General Organic Chemistry

bonds
Breaking and formation of
The bonds in organic reactions undergo
fission and formation The bond is shown as
a dash and the direction of movement
electrons is shorn using arrow head
of
when a
pair of é moves it is
denoted by Nr curved arrow

when a single é moves it is

denoted by M fishhook and
A covalentbond is broken in one
of the following twoways
HOMOLYTIC FISSION CLEAVAGE OR HOMOLYSIS

x
hmm
y treetradicat
es
I
Intuit
when a bond breaks in such way
a

that each atom retains one of the

bonded electrons then such a fission
is called HOMOLYSIS HomoLytic Fission
Homolysis always gives free
radicals
odd e species
paramagnetic in
nature
 HETEROLYTIC FISSION CLEAVAGE OR HETEROLYSIS

it Engx engy Tay I

anion
y
cation

9
n
Lace
Ii IE a
chloride

carbocation

n
It h
gig
Carbanion
t Ht

r
when more electronegative atom remains attached
with less atom then the bonded
electronegative
election breaks in such a that it
pair way
gets attracted to more EN atom getting it a
ve charge and the lesser EN atom a
ve charge This is called HETERO4515

ELECTRONIC EFFECTS
In organic reactions the electrondensity of molecules
the type reactions or
largely affects of
reactions There are two
mechanism
of
components in a reaction
Et Electrophile
tve
substrate puny Etfs Est
nucleophile
Nits Nus

I
ni ve

attacking molecule
undergoing
attack
 ei IIE
I.LI
2 Mesomeric Resonance effect M or R effect
3 Electomeric
effect E effect

between two atoms

ii of
it
St
nou
d

different electronegativity
then the bond pair
f
is shifted towards
the 1 chlorobutane
more electronegative atom
As a result of this the
is created between
a dipole
atoms
this dipole the other 6 bond in
Due to become
the chain are also shifted and
Inductive
is called
polarised This effect
effect UKN.nu
examples fÉÑgx FEED a

featuresay.FI Ianen effect

It is distance dependent and usually
a chain
dies out 3 carbons in
after
I
7
 It is operative through 6 bonds only
bonds
It doesn't affect a
electron movement in C H bond
The
is taken as a reference for
determination

of 1 effect
Inductive
effect is of two types
The atom or
groupofgeufggstechonghtdpa.my
mtff hwithdraw e and
are known as I group and
1 effect
such inductive effect is called
Their strength are in the following order

R R 8M N 27 5034

CHO COOH F d
CN
I OR 0H Nz NR
Br
ECM 6115
ch ch H

Fh R_alkylgroup

the atom or
groupof
ffn.cn releases e cloud ERG
1 group and
such
are known as
inductive is called 1 effect
effect
Jtf
Their strength are in the following order
5 05 C CH CH Chs cycth

437 D h
 IEEE

t.is
b

1 7 d It Jst
ronat
uz
cu to I.su
gg
9
8,4 EY
otitistimitisema esp carboxylic acids
I effect
acidic strength x
acidic strength tteffect
ef oh uz uz won on my of cha won
yy
I I d
41 ch uz uz cha won
in uz cry won
ti I I
acidic strength I I I I C Idistance
dependant
9 of won F Mz I n in N
I I
May won yo
ng O
Ma Cy Ma won
 effect order No FS N 4
4 2 year

0h 0M
ref C3 UM 424100N
a
Kaorder
at Coon
1117117
µ Iv
acidic stth
Barthold Basicstrength 1 effect

Basic Stryth
effect
9
H 0
413 _this
oath
p n1
Basic strengthorder Ky

µ g d
creation dipoles
Dipolemomentf.atinductive effect leads to of
Br
9
cuz a chaff Chz UTI
order dipole moment
duffitance of

if c at
at
Dipole moment I I
 Bondtength with increase in I effect bond length
decreases
with increase in I effect bond length
increases
due to increased ionic character

case ayee 2 agro CBI

carbocation and free radicals
stability g
x TI effect or
Yz effect
stability
9

caramn
É this.it
I H I I

stability order I It I I

was É ich ich

I I I I

stability order I It I I

carb anions
stability g
I effect
stability
x or
Yz effect
I
9 43
we
ns if iii TV
I I
stability men I IISE

