ALCOHOL, PHENOL & ETHER

ALCOHOL
Hydroxy derivatives

Aliphatic hydroxy derivatives Aromatic hydroxy derivatives

(I) Aliphat ic hydroxy derivat ive s :

Hydroxy derivatives in which —OH is directly attached to sp3 C (Alcoholic compounds).
(II) Aromat ic hydroxy derivat ive s :
Hydroxy derivatives in which —OH is directly attached to sp2 C or benzene ring (Phenolic compounds).
 Aliphat ic hydroxy derivat ive s :
(a) Classificat ion accordi ng to number of —OH groups :
(i) Monohydric [one –OH]  C H 3 C H 2 — O H
(ii) Dihydric [two –OH]  CH2 CH2

OH OH
(iiii) Trihydric [three –OH]  CH2 CH CH2

OH OH OH
(iv) Polyhydric [n –OH]  CH2 CH ------------- CH2

OH OH OH
(b) Classificat ion accordi ng to nature of carbon :
(i) p or 1° – alcohol  CH 3CH 2 – OH
(ii) s or 2° – alcohol  (CH 3 ) 2CH – OH
(i) t or 3° – alcohol  (CH 3) 3C – OH
 Str ucture of alcohol : :O:
3
sp

sp
3
3

Alcohols are bent molecules. The carbon atom (linked with 108.5° 1s
sp

'O' atom of –OH group) is sp 3

hybridised. The central 'O'
H3C 3 H 1s
atom is also in sp3 state of hybridisation. The bond angle is sp
108.50 . In sp3 hybridisation of O - 2s2,2px2 2py1 2pz1 Structure of CH3OH
orbitals hybridised to form sp3 orbitals

O      —
Non - bonding e pair
2s 2px 2py 2pz
sp3 hybridisation

In these four orbitals two containing one electron  bond O atom

each and two containing two electrons each.  bond
Orbitals containing two electrons do not take part
sp3 +. .×
in bonding. Other two half filled orbitals form 
S
bond with s-orbitals of H -atom and hybridised hybridised H atom
108.5°
orbital of C-atom (O—C). orbitals sp3 C atom
Due to lone pair effect the bond angle of
tetrahedral oxygen atom is lesser than normal
.× .×
S .× S
tetrahedral structure (109 028'). H H
S
H
 MONOHYDRIC ALCOHOL
 General met ho ds of preparat ion :
(a) From alka ne s (By oxidat ion) :
H  /KMnO
(CH 3)3 C—H 

4
 (CH 3 ) 3 C—OH

(b) From alkene s :

(i) By hydration :

H
CH 3 —CH CH 2  CH3 CH CH3
H2 O

OH
(ii) By hydroborat ion oxidat ion :
BH
CH 3 —CH CH 2 
3
 CH3 CH2 CH2 (1° alcohol)
H 2 O 2 HO 

OH
(iii) By oxymercurat ion demercurat ion :
(i ) Hg (OAc ) , H O
CH 3 —CH CH 2  2 2
 CH3 CH CH3
(ii ) NaBH 4 ,HO 

OH
(c) From alkyl halide s (By hydrolysis) :
Aq. KOH
C H 3— C H 2— C l   C H3C H 2—O H
or Moist Ag2 O

(d) From carbonyl compounds (By reduct ion) :

Reducing agent
>C O   >CH—OH

 Reducing agents may be,

LiAlH 4 /H   NaBH 4 /H 
Na + EtOH [Bouveault-blanc Reduction]
NaH [Darzen reduction]
Ni/H 2
LiAlH
R—CHO 

4
 R —C H 2—O H
H

NaBH
R C R 

4
 R CH R
H

O OH
LiAlH 4
CH3 C CH3 

 ?
H
O
 Mechanism :
H H
 
H H
CH3 C CH3  CH3 C CH3  CH3 C CH3
LiAlH4

O O OH

OD
H
LiAlH4
O
D
OH
D
NaBD4

H
 LiAlH
C H 3— C H CH—CHO 

4
 C H 3— C H C H— C H 2— O H
H

Crotonaldehyde
LiA lH
Ph—CH CH—CHO 

4
–
 P h — C H 2— C H 2— C H 2— O H
H / OH

Cinnamaldehyde
(e) From et her s :
R—O—R dil.H SO R—OH + R—OH

2 4


CH 3 —O—CH 2 CH 3 dil.H SO CH 3 —OH + CH 3 CH 2 —OH


2 4

(f) From acid a nd derivat ive s (By reduct ion) :
LiAlH
R—COOH 

4
 R—CH 2 —OH + H 2 O
H

LiAlH
R C Cl 

4
 R—CH 2 —OH + HCl
H

O
LiAlH
R C OR 

4
 R—CH 2 —OH + R—OH
H

O
LiAlH
R C O C OR 

4
 R—CH 2 —OH + R—CH 2 —OH
H

O O
LiAlH
R C NH2 

4
 R—CH 2 —NH 2 +H 2 O
H

O
(g) From e ster s (By hydrolysis) :
(i) By alkali ne hydrolysis :
NaOH
R C OR    R C ONa + R OH
O O
(ii) By acidic hydrolysis :

H

 
H O (excess) 
R C OR R C OH + R OH
2

O O

18 H O 18
CH3 C OC2H5 
3


 CH3 C OH + C2H5OH

O O
This reaction is reversible reaction and it's order is 1 and it is also called Pseudo-Unimolecular reaction.
(h) From p-ami ne s :
NaNO  HCl
R—NH2 
2
 R—OH + N 2 + H 2 O
or HNO 2

CH 3 CH 2 — N H 2 HNO CH 3 CH 2 —OH + N 2 + H 2 O

2

 Mechanism :
   
NaNO 2  HCl
CH 3 CH 2 — NH 2   CH 3 CH 2 — N 2 Cl  CH 3 CH 2  N 2  Cl
(Unstable)
 
OH
CH3CH2 OH [major]

Cl
CH3CH2 Cl

CH3CH2 
O N O
CH3CH2 O N O

H
CH2 CH2

Inter mediate is carbocation so rearrangement may be possible.

