Solvent

Electrophile Nucleophile Nucleophilicity Leeving Group ability

An organic rain
can be represented as

solvent
Reectant substrate Reagent product
t
Attackingspecies
Bond Dissociation
t
All rims are initiated with bond dissociation

as
Hemolytic
Heteroytic

A B s A e B A B A eB

Radials ions

Solvents

v
t
Non polar polar

v
v

protic aprotic

Acidic Hydrogen noacidic

hydrogen
 Remarks
Solvents Polar Protic Aprotic

H2O X Polar protic solvent

x polar protic solvent

cyote

x Polarprotic solvent
cycyon
solvent
H COOH X polarprotic

x polar protic solvent

tycoon
x Polar protic solvent
NH

CB Cy CHI
polaraproticsolvent
Helene

Ctf CY
f polar aprotic solvent
DimethylSulphoxide

H C N B
b V
o x polaraproticSolvent
Formsmide
Dimethyl
DMF

cy go
n
Yy polar apnoticsolvent

acetamide
Dimethyl
DMA

X Non polar
0 X

Non polar

X Non polar
 Reagents

1
A reagent three types
generates
of attacking species

I v t
Electrophiles Nucleophiles Radials

Electron deficient Electron rich Electron deficient

species species
species with
which can accept
having atleast one odd electron around
a electron
pairof unshared pair
of an atom
electron

Positivelycharged J t in aye L
Species negatively changed

H U Br species CH Coo gtfo

CH
CN on Bi I X etc
NOL

species with vacant Neutral

orbitals at central
NY H2O etc
atom

pus 502 Sog BH y

act as lewis
1 base
act as lewis
acid
Nucleophilicity

The tendency to give e pair to an electron deficient carbon

atom

Criteria
for Nucleophilicity

I The factors which increases atom

e
density at donar
increases
nudiophilicity

2 The more polarisable donor atom is the better nucleophile

Therefore size donor atomT nucleophilicity T

of

Periodicity

Left to right EN T Nucleophilicity I

c Nif of F
0 same as banjhapay

In a
group size T Nucleophilicity T

Acidic strength HI 7 H Br HU HF

I c Br c u e F
Basic strength Reverse

F a u e g I
Nucleophilicity
 In polar aprotic solvents

order will be same as basic strength

of nucleophilicity
ie
F s a Br I

Steric Effects on
nucleophilicity

cry
I 0 0
o b
a Cy g cry cry o

Ch

Note Because a can not approach to arson atom easily

So order is b a but bonicity

nucleophilicity

order is a b

Ambident Nucleophile

The Species which have more than one nucleophilic site

for reaction

Noi 8 on s etc
e.g
I 0
O CH S
 Comparision between Nucleophilicity Basicity

Remark
Nucleophilicity Basicity

l Cy NHI on s F Same if doneratoms

belong to
sameperiod

Same then nucleophilicity

L Phi SH y u
Sinj order
baricity
is same
a I Reverse
3 F c u e Br
down the group

c SH
Reverse nucleophilicity
4 oh
increases while

Reverse decreases
5 Ro a RS basicity

same
b Ro no
if donaratom is
same then
generally
0 same
7 Roo a photo Hoo e Ri nucleophilicity
09
R Il
c o
0
R S no
o same baricity order is same
d o
11
o

9 Ho H2o game

lo NHI s NHz Same

ti Fgcsoj a phew a Pho c Ro same

Leaving Group Ability Nucleofugality

Nu t R s R Nu t

1
loving group
O
Morestable x then its better
leeving group

ie X should be weeker base

Weeker bones are always better leeving groups nucleofuse

Activation energy 1 rate of rxnT

Leering group ability 4

Order
of leering group ability

0 0 0 0
1 I Br U F

0 0 0
2 a N c ou a F
Cy

O 0 0 O
3 RCoo Pho HO RO

0 0
4 SH 7 OH
o_O
o_O
I
0
5
o
p o 0,4
I
I
I O l 10 I
I I
NOz Cmg
 Some other better leaving group

