
-
-
j
~shaped

(Diacragnetic)
0
265Tripletcarbene Locm):-
L >

Po
"I 02
SP (lineal), paramagnetic
U C H

<Triplet carbone more

is stable than singlet)

x
+

Nitrene
<
(4:), is *Ser ze in bond - he nonbarded)

(d -)
C
Benzyne
(1),

-88 e
xweak
H H
I

"-
I
spo
"- I
-Il
rf
I
n
0 - L
-
-- o i
OSAb
bond

↓
n

- ↳In same
place)
LoseAr)

factor affecting stability of intermediates

< >

it when charge is present

on
differentatoms of same period,
stability
Then depends on E.x
of atom

(ii atoms
when
charge is presento n different of same group,
then
stability depends on
size of atom.

(iis when
charge is present on same atom at
diff species, then
consider electronic
effect.

Electronic effect
L >

*
Stability of ion
charge density (charge deity
=

Magen
*
"Celocalization of charge (Resonance)
17

cation/free radical stability increases in presence of donating

*

groups (+M, +U, +1) and

stability decreases in
presence of e

withdrawing groups (-M,-I)

* for anions, stability increases in presence of it with drawing
groups (-M,-1)
For Ifo r atom)
cation & free radicals, stability &
Scharacter)
*
same

for
*
anion, stability character
 General order
of stability of carbocations
< >
⑰
I C Ch
#
↑
* ⑰ I
I
Ct C⑧
t /
I 7
-

I / ⑰
-

cycloproperium
*
c m ↳

Cyclopropyl Allylic
Tropylium
-
->

con (6) *
2x (Ar.) 3 alkyl iBenzyl
R.S
methyl Carbo
3
*

-> Aromatic cation

⑰
⑰
-> 7- R.S ⑰
⑰ ⑰
R-c
⑰
I R R
⑰ CH Cu
Cr
-I
=

alkyl
E

R c C , to alkye
=

F ~
2
-

I I -
↳
Kingl
↑x cation
Ring Arge
Anti strain

E
unstable
Highly

Note
is cyclopropylmethylation is
highly stable due to delocalization
L

of loosely bonded o-bond electrons

ring of with vacant

p-orbital of five charge carbon.

(Dancing resonance

B
d
so
--

gall
8
sp - .....
....
C

8
-
Ct
⑰

sp &-8 - --------
~ ....... -

=
Sp3

I.......
⑰
⑭
ch L ->
-

3
--
-

-E

⑰
~ ph-cm
A
stability
I
⑦
*
* .

7 em > I
I
-

General of carbonions
order
of stability >
L
Sp
⑦ jp3
0
- - ⑦
⑦
- c
1 I >R > Pr -Em
c
=

- -
Oh
-

a ↳ -4
cm -
-

/ 2

In
-

657, Ar.) du
->

-> 5R.S ⑦

Lu
⑦ ⑦ ⑦ - ~O
⑦ I
R -c -
R R -
CH R-Ch ( r CH =

↳ R2 i

"
- 0

(Anti Ar.) -
Spi
Sp
General radicals
order
of stability of free -

L 3
Ph Ph

On-ca>Ph-im).<R-c
I
I

Ph 7
C
R-in) R-cm> in
-

R)
in ② R .

2 c iH
=

R -

c c
=

I
/
 Example of stability of intermediates: -
L >

(1 -
⑦
Ch <No
⑦
<n<r* (on the basis
of EN)
⑦ ⑦ ⑦
(25 PM <SF<C L -I ↳ S

[39 F
-

⑦
<ci <

⑦
Br < I
-

C size is the "factor)

H
145 04 L S
⑦
⑦

OR L S R
(59 -

⑦ ⑦
(6-7 0-ph <S-Ph
⑦
⑦ ⑦
2- R-cuz -
ct R -
cn = 21 R - c =
C

⑰ ⑰ ⑰
28 1 R-cm-cm R cn cn
R c
=
=

-
- c

191 R -
C - c > R-cn in
=

7 R -
C c
=

⑰
1 ⑰ Ph ⑰
401 -
c- Pn
⑰
7 Ph- -Ur 7 ↳ -
Ch

on Ph

On ⑦ Oh ⑦ ⑦

<II-1 C-Ph 7 ⑦
7 Oh-cm 7 Ch-c
Ph
Oh
⑰
⑰
E12-3 ⑰
191 2b] (C)
⑰
(1 a) <>
b>d(io-of d -n -

nc)
⑨
⑦
I
⑦j 02:
-

(13- (a1 (b) [1

b > > ac z
+
-

effect)

④
⑰
⑰
(4
291 b)
2, 2 ⑰ (d) b > cd> a
(an & Bridge cation)

⑰
⑰
4159 (a)
I
(Allylic)
⑰ (65 I (C) I a)b> c

(167 ⑦
⑦ a) b
19t I (b-)
I xf I

<Ye91
④
26t ~( 3
- ⑰ 10
(df / a)d)b)c
⑰
2
O
⑰
⑦
⑦

(18-199 (61 - ↑
2d
/ a)()b) d
⑦ ⑦

S
1.
(19 +

195
1
26t
.

c
⑤?.