Ex. NaNO2  HCl

CH 3 CH 2 CH 2 —NH 2   ?
S o l . Mechanism :

  
NaNO 2  HCl
CH 3 CH 2 CH 2 —N H 2   CH 3 CH 2 CH 2 — N 2 Cl  CH 3 CH 2 CH 2

  
HO H
CH3 CH CH3 CH3 CH CH3
OH

HNO 2
E x c e p t io n : CH 3 — NH 2   CH 3 — O — CH 3

(i) From Grignard reagent :

(i) p-alcohol :
H2 O
R—Mg—X + [O]  R—O—MgX   R—OH
[Same C-p-alcohol]

R R
 
HO
R Mg X + H C H H C H  H C H 2

O OMg X OH [one C more p-alcohol]

R R
  HO
2
R Mg X + CH2 CH2  CH2 CH2  CH2 CH2
O OMgX OH
[two C more p-alcohol]
(ii) s-alcohol :

R R
H2O
R Mg X + R C H R C H  R C H
O OMgX OH

R
R MgX
R Mg X + H C OR  H C R 
HO
H C R
2

O O OH
 (iii) t-alcohol :
R R
2 HO
R Mg X + R C R  R C R  R C R
O OMgX OH

R
R MgX
R Mg X + R C OR R C R  R C R
H2O

O O OH

 Physical proper t ie s :
(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 : C 1 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 solubi lit y :

C 4 H 9 OH > C 5 H 11 OH > C 6 H 13 OH

CH3
CH 3 CH 2 CH 2 CH 2 OH < CH3CH2CH OH < CH3 C OH

CH3 CH3

CH3CHCH
2 2
< CH3 CH CH2 < CH2 CH CH2

OH OH OH OH OH OH
[Number of —OH increases, H-bonding increases]
(v) Boiling points : B.P.  molecular weignt

1
If molecular wt. is same then B.P. 
branching

Order of BP : C 4 H 9 OH < C 5 H 11 OH < C 6 H 13 OH

CH3
CH 3 CH 2 CH 2 CH 2 OH > CH3CH2CH OH > CH3 C OH

CH3 CH3
CH3CHCH
2 2
< CH3 CH CH2 < CH2 CH CH2
OH OH OH OH OH OH
[Number of OH increases, H-bonding increases]
Ex. Boiling point of alcohol is more than corresponding ether. Why ?
S o l . Reason : H-bonding in alcohol.

O H---------- O H------------- O H ------------- O H ----------

R R R R
Ex. Boiling point of alcohol is less than corresponding carboxylic acid. Why ?
S o l . Reason : Dimer formation in carboxylic acid.

O H O
R C C R
OH O
 Chemical proper t ie s :
Monohydric alcohol show following reactions
(A) Reaction involving cleavage of O H
(B) Reaction involving cleavage of C OH
(C) Reaction involving complete molecule of alcohol

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

C H 3— O H > C H3C H2—O H > (CH 3 ) 2 CH—OH > (CH 3 ) 3 C—OH
(i) Acidic nature :
H 2O > R—OH > CH CH > NH 3 (Acidic strength)
Alcohols are less acidic than H2O and neutral for litmus paper and gives H2 with active metals (Na, K)
1
R—OH + Na  R—ONa + H
2 2
1
R—OH + K  R—OK + H
2 2
(ii) Reaction with CS 2 :
1
R—OH + Na  R—ONa + H
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 2 N 2  R — O — C H 2— H
 
R—OH Na R—ONa R X R—O—R
   
(Williamson synthesis)
(iv) Acylation :
R OH + Cl C R  R O C R
O O
(Acylation)
R OH + Cl C CH3  R O C CH3

O O
(Acetylation)

OH O C R
CH 2 COCl O
COOH   COOH

Salicylic acid Acetoxy benzoic acid

Acetyl salicylic acid
Aspirin [Used as analgesic]
 (v) Benzoylation : (Schotten Baumann's Reaction) :

R OH + Cl C Ph  R O C Ph
O O

(Benzoylation)
(vi) Esterification : Conc. H 2SO 4 is used as catalyst and dehydrating agent.
conc. H 2 SO 4
R C OH + R OH  R C OR + H2O
O O

 Mechanism :
H2SO4    H+ + HSO 4–
::

+
R—C—O—H + H R—C—O—H
O OH



OH OH OH OH
+
  –H
R—C—O—H + ROH R—C—OH R—C—OH2 R—C R—C R—C—OR'

OH O OR' OR' OR' O
 H R'

Note : This is a laboratory method to prepare ester.

Example : CH3 C OH + H OC2H5 

conc. H SO
 CH3 C OC2H5 + H2O
2 4

O O

18 18
Example : Ph conc. H 2 SO 4
C OH + H OC2H5   Ph C OC2H5 + H2O
O O

Dry HCl can be used as dehydrating agent.

Example : CH3 Dry . HCl

C OH + H OC2H5    CH3 C OC2H5 + H2O
O O

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 > CH3 C OH > CH3 CH C OH > CH3 C C OH

O O CH3 O CH3 O
 (vii) Reaction with CH CH :

BF3 / HgO
OCH3
CH CH + 2CH 3 —OH   CH3CH
OCH3

Methylal

BF3 / HgO OC2H5

CH CH + 2CH 3 CH 2 — OH   CH3CH
OC2H5

Ethylal
( v i i i ) Reaction with carbonyl compounds :
OR
R—CHO + 2R—OH H


R CH
OR
Acetal


R OR
R C R + 2R OH H
 C
R OR
O Ketal

OCH3
H
CH 3 CHO + 2CH 3 —OH  CH3CH

OCH3
Methylal
(ix) React ion w it h Grignard reagent :
 X
R—Mg—X + H—OR H
 R H + Mg
OR
(x) Reaction with Ketene : Ketene is used as acetylating agent.

