p
t
9
H
Y
#
cuad
|
+x
N
NHz
#Br
r
I
!
ko-fi com/yen 25
.
#RENE d
①
-- CHz
H
AlCls
I
t
H
-
C
Cl
-
heat
It
>
4
② Friedels-crafts acylation
T
③
①
P
&
CH's
L-
necess
La
Halogenation
T
c
+
#
·
i
ECTest
white fumes
I
HCl
+
white fumes
#
HO
HNO3
CH
⑤
white fumes
No
+
|
HLl
t
se
AlCls
Nitration
#
:
alkylation
Friedels-crafts
T
following reactions
methylbenzene undergoes the
H
+
CHz
I
# NOz
HOM
HNO3
+
+
H
oxidation
Side-chain
O
Alkaline KMnOu
#-CHz
followed by H
4
⑯
,
+
2
reflux
Hydrogenation
T
Hul
Ni
>
-
I
Mon
+
CO
Mechanism
↳
electrophilic
for
of
Formation
HasOy
substitution :
nitrobenzene
+
HNOg
+
NOz
↳
⑪
HSOy
Halogenation
↳
H+
+
of
,
H +
HyS04
&
benzene
-
Br- Br
H 0
+
#
&
+
No
H NOz
Not
HSO4
+
electrophile
+
⑤
#
FeBrs
>
Br
-
Br
-
Febr
# Beer Febr
when
methylbenzene
reacted
is
chlorine
with
group
the
instead
presence
of
the
UV
products
are
made
+
light
,
substitution
occurs
in
the
ring
.
4 Hy
,
CHz
&
#
#
of
two
+
#
(x
in
,
HBr
4Hz
4Hz
#Cl
However
gas
+
+
C
U
#
.
+
He
white fumes
methyl
Febr
Electron-withdrawing groups
Electron-donating groups
Ortho
,
meta
directing
para
deactivating group
activating group
I
·
-
I
Ortho
6
.
NH2<
-X2
-meta
4
para
Eg
directing
-OH
-
CH
-
NOz
>
-
LOR -LOzR
>
-X
,
-
halogens are
2 4
directing
,
#alogen
compounds
The
halogenourenes and halogenoulkanes
reactivity of
·
In
with
affected by
:
polarity of the C-X bond
The
halogenarenes
electrons
it
of
ms
of
the
the benzene
ring
the lone
,
the
are
covered above.
are
by resonance
stabilization
·
reactions
pairs
are
conjugation
in
.
let
Cl
G
atom
halogen
points
oce
cet
Il
#
↑
-X
M
&G
J
This stabization
character
.
that
of
As
by
a
resonance
,
haloulkanes
polar than
in
.
gives
the
result
Moreover
haloarenes
,
.
Thus
,
IV
III
Il
I
the
C-X
bond
a
and
C-X
bond
is
the
C-X
bond
of
halvalkanes
are
less
reactive
halourenes
shorter
double
partial
hence
are
than
bond
stronger
also
than
more
haloulkanes.
ALCOHOLAPHENOL
Just
like
form
esters.
CH3-CO
phenols
alcohols
,
M
I
4
stability
of
the
strength
acids .
of
The
.
negative
base
conjugate
A
stable
more
charge
can
be
must
·
-
+
to
by
the
base
HCl
effervesence↑
considered when
be
conjugate
results
in
points
determining
a
stronger
:
charged
positively
nucleus.
volume.
a
&
G
N2
ms
stabilized
Bringing the negative charge closer
larger
spreading charge over
·
+
water
,
the
1
warms
phenol ethanol and
of
#
H20
I
>
+ 10
acidities
white fumes
I
#
HCl
-
The
acid
,
HCl
t
OH
j
NaNOz
to
.
N+
#
chlorides
acyl
with
react
phenylamine
from
NHz
comparing
also
can
c CHy-c-CHECH
CHICHOH
+
prepared
be
can
aids
carboxylic
with
O
&
Il
&
#
↑
#
M
&G
J
Here
the negative
,
This
ring
.
acidity
.
III
IV
O-
is
delocalised into
be
more
Il
I
causes
charge
of
the phenoxide
I
the
ion
to
stable
,
the
benzene
increasing
phenol's
other
the
on
of
effect
hand
the
the
,
ethoxide
is
ion
electron-donating alkyl group
the
.