Chz
on cytus
stfu

I c

a
a

Cons I n
 I.IE iei a.ii ngEg e aradeym
stated
election is called resonance
electron density the in
Through vesmame the
molecule becomes uniform and this increases
molecule
the stability of

EI II t

IConditiongfnru.fipag
anginresoname must best or
c sp hybridised i e they should lie in thesameplane

The parallel orbital overlay

p
to each other
Moleculesmust have
conjugated system
a
3Ike
sp sp
 I
f1
consugtfu.IS
ftp.f IEd
dt
bmdn
auernatnghnepa.ie

in affiliat on
ÑHy

atternating

vehanffs.toing
in in in
m
Which thefollowing will show resonance
P of
m e on
my
in in on on
cry
me
7
IED EYE 1 in

age 3 jo.EE O

Iv
on a

cf
mating on
wires hybrid
fermane

19 a
of
a
a Write the resonating
structures
for tolling molecules

g mafia
t
It
a a an as

a a Renogbad
atoms must not
change
bonds
positions of
Him n ENT ch on EN
g z y
I c M Rentynd
Hanton a

MEEEEE EEE
EEE resonangybrids

on
Ete on
IF Cha

on ÉÉ o
g
c I
acylium ion
 and under c En on on if
lest
111 partial
if
Bond double
in a bond
I T T
bond lengths
are between C C
met in and c c
Iiii E Chemin

I
Tip on
ay
hypothetical but they all aenogy
contribute to a real structure
called resonance hybrid I
I
resonance hybrid is more
than
The stability
of structures
y

1
resonating
any other
The PE difference between
structure
resonating
the most stable called
and resonance hybrid is
RESONANCE ENERGY

Stability of undead
RESONANCE
ENERGY
If.ggjgaey
isonaticstructures

E energy
structure
ofEpmd
The most stable resonating
contributes the mat to the resonant
hybrid
 structures
stability of
Rules
for resonating

is more
structurewithout
The resonating any charge
stable
P
9
CFI in I
t
I I I
in in 8 I

Io as in o
me
I I
stability I I
bonds is more
of a
Structure with more no
stable
each atom is
Structure with complete octet of
more stable

I I

fi stability I I
ve charge on more EN atom and
Ve charge on less EN atom are more
stable

I
on fin ay É on

I I
stability

FYI on
II I stability
 NOTE If rule and are contradictory then go
with rule octetrule

eg.in tiEo on ÉÉ i
skiing
I

eg no in Ñ in in the
I
stability 117111 I to in in

Two different compounds in which one compound has

more conjugation than Teotheritmore stable

one m m in on in U
I on m m in in in ay
I I I
stability

In two is aromatic and anotheris

if
compounds one
non aromatic and conjugation is equal in both
then aromatic compound is more stable

artmatic aromatic
non
is more stable
Structure with linear conjugation
than cross conjugation cross conjugation
linear 11ᵗʰ

figgs
conjugation

men in in in as

conjugation with a third

group but notamongst
tMeff.ec tRettect ERG
when a group releases a electrons in a conjugated

system then it is called M R effectand such

groups are called M R groups
lone
Such groups have the first atom bearing a
pair
Order M Rgroups
of
NMR NRas in n ok
NICOR COR Ph F 7 ii
Er Ñ inc
I o

el

1 9
density
electron in
I n

increases

the ring IE n

margins a
I on

Reffect Ewa
tMHI.mn a group
withdraws a elections in a conjugated

system then it is called M R effect and such

groups are called M R groups

Order M Rgroups
of
NO 503h CN CHO GO
 0 R O R
g g q
Coon Nur
g

aeanders Ii E ii m fired
in M
E
T.EE
n
Iii effect
ortwandp.fi s
F ns

Aromatic

Éᵈ should be
TTomjund compounds

cyclic a planar are exceptionally

all Catoms in the ring stable

ie
should be sp or sp
There must
be a cyclic conjugation
should be
total 4 279 e thethuckle's RULE
where n 0,12,3
2n Gae lone