OR OR

CH2 C O + R—OH  CH2 C 


OH  CH3 C O

OC2H5 OC2H5

CH2 C O + C2H5—OH  CH2 C 


OH  CH3 C O
Ethylacetate
(xi) Reaction with isocyanic acid : Ethyl urethane is used in preparation of urea

OC2H5 OC2H5
NH C O + H—OC2H5  NH C 

OH   NH2 C O

Ethyl urethane
(xii) Reaction with oxirane :
OR
H+
R OH + CH2 CH2  CH2 CH2
O
OH

(B) Reaction involving cleavage of C OH: Reactivity order or basic nature is

C H 3— O H < C H3C H2—O H < (CH 3 ) 2 CH—OH < (CH 3 ) 3 C—OH

 (i) Reaction with halogen acid :
ZnCl2
R—CH 2 —OH + HCl   R—CH 2 —Cl
 + H2O

ZnCl2
R2CH—OH + HCl 
   R 2 CH—Cl + H 2 O

2 0 alcohol
R e a ctiv ity o f th e a cid s is HI > HB r > HC l > HF
(ii) React ion w it h i norga nic acids :

R OH + H O N O  R O N O + H2O
 
O O
Nitric acid Alkyl nitrate
R—OH + HHSO 4  R—HSO 4 + H 2 O
Alkyl hydrogen sulphate
(iii) React ion w it h phosphorous halide s :
3R—OH + PCl 3  3RCl + H 3PO 3
R—OH + PCl5  R—Cl + POCl3 + HCl
(iv) Reaction with thionyl chloride (SOCl 2 ) :

R—OH + SOCl2 

Pyridine  R—Cl + SO2  + HCl

(gas)
(v) Reaction with NH 3 : Alumina (Al 2O 3 ) is used as dehydrating agent.

Al O
R OH + HNH2 
2 3

 R—NH 2 + H 2 O
250 C

(vi) Reaction with halogens : Oxidation and chlorination takes place simultaneously.
CH 3CH 2OH + Cl 2 (dry)  CH3CHO + 2HCl (Oxidation)
CH3CHO + 3Cl2  CCl3CHO + 3HCl (chlorination)
chloral
(C) Reaction involving complete molecule of alcohol :
(i) Dehydration : Removal of H 2 O by two type
(a) Intermolecularly removal of H 2O [form ether]
(b) Intramolecularly removal of H 2O [form alkene]

0°C
(C2H)
5 2SO4

100°C
C2H5 OH + H2SO4 C2HHSO
5 4

(conc.) 140°C
C2H5 O C2H5 (Williomson's synthesis)
170°C
CH2 CH2 (Elimination)

250°C
C2H5 OH +Al2O3 C2H5 O C2H5
(Alumina) 350°C
CH2 CH2

Ease of dehydration follow the order : 3° ROH > 2° ROH > 1° ROH > CH3 OH
(ii) Catalytic Dehydrogenation : This reaction is useful in distinction of 1°, 2° and 3° alcohols.
Cu
CH 3 CH 2 OH 
300 C
 CH3CHO + H2
(p- alcohol ) (Acetaldehyde)
Cu
CH3 CH CH3 
300 C
 CH3 C CH3 + H2

OH O
(s- alcohol) (acetone)

CH3 CH3

CH3 C OH
Cu
  CH3 C CH2 + H2O [dehydration]
300 C
(Iso - butylene)
CH3
(t. alcohol)

(iii) Oxidation : This reaction is useful in distinction of 1°, 2° and 3° alcohols.

H  KMnO or [O ]
R —C H 2—O H  4
H  / K Cr O
 RC HO 
Room temp.
 RCOOH
2 2 7

(p-alcohol) (same carbon acid)

 [O]
R CH R' H /KMnO4 or
 R C R Room temp.
No reaction
H/K2Cr2O7
OH O high temp.
(s-alcochol) (same carbon) Acids (less carbon)

R
[O]
R C R Room temp.
No reaction

OH
high temp.
(t-alcohol) Acids (less carbon)

[O ] [O]
CH3CH2 CH CH3 
high temp. 
CH3CH2 C CH3   CH 3 COOH + CH 3 COOH
OH O
Carbonyl group goes with smaller alkyl group
(iv) React ion w it h phosporous pentasulph ide :
R—OH + P 2 S 5  R—SH + P 2O 5
Thio alcohol
(v) Reaction with salts :

CuSO4
CuSO4. 2CHOH
3

CaCl2
CH3OH CaCl2. 4CHOH
3

MgCl2
MgCl2 . 6CH3OH

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

(a) Lucas test : A mixture of HCl(conc.) and anhydrous ZnCl2 is called Lucas reagent.
ZnCl  HCl
p-alcohol 
2
 No turbidity at room temp. [On heating within 30 minutes.]
ZnCl  HCl
s-alcohol 
2
 Turbidity appears within 5 minutes.
ZnCl  HCl
t-alcohol 
2
 Turbidity appears within 1 minute.
(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—CH 2 —OH [1°] R 2 CH—OH [2°] R 3 C—OH [3°]





P + I2 P + I2 P + I2

R — C H 2— I R 2C H — I R 3C — I





AgNO2 AgNO2 AgNO2

R C H 2— N O 2 R 2C H — N O 2 R 3C — N O 2





HNO2 HNO2 HNO2

R—C—NO2 R 2C — N O 2 No reaction


N OH N
NaOH




NaOH NaOH

Soluble (Red) Insoluble (Blue) Colourless (White)

