EEMAIN.

GURU

ALCOHOL, PHENOL & ETHER

ALCOHOL
Hydroxy derivatives

Aliphatic hydroxy derivatives Aromatic hydroxy derivatives

( I ) Aliphatic hydroxy derivatives :
Hydroxy derivatives in which —OH is directly attached to sp3 C (Alcoholic
compounds). ( I I ) Aromatic hydroxy derivatives :
Hydroxy derivatives in which —OH is directly attached to sp2 C or benzene ring (Phenolic
compounds). ❑ Aliphatic hydroxy derivatives :
( a ) Classification according to number of —OH groups :
(i) Monohydric [one –OH] ⎯⎯⎯⎯→ CH3CH2—OH
(ii) Dihydric [two –OH] ⎯⎯⎯⎯→
CH2 CH2
OH OH
(iiii) Trihydric [three –OH] CH2 OH

⎯⎯⎯⎯→
CH2 CH OH OH
(iv) Polyhydric [n –OH] (ii) s or 2° – alcohol ⎯⎯⎯⎯→
⎯⎯⎯⎯→ CH CH (CH3)2CH – OH
------------- 2 (i) t or 3° – alcohol ⎯⎯⎯⎯→
(CH3)3C – OH
CH2
❑ Structure of alcohol :
OH OH

OH ::O
( b ) Classification according to sp
3

nature of carbon : 108.5°

(i) p or 1° – alcohol ⎯⎯⎯⎯→ s
p3
CH3CH2 – OH
Alcohols are bent molecules. The carbon atom sp hybridisation 3

(linked with 1
sp s HC3 H 1s
3

'O' atom of –OH group) is sp3 hybridised. The

sp3
central 'O' atom is also in sp3 state of
Structure of CHOH3 Non - bonding e pair
hybridisation. The bond angle is 108.50 . In sp3
hybridisation of O - 2s2,2px2 2py1 2pz1 orbitals
hybridised to form sp3 orbitals —

→ ↑↓ ↑↓ ↑ ↑
O
2s 2px 2py 2pz
and two containing two electrons σ bond
In these four orbitals two each. O atom σ bond
containing one electron each
Orbitals containing two electrons do not take partin bonding. Other two half filled orbitals form σ
 bond with s-orbitals of H sp3
-atom and hybridised
orbital of C-atom (O—C). sp3+
. .S 108.5°
C atom
H atom
hybridised orbitals
. S
Due to lone pair effect the bond angle of .
. tetrahedral structure (109028').
tetrahedral oxygen atom is lesser than
normal HH
S
H
S
EEMAIN.GURU ( b ) From alkenes :
( i ) By hydration :

MONOHYDRIC ALCOHOL
❑ General methods of preparation :
( a ) From alkanes (By oxidation) :
⎯⎯⎯→ CH3 CH
(CH3)3 C—H H /KMnO4 ⊕
CH3

⎯⎯⎯⎯⎯⎯→ Δ (CH3)3 C—OH

H ⊕

CH3—CH CH2 2 oxidation : BH

HO
OH

(i i) By hydroboration

OH
( c ) From alkyl halides (By hydrolysis) :
⎯⎯⎯→ CH3 CH2
Aq. KOH
CH3—CH CH23
H O HO CH2 (1° alcohol) OH
22

(iii) By oxymercuration demercuration : CH3

(i) Hg(OAc) H O
,
⎯⎯⎯⎯⎯⎯⎯→ (ii) NaBH
,HO CH3 CH
CH3—CH CH22 2

⎯⎯⎯⎯⎯→ CH3CH2—OH
CH3—CH2—Cl 2
 or Moist Ag O

( d ) From carbonyl compounds (By reduction) :

>C O ⎯⎯⎯⎯⎯⎯→ Reducing agent >C H — O H

◆ Reducing agents may be,

LiAlH4/H⊕, NaBH4/H⊕
Na + EtOH [Bouveault-blanc Reduction]
NaH [Darzen reduction]
Ni/H2
R —C H O LiAlH4 ⎯⎯⎯⎯→
⊕
H R —C H2—O H
R
RCO H

R NaBH4 OH
⎯⎯⎯⎯→ ⊕ R CH
H
CH3 C
O
◆ Mechanism : H
CH3LiAlH4 H
⎯⎯⎯⎯→ ⊕ ?
H⊕
LiAlH4⎯⎯⎯⎯→ CH3 C ⎯⎯⎯⎯→ H

CH3 C CH3 CH3 C CH3 CH3

O

O OH
⊕
H
OD OH
H D
O LiAlH D⊕ 4

NaBD4

EEMAIN.GURU

4
CH3—CH CH—CHO LiAlH
⎯⎯⎯⎯→
⊕
H CH3—CH CH—CH2—OH
Crotonaldehyde
LiAlH

H ⎯⎯⎯⎯→ ⊕ Ph—CH2—CH2—CH2—OH
Ph—CH CH—CHO 4

/ OH –

Cinnamaldehyde
( e ) From ethers :

R — O — R 2 4 dil.H SO ⎯⎯⎯⎯⎯→ R—OH + R—OH

CH3—O—CH2CH3 2 4 dil.H SO ⎯⎯⎯⎯⎯→ CH3—OH + CH3CH2—OH

( f ) From acid and derivatives (By reduction) :

R—COOH LiAlH4 ⎯⎯⎯⎯→

⊕
H R—CH2—OH + H2O
 ⊕
H R—CH2—OH + HCl
RCO
RCO OR LiAlH4 ⎯⎯⎯⎯→
⊕
ClLiAlH4 ⎯⎯⎯⎯→ H R—CH2—OH + R—OH
OCO ⊕
H R—CH2—OH +
RCO OR LiAlH4 ⎯⎯⎯⎯→ R—CH2—OH

NH2LiAlH4 ⎯⎯⎯⎯→
⊕
H R—CH2—NH2 +H2O
RCO

( g ) From esters (By hydrolysis) : ( i )

By alkaline hydrolysis :

RCO ⎯⎯NaOH⎯⎯→ CO
R
OR ONa + R OH

(i i) By acidic hydrolysis :
⊕
H
RCO 
RCH

OR  O(excess)
2
O
OH + R OH

OH + CHOH 2 518
18 H O3⊕
CH3 C O CH3 C O

OCH2 5 

This reaction is reversible reaction and it's order is 1 and it is also called Pseudo-Unimolecular
reaction. ( h ) From p-amines :

+
⎯⎯⎯⎯⎯⎯→ R—OH + N2 + H2O
NaNO HCl
R—N H222
or HNO

CH3CH2—NH2 ⎯⎯⎯⎯→ HNO2 CH3CH2—OH + N2 + H2O

◆ Mechanism :

+
⎯⎯⎯⎯⎯⎯→ ⎯⎯→ 2 CH CH N Cl 3 2
⊕ ⊕
NaNO HCl
++ 

CH CH — NH CH CH — N Cl 2
2
32232 (Unstable)

EEMAIN.GURU OH [major] OH
CHCH3 2



Cl ⊕
 CHCH3 2 Cl
H O CH2 CH2
N CHCH3 2 O

O
CHCH3 2 O N

⊕
Inter mediate is carbocation so rearrangement may be possible.

E x . CH3CH2CH2—NH2 ⎯⎯⎯⎯⎯⎯→ NaNO HCl 2 + ?