-
1 [de I Eef 2
i e) ()d)a)b

⑰ ⑰
[20 CM3 CD3
⑦ ⑰
Cr Ch -Dz cD2 <- n<c-D Bond energy,therefore m o re nic
2
211
-
-

Cu -D3
⑰ I ⑰ I

222-5 Ch- C- CHy CD 2 -

C -

CD3

au key
⑰ ⑰
(23 -) ac - (Dz

⑦ ⑰
⑰ ⑰

&1- )
(255 ⑰ ⑰
<Dancing resonance)
2267
⑰ ⑰ 22°c >/xfor]
④ ⑦
resonance)
(274 (Dancing
(20 -)
⑰ ⑰ + effect)
I

*
⑰ ⑰

s-) (at (b- (-) de a)b> d

< I I I

(Ars (NAr) (N. Ars Ar.)

(A
⑦ ⑦ ⑦ ⑦

d) b> >9
1309 al
2be I (2f (d-
I I
2-
-

A. Ar N. Ar. NAr. Ar

(3 i f(af ⑦ (be (C S (01 (a) b>d)

-
⑦ ⑦ ⑦
NO2
F
-Ieffect)
-N

0
⑰ ⑰ ⑰
cr-im x -n > cm-o ---
(32- (af Ch- - -M
-

+M effects
⑰ ⑰
(33 -) cm-im> Ph-c-Ph + M effect)
in

[341
⑦
Ch- N
0
=
7
⑦
2 - C
-
-

-
>
⑦
cr
-i-o-c >
⑦
cm -
-

- 8

[35919% (b-
⑰
LC1 a b c -
effect)
I

- 0 e &
⑰
O
⑰
⑰
cry!
CH3
2369 ~
(b) a <C) o-

(a-1
26t ⑧ (C ↓ - c (
-
I)
(+M)
⑦ ⑦ ⑦
2379 (as (61 (C1 - (a) bx c)
NOZ Yoz ( I)
-

7 i)
-

⑰
⑰

2381 /
I -I
I (Moreno. of benzanoid R.S.)
7 ↓
I

⑦ ⑦ NO2
(397
NOZ
Now ⑦

2
-

1) ( I)
-
L M)-

⑦ ⑦ & X-vacant
L
d orbital)
2405 F
CM <M-
c
-

(41f
⑦
CF3 < Oces
C

⑦ ⑦

2&- 2 5 cin-cF) > <m -

cx3 - I effect)
⑦ ⑦ ⑦

(139 cm-cl > Cl-Br ) < m -

I
(3d)(d)5d)
⑦ ⑦

(44I ↳
C
f
Ch Ch
Cu
cu S I S
Su / 8-
245-5 / /
(455
/

- -f
I I I
~
-
- 2 2 C
S-

f
I
be --

· ⑦
⑰

247
⑰u ⑦ Qu Ch
I -u
/ /
/ /
I
/
I
/
I I
/
I
(d I (C) If (9-)
(as -
(b+
-
((-)
- - ↳
-
↳ W
iP
du ↓- a ↓ -
c-c ↓ -

bu How

d) a)b)c)e)f >g
 ⑰

2485
⑰u ⑦ ech Qu
/ / / /
(as -
(b+
-
I ((-) - (d
-
I a) b) c>d(n-C)
I
I I
cu Ch

⑰u
⑰
a · Qu
[499 / / / /
I I I
(d
(as -
(b+
-
((-)
- - d) a) b)
I
I I I

B CD3
I)
24. zw.C) 2 +

⑰u ⑦ · Pu
I lint- <my
- -
-
3
UC
+
(0, PS

(0,M,P)
-
/ /
-I -
(505 (as (b+
I ((-) &I I (a)b7d
-
-
- - -
I

CB

⑰
(u
I ⑦ · Qu -
M(0 P)
=

-
-

NO2 NO2
(0,M,P)
-

I
/ (a)b > d
-

/
-

-
/
(5 If I &I I
(as -
(b+ ((-)
-
-
TOz -
I

NO ↓

⑰u ⑦ · Pu
I M(0 P)
--c
=
+

+
/ / / a))d)b o
(B

-
-

(52 -
I &I
->
- (0,,P)
(as -
(b+

- ((-)

0
I

-
c
-m
⑦ ⑦ ⑦ ⑦
Now (b) a)d
/ /
I
/
I
/
I
7535 (as -
(b+
-
Tow
((-)
- (5
I

NOZ

Rearrangement in carbonium ion is

>

*
Migration of a
group
or an atom with bond electrons on
adjacent
electron deficient atom. Breaking
r
U...formation
eg. <-
In -
⑰
cm > Cr -cn
......
*cm Scry-En-cu
P Transition stat 20 (More stable)
*
Reallangementcommon in -> carbocations, carbend, nitremes
/
r a re in -> calbanions, free radicals etc

*
Daughter cation should be m o re stable than
parentcation
Only 1-2 shift
*
possible in rearrangement.

