~ ISOMERISM

-
④Tautomerism
① Chain Isomerism Alkyl gp attached
side chain- parent chain
to ①Keto-Enol

Minimum Carbons for (Resonance 4 H-bonding ->Yses stability

of endform)
14 -> 2 chain isomers No. of CI 1.3
migration
(g -> 3
[8 -> 18 Alkanes -> 4 A 0 0 -
H

A
I 11 I

4
CH2-2-H CH2 = -H
stability ->2 2 -
30
=

16 5 (a 35 Alkenes
=

-> + ->

(keto) 99.9% 0.01% [enol

(
-
> 9 40 ->
75 Alkynes -
5
H
I
0
Il
OH

CH2 C

-* e
CH2-C- CH3 CH3
② position Isomerism
=
-

99.7% 0.3%
is
En
up, substituent, multiple bonds
·

ri H 24% 76%

Disubstituted benzones 3 isomers (0, p, m)

it ca
-

·
position isomers should have identical chain 98.8% 12 Yo
,
I is
·
Chain terminating p -No position Isomerism az chain different 114
89%

Monohalogenated Products Same chemical ->

ear (positional Isomers) A
won I compound with
=>
max enolisation
③ Functional Isomerism 0.1% 99.9%

① Alcohols (R-OH) 9 Esther (R-0-R) ② Nitro-Acinitro

② Carboccylic acid (R-COOH) & Esters

CHa-N -O
CHa -CH N
=
-

-> 0
0 -
H

③ Aldehydes, ketones, unsaturated alcohol, unsaturated ether Nitro form acinitro form

④Dienes, Allenes, Alkynes ③ Nitroso (-N 0) -Oscimino (=N-0H) =

DBE c =
-

1 2+
-
+
Idb I
=

ring -NEO -
CH3-CH=N-0-H

2db 2 ring
=>
=
1tp Nitroso occime

⑤ 10,203 Amines ③ (mine(=

NH) -
Enamine

-H
Outo n side chain-> aromatic alcohol
⑥ Aromaticals, Phenol, Aromatic ether NH
benzene -> Phenol CHz-CH CH NH2
= =
-

outon
-

k
⑦ Cyanide (-(N) a
Isocyanide (-NC) Imine Enamine

⑧ Nitrocompounds (N5%) a alkylnitrites (-0 -x 0

=
 Neutral, Nitz, H20, R-ITHz, R-it etc (epi

"
2H?No tautomerism

a
·
No
Ismigration Nu
·
a Hon SP2?No tautomerism
CN, OH, R, R-O,
Ye,
x etc
·
sp on bridgehead?No tautomerism [Bredt's Rule]
Neutral, Freeradical, Carbene, nitrene,
Atec,F3,
saturated chain, Yes possible (chain so etc
1,5 a 1.7 -

Not possible on on
conjugated (T)
Et
⑤ Metamerism -> Min 2 alkylgps NO2, NO, RT, xt, Ht
O e
- - o, -M N- Reps except halogens R9pS
-s-,
-

--, + 3
-
-
- -

0
Activating 9PS [+ R effect] Deactivating ps
Il
" 19

3
CHz-(H2-1 CH3
>
CH3 0 CH2-(H3
Halogens
0

I
- -

Alkyl gps
- -
-

4 IG Metamers
/Hyperconi, +I]
42
-1

42
0 H
- - -
- -

I9I

4 RESONANCE EFFECT Delocalisation of electrons

3Hys
-
-> H -
-
0 -
#a -> position Isomers

⑥ Ring Chain Isomerism Evidences of Resonance

① Alkenes -

Cycloalkanes ① c-c bund

length in benzene 1.39
② Alkynes -

cycloallnes ② Resonance Energy in benzene/R. Stabilization. I RE Aultor

= -

Antexpmt
③ Usaturated alcohol-cyclic ether -

Cycloalkano R. EC stability REbenzene 36 kcal/mol

=

Nitroalkane -> R -NU2

IT +H2 ·
Fl":$hH =-286kcal/mol
6 Id angles around sp3 - [ 1.54 Alkylnitrite ->
R-0-NO
A 2H2 + >
y-H
Hy

H;
DhH 2 x-28.6
=

kcal/mol

3 120° angles around sp2 2 1.34

=

Alkanenitrile -> R -

(N

·;Dutt
#
3H2 =-49.8 kcal/mol
2 1800 angles around sp c 2 = 1.20 A Carbylamine -

R -

NC

① i bond CH2 =(H =

=

He => [H2-CH CH
=
-

[H2

O
⑭
② the
charge (H2=-CH2 => JH2-CH CH2 =

iHe<- NIHR -NR2<-H <-8R -NiH - RC-8-c

(HCte
- F< C1 Brc I
③
+R
charge (= Hz-1H CH2
-
- > > - -

R > <

ve
-
0
↑
=

↑
0 0 0 O
⑧
Il il 1 Il Il il

-R N02 (Nc SUzH NH2

+ C H) =) > c-0 -) > x x ( 0R> (

=
- -

c -0H)
- - - - -
- - -

CH HzCitz-CH IHz
- - -
-

④14
-

Y-
⑧ 0 D
Il
=

11 Il

* MR2> -H3-NO2 FcCkBrcIs OAr -c-ORS -OR-OHS -NHaS(yHg

-

-(N1-SUzH
-

H - s - - -oHs H

- 100 R3
⑤ free radical (fiH2* CH2-CH= CH2
+- ReCHS RCHe (H3 TaD >H
-
-
 =>1 =(-2+)-
1 1.1.
Conjugated system II bond HC effect Methyls Ethyl (CH3)2CH-> (CH3)g)
=
=> 2 Hes ->
-

I
is d in resonance are treated as Tis 1l=>2 Tes

liters -die...
= involving
1 -

we
charge ->2TEs 0 H) the charge
6s
I free radical=>1Te sp3 sp2

tree radical
Site z=c2. guing i
<key atom)
& As
·
Up on atom DIRECTLY attached conjugated
to (chain->+ Reffect involving a

deficiency
(key atom)
·
e on atom DIRECTLY attached conj. (chain->
to
-

Reffect

CH-ite... gig!
Applications
⑤ HC involving bond NCH 2 =
THe is =

sp3 sp2 sp2

① ofAniline
Basicity Applications

>Less
of Alkenes
Ostability
Basic cuz up not available on N
of alkenes
stability a No. ofHC structures a No. of CH
CH3 CH3
RESiz=> Move
CH 3 H
basic stability of alkenes a 'DuH xc
=

xc
=

It cis It
trans -CH3
② Acidity
ofPhenol & Directive Influence of Alkyl Groups

* =
Alkyl gpso-p directors due to
HC
->

unj. base)
shortening adjacentto
=
Move acidic cuz phenocide stable due to Resonance ③ of C-2 sb c=2db

R-OH 5 R - => Less acidic **CHETH2 CH2=CH-He Expected ->

1.54A:Actual ->
1.49 E

③ Single Bond length in Buta-1,3-diene

Expected 1547;Actual
=> -> 1.46 INDUCTIVE EFFECT
·
Polarisation of C-c bond due of atom/qp
Electronegativity
to a chain
attached to

HYPERCONJUGATION (No bond resonance) Electronegativity-> O 0>0-

pelocalisation of C-H thatis incon; with free radial-reioushalkylaps=> CHCG Resonance independent
+
bond I distance)
· o es a + ve
charge, I or of

·
Opa -
ve =No hyperconjugation ·
+Ix size ofalkyl9p Stability -> HCs Rc I

effect
Alway donating. Always stabilizing
· I ·
Inductive Effect I

Distance
HC < no. It
of