NAME REACTIONS OF THIS CHAPTER

47 Kolbe 's Reaction :

É%
Tna ""

( remove 11205 ;÷
¥
sodium Acid
Phenoxide
↓
acidic medium Salicylic
(2) Reimer -
Tiemann Reaction :

Tna
-

g-Not "
OH

f¥;÷¥Ñ / """
°
"
±
☒
Salicyladehyde
OI
YH
saÉ,
%) HCl
dH°
Williamson synthesis :

RIONE + É¥£ ¥-2 ROR + Nax

ÉÑ
ether
sodium all halide

( Hsctlz Bo Gt3
: CHz0Na +
=µaCHz -0 Ctlz
- -

Ig
(4) Cumene Reaction :

( Hs Ctg -

!3-0-0-11 OH

☒
→
☒ ¥5s +
CHSCOCH
Acetone
cumene cumene

hydroperoxide
 PREPARATIONS
A. kokoki
(d) From Alkene :
→ By Acid Catalysed hydration :
)c=c( + H2O } -

Cf
↓ tote
elf: ( Hz ( H = ( Hz +
H2O -1€ Ctb -

CH -
Ctb

bit
oxidation :
→
By hydro carbonation
[µ [ H=CHz + (H B H2) 2 → ( " 3- ( H [ "≥

)
- -
-

te \BHz (µ (µ
,
-
=
ay

¢113 -

Ctb -

Cha )zB "=%Hz- ( th -

CH )zBH C-

L→2Q→ 3 ( H} -
C Hz -

( Hz -
OH + B(OH)3
OH

(2) from carbonyl compounds :

reduction of Aldehydes and ketones
→
By :

like Pt Pd
Add not H+ in presence of catalyst , ,
Ni ,NaBHy,LiAdHy .

It is
expensive ,
so used for some only
alcohol
Aldehyde give - 1°
2° alcohol
ketone
give -

RCHO + Hz Pᵈ_ R -
( Hz -

OH

RCOR
'
¥4s R -
CH -
R
'

th

KIB : We can
get alcohol from acids also via Esters .

¥sR R'OH
'

RCOOH COOR Rltk OH +

catalyst
③ From
Grignard Reagent :

HCHO
RMGX RCHZOMGX RCHZOH
My [OH )✗
→ + → +

'

%
R
R' du #R
→ RCHO +
Mgx → R- -

omg ✗
-
-

OH +
Myton)✗
¥
R'

¥
RCOR R'
Mgx R
-0mg ✗ R
Mg ( OHH
→ + → -
-
-

OH +
 Rheine'
4) from haloarenes :
%
+

É% + NaOH ¥7m ☒
-

(2) from benzene sulphuric acid :

E.
* ÷÷÷
(3) From diazonium salts :
N H2 42%-0
É N ¥0m
Benzene diazonium
+
iv. + me

chloride

(4) from Eumenes

↳ mentioned earlier
 CHEMICAL REACTIONS
Note : Alcohols acts as both nucleophile and electrophile .

4) Reactions involving cdevage of O -

H Bond :

F)
Acidity of Alcohols and Phenols :
(a) Reaction with metals : Alcohols and Phenol react with active metal
( Naif Al) to give Phenoxide ,

212-01-1 + 2Nd - 2- R -
O -
Na +
H2

ˢO)
413
6 ( Hz -
C
,
( Hz
-

OH +2 Al - 2

( ( Hz -

CH} 3
Al 1-31-12

test
butyl alcohol Aluminium tert butoxide -

% ima

☒ +2 Na → 2 ! 1- He

(b) Acidity of alcohols :

Acidity
no.at#a+ahgwup--e- releasing)
✗

R
R I
R -

CHZOH >
R
> (HOH > R -

f- OH
1° 20 R 3°

Phenols react with ag sodium hydroxide to

(c)
Acidity of Phenols : .

form sodium Phenoxide but alcohols dont .

R OH
- + NaOH - No ox
"

Ph OH-
+ NaOH - Ph -
ON a + H2O

P.e.
acidity : Ph OH > H2O > R OH
-
-

in
: É
eg Lot ☒
dH3 IN 02
(a) (b) (C)

c > a >b
Acidity :

F) Esterification : Alcohols and Phenols react with

carboxylic acid (coom) ,
Acid anhydride / Rico)z0 and acid ( R' cocl)
chlorides
to Ester
give
.
 Ar / ROH .
+ R' COOH - As / ROCOR
'
+ Hao
( R' 1020 R' COOH
'
Ar / ROH + As / ROCOR +

RI Ar OH + R' coal P¥É /

R Ar OCOR
'
+ HCl

40011 4004 "" %

NAH
41×004
+ ¢1131020 +

/Aspirin)
salicylic Acid
acid
Acetyl salicylic
(2) Reactions
involving clevageC-0of bond
C- 0 bond :
Pn Alcohols
Reactions of
clevage of only .