Example
 E EYED
AAAromaticity Very unstable
compounds
8Mmfoundshould be cylic a planar
ie allCaton in thering
should be sp or sp
be a cyclic conjugation
There must
should be there
total an a e CHUCKLE'S RULE
where n 1,213
49 bae Kae

I
Ey EY
A compound that is neither aromatic nor anti
aromatic is non aromatic compound
pains

roti
n
it
Aromatic
Pyrrole
pyridine

II pyran
mm at
 Activate
www.ne dem

m.tt o sanity t.in

My I Nk NAR
activating
NR 47
i
1
Ocon
TAC

2 he R alkyl fidgety
M F 9 Br 1 moderately
I
NC Deactivating
NO

I only FRs 8h Deactivating

a III 2
2 M no on
strongly

deactivating
Jc 0 Coon

COOR 503h
cool
Example Choose the most stable resonating structure

on on city
G
Cy in in as

Ch Ei
cry on in cuz

fi 4 I i En maswedaeanra a
r

double
1 is completelytransferred from
one of the atoms
or triple bond to

joined by the bond at the requirement of

attacking species

9 a ytE of as E
substrate Electrophile
canbe kt Not Ct etc
 If the attacking species is removed chargesdisappear
and the substrate attains its original form
Here it is temporary and reversible

Cast Elechomeric
effect may be supported or opposed

by I effet or M effect
g MET an
prefer

cast on z ly É Uh attacking
this c
I effect
n m m in ÉX
M
Eni in ur
ai
In g
9
and If multiple bonds is present betweentwo
different atoms the electron shift will take
electronegative
place in the direction of more
atom
M
JEFE JE E

ycEj.ni
siqii 4ectomen
tisknds
Ift Q of when the displacement
from the motel
a elections is
when electrophile
away attacks

a b Ian Br a Is
 elections is
E effect when the displacement of a
towards the molecule when nucleolphin
attacks

9 in a 8 0

onance
I HYPERCONJUGATION BONDRESONANC.EE
Necessary
condition If
carbon containing at least h
sp one

To a
spt carbon
sp 7 YES
emptyp orbital
or
1
III Ip e
si ie
gtcfsi
n

f g
When a C H bond ofsp hybrid carbon is
mitalihett
conjugative
filled L
then the ftp.fe
6 c n bond overlaps with adjacent p orbital
This phenomenon is called HYPERCONJUGATION
This is a stabilising effect p
conjugation

Q write the no
of α H in the following compounds
or no shuchum knowing hyperconjugtia
of continuity
Ch 4 cm ly ca cm as
on
mtg on on if
 in i ans ons
n
g
in on

KI It
100

iii
hydrogenation
Yexothermic
in alkene
stability
no
ga H
heatgrenation o hydrogenation

et
c Mam he on on

lay u
13
I Th
I
I I E
stability

M in okay on on on
check ay
I I Ty
order
hydryentin
Heat of hydrogenation Ohmongenation

Heatreleased upon adding the to 1 moleof is

a gaseous alkene alkyne to convert it into alkane
 Ht
Bondingtith
also affectedby
É 1 g g
Il I
de
Bondlength
g I Ht bond
hyperconjugation is less than expected
IE g Bondlength
g I CH bad
g is more than expected
sesottance
hybrid c n bondis longer thanexpected

carbocations and freeradicals

Stability of
no a n
stability a of

I I as
in
due to 2effect

on ons cuz Wz uz ont in

I I
I I I I
ai
Iya I Ehf IT
ni g n
Cuz
n in anetsested
as well as h c
on in cuz wz uz cig
I I
I I I I

I
is
IIFTE
 Q which carbocation is most stable

ay ay
ay us thing
in
Q on a
mtg
8
which of the following will notshow hyperconjugation
Q