S o l . Mechanism :

⊕
⊕
Cl⎯⎯→ CH3CH2 CH 2
NaNO HCl + —
CH3CH2CH2—NH2 ⎯⎯⎯⎯⎯⎯→ 2 CH3CH2CH2 N2
CH3←⎯⎯⎯⊕ HOCH3
CH CH3←⎯⎯⎯ H
CH3 CH OH

HNO
Exception : CH — NH CH — O — CH ⎯⎯⎯⎯→
2
3233

( i ) From Grignard reagent :

( i ) p-alcohol :
R—Mg—X + [O] ⎯⎯→ R — O —M g X ⎯⎯⎯→ H O2 R — O H
[Same C-p-alcohol]

R
R
−δ +δ

Mg ⎯⎯⎯⎯→ HO R C H⎯⎯→ H C
2

X+H H HC H
OMg OH [one C
O
X more
R p-alcohol]
R
CH2

−δ +δ CH2
CH2 CH2 CH2⎯⎯⎯⎯→

Mg H O2 X + CH2 R ⎯⎯→

O [two C more p-alcohol]

(i i) s-alcohol :
R
R
OMgX
OH
H O2
⎯⎯⎯⎯→ Mg X+RRC
R C H⎯⎯→ R C H H
OH R
O
OMgX
 R
⎯⎯⎯⎯→ Mg X + H H C
R C OR⎯⎯→ H C R R
MgX HO2
O OH
O
EEMAIN.GURU
(iii) t-alcohol :
R
R
2
HO Mg X + R R C
R C R⎯⎯→ R C R R
⎯⎯⎯⎯→
OH R
O
OMgX
R
⎯⎯⎯⎯→ Mg X + R R C
R C OR⎯⎯→ R C R R
MgX H O2
OH
O
O
❑ Physical properties :

(i) C1 to C11 are colourless liquids and high alcohols are solids.
(ii) Density of monohydric alcohol is less than H2O.
(iii) Density ∝ mol. wt. (for monohydric alcohol).
(iv) Solubility : C1 to C3 and t-butyl alcohol is completely soluble in H2O due to H–bonding.
1
solubility ∝ No. of side chainsc ∝

molecular weight

Order of solubility :
C4H9OH > C5H11OH > C6H13OH

CH3
OH < CHCHCH 3 2 OH
CH3CH2CH2CH2 < CH
OH 3C

CH3
< CH2 CH
< CH2 CH2
CHCHCH 3 2 CH3 CH
2
CH3
OH OH OH OH OH
OH
[Number of —OH increases, H-bonding increases]
(v) Boiling points : B.P. ∝ molecular weignt

1 B.P.
If molecular wt. is same then branching
∝
 Order of BP : C4H9OH < C5H11OH < C6H13OH CH3

OH > >
CH3CH2CH2CH2 OH CH3 C
CHCHCH 3 2 OH
CH3 CH3 CH2
< CH2 <
CHCHCH 3 2 CH3 CH CH2 CH
2

OH OH OH OH OH
OH
[Number of OH increases, H-bonding increases]
E x . Boiling point of alcohol is more than corresponding ether. Why ?
S o l . Reason : H-bonding in alcohol.

OH
---------- O H
------------- O H
------------- O H
----------
R R R
R
EEMAIN.GURU
E x . Boiling point of alcohol is less than corresponding carboxylic acid. Why ?
S o l . Reason : Dimer formation in carboxylic acid.

O HO
R C OH OC R
❑ Chemical properties :
Monohydric alcohol show following reactions
(A) Reaction involving cleavage of
OH
(B) Reaction involving cleavage of
C OH
(C) Reaction involving complete molecule of alcohol

( A ) Reaction involving cleavage of : Reactivity order (Acidic nature) is

OH
CH3—O H > CH3CH2—OH > (CH3)2CH—OH > (CH3)3C—OH
( i ) Acidic nature :
H2O > R — O H > CH CH > NH3 (Acidic strength)
Alcohols are less acidic than H2O and neutral for litmus paper and gives H2 with active metals (Na,
1 H
K) R—OH + Na ⎯⎯→ R—ONa + 2 2
1 H
R—OH + K ⎯⎯→ R—OK + 2 2
(i i) Reaction with CS2 :
1 H
R—OH + Na ⎯⎯→ R—ONa + 2 2
R—ONa + S C S ⎯⎯→ R O C S Na

S
Sodium alkyl xanthate (Used as floating agent)
(iii) Alkylation:
 R—OH
⎯⎯⎯⎯⎯→ CH N2 2 Δ R — O — C H 2— H
R—OH R—ON a R—O—R
⎯⎯⎯→Na ⎯⎯R −⎯X →
(Williamson synthesis)
( i v) Acylation :
(Acylation)
R OH + Cl C R O
⎯⎯→
R O C CH3 O
R OH + Cl C CH3 O (Acetylation)

OCR
OH O
⎯⎯→
ROCRO
COOH ⎯⎯⎯⎯⎯→ CH COCl COOH 2

Salicylic acid Acetoxy benzoic acid Acetyl salicylic acid

Aspirin [Used as analgesic]
EEMAIN.GURU

( v ) Benzoylation : (Schotten Baumann's Reaction) :

(Benzoylation)
R OH + Cl C Ph O
⎯⎯→ R O C Ph O

( v i ) Esterification : Conc. H2SO4 is used as catalyst and dehydrating agent.

R C OH + R OH + H+
24
⎯⎯⎯⎯⎯⎯→ conc. H SOR C OR +
O
HO2 O
◆ Mechanism :

H2SO4 ⎯⎯→ H+ + – HSO4

OH

R—C—O—H
R—C—O—H :

–H
+
:

⊕
⊕
O OH ⊕ OH OH OH ⊕

+ROH OR' OR' O

R—C—O—H R—C—OH ⊕
R—C—OH2 R—C R—C R—C—OR' OR'
OH ⊕ H R'
O

Note : This is a laboratory method to prepare ester.

OCH2 5 ⎯⎯⎯⎯⎯⎯→ conc. H SO CH3
24

Example : CH3 C OH + H O C OCH + HO 2 5 2 O

 O 18

18
24
⎯⎯⎯⎯⎯⎯→ conc. H SO
Example :
Ph C OH + H OCH Ph C OCH + HO 2 5 2 O
25

Dry HCl can be used as dehydrating agent.

⎯→ CH3 C OCH + HO 2 5 2
Example : CH3 C OH + H O
O
OCH2 5 ⎯⎯ ⎯ Dry. HCl

1
(i) Reactivity for esterification ∝

Steric hinderence .
(ii) Reactivity of R – OH [If acid is same] : CH3 – OH > 1° > 2° > 3° alcohol (iii)
Reactivity of RCOOH [If alcohol is same] :

CH3
H C OH
> > C OH
CH3 C OH CH3 C
> C OH
CH3 CH
O CH3 O CH3 O
O
EEMAIN.GURU

(vii) Reaction with CH CH :

CH CH + 2CH3—OH BF / HgO 3 ⎯⎯⎯⎯⎯→ ΔCHCH3OCH3

OCH3
Methylal

CH CH + 2CH3CH2— OH BF / HgO 3 ⎯⎯⎯⎯⎯→ Δ CHCH3OCH2 5

OCH2 5
Ethylal
(viii) Reaction with carbonyl compounds :

⎯⎯⎯→ R CHOR
R—CHO + 2R—OH H⊕ Acetal
OR

⎯⎯⎯→ COR
RCR+ R OR
OH H⊕
2R O Ketal
R

⎯⎯⎯→ CHCH3OCH3
CH3CHO + 2CH3—OH H⊕
OCH3
Methylal
( ix ) Reaction with Grignard
reagent :
 Ketene is used as acetylating

X agent. OR
⎯⎯⎯→ R H + Mg OR
R—Mg—X + H—OR H⊕ OR

( x ) Reaction with Ketene :

CH3 OCH2 5 ⎯⎯→ CH2


CH2 C O + R—OH
⎯⎯→ CH2 C OH 
CO 
CH3
C OH 
OCH2 5 CO

CH2 C O + C2H5—OH Ethylacetate

( xi ) Reaction with isocyanic acid : Ethyl urethane is used in preparation of urea

