a cauow otom vouy coon

ronn 3rdL
ga UD C=o . ktdenot AustorMLis hy druog =utt
" Amdmu
alo t ORGANIC CHEMISTRY 23rd ahon
KETO-ENOL TAUTOMERISM
b 2 Rat of 7
Po oF fuwd r Xna
Alsoknown as DESPOTROPISM.K ARYOTROnSM |PRosoN TR MJSCER 8okwd TXn
It is a special type of functional isomer in which the isomer exist in dynamic
equilibrium
with each
It arises due to migration of hydrogen atom from one poly valent atom to the other within the same molecule
otner.

(1,3 H-shift]
DIAGRAM 34
o-
-CM CH,CCM C C-CM
3

RING CHAIN ISOMERISM

isomer and the
chain and cyclic structure are called ring chain
LOmpounos naving same molecular formula but possessing open
phenomenon is called Ring Chain Isomerism.
ALKENE CYCLOALKANE OH
EXAMPLE
Butene [CH]
HC CH- CH-CH
H
H.
DIAGRAM 35 -H
oultanmi CM2CM H

ALKYNE- CYCLOALKENE

DIAGRAM 36
NOTE

CuM y o bstu ham

so
utw H Ueclkane
CH CH
MC CCH CH amd Mky ni moud cham

C itn ylocetuu

STEREOISOMERISM called stereo isomer and the

relative arrangement of atom or group in space are
Stereo which have same structural formula but have different
isomerism.
phenomenon is called stereo
Stereo isomerism

Configruational
Conformational

GEomeical Opticel (KI)

cONFORMATIONAL (T bond rotation) ISOMERISMn

I t is due to single bond rotation.

 melu mlmia MO. o
tereoisomer have diff. relative arrangement of atom within which can interconverted by rotation around a bond are all

conformational isomer.
2 Types:
1) SAW HORSE AND
2) NEW MANN PROJECTION
SAW HORSE
he molecules is viewed slightly above from the right and projected on paper.
he bondb/w the 2 carbon atom is drawn diagonally and is elongated for clarity.
The lower left carbon is considered to be towards the front and the upper right hand carbon towards the back.
DIAGRAM 37
A M

H-

M ond
d i pAd
NEW MANN
The projection is obtained by viewing the molecule along the bond
he
joining the two carbon atom.
carbon atom
DIAGRAM 38
near the eye is denoted by a point (,) and the carbon atom further is denoted by a circle (O).

M
stagg
The energy difference b/w staggered and eclipsed conformation is 12.55
KI/mol.
This energy is not large enough to prevent the rotation b/w the two forms.
T h e two forms are interconvertible to each
other readily.
RELATIVE STABILITY OF STAGGERED AND ECLIPSED FORM
DIAGRAM 39
tmouution o ethme

s Ms
M My

lipaal Poudtial stig ohal au taggusl

tdipus

Partiaily
Fully

pauhally pd Parhell agyued

 C C CCg ANT
OKDERED OF STABILI

STAU4tRtb ) P0RTIALUH STRA4G ERED7

PARTIALL eCLISED fuLLY eCLIPSED
NFORMATION OF BUTANE ORGANIC CHEMISTRY
DIAGRAM 40
Pahally shagannd fauially edipud amh-chagqind
CM3
Cha CW C

YT Y
M
uu dipsal C
C CW
M
(pahally CPaurally
Staggues)
cclipud) CM
cONFIGRUTIONAL ISOMER
Stereo isomer which can be interconverted only by breaking and making of covalent bond and not by only rotation and a bond are caled

configurational isomer.
Buut - n e C Ch
They are of 2 types. CH-CM=e - CM2
. Geometrical
. Optical isomerism
C rans

GEOMETRICAL ISOMER CLs

rotation is restricted around the double bond.
t
ocur around the double bond as the
I t shows cis-trans isomer.
Cis- If the 2 similar atom on adjacent carbon of double bond are on same side, then it is cis.
Trans isomer:- If the 2 similar atom on the adjacent carbon are on opposite side are called trans isomer.

DIAGRAM 41 ( Alsov)

PROPERTIES OF GEOMETRICAL ISOMER:-

TNCs 7 ia)
1. Melting crystal point: ( well in
that of cis. It is because trans is more symmetrical and hence pack
a
Melting point of trans isomer is highly than
and do not pack well in the crystal.
crystal lattice while is isomer has unsymmtrical
attraction in trans isomer is more as compared to its.
Therefore,
i. Dipole movemen:
Its isomer is more polar than the trans isomner.