(v ii) Dichromate te st :
H  K Cr O
1° Alcohol 
2 2 7
6

 Acid + Cr+3
orange [Cr ]

[green]
H  K Cr O
2° Alcohol 
2 2 7
6

 Ketone + Cr +3
orange [Cr ]

[green]
H  K Cr O
3° Alcohol  2 2 7

 No oxidation, No green
orange [Cr 6 ]

(v iii) Te st of alcholic group :

1
R—OH Na
  R—ONa + H
2 2
[effervesence of H2]
PCl 5 NH 3
R—OH  R—Cl + POCl 3 + HCl   NH 4Cl
[White fumes]
R—OH Cerric ammonium nitrate Red colour
  
(ix) Distinction between CH3 – OH and C 2 H 5 OH
C H 3O H C H 3C H 2O H
B.P. 65°C 78°C
I 2 + 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
 OH
CH3OH COOH3 Methyl salicylate
(Oil of wintergreen)

OH OH
Ph—OH COOPh Phenyl salicylate
COOH
Salol (Internal antiseptic)
O C CH3
Aspirin
CH3COCl O (Analgesic)
COOH

 Addit ional react ions :

(a) Oxidation by HIO 4 [per iodi c acid] :
HIO 4 2H 2 O
CH2 CH2  
 CH2 OH + HO CH2   HCHO + HCHO
OH OH OH OH

HIO 4 3H 2 O
CH2 CH CH2  
 HO CH2+HO CH OH + HO CH2   HCHO+HCOOH+HCHO

OH OH OH OH OH OH
(Glycerol)

 Condition for oxidation by HIO 4 :

At least 2 —OH or 2 >C=O or 1 —OH and 1 >C=O should be at adjacent carbons.
CH3 O
2HIO4
Example : CH3 CH CH C CH3  CH3CHO + HCOOH + CH3 C CH3
OH OH OH

O
HIO
Example : CH3 C CH CH2 C 4
H  CH3COOH + CHO CH2 CHO
O OH
Example :

CHO CHO CHO

O
O 2HIO
O –H O
4 2 COOH
O
 OH + HO C OH +HO
2 + CO2
HO CH2 OH (H2CO3) HO CH2 CHO
HO CH2
OH OH

(b) Pinacole - Pinacolone Rearrangement :

CH3 CH3 CH3

conc. H 2 SO 4
CH3 C C CH3   CH3 C C CH3
OH OH O CH3

Pinacole Pinacolone
 Mechanism :

CH3 CH3 CH3 CH3 CH3

 CH3
H –H O
CH3 C C CH3 CH3 C C CH3  CH3 C
2
C

CH3
OH OH OH OH2 OH

CH3 CH3 CH3


CH3 C C CH3

CH3 C C CH3 CH3 C C CH3
–H

O CH3 OH CH3 :O
.. H CH3
(Complete octet more stable)

AROM ATIC H YDROXY DERIVATIVES

 Phenolic compounds :

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

OH OH OH
CH3 COOH

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 neutral FeCl Violet colour


3


C H3C H2—O H neutral FeCl No colour


3


PHENOL (C 6 H 5 OH)
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 Met ho ds of preparat ion :
(1) From benzene sulphonic acid :
When sodium salt of benzene sulphonic acid is fused with NaOH phenol is obtained.
C6H 5SO 3Na + NaOH    C6H5OH + Na2SO3
(2) From benzene diazonium chloride :
When benzene diazonium chloride solution is warmed, phenol is obtained with evolution of nitrogen.

N2Cl OH
(Steam distilled ) H O


2
 + N2 + HCl
(3) By distilling a phenolic acid with sodalime (decarboxylation):

OH OH
COOH NaOH  CaO
  + Na 2 CO 3

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

Br
[O]
C6H5MgBr  H2 O
 C 6H5OMgBr   C 6H 5OH + Mg
OH

(5) From benzene :

OH
V2 O 5
+ [O] 
300  C


(6) From chloro benzene :

Ph—Cl Aq. NaOH No NSR at normal condition

 
Stable by resonance

R—Cl Aq. NaOH R—OH [NSR]

 
Aq. NaOH
Ph—Cl  
 Ph—ONa
300 C

Order of NSR :

Cl Cl Cl Cl
NO2 NO2 NO2 NO2
< < <

NO2 NO2
max. –I, –M
Aq. NaOH min. ed Aq. NaOH
300°C min. ESR 25°C
max. NSR
OH OH
NO2 NO2

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

Fractional
Coaltar  Middle oil (170-230°)
distillation
(Phenol, cresols, Naphthalene)

Coal

Naphthalene liquid
(Solid crystals separate out) NaOH (dil.)

C6HONa
5

CO2/H2O or sulphuric acid

C6HOH
5 + Na2CO3

(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.

O OH
CH3 CH3
CH C(CH3)2 OH
O

2 H SO ,H O
4 2
 + CH3 C CH3
2
130  C
 H  / 100  C
O
Cumene Cumene hydroperoxide
o
(c) Raschig process : Chlorobenzene is formed by the interaction of benzene, HCl and air at 300 C in
o
presence of catalyst CuCl2 + FeCl3. It is hydrolysed by superheated steam at 425 C to form phenol and
HCl.
1 CuCl FeCl
C6H6 + HCl + O 
2 3
 C 6H 5 Cl + H 2 O
2 2 0
300 C

0
C 6H 5 Cl + H 2 O 425 C
  C 6 H 5 OH + HCl
(super heated steam)
(d) Dow process : This process involves alkaline hydrolysis of chloro benzene-(large quantities of phenol
formed).
OH
Cu — Fe
C 6 H 5 Cl + NaOH   + NaCl
300 0 C

 Physical proper t ie s :
(i) Phenol is a colourless, hygroscopic crystalline solid.
(ii) It attains pink colour on exposure to air and light. (slow oxidation)
C 6H 5OH-------- O O----------- HOC 6H 5
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 .
 Chemical Proper t ie s :
(A) React ions 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
(–NO 2, –Cl) increase the acidity of phenol while electron releasing groups (–CH 3 etc.) decrease the
acidity of phenol.
 