Ms MIL
y
o
t Tx
Q the following has
which
of alkyl groups
men I effect
on
ay card
e
as

hyperconjugation
orbitals
Us l involves overlap of the following

o o
P p
a a
G p
 Ifam
reaction.IE
in organic chemistry
Three major typesof reaction
intermediates are there
Carbonium ions
Carbocations
Carbenes
Carbanions nitremes are
Free Radicals excluded

atemaasiie
ai.it
which contain 3 bondpairs
and a positive charge sp sp
CE
9 methyl carbocation
ethylcarbocation i
n
isopropyl i teitcaktha.at
carbocation

in
char.gg aspmpnaised I peye
isoform

effff hffyygq.gg I 7 ipad

9 I classical fiing L toisopeh

diamagnetic Ge
repelled from magnetic field all pairedé

a
2plane
 CHE Cn vinyl

R CI empty porbital

allyl stable Effigy

carbocation very
imdb.de com
whereat I ally vinyl
in stability
phenyl dueto conjugation
casboqtsu.de

if benzyl
carbocation
Kerry
table

stahfym.int
ftT stability of
carbocation

1 effect
hyperconjugation no of α H
Ef.IE
stabilisation conjugation
Resonance
substituent groups with lonepair
M effect of once Br
memorise
like

f 951am
as E as
Ling aging
in
age in 2
4,4
isopropyl

m u R CEC
ing
i vinyl phenyl
 daftest Igi
Cyclopropyemethyl
caseation

Ego gun omerms TT

s.TT
gig
ome
gy
Ms 2 ome
I Ey TH

mis any operative

my 1 group
Ea on 5 p
positions

T
EIn in IIa
TH
I he I Try operative
he is
any
on o I p
positions

a
É Er
I
Em Ed
HDV

M he EII.FI
 42

III in ftp.n.IE
E
fixer

EI.com in
Et

i ii iii
iiiiii

EE
I I I

I I TH

I 71 1

aaÉ ie aIea
I
 any É on ay 91 I I
T I I

Q Draw all the isomeric form of

G Hit carbocation

Predict which one is most stable

cy
cacecrEiz cycecqEnczOcgceEn

ce OusEcn.c
air QÉÉÉ
c a
going
I
n n in in azity m in
ma a

Tacy a nitida if I I TI

IA t.gg
this
 Tina I I TH

ÉÉÉ

I I TI

Rearrangement intermediate is formed

an carbocation
more stable one
in a reaction it rearranges itself to a

rearrangenet but only those

carbocations undergo
Not all
a stable species in the following
which can produce
can rearrange or
3ways
bond shift 1,2
H hydride Cnj methyl Phi phenyl
shifting of
strained sing to less strainedring
more
Ring expansion

Ring contraction

hydrideshift
Shittingoff
13
its a
g y
I
c
4
30
 n us pay

II ÉIi

inH
30

sina.tn
ffe
jf 3
m m
Ph
Ph

m.ITEE a

pin Y
D É ment
norearrange
cyclopropylmethyl
carbocation

whip
in
yo D
Q The correct
stabiling order is

11710717111
of I 17 117 111 Iv
j
11 1 5107111

1 h DID

Q In the following carbocation H CH that is

most
likely to migrate to the positively
charged carbon is CH at C 4
hate
I
a
4
I ton
Chg at C L

n at C 2

I
CARABANI.IN
termediate which contains three
bond and charge.is called
pairs a negative
carbanion
4 In Methyl carbanion

Chz ciz Ethyl carbanion

n C isopropyl carbanion
 hybridisation They can be sp3 sp or
sp
examples sp cnj cry or etc

sp Cup on 0
ME Ms
Sp nee

Stabilityotangtime stained by
75
9

I effect
M effect
or delocalisation of change
resonance

Examples
P HE
I be CE
F Sp TI
sp I I

I I y
sixt stability

É cei
sp
EI
sp sp
I I I
I
dunstmanes I I 7 I 7 I
E Lf 4 IS I
I

only inductive
stedfast
If
I I
1 2
E

7 1 17

I I
1badebnad
cnet.gsdance no backdig

TU EL cclzl.info
I A Uh
Ez I F on cy Ey
It CHz as I cry
on 2 oh

17 I I TI

EH NO Cho ICH
3
I Mi I 2 M 1
s ing at a
Ine I n 3 in É É.cn

I it I
gin s in cnet.us

572717374
M2

me
i ooh
M T

I
FREEg.IM Temediates
generated from tombs
of covalent bonds which contain unpaired
electrons are called free radicals

a mm
cactus

Atonditions for free radicals formation

assist
hw or UV
sunlight or
peroxides like 1102 Rio or
 high temperature
neutral
species with unpairedelectron
generated in form or in non polar
gaseous
solvents like benzene Clg
Paramagnetic in nature
no rearrangement sp hybridisation