⎯⎯→ NH 
NH2
OCH2 5 OCH2 5 C O
NH C O + H—OC2H5
C OH
Ethyl urethane
(xii) Reaction with oxirane :
OR
+ CH2 OH
R H
OH + CH2 ⎯⎯→CH2
CH2 O
( B ) Reaction involving cleavage of C OH: Reactivity order or basic nature is CH3—O H <

CH3CH2—OH < (CH3)2CH—OH < (CH3)3 C—OH

EEMAIN.GURU

( i ) Reaction with halogen acid :

R—CH2—OH + HCl ZnCl2 ⎯⎯⎯⎯→ Δ R—CH2—Cl + H2O

R2CH—OH + HCl ZnCl2 ⎯⎯⎯⎯→ Δ R2CH—Cl + H2O

20 alcohol
Reactivity of the acids is HI > HBr > HCl > HF

(i i) Reaction with inorganic acids :

R OH + H O N O
⎯⎯→
O N O + HO2
↓
O ↓
O
R
Nitric acid Alkyl nitrate
R—OH + HHSO4 ⎯⎯→ R—HSO4 + H2O
 Alkyl hydrogen sulphate
(iii) Reaction with phosphorous halides :
3R—OH + PCl3 ⎯⎯→ 3RCl + H3PO3
R—OH + PCl5 ⎯⎯→ R—Cl + POCl3 + HCl
( i v) Reaction with thionyl chloride (SOCl2) :
R—OH + SOCl2 ⎯⎯⎯⎯→ Pyridine R—Cl + SO2 ↑ + HCl
(gas)
( v ) Reaction with NH3 : Alumina (Al 2O3) is used as dehydrating agent. R

OH + HNH2Al O2 3
⎯⎯⎯⎯→
 R—NH2 + H2O
250 C

( v i ) Reaction with halogens : Oxidation and chlorination takes place simultaneously.

CH3CH2OH + Cl2(dry) ⎯⎯→ CH3CHO + 2HCl (Oxidation)

CH3CHO + 3Cl2 ⎯⎯→ CCl3CHO + 3HCl (chlorination) chloral

( C ) Reaction involving complete molecule of alcohol :
( i ) Dehydration : Removal of H2O by two type
(a) Intermolecularly removal of H2O [form ether]
(b) Intramolecularly removal of H2O [form alkene]
0°C synthesis) 2 5 CH2 CH
100°C 140°C 170°C (Elimination) 2
CH OH + HSO 2 5 2 4
(conc.) CH2 5 O CH2 5
250°C 350°C
CH2 CH2
(CH) SO 2 5 2 4
CHHSO 2 5 4
CH2 5 O CH
CH OH +Al O 2 5 2 3
(Alumina) (Williomson's

Ease of dehydration follow the order : 3° ROH > 2° ROH > 1° ROH > CH3OH

EEMAIN.GURU
(i i) Catalytic Dehydrogenation : This reaction is useful in distinction of 1°, 2° and 3° alcohols.

CH3CH2OH Cu ⎯⎯⎯⎯→ 300 C° CH3CHO + H2

(p- alcohol ) (Acetaldehyde)
CH3 C CH + H 3 2 O
CH3 CH OH
CH3Cu ⎯⎯⎯⎯→ 300 C°
(s- alcohol) (acetone)
OH CH3 C
300 C° [dehydration] 2
CH3 CH3 2

CH3 C Cu
⎯⎯⎯⎯→ CH + HO
(Iso - butylene)
CH3
(t. alcohol)
 (iii) Oxidation : This reaction is useful in distinction of 1°, 2° and 3° alcohols.

⊕
H KMnO or

⎯⎯⎯⎯⎯⎯→ RCHO [O] ⎯⎯⎯⎯⎯⎯→ Room temp. RCOOH

R —C H2—O H 4
H / K Cr O ⊕
227

(p-alcohol) (same carbon acid)

R' H /KMnO or 4 H /K Cr O 2 2 7 [O] reaction
Room temp.
R CH OH ⊕ →⊕ RCRO
⎯⎯⎯⎯⎯ No
carbon) R Acids (less carbon)
high temp.
(s-alcochol) (same
Room temp.
OH No
R reaction
high temp.
RC [O]

CHCH3 2 CH OH CHCH3 2 C CH3 ⎯⎯⎯→ [O]

(t-alcohol) CH3COOH + CH3COOH O
CH3[O] ⎯⎯⎯⎯⎯→ high temp.
Acids (less carbon)
Carbonyl group goes with smaller alkyl group
( i v) Reaction with phosporous pentasulphide : R—OH + P2S5
⎯⎯→ R — S H + P2O5 Thio alcohol
( v ) Reaction with salts :
MgCl2 4CHOH 2 3
CuSO. MgCl .
CHOH3 2CHOH 4 3 6CHOH 2 3
CuSO4 CaCl2 CaCl .

( v i ) Distinction between 1°, 2° and 3° alcohols :

( a ) Lucas test : A mixture of HCl(conc.) and anhydrous ZnCl 2 is called Lucas reagent. p-alcohol
No turbidity at room temp. [On heating within 30 minutes.]
2
ZnCl HCl +
⎯⎯⎯⎯⎯→

2 ZnCl HCl + Turbidity appears within 5 minutes.

s-alcohol ⎯⎯⎯⎯⎯→

2 ZnCl HCl + Turbidity appears within 1 minute.

t-alcohol ⎯⎯⎯⎯⎯→

EEMAIN.GURU

( b ) Victor - Meyer test : This is colour test for alcohol (pri. sec. & tert.) .
p-alcohol ⎯⎯→ Red colour
s-alcohol ⎯⎯→ Blue colour
t-alcohol ⎯⎯→ No colour
⎯
R—CH2—OH [1°] R2CH—OH [2°] R3C—OH [3°]
⎯
⎯

→ → →
⎯ ⎯
⎯
P + I2 P + I2 P + I2

R —C H2— I R2CH—I R3C—I

 ⎯ → ⎯
AgNO2 →
⎯

⎯
AgNO2 →
AgNO2
⎯ ⎯

RCH2—NO2 R2CH—NO2 R3C—NO2 ⎯ ⎯

⎯

→ → →
⎯ ⎯

⎯
HNO2 HNO2 HNO2

R —C — N O2 R2C—NO2 No reaction ⎯

N OH N ⎯

NaOH
⎯

⎯
⎯

⎯
NaOH
⎯
→
→

NaOH
⎯ ⎯

⎯ →

Soluble (Red) Insoluble (Blue) Colourless (White) (vii) Dichromate test :

⊕
H K Cr O

⎯⎯⎯⎯⎯⎯→+ Acid + Cr+3

1° Alcohol 227
6
orange [Cr ]

[green]
⊕
H K Cr O

⎯⎯⎯⎯⎯⎯→+ Ketone + Cr+3

2° Alcohol 227
6
orange [Cr ]

[green]
⊕
H K Cr O
⎯⎯⎯⎯⎯⎯→+ No oxidation, No green
3° Alcohol 227
6
orange [Cr ]

(viii) Test of alcholic group :

R—OH 1 H
⎯⎯⎯→Na R—ONa + 2 2
[effervesence of H2]
5 PCl R—Cl + POCl + HCl
R—OH ⎯⎯⎯→ 3 ⎯⎯⎯→ NH3 NH4Cl [White fumes]
R—OH
⎯⎯Cerric amm ⎯⎯⎯onium nitr ⎯⎯ate
Red colour
⎯→
( ix ) Distinction between CH3 – OH and C2H5OH
CH 3O H CH3CH2OH
B.P. 65°C 78°C I2 + NaOH No ppt Yellow ppt of CHI3 Cu/300°C Smell of formalin
[HCHO] No smell Salicylic acid Smell of oil of wintergreen No smell

EEMAIN.GU COOH COOH3

CH OH 3 Ph—OH
RU OH
COOPh

OH
OH
 (Oil of wintergreen)