(c1s) DIAGRAM42
CTRANS

(Pol) HO m polau)
II. Boiling point:: cis each other while trans isomer is non-polar
do not form
form strong interaction with
As the ts isomer is polar ot
molecule.
interaction and remain as discrate
compared to cis due to non-polar nature of trans.
Thus, thans isomer has low boiling point
as

V. Solubility (polar/ non-polar) isomer because like dissolve like.

As
cis
isomer has more solubility as compared to trans
.Therefore, cis is more soluble than trans due to its polar nature.
 Stxtut s C6M 0
23 2,4 0Punoudd

ELECTRONIC DISPLACEMENT IN COVALENT BOND

muds e , w,, cthe
Electrophile and Neutrophile
o octt H Hydrids
aluonolR-8-R, R-Oy
Electrophile (E*) (Nu) Netrophile
Electron loving Nucleus loving
This means E" will attack where e density is more. This means Nu" will attack where e density is less.
Electrophile may be +ve charge or they are electrically They can be either -vely charged or neutral species
neutral species (carrying lone pair of e")
+ve E* H*/CI"/Br*/NO* /NO; /R* ve Nu t /Bnz /NOZ /01"/CN"JCH,cO0
Neutral Nu Nub ctate
Neutral E BF3/ AlCl,/FeGl,/R, Free Redical
,0rdY1d
NOTE 1
NOTE
The electrophile which needs a pair of electron to complete its octet is called Lewis acid.
Some elements like
Al, fed
Ca*/Na* have +ve charge but are not electrophile. This Implies species carrying +ve charge is not always
electrophile.

FISSION OF COVALENT BOND

Bak
HOMOLYTIC FISSION HETEROLYTIC FISSION
Same breakdown Different breakdown

Free radical mechanism When a covalent bond joining the two atoms A and B
H-heat A break in such a way that both the e's of the covalent
E-Electric Current bond are taken but one bonded atom. ushun
L-Light/ Sunlight (hu)
P-Peroxidee
mou eluhouaatin.
R-Radical
I t can also be decided by seeing that 2 bonded atom are 2 bonded atoms are different one is more
same. electro-ve.
It is denoted by fish arrow
DIAGRAM 43 punkagt It is denoted by a curved arrow.

Pex oride. bm -o]

nydngam I t leads to the formation of cation and anion.
pexORi dL PHOxio

(0) H-0-0-H CM-o-0--M DIAGRAM 44

Su 7 Xe

HC O MC +OM

ELECTRONIC DISPLACEMENT IN A coVALENT BOND IS STUDIED BY 4 EFFECTS

1. Inductive effect
2. Resonance effect
3. Electrometric effect
4. Hypercom jugation effect

INDUCTIVE EFFECT

I t orient in sigma bond.

It is a PERMANENT EFFECT. at the end
saturated carbon chain whenever an e withdrawing group (halogen) is present
This type of displacement of o e along a
of the carbon chain is called inductive effect.

This effect weakness as the distance increases.

dut
 DIAGRAM45 ORGANIC CHEMISTRY

eMC-4, -

CM, - - t4 7 W-", -7 M
St
u 7Pe 14hw C
Inductive effect are of two
type: dist uML
+l effect
Electron donating grp Effect
I t denotes e to other. Electron withdrawing grp
It withdraws
Itself aquire +ve charge. e from other
Itselfaquire -ve charge.
Gives-ve charge to other.
Gives +ve charge to other
-NO2 > -CN>-COOH > F> C> Br>
1>H

ELECTROMERIC EFFECT
It is a temporary effect.
It involves the complete transfer of e of a multiple bond to one of the atom. Generally, electronegative atom.
It is also known as E effect.

NOTE:- It occur only in the presence of reagent. If the reagent is removed the molecule revert back to original position.

It is of 2
types

I f the e of the bond are transferred to the one of the If the e of the double bond is transferred to
atom of the double bond and the attacking reagent also one of the atom of the double bond and the
get attached to that atom only then t is +E. attacking reagent attaches to the another atom
DIAGRAM 46 is called-E.
DIAGRAM 47

CH CA, *
M M, n
luthopu et CN
C, C) fT
Nutloptu

LC - Nu
RESONANCE/ MESOMERISM
When a single Lewis structure of a molecule is not able to satisfectorily explain all the properties, in such case we write 2 or more than

2 Lewisstr. which differ in position ofe butnot in the relative position of atom.
These all are hypothetical str. also known as-eavenical/ resonating str./ Cononfta
The actual str. of the molecule is not represented by any of the resonating str. but is aresonance hybrid of these structures.
These resonating structures are separated bya double headed arrow. thas last energy andis moit
stcublu.
Resonance Energy: Resonance hybrid is always more stable than any of the resonating str.
t i s defined as the difference b/wthe energy of resonance hybrid and the most stable resonating str
More the no of resonating structures higher will be the resonance energy.