Stability
g Meffect
hyperconjugation
30720 17 3

example

aug in_us us 1
25 45
371726
as
if c us

debasese
a b c d e

win
a
iniman
b
if c d
c bids a
at is
a b c d

c d a b

Chzuzuzonii azincizong
a b d c b a

lab zÉcn Cal 9 C

C d
Relative acidic strengths acids
of organic
Definitions

ArrhenianspAamia
furnish ht ions in

aqueous solution are called Arrhenius acids

9 42504 HA ANO Chzcoon eh

Bringtagacania ht proton donors

are
are called Bronsted acids
Bronstedacids too
All Arrhenius acids are
es Nhat Hzo etc
Yim Lewis acids
which are electron pair
acceptors
Compounds
are Lewis acids They have a vacant electrophile

if É por d
orbital to accommodate that tone
pair ex BX3 Atx 2nXz eh
tema BFI where X F Cl Br 1

Scale for measurement of acidic strength

R Coon R Coo tht
I
constant
Ka acid dissociation
story acid
is the
A
Ka
4g f acid which provides
more Ht ions in
aqueous solution
 i k a x acidic strength

pka logka Kat pkad

higher Ka and lower pka

stronger acid

Inorganicgfanemonised in aqueous solution

called acids
Hence they are also story
HEO 11250 HEO not strength
g order

Maistre partially ionised

than
in aqueous solution
acids
weaker inorganic
Hence
they are
R 503h R Coon Ph on R on

sulphocas carbolic phenol alcohol

acids
Kander
Prediction acid strength
of
H X ht x
conjugate base
HX
of acid
11
Gwon t 41360
conjugate base of acid ch on

A stronger acid has a MORE STABLE WEAKER CONJUGATE BASE

 base anim
factors affecting stability of Conjugate
election withdrawing
presence of EWG
i e I M
groups
Resonance

W9
ERG
g a a on
open o ans n on
go g g mom
conjugate 1 gig
a t at I at

Ka order Y Y
g
on
on a on
g
pka order a a on
on a on
g g

9egeralanerofkavalues
Example
HBr
U in posh yoon pch The
Ides
It 503
R Sogn 2 3 4 s
HF
gon 40
Ph Coon

R Coon I 1120
6 7 8 9 10
What
 Ph on

420
2
55 5 5 9

R on Chzoon Cl Uz 2Coon chuncoon

3
R CEC h
a jun
Phzch
order α Feffect
s 4 37271 Ka
r.in
R
cnz Uy on

mycoon nycoon
Ka order

missing
angoon ers croon
a

11 COO ChpCoo
7effect Fiesta N 2 42004 Ka order
NC azoon
F Cycoon

11 Cycoon

Dicarboxylic acids stable unstable

cook 00
nt nt
1
oxalicacid
co coon
ta Yoon
I effect
doo
 i Kai Kaz
Coon Coon cuz Coon Coon

Loon q E coon
gaz
on coon
oxalicacid Coon
I malonicacidI Ii I shat.IE
I I TH SI
Ka order

pka one ICI CTI CTI

Maleic acid Fumaric acid

same
cis
Ict
pan
on
nooo yo hood IK

I
con
morestable I oh
dueto intra ood n
mean.sn to n
i
Ka for maleic acid Kaa for fumeric acid

Active Methylene Groups

An active methylene compound is a EWG Mop
compound that has the given
structural formula andthe h E
EWG m
withdraw elections m gmp
by resonance