Phenyl salicylate
Salol (Internal
Methyl salicylate antiseptic)
O COOH
Aspirin
CH COCl 3
❑ Additional reactions : (Analgesic)
C CH3 O

(a) Oxidation by HIO4 [per iodic acid] :

⎯⎯⎯⎯→ HIO4CH2 OH CH2 ⎯⎯⎯⎯→ −2H O2
CH2 CH2
+ HO HCHO + HCHO
OH OH OH OH
CH2 CH+HO 2 ⎯⎯⎯⎯→ −3H O HO 2

HIO4 HCHO+HCOOH+HC
⎯⎯⎯⎯→ HO CH OH + HO CH2
CH2 CH
OH OH (Glycerol) OH OH
OH OH

◆ Condition for oxidation by HIO4 :

At least 2 —OH or 2 >C=O or 1 —OH and 1 >C=O should be at adjacent carbons.
CH3 OH
Example : CH CH O
O
2HIO
⎯⎯⎯→ 4

CH3 CH3 C H⎯⎯⎯→ CHCOOH + CHO 3 CH2

CHCHO + HCOOH + CH 3 3 C CH3 CHO HIO4
OH OH

Example : C CH
CH3 CH2 C
O OH
Example :
O COOH
CHO O 2HIO4 –H O2
+
CHO O HO CHO
OH +HO + CO 22

O C OH
⎯⎯⎯→ ⎯⎯⎯→
HO CH2 HO CH2 OH HO CH2
OH OH (HCO) 2 3
CHO
 ( b ) Pinacole - Pinacolone Rearrangement :
conc. H SO 2 4
C CH3 OH CH3 C CH CH
3 3
CH3 CO
CH3 C OH CH3
⎯⎯⎯⎯⎯⎯→
CH3
Pinacole Pinacolone
m:
EEMAI

N.GUR
CH3 CH3 CH3 CH3
UMechanis CH3 C CH3
⊕
H CH3 C C CH3 ⎯⎯⎯→
–HO2 ⊕
C
CH3 C
CH3 C CH3
OH ⊕

OH OH OH2 OHCH3
⊕
CH3 –H CH3 C C CH3 ⊕
CH3 C ←⎯
CH3 CH3
←⎯⎯ C CH3 CH3 C CH3
CH3 OH CH3 C :O
O ←⎯⎯
⊕
stable) CH3
(Complete H
..
octet more

AROMATIC HYDROXY DERIVATIVES

❑ Phenolic compounds :

Compounds in which —OH group is directly attached to sp2c [Benzene ring]

OH
COOH
OH OH CH3

Phenol o-cresol Salicylic acid

OH OH
OH
OH
OH
OH
catechol resorcinol quinol
All phenolic compounds give characteristic colour with neutral FeCl3.
Ph—OH 3 neutral FeCl

⎯⎯⎯⎯⎯⎯→ Violet colour

CH3CH2—OH 3 neutral FeCl

 ⎯⎯⎯⎯⎯⎯→ No colour

PHENOL (C 6H5OH)
Phenol is also known as carbolic acid or Benzenol or hydroxy benzene.In phenol —OH group is attached
with sp2 hybridised carbon.It was discovered by Runge in the middle oil fraction of coaltar distillation and
named it carbolic acid (carbo = coal; oleum = oil) .It is also present in traces in human urine.
❑ General Methods of preparation :
( 1 ) From benzene sulphonic acid :
When sodium salt of benzene sulphonic acid is fused with NaOH phenol is obtained.
C6H5SO3Na + NaOH ⎯⎯→ C6H5OH + Na2SO3
( 2 ) From benzene diazonium chloride :
When benzene diazonium chloride solution is warmed, phenol is obtained with evolution of nitrogen.
OH
NCl 2
(Steam distilled) H O + N2 + HCl
2

⎯⎯⎯⎯⎯⎯⎯⎯→ Δ
EEMAIN.GURU
( 3 ) By distilling a phenolic acid with sodalime (decarboxylation):
NaOH CaO + Salicylic acid
OH
OH
COOH⎯⎯⎯⎯⎯⎯→
+ Na2CO3

( 4 ) From Grignard reagent : (The Grignard reagent on reaction with oxygen and subsequent hydrolysis by acid
yields phenol)

MgBr OMgBr Br
C6H5 ⎯⎯⎯→[O] C6H5 ⎯⎯⎯→ H O2 C6H5OH + Mg OH
( 5 ) From benzene :

OH
+ [O] V O2 5 ⎯⎯⎯⎯→ 300 C°

( 6 ) From chloro benzene :

Ph—Cl
⎯⎯⎯⎯⎯→ Aq. NaOH No NSR at normal condition
Stable by resonance
R —C l
⎯⎯⎯⎯⎯→ Aq. NaOH R — O H [NSR]

Ph—Cl Aq. NaOH

⎯⎯⎯⎯⎯→  Ph—ONa
300 C

Order of NSR :
Cl Cl NO2 NO2 NO2
Cl NO2
Cl
 <<< max. –I, –M
NO2

NO2
min. ed ESR
Aq. NaOH min. Aq. NaOH
25°C
300°C
max. NSR
OH OH
NO2 NO2

NO2
2, 4, 6–Trinitrophenol (Picric acid)
( 7 ) Industrial preparation of phenol:
Phenol can be prepared commercially by :
(a) Middle oil fraction of coaltar distillation
(b) Cumene
(c) Raschig process
(d) Dow's process
EEMAIN.GURU
( a ) Middle oil fraction of coaltar:

Coaltar ⎯⎯⎯⎯→ Fractional

distillation Middle oil (170-230°)
(Phenol, cresols, Naphthalene)
Coal

Naphthalene liquid
(Solid crystals separate CO/HO or sulphuric acid 2 2
out) CHOH + Na CO 6 5 2 3
NaOH (dil.)

CHONa 6 5
( b ) From cumene (Isopropyl benzene) : Cumene is oxidised with oxygen into cumene hydroperoxide in
presence of a catalyst. This is decomposed by dil. H2SO4 into phenol and acetone.
130 C° hydroperoxid H /100 C +
CH3 CH3 CH O OH e ⎯⎯⎯⎯⎯→ °

C(CH)3 2
Cumene OH
2 O
O ⎯⎯⎯⎯→ H SO ,H O 2 4 2 + CH3 C CH3
Cumene

( c ) Raschig process : Chlorobenzene is formed by the interaction of benzene, HCl and air at 300o C in
presence of catalyst CuCl2 + FeCl3. It is hydrolysed by superheated steam at 425o C to form phenol
 and HCl.
1 O
C6H6 + HCl + 2 22 3
CuCl FeCl

⎯⎯⎯⎯⎯→ C6H5Cl + H2O

0
300 C

C6H5Cl + H2O 0
⎯⎯⎯⎯→ 425 C C6H5OH + HCl
(super heated steam)
( d ) Dow process : This process involves alkaline hydrolysis of chloro benzene-(large quantities of phenol
formed).
OH
Cu — Fe
⎯⎯⎯⎯→
C6H5Cl + NaOH 0 (i) Phenol is a colourless,
300 C hygroscopic crystalline solid.
+ NaCl
❑ Physical properties :

(ii) It attains pink colour on exposure to air and light. (slow oxidation)
OH--------
C6H5 O O----------- HOC6H5
Phenoquinone(pink colour)
(iii) It is poisonous in nature but acts as antiseptic and disinfectant.
(iv) Phenol is slightly soluble in water , readily soluble in organic solvents.
(v) Solublity of phenol in water is much lower than alcohols because of larger hydrocarbon part in the
molecule.
(vi) Due to intermolecular H-Bonding, phenol has relatively high boiling point than the corresponding
hydrocarbons, aryl halides etc. but intermolecular H-bonding in o–derivatives is used in the
preparation of dyes, drugs, bakelite and it's melting point (MP) is 43° C and boiling point (BP) is
182° C .