C 6 H 5 OH 

 C6H5 O  H3O
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.
2C 6 H 5 OH + 2Na  2C 6 H 5 ONa + H 2
(iii) Phenol reacts with strong alkalies to form phenoxides.

 
C 6 H 5 OH  NaOH  C 6 H 5 O N a H 2 O
(iv) However phenol does not decompose Na2CO3 or NaHCO3 because phenol is weaker than carbonic acid.
C 6 H 5 OH + Na 2CO 3 or NaHCO 3  No reaction
Ph—OH + NaHCO3 Ph—ONa + H 2 CO 3
Acid-I Base-I Base-II Acid-II

Acid-I < Acid-II

Reaction in reverse direction.
Base-I < Base-II
(v) Phenol does not react with NaHCO3.

CH3 C OH + NaHCO 3 CH3 C ONa + H 2 CO 3 [H 2O + CO 2 ]

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

Acid-I > Acid-II

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

(vi) Acetic acid reacts with NaHCO3 and gives effervesence of CO2.
 Reaction with PCl 5 : Phenol reacts with PCl 5 to form chloro benzene. The yield of chlorobenzene is
poor and mainly triphenyl phosphate is formed.
C 6H 5 OH + PCl 5  C 6H 5Cl + POCl 3 + HCl
3C 6 H 5 OH + POCl 3  (C 6H 5) 3 PO 4 + 3HCl
 Reaction with Zn dust: When phenol is distilled with zinc dust benzene is obtained.
C 6 H 5 OH + Zn  C 6 H 6 + ZnO

CH2 OH
Ex. Zn
 ?

S o l . No reaction
 CH3
OH Zn
Ex.  ?

CH3
Sol.

CH3
CH3 Zn
Ex.   ?

S o l . No reaction

COOH
OH Zn
Ex.   ?

COOH
Sol.

 Reaction with NH 3 ( Bucherer reaction): Phenol reacts with NH 3 in presence of anhydrous ZnCl 2 to
form aniline.
Anhydrous ZnCl or (NH ) SO / NH 150  C
C 6 H 5 OH + NH 3 
2 4 2
300  C
3 3

 C 6 H 5 NH 2 + H 2 O

 Reaction with FeCl 3 : Phenol gives violet colouration with FeCl3 solution (neutral) due to formation of a
complex.
C 6H 5 OH + FeCl 3  Voilet colour
This reaction is used to differentiate phenol from alcohols.
 Acetylation (Schot ten-Baumann reaction) : Phenol reacts with acid chlorides or acid anhydrides in
alkali solution to form phenyl esters.
NaOH
C 6 H 5 OH + ClCOCH 3   C6H5O—C CH3
 HCl

O
NaOH
C6HOH
5 + Cl C C6H5   C6H5O C—C6H5
 HCl

O O
 Ether formation (Alkylation) : Phenol reacts with alkyl halides in alkali solution to form phenyl ethers.
(Williamson's synthesis)

alkali solution RX
C 6 H 5 OH + NaOH   C 6 H 5ONa 
 NaX  C 6 H 5 OR

Sodium phenoxide
C 6 H 5 OH + CH 2 N 2  C 6H 5OCH 3 + N 2 

 Reaction with P 2 S 5 : 5C 6 H 5 OH + P 2 S 5  5C 6 H 5 SH + P 2 O 5

(B) Reaction of Benzene Ring : The —OH group is ortho and para directing. It activates the benzene nucleus.
 Halogenation : Phenol reacts with bromine in CCl 4 to form mixture of o–and p–bromo phenol.

OH OH OH
CHCl 3 or CS 2 or CHCl 4 Br
+ Br 2 
low . tem p.
 +

Br

Phenol reacts with bromine water to form a white ppt. of 2,4,6 tribromo phenol.

OH
OH Br Br
+ 3Br2 H O + 3HBr

2

Br

 Nitration : Phenol reacts with dil. HNO3 at 0°–10° C to form o- and p- nitro phenols.

OH OH
OH
dil. HNO
3
NO2

0 10 C
 +

(40%) NO2 (10%)

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

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

 Sulphonation: Phenol reacts with fuming H 2SO 4 to form o–and p–hydydroxy benzene sulphonic acid
at different temperatures.
OH
25°C
SO3H
OH

+ conc. H2SO4
OH
100°C

SO3H
 Friedel-Craft's reaction : Phenol when treated with methyl chloride in presence of anhydrous AlCl 3
p-cresol is main product.

OH
OH OH
Anhydrous AlCl
CH3
+ CH 3 Cl 
3
 +

CH3
o-cresol p-cresol
 OH OH
COCH3
OH +
+ CH 3 COCl Anhydrous AlCl

3

COCH3
o – and p – hydroxy acetophenone
 Gattermann aldehyde synthesis : When phenol is treated with liquid HCN and HCl gas in presence
of anhydrous AlCl3 yields mainly p- hydroxy benzaldehyde (formylation)
HCl + HCN AlCl HN CHCl

3


OH OH OH
AlCl3 H O
+ HN CHCl 
HCl    2
 NH


3

CH NH CHO

 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.