Type of shift is
9 >

is Hydride shift (ii) Age shift (iis Ange shift (ivf Ringexp-
ansion (V- Ring contraction etc.

examples:
⑰ H-shift ⑰
>
21-
-

225
④⑰ r-Drift
↳
⑰

CH3 c shift ⑰
(3) O
I >
⑰
24)
,
⑰ >
20
↳
⑦
3
 ⑰

(55
⑰
u-chitt X
>
>
⑰
⑰
2" (d")
20 5 a n
[Stable)
Ph Phstift Oh Oh
④ L
26t Oh
Ph
Pr
⑰

(7- >
- ↳Allylic cation)
⑰

[n* nnl
I

28+ 7 >
Om I Ph 1 Oh
3
⑧

inses
⑦
294 *
>
>

In Ph de
0
⑭ 0 I
> >
2101 ⑰

⑰
(11- ~ ⑰
>
-
⑰ >
-

425 Me
⑧
⑰ >
Me
:
-

⑰
(major)
④
O 0
S
[137 Me Me
⑰
(major)
⑰

&41 oh / ↳

ph
⑰

[155 one > -Me

Ph ⑰ Oh

Oh ⑰ Oh Ph
Ph ⑦ ⑰
3 >
2161 ⑰ >
Ph Oh Ph
Ph

2175 ⑰
> ⑰
0 0
-

⑰
(18f > ↳
⑰
0
0 0

Ph
⑰ On ⑰
294 On
< -
on
Ph Oh

(201 > No rearrangement

20

22't ⑰ S No
rearrangement

Note:*When time charge in carbonium ion

presento n adjacent
L >

position of membered
5
king then
ring is
expansion
4 or

possible.
give present four membered
When
*
charge is on atom
of or seven

contraction is possible
Ming then
wing

⑰
F. s *
222f (More stable lever sing strain
 Ring exp

(Major) (2.
t
2235) S
0
⑪

(IS >
(Minor)
⑰
E3
⑰ ⑰
⑰
stable)
.......

>241 I
i > <More

⑰ ⑰
⑰
2 53
I (No wing strain) >
<3
(1
~
X ⑰
⑰
> I
Note:t * ⑰ *

L 7 ⑰ ↑
↑v X

v ⑰
⑰ X ⑰
I
⑰
* I
*

R r
I -

⑰
⑰
u shift
2265 I
(Ar, 2xe)
⑦ ⑰
R. ex
[21- 1 I
>
I
⑰
Ring exp
2209
⑪

W
[295 ⑦ >
⑰

us ⑦
⑰
230/ -
(5)
(If
> [N
More stable)
Il
L -
CN
-
(11) -
⑰
<Lever stable due to [wa,ci)
[N

↑
⑦
4319

- I
(I)
↳ * stable)
(Most

(10)
211- > ↳Lest stables

④ ⑰
⑰ -
&. ex p re-Shift ⑰
>

(327 7 ↳

Acidic strength: ->

↳ >

Arrhenius
*
acid ->
ntdonor in
ag
medium
eguce, 30p, UNOS etc.

LOUdonor in a medium - base)

Bronted
*
-

lowry acid t Proton donating species in of o r mon

ad
medium.

UC +ro=-c+
-
rot
Batt Base Acid
Acid
 20
0
+
Nu -
0
nO + N
-

Acid Bass Base Acid

*
Lewis acid -> Love pair acceptor ->
Acid
donor ->
Love
pair H
Bale

NB
I
BF3 ->
n -
i 3 =
-
f
Base Acid ↓

Organic acids a re in general weak acid.

↳++A
-
HA
-

(w-AS <Base) ka
=
[A] [n+]

[UA]

pr=-log[ut) pou --log [OU]

Ka
=
-log Ka
prb log kb
4
-
=

P
-
pR* = 14 at 25°C
(for conjugate-acid bare
pair)

factors strengths
affecting of acidic
C >

A -

H.*, AO + H*
C. Base

- Acidic
strength increases - Value of Kass value of pat
conjugate anion
- 11 I - -
<Stability of
A -U Bond
strength t
- 1 3 1
↳ C >

Oxidation
of central atom
of At 4
- 2
'I 1 / ↳ no.

Presence M,-1)
>
of Ewo (
↳ ↳ L
-> 4 * -

-> U 7
decreases < >
I/ -7
=DG +M, uc, +
+

1)
-> Acidic
strength also depends on nature
of solvent.

General acids
<
order of acidic
strength of organic
7
E

-on>
on

R-Y-ou>
I

R -
/
I Cr-on > M0> R-ON > R-CEC-H > NB) CHR
I
2

_st,<c-ofoutM-o I
in*
M-c= E
!
↳
2

conjugate
anion
stability
⑧

R-S
11
-oU p'- c -
0H
Strvespective of E va & EDC)
!