EEMAIN.GURU

❑ Chemical Properties :
( A ) Reactions due to –OH group :
◆ Acidic Nature : Phenol is a weak acid. The acidic nature of phenol due to formation of stable phenoxide
ion in solution. The phenoxide ion is stable due to resonance. The negative charge is spread
through out the benzene ring which is stabilising factor in the phenoxide ion. Electron withdrawing
groups (–NO2, –Cl) increase the acidity of phenol while electron releasing groups (–CH3 etc.)
decrease the acidity of phenol.

C H OH 6 5   C H O H O 6 5 3⊕

+

Phenol is stronger acid than alcohols but weaker than the carboxylic acids and even carbonic
acid The acidic nature of phenol is observed in the following:
(i) Phenol changes blue litmas to red.
(ii) Highly electro positive metals react with phenol.
 2C6H5OH + 2Na ⎯⎯→ 2C6H5ONa + H2
(iii) Phenol reacts with strong alkalies to form phenoxides.
⊕
+


C H OH NaOH 6 5 + ⎯⎯→ C H O N a H O 6 5 2
(iv) However phenol does not decompose Na2CO3 or NaHCO3 because phenol is weaker than carbonic
acid. C6H5OH + Na2CO3 or NaHCO3 ⎯⎯→ No reaction
Ph—OH + NaHCO3 Ph—ONa + H2CO3
Acid-I Base-I Base-II Acid-II

Acid-I < Acid-II

Base-I < Base-II Reaction in reverse direction.

(v) Phenol does not react with NaHCO3.
CH3 C O OH + NaHCO3 CH3 C O ONa + H2CO3 [H2O + CO2↑]

Acid-I Base-I Base-II Acid-II

Acid-I > Acid-II

Base-I > Base-II Reaction in forward direction.

(vi) Acetic acid reacts with NaHCO 3 and gives effervesence of CO2.
◆ Reactionwith PCl5 : Phenol reacts with PCl5 to form chloro benzene. The yield of chlorobenzene is poor
and mainly triphenyl phosphate is formed.
C6H5OH + PCl5 ⎯⎯→ C6H5Cl + POCl3 + HCl
3C6H5OH + POCl3 ⎯⎯→ (C6H5)3PO4 + 3HCl
◆ Reaction with Zn dust: When phenol is distilled with zinc dust benzene is obtained.
C6H5OH + Zn ⎯⎯→ C6H6 + ZnO

Ex. ⎯⎯⎯→Zn
CH2 OH ?

S o l . No reaction

EEMAIN.GURUC

H3

E x . S o l . CH3 CH3
OH⎯⎯⎯

Ex.
 3 Zn
→
Zn
? CH ⎯⎯⎯ → ?

S o l . No reaction

COOH

OH⎯⎯⎯→Zn ?
Ex.

COOH
Sol.

◆ Reaction with NH3( Bucherer reaction): Phenol reacts with NH3 in presence of anhydrous ZnCl2 to form
aniline.

C6H5OH + NH3Anhydrous ZnCl or (NH ) SO / NH 150 C 2 4 2 3 3

°
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ ° C6H5NH2 + H2O
300 C

◆ Reactionwith FeCl3: Phenol gives violet colouration with FeCl3 solution (neutral) due to formation of a
complex.

C6H5OH + FeCl3 ⎯⎯→ Voilet colour

This reaction is used to differentiate phenol from alcohols.
◆ Acetylation (Schotten-Baumann reaction) : Phenol reacts with acid chlorides or acid anhydrides in alkali
solution to form phenyl esters.

C6H5OH + ClCOCH3NaOH
⎯⎯⎯⎯→ CH3
CHO—C 6 5
−HCl

O
65 O
C CH6 5NaOH C—CH6 5 O
CHOH + Cl 6 5
−HCl
⎯⎯⎯⎯→ CHO
◆ Ether formation (Alkylation) : Phenol reacts with alkyl halides in alkali solution to form phenyl ethers.
(Williamson's synthesis)

OH + NaOH
C6H5 ⎯⎯⎯⎯⎯⎯→ alkali solution C6H5ONa RX ⎯⎯⎯⎯→ −NaX C6H5OR

Sodium phenoxide

C6H5OH + CH2N2 ⎯⎯→ C6H5OCH3 + N2 ↑

◆ Reaction with P2S5 : 5C6H5OH + P2S5 ⎯⎯→Δ 5C6H5SH + P2O5

EEMAIN.GURU
( B ) Reaction of Benzene Ring : The —OH group is ortho and para directing. It activates the benzene nucleus.
◆ Halogenation : Phenol reacts with bromine in CCl4 to form mixture of o–and p–bromo phenol.
+ Br23 2 4 OH Br
OH
OH
low.temp.
⎯⎯⎯⎯⎯⎯⎯⎯⎯
→ CHCl or CS or CHCl Br +
Phenol reacts with bromine water to form a white ppt. of 2,4,6 tribromo phenol.
O
2

OH
OH Br Br Br + 3HBr
+ 3Br2 ⎯⎯⎯→ H

◆ Nitration : Phenol reacts with dil. HNO3 at 0°–10° C to form o- and p- nitro phenols.
⎯⎯⎯⎯⎯→ 0
OH 10 C − ° (40%)
OH +
OH NO2 (10%)
3 dil.HNO
NO2

When phenol is treated with nitrating mixture to form 2,4,6- trinitro phenol (picric acid)

OH

OH NO2 NO2
Conc.HNO
⎯⎯⎯⎯⎯⎯→ Conc.H SO
3 [2, 4, 6–Trinitrophenol (Picric acid)]
2
4

NO2

◆ Sulphonation: Phenol reacts with fuming H2SO4 to form o–and p–hydydroxy benzene sulphonic acid at
different temperatures.
OH
25°C 100°C
OH

+ conc. HSO2 SOH3

4

SOH3

OH
◆ Friedel-Craft'sreaction : Phenol when treated with methyl chloride in presence of anhydrous AlCl 3
p-cresol is main product.
CH3 OH CH3
⎯⎯⎯⎯⎯⎯⎯
OH → Anhydrous AlCl 3
+ CH3Cl OH +
o-cresol p-cresol
EEMAIN.G + CH COCl 3

URU ⎯⎯⎯⎯⎯⎯⎯→
Anhydrous AlCl 3 COCH3
COCH3
+
OH
OH
OH
o – and p – hydroxy acetophenone
◆ Gattermann aldehyde synthesis : When phenol is treated with liquid HCN and HCl gas in presence of
anhydrous AlCl 3 yields mainly p- hydroxy benzaldehyde (formylation)

HCl + HCN ⎯⎯⎯⎯→

3
AlCl HN CHCl
OH ⎯⎯⎯⎯→
HO

OH −NH

+ HN CHCl AlCl3 2
CHO
⎯⎯⎯⎯→ HCl CH NH 3

OH
◆ Riemer-Tiemann reaction : Phenol on refluxing with chloroform and NaOH (aqueous) followed by acid
hydrolysis yields o–hydroxy benzaldehyde. When CCl4 is used salicylic acid is formed.
OH H OH
ONa ⎯⎯⎯→ +
CHCl3
⎯⎯⎯⎯→ Salicylaldehyde
2
OH CHCl2 NaOH
CHO HO CHO
60°C NaOH (aq.)
NaOH
OH H
+
ONa
⎯⎯⎯⎯→ OH
CCl4 ⎯⎯⎯→
60°C NaOH (aq.) CCl3 COONa Salicylic acid
2
HO COOH

Mechanism : CCl2 is neutral attacking electrophile (formed by α,α− elimination reaction)

CHCl3 ⎯⎯⎯→ KOH :CCl2

OH
H
OO O  Cl
HO CCl Cl
⎯⎯⎯→ : ⎯⎯⎯→ 2

–H O2 ←⎯⎯→ C

CHO O
OOH Cl
OH 

⊕
H CH ←⎯⎯⎯ OH CH
←⎯⎯⎯ –HO2 OH Cl

◆ Kolbe 's Schmidt reaction : This involves the reaction of C6H5ONa with CO2 at 1400 C followed by acid
hydrolysis salicylic acid is formed followed.
 ⊕⊕
O Na OH
OCOONa COONa OH
⊕
H+ COOH
140° C Rearrangement
⎯⎯⎯⎯⎯→
+ CO2 ⎯⎯⎯⎯⎯→ 6 atm.
⎯⎯→ H O2
pressure
Sodium phenyl carbonate Sodium salicylate Salicylic acid
EEMAIN.GURU

◆ Hydrogenation: Phenol when hydrogenated in presence of Ni at 150-2000C forms cyclohexanol.