K
9 and Cz
of
and 5
I OEt o Ing
 if
Now
The conjugate base active methylene compound is
of an

highly resonance stabilised Consequently these compounds are

highly acidic and can be deprotonated irreversibly

bases like on_ Rete
using common strong

int at
si J
In such cases
Ka is very large

Aromatic acids
stabilityfactors for conger
Electronic effects I M etc
Intermolecular Intramolecular H bonding
Steric Inhibition
of Resonance SIR ortho effect

Steric Inhibition ofResonance SIR

In case
of 1
stituted benzoicacids if
the substituents are otherthan H then due to steric
 repulsion the coon group goes out of theplane
art benzene ring This effect increases the acidic
strength of carboxylic acid irrespective of the nature
of group a

aurea maybe

Ej gig
a
a

Example
Yoon Ka order

EI EI
no
El isms
n

I I Ionly ME 2 M I

ÉÉ
I
Ii
I É
Ken I I 3 Ii N p

É II Ionly
É I
17117111 IV

I I Cly
 joon
on

45
my

joon

I
ai
I TH I 1 IV 117111
1 he

A
L Etnot
Y applicable
here

in in a

Em
et

Ét
if am

iii akin
I

I I
Basicf.ttmmenim Base onion donor
9 Nam Kon etc
theyhave
a
Bronted Base H ion accepter generally lonepoi
ee Nig R Nh Rio
Ht
Lewis Base é pair donors notonlyto
q Amy R Witz R En
Basicity Tendency to accept ttion

Naz Ht NH3 120

t Mat
H
1120 got
elements
Less EN atom can donate e pairvery easily forsameperiod

lna9mmtfn.ie yo z ans t on
Base conjugate
acid
K 21gal
Base dissociation constant

logk Pkb K A blight Pkbd

9 stable b
55
Sps
1,2 sp
t
0

sp
no weak base 3
CEN T S character K J
ans Chi in a
 aim It aggging
reverse we

11
7
stability
Ty on ay a
Emanates

berth
IF
delocalized
a

ve mangeassonance
Iran
localised
ve change ftp
FIEF
it

fIÉÉfef 5 m he increase basic strength

M
while
I decreasebasic strength

Hybridisation sp sp sp
Kb order
RYE Eris ÉÉ
Nitrogenous bases
aliphatic amines Ritz Rann Rsn
Aromatic amines Phring or aniline pyridine
pyrrole
Amides R
gents
Amidines
C.ÉÉÉn
k order
w I 7 117 111

amines
Basicity
of
ingaseousphase Ks one
 R
YE rent RT n n n n

i I
ment inagueousphase savarin stericeffect hydrogen
hey
termethyl can zni Charity cupro Nhs
group

i e
for otheralkyl R N R nth 7 Nhs
Rani
groups

Example
ofKborder Equine figurine
Whit's in twist Mizton
ammonia hydrazine hydroxylamine

NH n a h
E Er RE
Cyclic amines are more basic than aliphatic
amines if degree is same

F
me It 111 1 I N
I I I

I I I
 involved in
in
L.ie resonance

igntpyridine
pyrrole

ANIy.factos ergi.ee Mine Kb

Ewy i e M I Kb

tweeting
examples
ff ith
p

E
I
no
Ed
I I
Kg over

i
i
as

I n
I TH

11
Ñ
tÉÉf
É
in tonepair
Y
non conjugated
available donation Ked
Q K order
N it MI

É I
Ii I do I I

g É
I
II
I
É a
TI I
in

I
It II
I
c ÉTty I
11171071171

is most stable
A which of the following
carbocation

Iffy Ith a a a

III
o
thy i
A which at the
para position of phenoxide
one

has the most stabilising effect

Ch ooh I ay do gon
I the My I m I I am
 To stabilise an anion we need EWG

Q The strongest acid among the following is

H COOH H Coo

Cng cycle a Coon

4
a
crummy Coon Egg
Cuzcoon

acidic strength x I
structures
9 contributing showing
The total number of
involving c n bonds for the
hyperconjugation
following carbocation is n e
s

3 5
in other words
Iya no
y
6 do 2 a na

if i i u
n
f n

f n