3 (Electronegativity)
<1 -

> Cly-1 <NB <10 CHF

(2- P <As < nce

23I Lif use (UBU<HT (Size)

24+ 10 Mr S

25I Me-on MeSH

(of Ph-on Ph-SH

P
oH
27 -
d n c > CB -c -
<6 - 1504 I SO3

191 UNOS > UNOZ

[10- Ucox>nceos> ucon) noce

<I f-on <a-ou Back bonding F-o-<a-o-)

412- C-on)Br-on >I-ON (EN&B. Bonding)
434 UCOS UBrOS 4I03

(145 Hop> UBrOp> 1104

(155 BF BCS B Brs ↳Lacid nature, love pair acceptance tendency)

Pre) &_Br
r -> B a -
B - ce
Br -
B -
Br
↳B. Bonding strength)
F ⑧
-

0
02b - 2b 2D -
3D 20
-
4P
0
P
(16- H-4-04 r
-
c -
0 - on

<Formic acid) <performic acid)

4-o-NE
<125 (Nitric acid) n-o-o-58 parory nitric acid)

(18 -) n -
0 -
1 -0 -
0 -
n
Caro'sacid, peroxy sulphonic acid) (a)b)
⑨ ! ⑬
⑧
E

11

(199 n-c- on Formic acid) u -o - - on

<carbonic acid)
D -

2209 ch-2-on <1- o --on

vitamine-C)
no
acid,
22 1)
no
-
EAscorbic
on
a >b (More conjugation in
a)
vg ③

(22-)
"
oon
-4 -

SOH
on
0

a 11
(20 3 n, n coon
-

-
N I

0
F D
Barbutaric acid (24 n -
c -

on (a) b)xd)
②
(a bx) Imond
"
=

on
I
0

(253 u (b) a)c)d)(201 ⑧ 0 Il d) a)b>

b
Il
H
②
no
- I in
⑨ ③ ②
⑨

aon
0

2275 H -
0

"In
S
an in (a) e)b> d)c)
⑨
⑥
coon
cool
(28-u-coon crycoon coon coon

(Formic A) (Acetic A. (Propionic A) (Butyric A Veteric A. (caproic A.)

[295 <r-coon crc-coon cuch-coon <<cy-coon (-E-effect)

c
coon I coon coon

[30- <-I effect)

'Ce
(31 - cr-zoom <CMB-coon <cnce-cOon<cmE-coon

coon coon coon

Loon COOn coon
>
(32-) coon coon coon coon
cron
cooU

[Orcalic A.) (Malonic Al &Succinic A (AdipicA <Pimellic A

<Glutaric A.)
[OMS GAP)
 H
n CA

<335 C- - > =-
C
coon
7

M ooH H

- coon
n
-DOU
(34) (k)m) (ren)
4 4
m

H coon U (R,) f) (max)

coo

(Maleic acid) [Fumaric Acid) (10) m) (Ka,)f >>

(kar) =) (Ken) or

(Ray
4
⑧
11
o
U
-

C-o-
N Kaz
....
⑭ i
I
R ⑧

-o
-

o
-
9
n
H

phenol and
Acidic
strength of derivatives
of phenols
L S

Acidic
strength of phenol) Acidic strength of alcohol

Ar - 0 R-00

(More stable

ou on on o oh on on
on
I
(351
I I I I I I I

/ / / / / /
I I I I I I I
/

(a- I
(b) CC-1 -
(d1 (e-) - 55
- - 7
(h) -
boon8
- -

i cir ↓CH sogn ↳

xN
0
=

( M) ( I)
(M) ( 4) (M)
-

0 +
+

q)f)b)d>a)a)e
or ·H or on on
⑧
I

in -
I

(365 (32-) G
I > 'I (6-
3
/
I L cus--on
2 - -
-

a Now Now
<n.)
or or ·H
or n)
(
I 0
+

I I I 30 = + H
+

cus Cr
(39) Caf
-
I (b) I
I
2< ) - /
I
(d
I
(0),)p - I
+

2 -
-
- W
d>b) a)c

2, n) +
C I) +

or or ·H
or C Ib
-

I I I
c I
-
Caf (b) I 2< ) / (d / b)a)d
[10 I ()
-

I I I

↳ - - - W

Cl
C ( -
I) 2
-

I)

or or ·H
or I
0 -Me
c + M, -

I I I ·Me I
-
Caf (b) I 2< ) / (d /
24 1 I c)
-

I I I b) a) a

2 - - - W

↳ 0 Me
OMe

or or ·H
or
I I I I -
M, I
CN
eN
- -

-
(a) (b) I / Cd /
(42) I 2< ) -

I I I
d
2 - - - W
()a)b)
[N
-...
↳

CN 8

or
or or ·H
1
-0
/

-
I

I
I
/
I
NO 2
I
- Due intrance
to ordingin
(a) I (b) 2< ) -
(d /
NO2* -M, ↓
I I I
2 - - - W

↳ NO2
-)a)b)d X a)()b) d
NOL
 or or ·H
or
Note
L
is -
I I I
G
I
I / /
(D) I (m) I 20) I (n) I
2 - - - W