HH high electron density
I
H
-
2
-
c
It
·
of
Reactions
D
Order of
phenols
-
0:
it
acidity :
phenol
water
>
:
ethanol
.
acid-base
O Nat
OH
+
I
#
NaUHcays
Ho
+
colourless
②
acid-base
O Nat
OH
I
-X
4
③
coupling
I
t
Na
>
#
↑
ence
reaction
orange dye
N
OH
+
1Il
↓
cle
N
j
#
4
I
+
This reduces ethanols acidity
.
compared to water
by
destabilised
#
H
+
Nace
+
H20
①
Nitration
OH
M
OH
,
diHNO
NO
H
OH
OH
I
T
conc
ON
HNO
.
,
Yo
t
NOz
⑤
Halogenation
OH
Bry/X-Br
OH
I
+
3 Br
I
(ay)
Br
↳ Bromine water decolourised
white
OH
reacts
This
overlaps
there
is
readily
more
because
is
one
an
increased
The electron-donating
directs
Due
to
electrophilic
lone
electron
the
it
-
OH
difference
substitution
in
to
the
reactivity
reactions
of
,
to
benzene.
oxygen
atom
in
benzene
the
in
ring
.
As
phenol
a
result
ring
.
2-,4-and
the ring
6-positions.
the
and
whenol
in
compared
the
of the
density
group
as
on
pairs
system
electron
incoming electrophiles
this
electrophiles
with
the
of
with
and
-Bu
2734"M
4
Phenol
ppt
OH
Brz/CS2
#
3HB
+
,
Phenols
therefore
,
reagents
and
activates
benzene
conditions
will
for
differ.
ko-fi com/yen 25
.
CARBOXYLIC ACIDS
DERIVATIVES
Acyl chlorides
be
can
CHyLOOH
+
PClj
3CHzLOOH
+
PCCs
CHzCOOH
+
SOCez
>
-
>
-
>
-
some
acids
carboxylic
①
their
from
prepared
heat
POLIg
&
CHILOCe
+
>
3CHy(OCl
+
>
CHzCOGR
further
be
can
carboxylic
respective
acids .
+
HLl
+
H(l
HyPOs
SO2
oxidised.
acid
Methanoic
H-IOSCO
-
The aldehyde group of methanoic acid
Tollen's
or
8
reagent
Methanoic acid
.
can
can
be oxidised
also
be
by
Fehling's solution
oxidised by KCr0z
or
KMnOy.
Ethanedioic acid
O
O
"j
-
c
comparing
The
KMnOy
or
acidities
of
·
be
can
carboxylic
used
acids
depends on
the strength of the O-H
acidities
·
the
=
22
and
alcohols.
+
2H20
OH
HO
Kalrz8z
2[0]
+
stability of
,
here.
phenols
:
the
bond.
conjugate base.
ms
points
In
the electron-withdrawing
Carboxylic acids
,
away from
the
O-H
Hence
and alcohols .
bond
dissociate
can
the
between
conjugate
buse
the two
oxygen atoms.
highly
carboxylic acid
(carboxylate irns)
alohols
,
the
localised
Again
stabilization
,
electrons
on
the
on
oxygen
making phenol
a
delocalised
is
stabilizes the conjugate
·
making
base
,
the
,
R-0
:
alkyl group donates electron density to the
for He to dissociate
making it weaker
atom
the
oxygen
due
to
resonance
atom
to
be
stronger
j
I
-
oxygen atom . This makes it harder
acids.
Alkoxide ions are also not stabilised
remains
negative charge
acidic .
mentioned before
as
,
phenols
in
to
compared
as
H
resonance
·
RIn
weaker
density
p
-
This
electron
group withdraws
easily·
more
↑
R
In
be
it to
causing
,
H+
carbonyl
,
less
,
by
resonance ,
making
it
on
the
available
stable e.
less
phenoxide
ion
makes
formation
bund
for
negative charge
the
so
the
with H+,
acid.
-
&
O
11
II
&
#
G
↑
#
M
M
J
&G
However,
o
the
delicalisation
electronegative
carboxylate
oxygen
IV
III
Il
I
of
atoms
charge density
.
So
phenoxide
is
on
ions
carbon
are
atoms
less
instead
stable
than
ions .
·
Order of
acidity :
carboxylic acids:
phenol
>
ethanol
of
Effect
substituents
acidity
the
in
of
carboxylic
Electron-withdrawing groups
further
weakens
draws
density
from
the
of
delocalisation
the
extends
electron
more
even
carboxylate
the
of
the
this
negative
bund
acids
O-H
.
charge
bond
,
Furthermore
,
as
it
the
EWGs
theLOO-
on
group
ion.