Phenols show this only with zinc .

E) Reaction with
hydrogen halides :
R OH HX -
+ - RX +
H2O
Alcohols soluble Pn lucas their halides immiscible and produce
reagent ,
are

turbidity .

Tertiary alcohols → immidiate turbidity

Primary alcohols - no
turbidity at room
temperature
% Reaction with Phosphorus trio halides :
3 R OH - + PX} →
3R -
X + Has PO}
(✗ = Cd , Bo)
Iii , Dehydration Used also ↳ Poy
anhy chloride

¥¥,aᵗᵈYˢᵗ
,
. zinc

-
d- d- Hzc =CHz + H2O

14 1011 Hzsoy 443K

°
[

under milder condition :

2° and 3° alcohols are
dehydrated
YH
( Hz -
CH -
CH } ÉÉcH3
440k
-

CH = ( Hz + H2O

4113 14112
CH} -

C- OH t CH} -
C -
CH} + H2O
I 358k
C Hz

for
dehydn : 3° > 2° > i

(Pv) Oxidation (
dehydrogenation ) : It means formation of carbon
oxygen
double bond with
clevage of an O H and C H bonds
- -
.

H
¥ -01^-1-1 -
¥-0
A-bond breaking
 Nate : •
loss of dihydrogen from alcohol molecule .

alcohol oxidise to
•

Depend on oxi
agent used I
-

acid
aldehyde then oxidised to
↑
carboxylic .

in
RCHZOH R -
C - O -
R
-
G- 0
aldehyde
ARCH
c.

OH RCHO
,

strong oxi
agent like acidified
permanganate potassium
•

Reagent for oxidation of tiako to

aldehyde
chloro chromate ( Pcc)
in
good
complex
yieldPs
pyriodpnium ,
a

of chromium trioxide with

pyrite and Hel .

CH} -

CH = ( H -
CHZOH CH 3- CHIH -
CHO

• 2° alcohol -
ketones
'
'
R -
CH -
R R -
C -
R

GH
Ketone

3° alcohol do not do oxd but

vapours of 1° and passed over
"
• 2°

heated Cu at 573kg It takes place and aldehyde or

ketone is formed
4113
.

4113
( Hz
-4 ¥-3k (Hz -

C=CH2

( Hz

RCHZOH ¥É RCHO

'

s ks
'
R -

CH -

R R -
C -
R

OH ¥

(3) Reactions Of Phenols only :

E) Electrophilic aromatic substitution :
(a) Nitration
pH % N°2 9
"

É
☒ ☒ +
☒
¥02
Imp :
-
O and P isomers can be separated by steam distillation ,
0 Nitrophenol is steam volatile due to intramolecular h
-

while P Nitro phenol is less volatile due to intermolecular

-
-

bonding .

b-
bonding .
 H NO≥
NO,
N03,
( picric acid)
T
G but of this MMPs poor
yield .
So
, Noz
Now a days P A - -

is formed by
,
i"
N°2

hog %%
¥02
(b)
Halogenation solvents like
→ Reaction is carried out in low
polarity
Ctlclz 08 Csz OH

[¥
'"
e-
nE +

273K

→
Phenol treated with Boz to
104 PM
B BE
+ 313oz _ +
3. HBO

I
1382
( white ppt)

(c) Kolbe 's reaction

(d) Reimer Tieman Reaction
-

(e) Reaction of phenol with Zndust

YH
+ Zn -
+ ZnO

(f) Oxidation
i
7,
Hzsoy
( conjugated )
di ketone

to
Benzo
quinone
 Ethers
'

\ \ \

PREPARATION :

4) By dehydration of alcohols
CHECK

Ctb CH , OH
|
-
_

, 121150 C2H5
413K

(2) Williamson synthesis :

3° is used then alkene is formed
Only for i alkyl halide , if .

'

R -
X + R
'
-
ONA - R O - -
R + Nax
9- R
phenols
of:erkd
+ NaOH -
É¥ 1¥

ÉLAN :

4) bond in
Cdevage of C- 0 ethers :

R -

O -

R + HX → RX + R -
OH

R -

OH + HX - R -
✗ + H2O

+ HX - + R -
✗

1-7
' '
R -

OR +
HX -
R -
✗ + R -

OH

HI > HBO > HCl reactivity of hydrogen halide

for 3° :-
f &
C - C -
O -

Ctb + HI - CH} OH + C- -

' '
c
c

(2) Electrophilic substitution :

CH3 10443 '"

Halogenation ☒ ÷÷
→ :
+

Anisole
tsr
→
Friedel-Crafts -8in
PCH } OCHS

xcᵗʰ
"

É
+

Abel
☒
+
csz
{ Has
3

cH3Cl ˢ
Log
+

Adel,
+ °%tho

→
Nitration
c↓CH3
3
÷÷
one
+
ortho

02