CHCl3
OH ONa + OH
NaOH H
 
60°C NaOH (aq.) H2O
OH CHCl2 CHO CHO
Salicylaldehyde

CCl4
OH ONa + OH
NaOH H
 
60°C NaOH (aq.) HO
CCl3 COONa 2
COOH
Salicylic acid

Mechanism : CCl 2 is neutral attacking electrophile (formed by  elimination reaction)

KOH
CHCl3  :CCl 2


OH O O O
 H Cl
HO
  :CCl
 2 C
–H2O Cl



OH O O
CHO OH Cl

H CH OH CH
  Cl
–H O 2 OH

 Kolbe 's Schmidt reaction : This involves the reaction of C6H 5ONa with CO2 at 1400 C followed by
acid hydrolysis salicylic acid is formed followed.

O Na OCOONa OH OH

COONa COOH
140° C Rearrangement H+
+ CO2   
6 atm. pressure H2O
Sodium phenyl carbonate Sodium salicylate Salicylic acid
 Hydrogenation: Phenol when hydrogenated in presence of Ni at 150-200 0C forms cyclohexanol.

OH OH
Ni
+ 3H2 
150 – 200° C

Cyclohexanol. (C6H11OH)
(used as a good solvent)

 Frie s rear ra ngement react ion :

Anhydrous AlCl 3
C 6 H 5 OH + CH 3COCl   C 6 H 5 OCOCH 3

OH
60°C

anhydrous AlCl COCH3

C6H5OCOCH3  3

OH
Phenyl ester (acetate)
COCH3

 Duff 's reaction: This method gives only the o-compound which is hindered by the presence of a –I
group in the ring.

OH OH OH
Glycerol
CH NCH3 H O CHO
+(CH)
2 6N4   2

Boric acid

Hexamethylene tetramine acidified with HSO

2 4

and steam distilled (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
N2Cl + 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.

O O OH
O C C OH OH H SO
O C C
2 4
+  OH
–H2O
H OH

Phenol (2 molecules) Phenolphthalien (Colourless in acidic

medium and pink in alkaline medium)

 Lederer Manasse (Condensation w ith formaldehyde) : Phenol condenses with HCHO (excess) in
presence of NaOH or weak acid (H+) to form a polymer known as bakelite (aresin).
 OH OH OH
CH2OH
NaOH
+ HCHO  +
(20%)
CH2OH


(40%) Polymerisation
condensation with HCHO

HO CH2 OH

CH2 CH2

OH CH2 OH

CH2 CH2

Polymer bakelite (Phenol formaldehyde resin)

 Leibermann's nitroso reaction : When phenol is reacted with NaNO 2 and conc. H 2 SO 4 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.
2NaNO 2 + H 2 SO 4  2HNO 2 + Na 2 SO 4

OH OH O
HONO 6 5C H OH H2O NaOH
 Green phenol Red  Blue Sodium
H2SO4
or blue colour Indophenol Salt (original
H NO N OH ion green or blue
colour is restored)
 Reaction with acetone: (Condensation with acetone)

OH OH OH OH
con. HCl

–H2O

H H CH3 C CH3
O Bis - Phenol-A
p-p'– Isopropylidene diphenol
CH3 C CH3
 Oxidation:

Air [O]
O O + H2O p-Benzo quionone (Red)
CrO2Cl2

OH COOH
 H OH
(O) H/KMnO4
Meso tartaric acid
H OH
(Phenol)
COOH
K2S2O8/KOH
HO OH (Quinol)
(Elb's persulphate reaction)
1, 4 – Dihydroxy benzene
 Te st 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.
NaNO 2
Phenol in conc. H2SO4 
excess of water

 Red colour 
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.
 Difference s bet ween phenol a nd alcohol (C 2 H 5 OH) :
(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.
 ETHER
R—O—R (Dialkyl ether), alkoxy alkane. It's General formula is C n H 2n + 2 O.
CH 3 —O—CH 2 CH 3 (Methoxy ethane) or ethyl methyl ether or 2–oxa butane
Ether is monoalkyl derivative of R–OH and dialkyl derivative of H 2 O
H 2H
R—OH 
R  R—O—R 
2R  H—O—H

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'
Str ucture :
: O : sp3 hybridized 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 due to the repulsion between bulky alkyl groups.
bond  110°  bond
Due to bent structure, it posses dipole moment and hence are polar
R R
molecules.
 General Met ho ds of Preparat ion :
(A) From alkyl halide s :
(i) By Williamson's synthesis :

R—X + Na—O—R  R—O—R + NaX [ S N 2 Reaction]

Example : CH 3 —I + C 2 H 5 O – Na +  CH 3 —CH 2 O—CH 3 + NaI

Mechanism : [ S N 2 Reaction]

 
C2H5ONa C2H5O + Na

H H H H
Slow Fast
C2H5O C— I C2H5O------ C ----- I C2H5—O—CH3+ I

H H


Na + I NaI

CH3 CH2

Example : CH3 C Cl + CH3ONa  H3C C

CH3 CH3

CH3 CH3
Example : CH3 
C ONa + CH3 CH2 Cl  CH3 C O CH2 CH3
CH3 CH3

Example : CH 2 CH—Cl + CH 3 CH 2 —ONa  No reaction

[Stable by Resonance]
 (ii) Reaction with Dry Ag 2 O :

2RX + Ag 2 O  R—O—R + 2AgX




Example : 2CH 3 —CH 2 —Cl + Ag 2 O  CH 3 CH 2 OCH 2 CH 3 + 2AgCl

(B) From R–OH:

Con. H 2 SO 4
(i) By dehydration : R—OH   ?