EWG
The COO
stabilised
with
Ht
and
vice
and
.
is
Hence
,
is
now
even
to
less
likely
ENGs
increases
↳
more
bond
Cl
O
I
Il
H - -
-
0
-
H
it
acidity,
versa.
Reactions of
.
D
group
acyl
chlorides.
Esterification
CH3-CO
+
CHICHOH
CHy-c-CHECH
t
white fumes
i
⑭
N
Die
+
CHICH2OH
:
HCl
NACCHCHa
+
AC
② Aminolysis
p
Il
Ha "O
+
NHz
⑧
1)
S
Hy Not
2
HLl
white fumes
H
p
Il
Ha "O
t
9
+
CHzCHzNHz
2
Hy - CH2CH
it
+
HLl
Hydrolysis
⑤
p
Il
Ho
Ha
Preparation
of
p
Il
2
Hi
HCl
t
OH
white fumes
benzoic acid.
O
Alkaline KMnOu
#-CHz
followed by H
4
Ease of
Calky)
>
-
Mon
,
+
2
reflux
hydrolysis of
different
acyl
chlorides
,
aryl
,
organic compounds .
The trend
depends
on
acyl
chlorides
the carbonyl carbon
·
In
,
it
carbon
is
weakened
and
In
alkyl
atom
it
so
leaving
it
,
,
stronger.
The
refluxed
with
strength
delocalised
bond
·
It
of
attached
to
is
more
prone
the
C-Ce
carbon
As
nucleophilic
attack.
is
only
to
attached
a
electron
,
a
lone
system
making
hydrolysis :
.
it
The
pair of
the
Ce
This gives the
.
Acyl chlorides
C-Ll
atom
,
away
C-Cl
is
overlaps
bond
a
Alkyl chlorides
>
so
from
bund
to
therefore
be
Nl
Hydrolysis will not
>
points
electronegative
bond
alkali
+
atom
the
,
one
L-Cl
strong
R-OH
stringer
result
a
to
comparitively less electropositive (3 ).
hydrolysis of alkyl chlorides requires
,
oxygen
an
This pulls electrons
.
is
character
Ease
also
bond.
%
anyl chlorides
In
is
C-Cl
fairly positive
it
than
R-- C
·
the
of
.
,
chlorides
the
ms
strongly electronegative atoms
two
to
carbonyl
the
·
bonded
is
CO
+
with
the
partial double
occur .
Aryl chlorides
Addition elimination mechanism
-
reforms
1= 0
Nucleophilic attack
deprotonation
Cl- pushed off
O
·
It
>
-
Che
&
H
·
>
-
CH3-c0
-O
-
H
Nice
H
Compounds
Itrogen
of
Preparation
①
amines
halogenoalkanes
substitution of
ethanolic
8
+
CH3-CHz-Br
+
Reduction
nitriles
of
CHs -C = N
8
NHS
CH3-CHz-Br
Deduction
9
S
N-H
HzC
H
of
heat
CHi-CHz-NH2
LiAlHu
dry
ether
Y
ammonia
CH3-CHy-NHz
>
in
sealed tube
ethanolic
amine
Y
neat insealed tube
(HzCH2
HBr
+
CHaCHz/NH
HBr
+
CHyCHzNHz
amides
At
H-
-
H
Ha
H
ko-fi com/yen 25
.
basicity
of
amines
Just like
,
The
basic .
Them
of
the
basis
In
amines
the
,
Thus
,
lone
basicity
of
-
N
N
order of
basicity
is
-
↑
R
↑
the
<
H
amines
due
pair ,
amines
are
This
because
delocalisation
ammonin
the
least
the
lone
pair
with
the
riny
,
-
inductive
of
basic
of
the
causing
is
of alkyl
effect
30 amine
basicity
is
as
such :
R
↑
-
<
H
R+ N
-
H
--
20
amine
hindrance
steric
This
atom .
nitrogen
atom.
H<R + N = R
of
↑
experiences
amine
whereby the bulky
,
reduces
the
availability
#
:
Order
of
basicity :
of
space.
and
phenylamine.
compared
to
nitrogen
it
to
and
ammonia
atom
in
less
be
aliphatic
aromatic
amines.
amines
available.