↳ G
G - 0

If G
N02/ -cn01 -4 R1 4 0R = P >0> m)n Acidic strength
= -
-
- -

-
Intramoleculal H-bonding occul

0
I

/ I Or
↑31 /
E I I
↳ / /
↳

a-Naphthal B
-
Naphthol

and derivative it
Acidic
strength of benzoic acid its

L >

Ortho effect / ortho rule t Ortho substituted benzoic acid is most

L >
acidic than benzoic acid and its ison-

els (meta & pare). (Due to SIR effect)

0 00 M
03 vo 0 &0
=
no-c c
= -
-
c
=
-
0
=

c
I I

!
I
Me
4455 /
I > -Me >
/

-
W W
acb

0
a
<Less stable) 0
b
·More stable

coon coon cook coon coon

! ! !
I
(16-3 -
I
~ ! -

I I I I
2 - - W W

coon coon cook coon coon

[17
! ! !
I

-I
~f ! d Br I
) SER effect)
I I I I
2 - - W W

coon coon cook coon coon

! ! !
I

(185 -
I
!
2 - -
I
W
I
W
I

I
I I I
C Br I

coon coon cook coon

Note:
! !
I

L 3
-
I
! G

I I I
2 - - W
G
20S a (a) LOS <n)

If G - -

cb( +
n, +
I) b O >n ) n) p

1.
-> -
c( -
1) 3 0 ) m) p>h

"
- - 2N( -M,-5) - 0 > P > m> n

1/ ↳
3 NO2
-
( -M, -5) - 0> 0 > m
> n

j
. . . -

-((+ M, -t) - 0> m) n

>P

9 - -
-
on (+M,-5) -> 0 ( m) n > B
/
-

(No or the effect) ->

(Intramoleculal H-bonding)
 Note: t acid is acidic than and other
*
Salicylic most benzoic acid
L >
isomers due to intermolecular U-bonding.
on
-
...↓ 8
-

0 ..........
...
--

- M
/
I
>
I ↓
-
- nO /
I

coon coon coon coon coo

I I I I
I
on
-
o
; -NOW / / on or

24 95 I I (587 0 ⑧
- 2 -

< Ortho-effect)
(Ortho effect)

importantorders
strength,
acidic
L
some
of
on 0
O
I

<1-S
'I
r -c-0H > / R -- o n
I
-
on

von I
-Non
/
Ley , cuycoon

A.)
-
(Piaric
Now
0 0 on
O =O rou
on
"or Il I
0

Now
I
O 0
0 /
(3-) =

--on
=
i
-on
crycoon > n-o
/
I
o

on oh zoU -

I -on
Non
59
↳varic acid C
-
<XI - ⑦

11
rO
E 11
-

n
11 <Ar)

<55 G Ch- G > 10 <a - Active

methyl group)
M) ( -M)
(
-

0
0
Il
11
mo>R-cECU
201 11

strength different
of family,
Acidic
L

sulphonic acid Picric acid > Squaric acid) Dinitrophenol

Carboxylic acid) Carbonicacid) Mononitrophend) phenol) Ammonium)

CH0U

Basic strength-
L ↳

(i) Arrhenius base -

or donor in as medium

(ii) Brouted
Lowery bases itacceptor

(iis Lemis base - home

pair donor

B: ut
+ > B -U

(Anionic base) conjugate acid

⑰
B nt
+ > B-n conjugate base
 factors strength
affecting basic
[ >

it Anionic base 7 Neutral base (Basic strength)

(ii) for anionic bases

stability
Basic
strength C
of ionic base)
acid
(iii) Basic strength stability of conjugate
donating nature
strength
Basic ( Lone pair
(ivs

(v e
availability on donor atom.

<- Basic strength increasy in presence of EDG C+ M, +1, +I) on

love pair donating atom

(vi) decreases (-M,-I)

Basic strength in presence of Ewo on love

donor
pair atom.

(viis other factors like U-bonding, SIR, steric hindrance, salvation etc.

Examples in
< >

⑦ ⑦

(1) Nm) Nu (2 -) On > 20 (3-3 Em> non> f

① ⑦
⑦
NaNC) R- c u R CR-cm
NaCry > NaOU (5) R c = cn
=

(4) C
-

25/ NaCMy Lich 26-7 x2b 20

o
I

P
27 <1 -

5 -
08 ab--ot 0 ·u R -
08
is
⑦
⑦
so O
(6 -
)
⑦
19 -) cr-ot
Cal [bt [Ct

(a))b)
⑳ ⑦ ⑦ ↑8
2105 Me-NU NU2 Ph NU R- C -
NH

<I fo a Br I- <125 not us

⑦
0 s
213] <r Cub 0
- -

⑦
i 11
c
Basic R
strength order > c
145 11 ⑦
-

⑦ Oh
⑦
Carbarion
stability(
⑦

(Reverse Oh Ph c-Pn
of ⑰ CH
-
-

⑦ ⑦ Ph-CM ⑦
c hc H
in
=

[1

(15)
in
·

"in
0 NH

-
11
-

NU
Il
R -

c c
=
Ph-, on One in Ph-sr
-

in

i ca=xn ) Nn =

916-) cry-ceh-sch CUz-c Na =

e r- i
i
(1 f -
-

Nich N -
b > >9
(a) <t
(35
W

[185 cr-im) / Nu cm
-
* im
-

(Al amide) (Ar. Amide) (Amiche)