+ 3H2
OH ⎯⎯⎯⎯→ 150
– 200° C

Ni
OH

Cyclohexanol. (CH OH) 6 11

(used as a good solvent)
◆ Fries rearrangement reaction :

3
C6H5OH + CH3COCl ⎯⎯⎯⎯⎯⎯⎯→ Anhydrous AlCl C6H5OCOCH3

OH
60°C
COCH3
OH
anhydrous AlCl
⎯⎯⎯⎯⎯⎯→ COCH3
CHOCOCH 3
653

Phenyl ester (acetate)

◆ Duff 's reaction: This method gives only the o-compound which is hindered by the presence of a –I
group in the ring.
+(CH) N2 6 4 Glycerol
CHO
OH OH NCH3
⎯⎯⎯⎯→ HO2
CH OH
HSO
24
Hexamethylene tetramine and steam distilled
Boric acid⎯⎯→ acidified with (15–20°C)
◆ Coupling reactions: Phenol couples with benzene diazonium chloride in presence of an alkaline solution
to form a dye (p- hydroxy azobenzene) red only.

NaOH
⎯⎯⎯→
NCl + 2 OH
–HCl N N OH
 p–hydroxy azobenzene (Orange dye or Red dye)

Phenol couples with phthalic anhydride in presence of conc. H2SO4 to form a dye
(phenolphthalien) used as an indicator.
OH + OCC
H OH OH OH
O H SO2 4
OCCOH ⎯⎯⎯→ –H O2
O
Phenol (2 molecules) Phenolphthalien (Colourless in acidic
medium and pink in alkaline medium)
◆ Lederer Manasse (Condensation with formaldehyde) : Phenol condenses with HCHO (excess) in
presence of NaOH or weak acid (H+) to form a polymer known as bakelite (aresin).

EEMAIN.GURU

OH OH
OH
CHOH2
+ HCHO +
⎯⎯⎯→
NaOH CHOH
(40%)2 (20%)
⎯

⎯ condensation
→

with HCHO
CH2
Polymerisatio
n OH
HO
⎯

CH2 CH2
OH CH2 OH
CH2 CH2
Polymer bakelite (Phenol formaldehyde resin)
◆ Leibermann's nitroso reaction : When phenol is reacted with NaNO2 and conc. H2SO4 it gives a deep
green or blue colour which changes to red on dilution with water. When made alkaline with NaOH
original green or blue colour is restrored.
This reaction is used as a test of phenol.
2NaNO2 + H2SO4 ⎯⎯→ 2HNO2 + Na2SO4
or blue colour green
OH OH HONO or blue
NaOH
N OH
⎯⎯→ Blue colour
O
Sodium Indophenol ion is restored)
C H OH 6 5
H NO Salt
H SO2 4Green phenol (original
H O2
⎯⎯→ Red ⎯⎯⎯→
◆ Reaction with acetone: (Condensation with acetone)
 O OH OH CH3 Bis -
OH H OH H Phenol-
⎯⎯⎯→
con. HCl A
–HO2
CH3 C
CH3 Isopropylidene
CH3 C
p-p'– diphenol

◆ Oxidation: OH
Air [O] CrO Cl 2 2
p-Benzo
O O + HO2 COOH quionone (Red)

H/KMnO4
OH Meso
(Phenol) HH
⊕ COOH tartaric acid
(O) OH
HO OH
(Quinol)
K S O /KOH 2 8 2
(Elb's persulphate reaction)
1, 4 – Dihydroxy benzene
EEMAIN.GURU
❑ Test of Phenol :
(i) Phenol turns blue litmus to red.
(ii) Aqeous solution of phenol gives a violet colour with a drop of ferric chloride.
(iii) Phenol gives Lieber mann 's nitroso test.

Red colour
Phenol in conc. H2SO4 NaNO2 ⎯⎯⎯⎯⎯⎯⎯→ excess of water ⎯⎯⎯⎯⎯⎯→ NaOH excess Blue
colour
(iv) Aqeous solution of phenol gives a white ppt. of 2,4,6 tribromophenol with bromine water.
(v) Phenol combines with phthalic anhydride in presence of conc. H2SO4 to form phenolphthalein which
gives pink colour with alkali.
(vi) With ammonia and sodium hypochlorite , phenol gives blue colour.
❑ Differences between phenol and alcohol (C2H5OH) :
(i) Phenol is more acidic than aliphatic alcohol due to resonance in phenoxide ion.
(ii) Phenol gives violet colour with FeCl3 while aliphatic alcohol does not give.
(iii) Phenol gives triphenyl phosphate with PCl5 while aliphatic alcohol gives alkyl chloride.
(iv) Phenol has phenolic odour whereas alcohol has pleasent odour.
(v) Phenol on oxidation gives quinone while alcohol gives aldehyde or ketone and acids.
❑ Uses of Phenol : Phenol is used :
(a) As an antiseptic in soaps and lotions. "Dettol" (2,4-Dichloro-3,5-dimethyl phenol)
(b) In manufacture of azodyes, phenolphthalein , picric acid (explosive), cyclohexanol (Solvent for rubber),
plastics (bakelite) etc.
(c) In manufacture of drugs like aspirin salol, phenacetin etc.
(d) As preservative for ink.
EEMAIN.GURU
 ETHER
R—O—R (Dialkyl ether), alkoxy alkane. It's General formula is CnH2n + 2O.
CH3—O—CH2CH3 (Methoxy ethane) or ethyl methyl ether or 2–oxa butane
Ether is monoalkyl derivative of R–OH and dialkyl derivative of H2O

R — O H HR
−
⎯⎯⎯→ + R — O — R 2H
−
←⎯⎯⎯ + H—O—H
2R

Classification : They may be classified as :

(a) Simple or symmetrical ether. e.g. R–O–R
(b) Mixed or unsymmetrical ether e.g. R–O–R'
Structure :
( i ) By Williamson's synthesis :
: : O sp hybridized 3 The molecule of ether is bent due to lone pair of
electron on oxygen atom- bond electron repulsion. The
bond angle is 1100. It is greater than that of water 1050
bond σ σ bond 110°
due to the repulsion between bulky alkyl groups. Due to
RR
bent structure, it posses dipole moment and hence are
❑ General Methods of Preparation : ( A ) From alkyl polar molecules.
halides :

S
R—X + Na—O—R ⎯⎯→ R—O—R + NaX [ 2 N Reaction] Example :

S
CH3—I + C2H5 O– Na+ ⎯⎯→ CH3—CH2O—CH3 + NaI Mechanism : [ 2 N Reaction]

⊕ ⊕
C Na 2 HO5 C + Na 2 HO5

HHHH
Slow Fast
H—O— + I
C2 C 5 3 CH 2 HO5 C— I C2 HO5 ------ C ----- I H H

⊕
Na + I NaI
CH2
CH3 ⎯⎯→ HC3 C
CH3
Example : CH3 C Cl + CHONa 3

CH3 CH3

CH3
Example : CH3 CH3 O CH2 CH3
CH3 C ONa + Δ
CH2 Cl ⎯⎯→ CH3 C CH3
 Example : CH2 CH—Cl + CH3CH2—ONa ⎯⎯→ No reaction [Stable by
Resonance]

EEMAIN.GURU

(i i) Reaction with Dry Ag 2O :

O
2RX + Ag 2 ⎯⎯→Δ R—O—R + 2AgX

O
Example : 2CH3—CH2—Cl + Ag 2 ⎯⎯→Δ CH3CH2OCH2CH3 + 2AgCl ( B )

From R–OH:

( i ) By dehydration : R — O H Con. H SO 2 4 ⎯⎯⎯⎯⎯⎯→ Δ ?