Oo S R o S o R
o o

Akanesulphonate ion Alkylsulphateion

Oo S 0
Io CH
Ff so
o
im
Tosylate Tso Triflate
ion a super
leaving group

Note
0 0
Br R oh X 7 RBr t 0h
j
base poor leavinggroup
strong

NP e
enjoy X cry Nu e cryo

nota leavinggroup

The should have lower bond enthalpy

with carbon
leering group

iii stable either dispersal or

Negative charge should be more by
delocalization
 Reections acidic Hydrogen
of
compounds reactive or acidic hydrogen gives acid base
having

reechon

i Run with metals

CyCooH
e
t Na s CycooNa I

ii Ran with alkalies

crycoom t NaOH 7
CyCooNa t Hyo

iii Rain with bicarbonates

CyCooNa
e
C
tycoon e NaHwy
s 629 H2O

iv Ran with Nam

CyCooH
t Nam s
CycooNa
e
Hz

v Rxn with Grignard reagent

0
Rmgx
GH RI Myx 21
cynyx
Group containing
Cy g
age
acidic Hydrogen

q
y
OH
 Eti o
rn mgxc

mix
KM
Rickon R'Nth
µµ e NHK
RH l ryx
fr E o1mg
x H CEC r
e
v

RH e x c c R't
ng

Nucleophilic Addition Rxns of Carbonyl compounds

It is a characteristic rxn
of carbonyl compounds
Aldehydes Ketones

This man involves addition of a nucleophile and anelectrophile

double bond
across the 7 0

The general nucleophilic addition rxucen be represented as

0
AO E Nu
C OE

nu
 The mechanism can be carried out in
following
two

manners

a Acid catalysed first attack is of electrophile

c O s C OE s C OE
I w V r d s l
Nu
E IO OE 7
c OE
rds l
Nu

b Base celelysed attack is of nucleophile

first

O
TO s C
0
O
Eeo
s c OE
v r ds l I
Nu Nu

Acid catalysed nucleophilic addition is generally faster than

base catalysed

The reactivity of the carbonyl group

arises from the electro

atom and the resulting polarisation

negativity of oxygen
double bond
the carbon oxygen
of
St S
CIO
 cerbm atom is sp hybridised
The electrophilic carbonyl
open to attack from
and feet hence it is unhidered and

either face of the double bond

Reectivity
reactive than ketones in
Aldehydes are more

nucleophilic addition rxus

7 7
fy
o o o
my Rn

There are two feelers which influence the reactivity of

ketone and aldehyde

Inductive effect ii steric factor

it

decreese the amount of charge

I effect
of alkyl group
on c E 8 in ketones

steric effect also causes the less reactivity of carbonyl

group
 i Addition of Hydrogen cyanide
HCN

0
HCN OH CN e H2O
e

TH 40H

f gift
c

tetrahedral
intermediate

OH
Acid OH
e e c
OOH hydrolysis
CN
Hayne
L hydroxy acid cyanohydrin

OH
µydrdV
c µ
thyme s d oh Hao
OH
B go
Joyride

OH 1 NH3µ NHL
C c
I µ
ii Hz0 h
coom

L amino acid
 In use
of ketone cyanohydrin formation is reversible

due to bulky ketone which hinder the formation

groups of

f cyano
Nacht
CA 1h4m0s B
thou
11NBN
I
v
l tL4n
Han
C
Naia

Answer

Clg 11
El n
CN
en WH coom
s
Cy gu Cy gm
OH A OH
B
cyanohydrin

an 1 NBN
Cy Yog e 114 h
I on
C CH COOH
q
chg IN tmz Cl
Alanine1
Ii Addition of Grignard Reagent