(199
/ ~
I I I a)b> c) d
(41 2..
NM
(3] -
-
-

N
~ CC1 W

~
↓
id
in↑ ~

Parral
Pipyridine Pyridine Aniline
 ⑲ Krz
~

- No d) b) a)
220-
I ⑨
in
2
↳ ~
N

⑧ -> n*
I
Ne
Il
C
stable due to
equal R.S)
<2 If
-
C
NU
(Highly 3

N Fr Nth

Guanidine (highly basic

+
* M effect of two-NM group.
Conjugate
* acid in
highly stable.

Nm
ep"
NH NU N
Il 11 Il
2225 (a
NM sm
(b)
N
(C)
(d)
(a)b>d))
2

0 0 0
②
11 11
11 11
(235
N Nch
(a)a)b)
Na Ni

(a-) (b) x -(Urea)

⑨ N NH2 ②
f

i Yrz
-
1243 \N: ⑯ b) c)d>9

- u7
26
NM
(255 /
⑨
-
N -
N

(a)b)
(22 -3 Cl-NMe HO-NR NM-NUR

Chloramine Hydroxylamine hydrazine

amine
(285 Aliphatic R

i:
-

NA R-NM & -
NH R -

↓ ↓ R ↓
,
W
W
⑰
N4q R - * R -
⑰
NM R -
N

↳ R
-x
stability increases
from L-R.

Hence
* basic
strength should be increases from leftto right
Butsolvation from leftto rightand
* decreases
hydrogen bonding
decreases from leftto right.
Therefore,
* basic
strength (experimently) in polar salvent -

E
R Me
=
-> 2">1073° Nub

R Et
=
- 20 > 30)10> NU

* Basic strength in
gas phase & nonpolar solvent -

3°) 2'> 1 >NB

General
* order
of basic strength for in-containg compounds
Imidine) Aliphatic quire) Aromatic quire) Amide
in
>

11
Na (pn-Nm) un

Basic strength of aromatic amine:-

< >

Or
* the effecti t when substituenti spresent on or the
position
Nth them decrease due
of group basic
strength
-

to steric hindrance.
 "
I

No
U
n -
N
↳ I
[295
(a- ⑧ >
⑧

⑰
(a) ble Basic
strength
Muz e IV
H

Me
⑰ I
Me

0
(b)
/
0

Kesser salvation)
CO-Tolvidine)

SIR effect: s when a substituent is present on ortho position

L >
due to SIR
of -NR2 then basic
strength increases

effect. R. R
R
R-
↑
-
N

~
G
G
6 ->
sterically active
group.
~
(30f - -
I

I higher in
density on is due to lack
of conjugation
NM Nu Nich M NM N Nu NUz
I I I I I I I I
L ch
(31) / / / / (32 )
-

0 o
I
1- I I ① >

- -
- cm W
(P)
-
(m) cl
C n)

(b)
Cu(u.c (m)
E+ I)
(0) (n)
de (O)

p> m) n >0 n>b)m)0

(ortro effect)
NM
NM N
im on NUz im Nu NUz

[325
I I I
I I I Me
E -

0 o ①
0 0 >

<33
>

(P)
① -

-
oMe
(P) (m)
-
or
(m) (n)
I (n) I
(O)
on
cos OMe

p>0> n) >
I
m
p> n) 0
om,
m

Me - Me
Me,-Me NMe2Mez
I ⑰
Me
-
ier...
I 8t
NMC2
I I U
6 NI
2359 I
+

⑧ 0 I
① 0 0
(34 S
- ⑧

Me
Me
<righly basic
I

NO2 NO2

( M)-

St
(367

" -
↑.... N

So, 0

n, ⑧

↳Highly basic)
Acid-Bare reactions:I
L 7

condition for acid-base reaction: -

Acid should product

of reactantside
acidof
* be
stronger than side.

Base
*
of 1 1 ·
I 11
- - / ↑

Ar f BO S AO + BH

Acid
Acid Base ↳Base C.

⑦ 0
A
t
> Br -> Acidic strength B) A (Basic strength)
coon -Nat 200Na
Examples
ou
-> (-) I I ↑
W
① I 0 I I
D 0
L

Acid Base C.B 2. A

 on
I
oNG
I
v
+ Na NM >
(2 - O
O
+NB
I

(Acid)(Base)
235 Cry-2 = c U +NaOU S
<B -c = Nat + MO
-
(Acid) (Base) (Base) (Acid)

coon
o
Na
I
<R- v
I

O + NaUCO3 >
O
+
uCO3
L

(Acid) (Base)

on
I
oNG
I

O + Na UCO3 ↳
(5) L
O
+ UCO3

(Acid)(Base)
v

261 CrNa+ cr -c c-n

=
<
>
CB C 2 Na
= + (44

on O ⑧
⑦
o
I I I
I
3 S
O I O O I O
[

v
(Acid) Noz ↓On
(- M)
⑰ ⑦
Nice -

Nich
I
365 v
I

Nu
=>
I
O
O
NHC
+

(Acid)(Base)
⑦
⑭ ~ 11
+ Nnac > t
199
E
-
NUb
C
-
NR Nth Na N

C Base) (Acid)
(109
- -
I I I
S
I I
1
I - ~
- ~
- [ - - ~
-
-

N
⑰
-

N⑰ v N
N · -
H
in In
In
(Acid) (Bar) Base Acid

Que Identify bas which can

form my with
supe !