CH2 CH2 Al O2 3 140°C 170°C synthesis)
3 ←⎯⎯⎯ CH3
CHCH3 2 O CHCH2 CH2 OH⎯⎯⎯⎯→
conc. HSO
250°C 350°C 24
CH2 CH2
CHCH3 2 O CHCH2(Elimination)
3 (Willomson's

(i i) Reaction with CH2N2 (diazomethane) :

⎯⎯⎯→Δ R—O—CH2—H + N2
R—OH + CH2—N2 BF3

❑ Physical Properties :
(i) CH3OCH3 , CH3OCH2CH3 are gases and higher are volatile liquids.
(ii) Ether are less polar [μ=1.18D].
(iii) Ethers are less soluble in H2O.
(iv) Ethers have less BP then corresponding alcohol.
E x . Ethers are less soluble in H2O . Why ?
S o l . Reason : Due to less polar, it forms weaker H–Bonding with H2O.
E x . Ethers have less BP then corresponding alcohol. Why ?
S o l . Reason : No H–Bonding in ether molecules.

❑ Chemical properties :
Ethers are less polar so less reactive and do not react with active metals [Na,K], cold dil. acid, oxidising
and reducing agent.
Reason : They do not have any active functional group.
1 . Basic nature : Due to presence of .p on oxygen atom ether behave as lewis base
Ethers react with cold conc. acid and form oxonium ion

.. ⊕ 
.. Cl (diethyl oxonium chloride)

Example : ⎯⎯⎯⎯⎯⎯→ .. ⊕
cold ; conc. HCl ..
CHOCH 2 5 2 5
cold ;
CH2 5 O H Example : ⎯⎯⎯⎯→
 conc.
CH2 5 O
CH2 5

25
CH2 5 O CH HSO HSO4 2 4

(diethyl oxonium hydrogen sulphate)
CH2 5
H

Ether form dative bond with Lewis acids like BF3, AlCl3, RMgX etc.

EEMAIN.GURU

RR
..
O ..
Example :
R Mg X
.. R B F ..
..
O : R F F [Ether is used as solvent] for O
RR
Grignard reagent.

2 . Halogenation : Cl /dark 2
CH CH3 Cl
CHCH3 O Cl
CHCH3 2 O
CHCH2 3
10 HCl 2 5
Perchlorodiethy
10 light Cl2
l ether
α,α'–Dichloro
diethyl ether
CCl 2 5 O CCl +
3 . Formation of peroxides : Ether add up atmospheric oxygen or ozonised oxygen. It is explained by Free
radical mechanism as intermediates is free radical.

2
C2H5—O—C2H5O (nonpolar) ⎯⎯⎯⎯⎯⎯→ Long contact CHCH3 2 O CHCH3
(Non polar) sunlight or UV O O H
.. .. ⎯⎯→ CHOCH or (CH) O
.. .. 2525252

CHOCH + O 2 5 2 5
.. O
..
⎯→
↓ 2
∙
—Ph ⎯⎯⎯→ O CH3 O CH
..
O ..: : CH3CH2—O—CH2—Ph O2 ⎯⎯⎯⎯⎯⎯→
long contact CH3—CH2—O— CH

stable by resonance
Peroxides are unstable and explosives.
 Test for peroxides
hot dil
⎯⎯⎯⎯→ H SO 2 R—O H
ether (peroxide)4 . Reaction with hot dil. H2SO4 : R — O — R

24 5 . Reaction with hot conc. H2SO4 : R — O

ether (P
— R 2 4 hot conc. H SO ⎯⎯⎯⎯⎯⎯⎯→ 2RHSO4

CH2 Ph O O H

O CH2
cold dil.

cold conc. hot dil.

hot conc.

No Reaction
Oxonium salt

Ethyl alcohol
Ethyl hydrogen
sulphate
24
H SO CH2 CH3 CH3

6 . Reaction with PCl5 : ROR + PCl5 ⎯⎯⎯→ heat 2RCl + POCl3 7 . Reaction with BCl3
: 3ROR + BCl3 ⎯⎯→ 3RCl + (RO)3B

EEMAIN.GURU ⎯⎯⎯⎯→ RCOOR +RCl

AlCl
8 . Reaction with RCOCl : ROR + RCOCl 3 ZnCl heat
2

9 . Reaction with CO : ROR + CO BF / HgO 500 atm 3 ⎯⎯⎯⎯⎯⎯⎯⎯→ 150 C°

RCOOR 

1 0 . Reaction with C2H5Na : CHCH2 2 O CHCH + CH⎯⎯→ CH CH OH + CH CH +C H

3 2 2 2 2 6
2225

HH Stronger base

1 1 . Dehydration :
CHCH3 2 O CHCH 2 3 ⎯⎯⎯→ Al O 2CH2 CH + HO 2 2 1 2 . Reduction
23

: CH3CH2OCH2CH3Re d P HI
+
heat ⎯⎯⎯⎯⎯→ 2CH3CH3
1 3 . Oxidation :

CH3CH2—O—CH2CH3H / K Cr O 2 2 7 +
OH CHO
⎯⎯⎯⎯⎯⎯→ 2CH3CH2 ⎯⎯⎯→ [O] 2CH3 ⎯⎯⎯→ [O] 2CH3COOH
 1 4 . Combustion : C2H5OC2H5 + 6O2 ⎯⎯→ 4CO2 + 5H2O (explosive mixture)

1 5 . Reaction with HX : Reactivity HI > HBr >

HCl
of HX ❑ Reaction with cold conc.

HX :

Ethers forms oxonium salt with cold and conc. HCl (less reactive)

Cold conc. HI and HBr (more reactive) break C–O bond. CH3

E x . CH3 C O CH3 CH2 CH3Cold and conc.

S o l . Mec hanis m ⎯⎯⎯⎯⎯⎯→ HI ?
..
CH3
CH3
CH3
H
.. + CH3 C O
CH3 C O CH2CH3 ⎯⎯→
CH3 H CH3 CH3
CH3
⊕
CH2CH3 ⊕
(Oxonium ion) CH3
C I + CHCHOH 3 2
I
CH3
CH3
⊕
CH2 CH— C⊕H2, (CH3)3 C⊕] then SN1 reaction occurs.
◆ If oxonium ion gives more stable carbocation [ Ph CH , 2

◆ If oxonium ion gives less stable carbocation [P h⊕, CH2 C⊕H, CH3 C⊕H2] then SN2 reaction occurs, and X
attacks at less hindered carbon.

E x . CH3CH2—O—CH2Ph Cold con. ⎯⎯⎯⎯⎯→ HI CH3CH2—OH + PhCH2—I, write mechanism of given

reaction. S o l . Mechanism :
..
.. H⊕CHCH3 2 O CHPh 2
⊕
CH3CH2OH + I Ph CH2
CHCHOCHPh 3 2 2 ⊕
⎯⎯→PhCH2I + CH3CH2–OH
H
EEMAIN.GURU

E x . CH3CH2—O—CH3 ⎯⎯⎯⎯→ anhy.HI ?