U
R
ny
x c
l
88gx
R

120 4
v

on

R
gR myconlx

Alcohol

H
l Rmgx
o
I Hzo µ
Razon
H Io alcohol1

R'e il Rmgx
C O R H om
H n
yo mo R
alcohol

1 R
R l Rmgx g I
R om
c O
g
r t ii Hzo n R
30alcohol I
e.g
e
thelH cry
CHOM
1 CHO
Cy PhryBr i
Ph

CzH5
I
Hettie ctfu
ii CY go cqcyegns.mgw
s Cy g
OH

GR
t butyl alcohol by
gig
c c cry
y
OH
CB
1 cyngBr B 4 3
31 0 neo OH
C
I n
go
Acetone
 Bimolecular nucleophilic substitution reection with tetrahedral

intermediate
fifth

Characteristic rear acid and its derivatives au'd halide

of
ester amide is Sn2Th
anhydride

CHIo
acyl substitution usuallytakes place by
an
Acyl Nucleophilic

8 addition elimination mechanism The incoming nucleophile

adds to the carbonyl to form a tetrasubstituted intermediate

with a tetrahedral carbon

Nu
0
R f

fI
o i

leaving spa 1
group J weeker
trigonalplanar
Transition base
state leavesmore

awe activated readily

f N'T
 RCooH
R coil
conditions
I
RCooR
R If 4 e
Ny r i ivu L

0
must be better than Nuo i e
il L
leeving group

then LO
banicity of NP should be more

0 KOL
il't Nu must be a nucleophilic to attack
strong enough

reect with
it carbon must be enough electrophilic to
Cerbonyl

Nu0

order
Reectivity

R
di u R di o di R R d or R I NH

Basic u c 8 di r e Tor a
q
strength
 Hypos o
SN Th Reaction carboxylic acid It on
of I
on
H i
O
e on
EEP
n l
OV
KIIism I
L
i Formation
of acid chlorides

O
PU5
R d U e POU t Hu
R COOH pyridine
M It willnotallowto produce Hu intialstye
ite O
je PU3 R c y e Hypo
e
OH PU H Pyridine
Rgo a
0
p o l I
I
p ko ti i SOUL di
G
u
i 46a s R u e
Sou HU
r 4
rejuerous do na
EI
ii Fisher's Esterification

Condensation Rxn

O
R d t Iii Fujio r s
R i o r e ko
i
ng

iit formation
of
amides

R
di om e
d
s r di o_O my
Ng
e
150C Zook

R F NH e Hyo
 In amides an not be prepared from carboxylic
feet
heeted
acids and amines unless the ammonium salt is

Strongly to dehydrate it This is not usually a good

method amides
of preparing

Iv Formation acid
of anhydride
Agent
Dehydrating

2R d oh
K 5
R d o ER H2o
0

e.g
g CH Con e Sozte HUT
Ctg COOH

µ
EH d o CH e 1120
GHg CMI t
Chgoy

the puccoon ph
Ph Coon Nye H2O
O

CH Cootf e CGH cook

205
cy
di o F gu t
ng
o
 Th reection of acid derivatives
IN
derivatives
acid derivatives to other acid
4 Conversion
of
0
o

R Ctu e 2
Ng s R c
NHL
N
Hy U
Ingenue
O
it 0
y R Il 0
NH e Ro Na

1
NN R c
Gor e
Nantz
on
thy 0
paid e R E NH
fo I
R c or
di R R'on a
R

R c e Hu X
f ng

when nucleophile is more

Note An Sm Th reection is feasible

basic than the leering group

acid derivatives
if Hydrolysis of
0
h Iyo n
y R C oh 1 GH
R c
49 or
H2o Ot
acidic or basicmedium
derivatives will hydrolyse in
All acid
and will produce acid
 O R E8 Roon
neo
R
G
i h H
p Il om e ROH
R c 40
H
R

p
id o F R Hittle r
di om e R I og

R c
0
a
h H
R I om e HU

R I 1
R E one NHg
ng

amides and esters are not possible in

Note Hydrolysis of
neutral medium