11
CayPh-NM (b-ph-Nn-Ph 2- Nm (d+ NM <e-)crb-2 NM
0 NH v
W
11
11
2f-1 (83 s
why ~ins
sh Nu
-

sal? Base Mnch

+ > (Base-n)N
Base] Nr (Basic strenght)
(2), (d +, (8)
 Tantomerism/Dermotropism/Alleloprotism/Kryptomerism
L >

Structural
* isomers which a re interconvertible to each other

naturally changing position of atom/generally 4-atou).

68.
an

H ↳H
I
*
I

eg. crb
-
-

erb -ah c
= -

ct

Keto form end form

3
I
7

ce 'c
n
Noti n syllabus
~

So - 3
>

Tantomers exist in equilibrium state in

liquid and
* are
gas,
solution (acidic/basic).
* Tantomens a re isolable isomers.

Types of tantomerism.-
< >

Tantomerism

open chain tantomerism Ring-chain tautsmerism

↳In carbohydrates)
W
Diad
system Friad system Conjugate system

Tantomerism in diad when a-shiftfrom st to 2nd

I system it
< 3
position.
"

H-CEN. U-NEC
eg.
[Hydrogen cyanide) ↳Hydrogen isocyanide)

it (icEr.'
->

Note:- R CN
-
X : R -NC (No tantomirism)
(These are
functional isomerism)

21 Tantomerism in triad
system: -
WD-shift from itto 3rd position.
L 7

I b 8- b -
H

Itshould
C
polar
-

4
** a
=

be
-
-

"a
H
I
+
b 2
-
N
=
b
* N
-

~ 2 9

H 0 a b
= -
0 b H
* -
a
=

Examples: -

Keto-end
is
L
tautomenism:
E Or
I

<1- cr -
-
u - Ch c =
-
U
 0 on
11 I
(2-1
-
i I enolisable n)
-

↳ I
n

231
Il
c
-
r
-

c
- ↳2 endisable n
02

CAT Or -
In
in
l
0 On
on
11
I
/ --
2
Or
(51 <

(ii) Imine -
Enamine tantomerism
L >

I
Ch N H
It
<By cr c
=

(Imine) (Enamine)
(iii Nitroso-oxime tantomelism
C >

U
I
Cu -N 0
"<rb N oh
=

Cu cu =
-

<Nitroso Losines
Livi Nitro-acenito tantomerism
L ↳

2
H
on
-
,0
I ↳

x c N
=

C
as
↑ -

30

i
a

(NitroS [Acenitros

Lactum-Laction automerism:
(V-S
<
-
0 0M

3
Il

& cyclic
Lactone
enter:
/ cyclic
N H
I I
amide-Lactum
-

-
I N

(vis In - N -
CB cn =

NU
(4 c
-

(viis Ph IN 0
=

-
2

Oh-N N-on
=

n
H

(viii)
P ha x
= i
-

ph - x -
x x
=
- n
-

Fantomerism!-
13 Conjugate
L >

I
(i) (r <n- C U
Res-v Taut. X
=

->
-8 -

or
11
k
(ii) cr - c n <m cn cn n
<1-5 shift)
=
cm-cH=
=
- - -

87 S- 87
Le
-

8
Su 11

siit Ch I c Res. 2 Taut. -> X

is
- -
H

87 8-

Pe on
I

(iv 2)
W
I
-
It
-
 -n
O o ⑳
⑳
Il I Il I

2
(vis
W

) W
(V &
-

I I I
I 1
7
I
-
- /
-
- N
h h
05 8 ⑧
I Il 11

(vii- ↳ W

(ix- No tantomenism
14
->

- 1 1 I
s

!
·Para quinone)
I -
0
=
↓ -
-
n

I
No tantomerism
(x) I
=
-
O

Mechanism
of tautomerism (Keto-end tautomerism) in

2 >

ci- In acidic medium:-

H
H H
-... 0

n Vil
-

H
Yo C 2 I

an -u I

Cr
in S a <B- Ch -
C H

Cus
-

- ⑰

-
-

-on
-c c
=

A
CB

aii- In basic medium-

C ↳

U O ⑧ s
ou ⑦
4
11 I

2
- cn -
-

n
<b-cr-c-n
<
(cry - ( H c
=
-
4

d -
10

mo (-ont)
↑

or
I
CH c
=
4
<1
an
-

D
N ⑧

cm=en-Eu -4-n
②

cm-cr
* cn
=
-
k- n
2
↳
&
m -
cn =
cn - 4 - 0 c >

-
10 T L

L
Sem an-c--n 3
I =

cn c U
CB cn
= -
= -

20(-on)

cm
=
ch-cu c
=

L
Note: t
>
CI*
Generally Keto
forms a re
thermodynamically m o re stable

end because bond form

than
form of energy of Reto

greater than bond energy of end

form.
Resonance
*
energy of keto
form greater than resonance
energy
end
of form.