..
CH 3 CHCH3 2 O⊕CH3ICHI + CHCHOH 3 3 2
..HI
S o l . CHCH3 2 O
H
Oxonium ion gives less stable carbocation
SN2 reaction I attacks at less hinderd carbon.

E x . CH3—CH2—O—Ph ⎯⎯⎯⎯⎯→ (aq.)HBr ?

 ..
⎯⎯→H+
.. Ph CH3 O⊕
CH2 CH2 Ph⎯⎯→Br CHCHBr + PhOH 3 2
S o l . Mechanism : CH3 O
H

S 1
N CHCHOH + I 3 2 CH CH3
2°
⎯→
cold and conc. HI CH3
CH3CH2 O CH CH3⎯⎯ ⎯⎯ ⎯
CH3 S 2 CHCH3 2 CH CH3 I + HO
N

I
1° alkyl hallides are formed.

CH3
◆ If excess of HI is used then two moles of

HI
⎯⎯⎯→ + CH CH — I PhCH — I
Ph HI
◆ CH3CH2—O—CH2 ⎯⎯⎯→ CH3CH2OH+PhCH2I 3 2 2 ( B ) Reaction with hot and conc.

HX :

CH3CH2—O—CH3 ⎯⎯⎯⎯⎯⎯⎯→ hot and conc HI CH3CH2—I + CH3—I

E x . C2H5—O—C2H5 ⎯⎯⎯⎯⎯⎯⎯⎯→ hot and conc. HBr ? + ?

S o l . C2H5—Br + C2H5 — Br
❑ Uses of ether :
(i) General anaesthetics agent.
(ii) Refrigerant a mixture of ether and dry ice gives temperature as low 110°C.
(iii) Solvent for oil, fats, resins, Grignard reagent.
(iv) For providing inert & moist free medium to organic reaction example : Wurtz reactions.
(v) In perfumery.
(vi) Di-isopropyl ether ⎯⎯→ Petrol as an antiknock comp.
(vii) Mixture of alcohol and ether is used as a substitute of petrol. Trade name "Natalite"
(viii) Halothane (CF3CHClBr) used as an anaesthetic because it produces unconsciousness without
affecting lung and heat.
❑ Preparation of Epoxides :
(i) Epoxidation of alkenes by reaction with peroxy acids
(ii) Base-promoted ring closure of vicinal halohydrins
(iii) Epoxidation of alkenes by reaction with peroxy acids
EEMAIN.GURU
◆ Epoxidation of alkenes by reaction with peroxy acids : O
 O
C=C C—C Peroxy acid Epoxide
+ R–C–OOH Example :
+ R–C–OH
O

OO
(a) CH–CH(CH) CH + CH–C–OH 2 2 9 3 3
CH= CH–CH) – + 2 ( CH 2 9 3
O
O O

CH–C–COOH 3
+ CH–C–OH 3
O
(b) + CH–C–OOH 3

(c) Epoxidation is a stereospecific syn addition :

C=C H
H CH6 5 + CH–C–OH 3O
CH6 5 + CH–C–OOH 3O
H
CH6 5

H O CH6 5
(E) -1,2-diphenyl ethene trans -2,3-diphenyl oxirane Mechanism :

HO C –– C
CH–C3 OO CC OO
CH–C3 H
OO +
CH–C3 O
C O––C
transition state Epoxide
◆ Base-promoted ring closure of vicinal halohydrins :
RC––CR 2 2 HO
R2C = CR2 22x HO–
X RC–––CR 2 2 O
⎯⎯⎯→H o
Vicinal halohydrin Epoxide
Mechanism :
R R
X X
R C––C R R C––C R + HO—H
Step I ..
HO– H ..R R
O O
.. .. ..
..

.
–
.
 O
.. O ..
.
.

R ..
..
R
XR
R + X– .
.

Step II .

R C––C R C––C .

R .

– R
..

EEMAIN.

GURUExampl
H Br H
e:

NaOH
OH
(i)

OH OH

trans-2-bromocyclohexanol 1, 2-epoxycyclohexane
Br /HO 2 2
Br HC3
3 H
HC H
HC3 H
Anti additioninversion of HC3
(ii) HC3 configuration H
H HC3 H
OH O
cis-2-butane 3-epoxybutane

H Br H
CH3 CH3
H
Br /HO 2 2 CH3
cis-2,
Anti additioninversion of
HC3
(iii) HC3 configuration H
H HC3 H
OH O
trans-2-butane trans-2, 3-epoxybutane

◆ Reaction of Epoxides : ◆ With Grignard

reagent :
(1) diethylether
RMgX + HC––CH 2 2
(2) H O ⎯⎯⎯⎯⎯⎯→ + RCH2CH2OH (primary alcohol)
3
 O
CHMgCl 2 + HC––CH 2 2 Benzyl magnesium (i) diethylether (ii) H O3+

O CHCHCHOH 2 2 2
chlorideEthylene

oxide3-phenyl-1-propanol
◆ Nucleophilic ring opening reactions of epoxides :
–––CR2 Y
Y
⎯⎯⎯→ H O2 RC– 2

Y: + RC– – ––CR2
2 RC– 2 ––CR2
O
.

O .. OH
..
.
.
.. .
.

water, 0 C°

HC2 –––CH2 O CH3––CH2CH2––CH2SCH2CH2O

KS CH CH CH 2 2 3
⎯⎯⎯⎯⎯⎯→ ethanol H 2-(butylthio) ethanol

EEMAIN.GURU

Note : Nucleophilic ring opening reactions of epoxides is the characteristic feature of 2 N S reaction.
H ⎯⎯⎯⎯⎯→

H OCHCH2 3 H
NaOCH CH
(i)
O
23
H
CH CH OH
32 OH
HC3 CH3
32
NH/HO
H
OH

OH
HN2 H
HC3 H
CH3
CHO3 CH3
NaOCH

HC3 CH3

(ii) C––––C
⎯⎯⎯⎯→
3

CH–3
H –CH––C––CH3
O CH3 3 OH
CH OH

◆ Nucleophilic ring opening of epoxides :

⎯⎯⎯⎯⎯⎯→ + CHCHCH– 652 –CH3

C6H5MgBr + HC2 –––CHCH3
 3

O OH
1, diethyl ether
2, H O

.. ..
RR R – ..
R
O OH
..
.
.

Y:
Y ....δ–
–

δ–
Y
Y
OO

epoxide transition state alkoxide β-substituted alcohol

CH2–––CH(CH) CH 2 7 3 O ⎯⎯⎯→ HOCH2CH2OH
⎯⎯⎯⎯→
CH–3
–CH––(CH) CH 2 7 3
1. LiAlH
4

2, H O

OH

(i) HC2 –––CH2 O

(ii) HC2 –––CH2 O

HC2 –––CH2 ..
O +H
Mec hanis m :
HBr
Step-1 : HC2 –––CH2 +
⎯⎯⎯→
BrCH2CH2OH H—O H
10 C°
::
O
CH CH OH HC2 –––CH2 + H2O: :O+
⎯⎯⎯⎯⎯→
H
CH3–CH2OCH2CH2OH
32

H SO , 25 C°
24

+ H2O H O3 +

EEMAIN.GURU

HHC– 2 ––CH2
 + .. H
: : H—O CH–CH–O–H 2 2 .. ..
Step-2 :
O+ H
HO + ..
.
.
Slow

+
HH—O
H

Step-3 :

H:O: +
Example :
CH–CH–O–H 2
.. OH
2 .. HBr
.

. HO
HO—H + OH
H H
+
.
H HOCHCHOH 2 2 .

.. .. H
.. ..
1,2-Epoxycyclohexane trans -2-bromo cyclohexanol
CH3 –CH––C––CH3
CH OH
HC3 OCH3 3

H SO
C–––C ⎯⎯⎯⎯→ CH–3
H O CH3
24 HO CH3
2,2,3-trimethyl oxirane 3-methoxy-3-methyl-2-butanol