RULES FOR wRITING RESONATING STR.

The relative position of atom should not differ, only difference in position of e®
All the resonating str. have same no. of unpaired electron.

cONDITIONOF WRITING R.S

 I t has alternate double and
single bond configuration
DIAGRAM 48

2.
Conjugation should be seen with the +ve charge
DIAGRAM 49

3.
Conjugation should be seen with the Lone pair of e
DIAGRAM 50

4.
Conjugation should be seen with the negatively charged atom.
DIAGRAM 51

N m qH-m# N = M -M = CM -
Resonance of 2
types
+R R
e donating ewithdrawing
It acquired +ve charge on itself and -ve It acquired-ve charge onitself and ve
charge on other charge on other

6xampl -on-oR |-NM |-f.: t plu -C

cN
DIAGRAM 52 CHLOROBENZENE/ PHENOL/ANILINE/ BENZYL CARBOANION R)

OnT
0 Ont
:0M

ut

NM N

DIAGRAM 53 BENZALDEHYDE/ NITROBENZENE/ BENZYL CARBOCATION CR)

dtuo uMy u v e dimaituw
NOTE Eup om
poulions amd ik uchophulL adduo
qs a d o outhe amol pna
poAtos R gLoup a allud oukuopan dudim Loupa
 CMO ORGANIC CHE MISTRY
C-M C

CM,
C CM CM

ORN0 0

NOTE:
f we add e donating group to the benzene ring then e density of benzene increases and the electrophile which is e deficient will
easily attack on benzene ring while the nucleophile which is eO rich will be repelled by the benzene ring.

When e withdrawing group is attached to benzene ring then benzene ring decreases itse density. Therefore, nudeophile which is
electron rich will be attached on benzene ring and electrophile
will not be able to get attached.
Tf on benzene ring -R goup us audaud m dlunsi
HYPERCONJUGATION ( -T eonjugation) diurtau ar ostho amd pora and te elauhropilu will atat a
Hyper conjugation is anextension ofresonance. Itinvolve the delocalisation of sigma e® through overapping ofp orbital of the double painon.
bond with thesigma orbital of adjacent single bond instad OF ormo para POAL
The structures drawn are known as hyperconjugative structures. us
-R oupf
mut duLuHng amd
Baker Nathan effect
free Radical
othopaxoadtathvauh
No bond resonance
Occur in carbocation (C*)
Freeradical (C°) -CCH
Double bonded carbon

The structure have a-H doute Bond

More the number of a -H
More the Hyperconjugation str.
More will be the stability
DIAGRAM 54 M-CteH -con- ¢=M-u n- =cn-
CM CH, (32-)

M-C CM
Ht

REACTION INTERMEDIATES C C-

3A C 2dc

9 G- 3-
 These are short lived
highly reactive and hence cannot be isolated.
These chemical species are those
through which many organic reactions takes
piaue
There are 6 reaction intermediates:
Carbocation
Carboanion
Free redicals
Nitrene
Carbine
Benzyne

CARBOCATION/ CARBENIUM
Carbon bearing a +ve charge.
I t is e deficient. It has 6ein the central atom.
Orbital diagram:
DIAGRAM 55
P-orbiul

Sp 3r bond 6e(stxr )
goual ptama raccmr p-orbitul cupt Lome pa oF
Stability
e donating grp_
Stability of Carbocation « e withdrawing grp
c 7+R
C 1-R
Carbocation bearing a +ve charge will get stablised by e donating groups which disperse the charge on the carbon whule the e withdrawing
group pulls more e from carbocation making it more e deficient but thus intensifying the charge making it unstable.

STABILITY OF CARBOCATION
1. By inductive effect
2b 4
DIAGRAM 56 CM3 CA

C+ CM
2' 7
ispeeA 3
Charge is getting dispersed to maximum (most stable)
I n tertiary carbocation the charge is getting dispersed to the maximum because these are 3 E.D.G which try to neutralise the

charge on the carbocation making it stable.