250°C 140°C
CH3CH2 O CH2CH3 CH3CH2 O CH2CH3
Al2O3 conc. H2SO4 (Willomson's synthesis)
 CH3 CH2 OH
350°C 170°C
CH2 CH2 CH2 CH2
(Elimination)
(ii) Reaction with CH 2 N 2 (diazomethane) :


R—OH + CH 2 —N 2 
BF  R—O—CH 2 —H + N 2
3

 Physical Proper t ie s :
(i) CH 3 OCH 3 , CH 3OCH 2 CH 3 are gases and higher are volatile liquids.
(ii) Ether are less polar [=1.18D].
(iii) Ethers are less soluble in H 2 O.
(iv) Ethers have less BP then corresponding alcohol.
Ex. Ethers are less soluble in H 2 O . Why ?
S o l . Reason : Due to less polar, it forms weaker H–Bonding with H 2 O.
Ex. Ethers have less BP then corresponding alcohol. Why ?
S o l . Reason : No H–Bonding in ether molecules.
 Chemical proper t ie s :
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

.. cold ; conc. HCl 

Example : C2HOC
5.. 2H5
 C2H5 O C2H5 Cl (diethyl oxonium chloride)
H

.. cold ; conc.  
.. C2H5 
Example : C2H5 O H SO
C2H5
2 4
O C2H5 HSO4 (diethyl oxonium hydrogen sulphate)
H

Ether form dative bond with Lewis acids like BF 3, AlCl 3 , RMgX etc.
 R R
..
O
..
R .. F
Example : O: B F R Mg X [Ether is used as solvent] for Grignard reagent.
R F ..
O
..
R R

2. Halogenation :
Cl2/dark
CH3CH O CH CH3
Cl Cl
CH3CH2 O CH2CH3
'–Dichloro diethyl ether

10 Cl2 light
C2Cl5 O C2Cl5 + 10 HCl
Perchlorodiethyl ether
3. Formation of peroxides : Ether add up atmospheric oxygen or ozonised oxygen. It is explained by Free
radical mechanism as intermediates is free radical.
O (nonpolar )
C 2H 5— O — C 2H 5 
Long contact 
2
CH3CH2 O CHCH3
(Non polar) sunlight or UV O O H
.. .. ..
C2H5..
OC2H5 + O
..  C2HOC
5.. 2H5 or (C2H5)2O
 O

..
:O
.. :

O 
CH 3 CH 2 —O—CH 2 —Ph  2
long contact

 CH —CH —O— CH —Ph O2
  CH3 CH2 O CH Ph
3 2

stable by resonance O O H
Peroxides are unstable and explosives.
Test for peroxides
FeSO / KCNS
ether (peroxide) 
4
 Red colour

ether (Peroxides) + Fe + 2  Fe + 3 
CNS
 Fe(CNS) 3
(Red)

hot dil
4. Reaction with hot dil. H 2 SO 4 : R—O—R 
H 2 SO 4
 2R—OH

5. Reaction with hot conc. H 2 SO 4 : R — O — R hot conc. H 2 SO 4

  2RHSO 4

cold dil.
No Reaction

cold conc.
Oxonium salt
H2SO4
CH3 CH2 O CH2 CH3
hot dil.
Ethyl alcohol
hot conc.
Ethyl hydrogen sulphate

6. Reaction with PCl 5 : ROR + PCl 5 heat 2RCl + POCl 3

 
7. Reaction with BCl 3 : 3ROR + BCl 3  3RCl + (RO) 3 B
 AlCl
ROR + RCOCl  
3
8. Reaction with RCOCl : ZnCl heat RCOOR +RCl
2

BF3 / HgO 500 atm

9. Reaction with CO : ROR + CO 150  C
 RCOOR



CH2CH2 O CH2CH2 + C2H5
10. Reaction with C 2 H 5 Na :  CH 3 CH 2 OH + CH 2 CH 2 +C 2 H 6
H H Stronger
base

11. Dehydration : CH3CH2 O CH2CH3 Al O

 2 3
2CH2 CH2 + H2O

Re d P  HI
12. Reduction : CH 3 CH 2 OCH 2 CH 3 
heat  2CH 3 CH 3

13. Oxidation :
H  / K 2 Cr2 O 7
CH 3 CH 2 —O—CH 2 CH 3  [O] [O]
 2CH 3 CH 2 OH   2CH 3 CHO   2CH 3 COOH
14. Combustion : C 2 H 5 OC 2 H 5 + 6O 2  4CO 2 + 5H 2 O
(explosive mixture)

15. Reaction with HX : Reactivity of HX HI > HB r > HC l

 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
Cold and conc.
Ex. CH3 C O CH2 CH3  HI  ?

CH3

Sol. Mechanism
CH3 CH3 CH3
..
CH3 C O CH2CH3 H+ CH3 C

O CH2CH3  CH3 
..
CH3 CH3 H CH3
(Oxonium ion)
CH3 I
CH3 C I + CH3CH2OH
CH3
  
 If oxonium ion gives more stable carbocation [ Ph CH 2 , CH2 CH— C H2, (CH3)3 C ] then SN1 reaction occurs.
  
 If oxonium ion gives less stable carbocation [P h , CH 2 C H, CH 3 C H 2] then SN 2 reaction occurs,
and X attacks at less hindered carbon.
Cold con.
Ex. CH 3 CH 2 —O—CH 2 Ph 
HI  CH 3 CH 2 —OH + PhCH 2 —I, write mechanism of given reaction.

S o l . Mechanism :
.. H 
I
 
CH3CH2OCH
.. 2Ph CH3CH2 O CH2Ph CH 3 CH 2 OH + Ph CH 2  PhCH 2 I + CH 3 CH 2 –OH

H
 anhy.HI
Ex. CH 3 CH 2 —O—CH 3  ?

.. HI  I
Sol. CH3CH2 O CH3 CH3CH2 O CH3 CH3I + CH3CH2OH
..
H
Oxonium ion gives less stable carbocation
SN 2 reaction I attacks at less hinderd carbon.
(aq.)HBr
Ex. CH 3 —CH 2 —O—Ph  
 ?