c 0 ) =
⑦ c = c c > ⑧

ciit All endisable

hydrogens a re replaced by D in presence of
&D +
D20/40 + D20, It called
is
D-exchange.
4
⑦ ⑧
D20 0 D 4 n
+

cm -n
egit cDy
-
-

> -

⑦ -

D20+OD Il
(2-) Cl-cm-CHO > Cu -

cD1 -
c - 4
-

0
11 0

D20 + 6D D
11

[3f > D
D
 Mechanis ⑳
m 0
⑧D ⑦
0

↓
L

cry-con"-n x
xc x c
=
-
-
CH
+

Cu
-

-
In -
0 -

x)
'D20 ⑦
-$28
- oD
↑
0D
↳
H 0
I Il C
cn
=

C c H <- M
Ch
-
-

I'
I ⑰
O D

o
&
0
⑦
Il
-c -c nc ) (b cD c
=

Cr
-
-

ci I
⑦
OD D20
L
I
0D

(1 cD c
=

3
-

0 W

E
&

n
-2D
-

C
-

8 +2O,
⑧ ⑧

4 n !- n
<4- <rb-cu cm D3 cn cD
=
- =
-

3
-
V - ⑥

E
⑧

I
-
⑦
in cn 4 -
nc (cm cn =
-
cu
-n
+ (ck cn
=
- cn k
=
-
n
Ch
=

I more stable) (Les stable)

4P n-468
⑧
Des
+

cy (Dy 2H cD
(59
-
cu -
(r
- =
=
-
-
- -

<Major)

End content Reto-end equilibrium

·
it
in

Lit.End end
content
of form (due
to
stability resonance,

aromaticity 14-bonding etc.)

(ii) i. End content a Acidic
strength of endisable hydrogen.
(iiit. End (temperature
content

End content end)

otarity
<
(ivs %.
↳Polarity Keto >

of salvert)

General
<
order
of 1 and content is
S

Phenol) B-diketones B-Diketory P -keto-esters B-diester Aldehyde 1

without
sing i
i aromatic,
!
a romatic

i
with Ketone

isi i it
⑧ E
W E
0
I
11 11
11 11 Il I
OR
oR
0 Oh
R r

I
= I

i n'n I N M

~15E.,
I

!Y
"
90-994 ~264. ~ 7Y
!
~
O

Ester
4 cy--OR

3
<
R
cr - - 0

No tantomerism
0
(w0Yend)
o
!N s
 ⑧ or on
0
11 I 11 I
W
E W

21-1 I -
I (Ar) [25 1 I -

I
~ ~
10%)
/

n'n C
~

n.....
(N. Ars ~ 100% 00
I

!-
8 8 O
0 S
11 11 II
Il
:B (3
(3+ i <-
↳

a
n

in
↳ H
N
/
-N Acetyl actors (16%)
↑.... conj.ev a
bonding - v

⑪ ⑧ O

- I
(5)
-I
↳

↳
↑
More
! (Major product
acidic ~ 90-99%

-
7

/ (cross-conjugation)
!
[Less stable)
⑧
-...
0
Il 11
C
0
I
is
C
L
C C
26- Cr cm
⑧ C245 en
2 02245
Cr cm

acetoacetic ester
Ethyl ~ 7%
or

Ethyl aceto acetate

0 - H on
0

11 I

<7 I - or

(a +) (b) (i)

(9%) > by)

i
-X
on
(8- (NO tautomerism)
_

10%)
(1004) [Unstable)
or
-o X
191 ↳
1 (No tantomelism)
↳
(0-1)
re
(100%) >Anti anomatic)

10 o
-

(109 ↑8
-

- No
<Aromatic)
of ⑧
-

<100% end)
O
0
1
Il

Note - * - -
- -
2x2 (romatic)
⑳00
2 >
-O
* I C >
ze (Aromatic)
-D
⑰
-

-
- v

-
-

p-
i 1 Il /

211t I ro o f. (
-
(Lesser repulsion
H
0 0

...2
E

42 2 /
-

(major)
(minor)
I arec a n rotate around a
bond)
 Note:
When endisable
hydrogen is presento n chiral carbon, then

in acidic/basic medium, more than one stereoisomeric product

are
formed due to tantomelism.

u - 3
=
0

sie
- = c
0
=
c
c
nit/or (mo) Resmic mixture
U 3 M I H Ch
C

C245 22 45
C2"5

<Pure optically active) -

7
-

non
!
au5
CB

E 3
↑, 0
un
o ↑, 0

<i
ca H

/ou (B
H
H C43 Diasterioners
S
Ch
Ch t Ch

D H
D H
D H

Cus
Cus Cus