(NHz
#
on
-
R+ N
<
ethylamine
,
atom
-
luck
to
nitrogen
↑
the
around
crowding
Aromatic
in
order
30 amine
of
is
the
,
R= N = R
tertiary
nitrogen
amine
-
basility
comparing
20
R
-
the
--
amine
compared
I
H R+ N
↓
because
lone
-
be
such :
I
solution
agreous
an
causes
groups
as
the
makes
amines
in
can
around
positive
-
Ammonia
is
the
H
R+ N
<
H
-
This
around
the
↑
-
pair
to
in
H
lone
due
Ammonia
,
pair
ammonia ,
-
However
lone
the
atom
amines
the
to
↑
H
of
nitrogen
and
ammonia
of
availability
the
of
pair
availability
the
higher compared
groups.
the
ammonia
phenylamine
>
ammonia
< ethylamine
participates
nitrobenzene
used
is
to
phenylamine.
prepare
NOz
I
#
G[H]
+
4
NHz
I
#
.
excess
NaUHcaq
>
of
diazonium ions
and
phenylamine
2H20
+
4
almond-like odour fades
↓
Reactions
Sn/conc HCl
① Halogenation
NHz
BryB
NHz
I
#
|
3 Br
+
(ay)
↳ Bromine water decolourised
white
②
ppt
diazotisation
M
NHz
I
T
Hee
-No
j
+
#
Nach
+
4
Further
③
.
warming gives phenol
Hydrolysis
M
N
OH
+
cl-
j
#
+
warm
H28
4
①
2H20
coupling
I
T
t
N2
HCl
↓
effervesence↑
white fumes
reaction
orange dye
N
OH
I
>
+
1Il
+
N clj
#
4
#
H
+
Nace
+
H20
Amides
be
can
p
Il
NHz
t
Ha "O
through aminolysis
prepared
.
⑧
1)
S
Hy Not
2
9
Ha "O
CHzCHzNHz
+
Hy y CH2CH
2
it
of
amides
.
Free amines/ammonia
CH3-CH
CHz-c0
-
dil HCl
H ,0
7
CH3-C-Nat
7
reflux
NHz
produced
when
acid
is
limited
NHy"cl
+
OH
NaOH (aq)
H ,0
t
are
CHy-0
.
reflux
NHS
Deduction
9
H
HHA
-
-
H
of
Basicity
In
HLl
+
-
① Hydrolysis
②
white fumes
H
p
Il
Reactions
HLl
t
amines
amides
,
H
H
amides
the
lone
,
it
is
pair
delicalised
of electrons
into
the
C=0
through
&
-
HC-C--H
it
H
Thus the lone pair
,
.
in
amides
becomes
less
available
nitrogen atom.
the
.
However
in
resonance.
HaH
H
amide
amine
amines
group
around
if
Hs)-N H
bases than
localised
is
for
Ht
,
and hence
much
weaker
acids
Amino
react
can
to
dipeptides and tripeptides.
form
Peptide
↑
H
H
HIN-CH -
O
-
Re
R
linkage
HH
it
R
I
>
-
OH
This is
Isomerism
H
He
the
when
shown
is
CH30
I
N
-
c
-
C
peptides
H
t
He
↓ OH
H
Alanine
Hy
He
-
0
I
c-
Hy
t
OH
It
of
Since
a
He
acids
contain
both
the
molecule
.
forming
,
the
amino
with
a
(Ala G(y)
-
I
c
-
a
,
will
not
Amino
In
↓
C
>
-
OH
↓ OH
(Gly A(a)
-
group
the
a
zwitterion
ion
with
that
proton
as
acts
group
.
base
a
as
charge
-ve
a
interactions
acid-base
,
forming
,
can
an
acid
and
loses
At
the
same
time,
an
ammonium
ion
.
is
get attracted
acids
groups
carboxyl
carboxylate
accepts
charge
the
Here
basic
and
acidic
+
in
Thus
N
>
-
↓ OH
-
condensation reaction.
monomers .
Alanine
within
proton
C
a
zwitterions.
amino
occur
-
CH30
N
Glycine
Formation
c
non-identical
Glycine
H
N
-
from
⑧
I
N
formed
are
H
+
Ra
H
exist
a
to
as
dipolar
any
-
C
-
H
I
100
ion
of
NHz
I
R
>
-
the
zwitterious
with
poles
at
no
overall
when
their
-
charge
placed
in
isoelectric
This
.
an
means
electric
point.
that
field.
it
A
low
the
pH
solution.
field
electric
carboxylate
the
,
This
will
it
would
,
R
R
they
-
exist
the
analytical
electrical
field .