.. +  
S o l . Mechanism : CH3 CH2 O H
Ph  CH3 CH2 O Br
Ph  CH3CH2Br + PhOH
..
H

SN1 2°
CH3CH2OH + I CH CH3

CH3CH2 O cold and conc. HI

CH CH3   CH3
I
SN2
CH3 CH3CH2 I + HO CH CH3
1°
CH3

 If excess of HI is used then two moles of alkyl hallides are formed.

HI HI
 CH 3 CH 2 —O—CH 2 Ph   CH 3 CH 2 OH+PhCH 2 I   CH 3 CH 2 — I  PhCH 2 — I

(B) Reaction with hot and conc. HX :

hot and conc HI
CH 3 CH 2 —O—CH 3   CH 3 CH 2 —I + CH 3 —I

Ex. C 2 H 5 —O—C 2 H 5 hot and conc. HBr

  ? + ?


S o l . C 2 H 5 —Br + C 2 H 5 — 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.
 Preparat ion of Epoxide s :
(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
 Epoxidat ion of alkene s by react ion w it h peroxy acids :
O O
C=C + R–C–OOH C—C + R–C–OH

O
Peroxy acid Epoxide
Example :

O O
(a) CH2= CH–(CH2)9–CH3 + CH3–C–COOH CH2–CH(CH2)9CH3 + CH3–C–OH
O

O O

(b) + CH3–C–OOH O + CH3–C–OH

(c) Epoxidation is a stereospecific syn addition :

C6H5 O O
H C6H5 H
C= C + CH3–C–OOH + CH3–C–OH
H C6H5 C6H5
H O

(E) -1,2-diphenyl ethene trans -2,3-diphenyl oxirane

Mechanism :
H
O C O O
C
CH3–C O CH3–C H +
C CH3–C O O––C––
O C
O O C

transition state Epoxide

 Base-promoted ri ng closure of v ici nal halohydri ns :
–
x2
HO
R2C = CR2 
H o

 R2C––CR2 R2C–––CR2
2

O
HO X
Vicinal halohydrin Epoxide
Mechanism :
R X R X
R C––C R R C––C R + HO—H
Step I
–O
..

O
..
..

.. – .. R .. R
HO
.. H

R X R R
..
Step II R C––C R –
R+X
..
..

R C––C ..
–O
..
..

O
..
..

.. R
 Example :

H H
OH
NaOH
O
(i)
OH
Br H
trans-2-bromocyclohexanol 1, 2-epoxycyclohexane

H3C Br
H3C
H H
H3C H
Br2/H2O inversion of
Anti addition configuration H3C
(ii) H3C H3C H H
H
OH O
cis-2-butane cis-2, 3-epoxybutane

H Br
H
CH3 CH3
H CH3
Br2/H2O inversion of
Anti addition configuration H3C
(iii) H3C H3C H H
H
OH O
trans-2-butane trans-2, 3-epoxybutane

 Reaction of Epoxides :
 Wit h Grignard reagent :

(1 ) diethylether
RMgX + H2C––CH2 (2 ) H 3 O 

 RCH CH OH (primary alcohol)
2 2

(i) diethylether
CH2MgCl + H2C––CH2 + CH2CH2CH2OH
(ii) H3O
O
Benzyl magnesium Ethylene 3-phenyl-1-propanol
chloride oxide
 Nucleoph i lic ri ng openi ng react ions of epoxide s :

Y Y

Y:– + R2C––––CR2 R2C–––CR2 H2O

  R2C–––CR2
O O
..
..

OH
..
..

.. ..

KS CH 2 CH 2 CH 3
H2C–––CH2 
ethanol water, 0  C
 CH ––CH CH ––CH SCH CH OH
3 2 2 2 2 2

O
2-(butylthio) ethanol
Note : Nucleophilic ring opening reactions of epoxides is the characteristic feature of S N 2 reaction.

H OCH2CH3
NaOCH 2 CH 3
(i) H  H
CH 3 CH 2 OH
O H
OH

CH3
H3C

H OH
NH3/H2O
H
O
H3C H2N H
H
CH3

H3C CH3 CH3O CH3

NaOCH 3
(ii) C––––C  CH3––CH––C––CH3
CH 3 OH

H O CH3 OH

 Nucleophilic ring opening of epoxides :

1, diethyl ether
C6H5MgBr + H2C–––CHCH3  

 C6H5CH2CH––CH3
2, H 3 O

O OH

R R R
R
.. – ..
O
..
.. OH
..
–
Y: – ..– Y
Y O Y
O ..
epoxide transition state alkoxide -substituted alcohol
1. LiAlH 4
CH2–––CH(CH2)7CH3   CH3––CH––(CH2)7CH3
2, H 2 O

O OH
HBr
(i) H2C–––CH2   BrCH2CH2OH
10  C

CH 3 CH 2 OH
(ii) H2C–––CH2   CH3–CH2OCH2CH2OH
H 2 SO 4 , 25  C

H2C–––CH2 + H2O H3O



HOCH2CH2OH

O
Mechanism

+ H ..
H2C–––CH2 + H—O: H2C–––CH2 + H2O:
Step-1 :
H :O+
:O:
H
 H2C–––CH2
H .. + H
Slow
:O: + O+ .. ..

..
Step-2 : H—O
H
H
..
CH2–CH2–O–H

+ H
H—O ..

..
H H .. ..
Step-3 : :O: + ..
CH2–CH2–O–H +
.. 2CH2..
O—H + HOCH OH

..
H H
H
Example : H
OH
HBr
O
OH
H H
1,2-Epoxycyclohexane trans -2-bromo cyclohexanol

H3C CH3 OCH3

C–––C CH 3 OH

 CH3––CH––C––CH3
H 2 SO 4
H O CH3 HO CH3

2,2,3-trimethyl oxirane 3-methoxy-3-methyl-2-butanol