While in primary carbocation only 1 E.D.G, therefore, charge is getting less dispersed.

2. By resonance
DIAGRAM 57

makm dispoud T

3. By Hyperconjugation
DIAGRAM S58

7 ,-t. 7
n7
Cs 3A-M
6 dM
CARBOGATHeN ANION
.Carbon leaving a-ve charge.
 It has 3 sigma bond and a -ve ORGANIC CHEMISTRY
charge on it.
Orbital structure
DIAGRAM 59 CW CO

qcomu Terandral
Shape Pyada
STABILITY OF CARBOANION Y

Stability of Carbocation ewithdrawing

As carboanion already has a oge donating
o stabilise the
charge making it e rich.
-ve
-ve
charge we add e
donating grp it will increases the e® withdrawing grp which disperse the charge of carboanion making it stable while if we
density and intensifying the charge making it unstable. e
-/-R
co 1/+R
By inductive effect
DIAGRAM 60 3 ¬D 2D
Ch e D OE D
C Ce
mwniit
mitau CHg 3 2
In tertiary carboanion there are 3e donating groups which increases the edensity on the carboanion making it unstable while in
primary carboanion there is one ee donating group which inc, the
e density to lesser extent as compared to 1°.
2. By resonance
DIAGRAM 61

Ymaximum disptia
a 3 bungens
-
gs a

3. Hybridization:
More the S character, more the lector negativity, more the tendency to acquire negatively charge.
DIAGRAM 62
X100
X1o0 3 34
25
sp3 sp
CM C ce -H ethonaHvi

J-nt

n
FREE RADICLE
DIAGRAM 63

Orbital str.
C
DIAGRAM 64
C
C-
Odd no of e® in central 7e
It is e deficient
Due to unpaired e
Magnetic property
 Coloured compounds
EDG+I/+R
AS free
Stabltyof i EWG -1/-R
redical Is e deficlent, it get stabilised by donating group which increases its e density and tulfil its
deficiency but
we add E.W.G it will create
deliciency on carbon making it unstable.
STABILITY OF FREE RADICAL CAN BE EXPLAINED BY
1) INDUCTIVE EFFECTT
DIAGRAM 65 Y
CM
C 7 CMC C, ( CC,
AS
tertiary str. has 3 E.D.G it stabilise the free
radical by donating then e while in primary there is only 1e donating grp.
2) BY RESONANCE
DIAGRAM 66

m a xm

C
duspund
7 C 7
as 3 uud
aul pabnnt

TYPES OF ORGANIC REACTION (DIAGRAM 67)

1)SUBSTUTIONREACTION
2) ADDITION REACTION
3) ELIMINATION REACTION C 7
4) REARRANGEMENT REACTION Cn-M - M 7
CH 3-
1) SUBSTITUTION: CMs -
1. Nucleophilic substitution reaction
6-
R-CL To
2. Electrophilic substitution reaction

+u u
3. Free radical substitution reaction
2) ADDITION: HELPK C +H CL
It can be seen in the carbon chain containing double bond.
NOTE: Addition reaction do not occur in benzene ring. aOLWel mubpe hod (-l=)
a) Mydbuogmatiovn 5) Maloguvaliom
Ca , +Ma7 Ni

C-f
Br
3) ELIMINATION

Oehycuohauegumaom
T Rworal waA
mora hydrogum ul8-|I alc. koM

B-c d-C
Q. Draw resonating str of benzyl free radical.
DIAGRAM 68 Cn, ,tM,6
CM2 M (On
 ORGANIC CHEMISTRY

a. How you can say CH3 is an

e donating grp?
DIAGRAM 69 8maenne
C dematimg uup brseuul Aruiuue
dn.10
caueM m AnenalimY
edimAlby muuastu amzu
Q. why carboanion donot shovw
Hyperconjugation?
DIAGRAM 70
CH2 wataule
wign c do mot h a camt 'd'
As we can see in the hyperconjugative str. carbon acquire 10e in its outermost shell which is not possible as carbon is of 2d period element
and can only accomodat 8e"s in its outermost shell, so hyperconjugative str. of carboanion is highlyunstable.

PIAGRAM 6

C,
 u0lue pantialLy aggnd fom
state ouH- staggued om ?
-BoMd
O Ov

CM o
M
o OM

O
eupud
G AuCHE7 ANTISTAYYRD --me
staggeud CGAUCe sKew)
duti ataggind