Ve
electrode
while
Ve
electrode.
The
an
+
in
the
R
Y
When
.
placed
from
in
an
electrode.
-Ve
Ht
WHz
ion
protons
accepts
CH-COOH
-
+
WHz
OH
y
WHz
-
CH-100-
Wiz
their
at
zwitterious
as
R
-
isoelectric
point.
electrophoresis
Interpreting
is
charged
forwards
migrate
and
base
a
positively
a
CH-100-
-
+
It
as
versa .
vice
Hence
form
CH-100-
-
+
and
acts
group
the
technique
which
in
ions
The positively
charged amino
the
negatively charged
amino
present
acids
amino
them
placing
in
acids
will
move
forwards
the
acids
will
move
forwards
the
of
zwitterious
form
the
in
by
separated
are
will
remain
well.
IIII
-
.
2
The
these
which
at
rate
·
The
larger
ions
more
ions
depends
affected
the
ion
,
by
more
on
the
pH.
depends
more
size
of
the
slower
it
than
those
quickly
the
ions
pH
of
the
the
on
ions
moves
,
with
solution
,
:
charge
and
of
vice
the
ions
Similarly
versa .
,
less
the
charge
.
Since
the
of
the
movement
highly charged
charge
ions
of
is
these
therefore
-Indensation
Polymerisation
Bifunctional
groups
monomers
Polyesters
>
-
different
be
may
for
identical
or
formed
be
can
essential
are
condensation
two
+
(1)
functional
other.
each
to
The
polymerisation.
as :
(one monomer (
Homopolymers.
-
CH3
I
HO-C
-
C
-
self-condensation
OH
Y
I
H
V
-
>
-
copolymers
(two
.
more
or
monomers
-
n
(
-
-
↓
X
O
H
+
HO-CH= CHI - OH
U
>
-
n
-
0
-
CHE CH 0
-
-
-
-
(2n 1) H20
+
D iols
can
react with
also
-
dioyl chlorides.
-
*
C(CH2)
cl
C
Ho-X
t
n
-
-Cha-0-0-
o
H
>
-
N
N
-
-
D
(2n 1) HCl
+
-
white fumes
The
same
goes
for
polyamides.
+
-
Ho
- ((Hz)p C OH
-
-
H
H
O
O
HzN-(CH2)j NHz
-
-
V (Hz)j N
>
-
-
-
-
O
-
N
N
c
-
↳
((Hz)p "
-
-
-
(2n 1) H20
+
-
-
-
cent-Chalce
+
N
HeN-CHals NH
-
>
-
N
n
H
O
(CHa)-C-N (H)
-
-
-
+
n
(2n 1) H(l
-
Amino acids
undergo condensation synthesis to form polypeptides
,
which
-
-
H
H
I
V
-
-
H
cC
R
H -
H
O
I
-
-
>
-
R
HO
-N
R
-
(2n 1) H20
+
-
it.
-
-
- (2)
0
-
-
.
retr"
-
-
-
X (H2)
HOOC-COOH
dil HLl
0
-
O
-
j-
undergo degradation through hydrolysis
Polyamides and polyesters
polyamides.
also
are
0
-
-
NaOH (aq)
0
NaOCCONa
Y
reflux
HO-CH2-OH
+
HO-CH
+
-
-
This
reaction
not reversible.
is
-
-
H
-Chal-N-CH
O
diltea
HOUC-(CH2lCOOH
~
HoNE(CHalj-NHyT
+
-
-
-
-
H
NOCOONH-HN
NaOH (aq)
reflux
-
-
condensation polymer
-
Addition
are
a
2C
There
is
also
chain
,
Finally
some
,
an
unlike
Hence
.
they
,
of
absence
polyesters
polymers
such
as
are
polarity
and
they
light.
chemically
in
the
.
inert
backbone of
O
-
C
-
(H2)-
-
Hit H it I It i
I
I
1
2
,
the presence
-
-
-
polyethylene polypropylene and
in
H
H
↓ (CHz)j N
polyamides.
polystyrene can undergo degradation
UV
as
,
long chain of saturated compounds consisting of many
single bonds
the
decompose hydrolytically
do not
polymers
of
-
2
-
2
-
2
-
2
-
2
-
2
-
2
# is it is it is its
-
Addition polymer
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.