Alcohols, Phenols

and Ethers hapter

BASIC
CONCEPTS

t. Introduction: Alcohols and phenols are the compounds containing one or more hydroxyl groups (-OH).
The alcohols contain the -OH group attached to the alkyl group whereas in phenols, the -OH group is
attached to the aromatic ring.
Alcohols:
CH3 -0H CH2-CH2 CH2 -CH--CH2
Methyl alcohol I I I I I
(Monohydric)
OH OH OH OH OH
Ethylene glycol Glycerol
(Dihydric) (Trihydric)

Phenols:
OH OH

@
Phenol
~H
Catechol
@=g:
Pyrogallol
(Monohydric) (Dihydric) (Trihydric)

2. Common and IUPAC names of some alcohols:

Table 11.1: Common and IUPAC Names of Some Alcohols
Common Name Structural Formula IUPAC Name
Ethyl alcohol CH3-CH2-0H Ethanol
n-Butyl alcohol CH3-CH2-CH2-CH2-0H Butan-1-ol
sec-Butyl alcohol CH3-CH2-TH-CH3 Butan-2-ol

OH·
CH3
I
lsobutyl alcohol CH3-CH-CH2-0H 2-Methyl propan-1-ol
CH3
I

tert-Butyl alcohol CH 3 -C-CH3 2 -Methyl propan-2-ol

I
OH
414 ,Xam idea C
h e m is tr y -X
II -- -- -- -- --
-- -= ~ -- ,- -:
-- ~ -; -- ~ _ _ _ ,~ ~ ~
CH3
.
neo-Pentyl alcohol
'
C H 3- C -C ff 2- 0H 2, 2

CH3.
CH3
'
tert-Pentyl alcohol
I
CH -e -C H 2- C 2-Methyl butan-2-o
H3 l
3 I
OH
Some more exampl
es of alcoho1s are given below:
4, 5
C2Hs
C H 2= C H -O H \3 2
CH -C -C H -C 1 H2 C = C H -C H 20
Vinyl alcohol H3 H
(Etbcn-1-ol) 3 \ \ Ally\ alcohol
CH3 OH (P ro p- 2- en -l- ol)
3, 3-0imethylpentan-2-
ol

CH3 -
l 2 '3 CH3
O I3 -r n -C H 4 5 4
-r n3 3 21 1
CH3 -C H - CH - C - ff i2 O
2

'
H
OH I I
3-Methyl butan-2-ol CH3 2-Methyl cyclopcnta
01 3 nol
2, 2, 3-Trimethyl pe
In IUPAC system ntanol
, dihydric alcohol
alkanetriols. s are named as alk
anediols and trihy
dric alcohols are
named as
1
CH2 OH
I
2
CHOH
Ethylene glycol I
(Ethane-1, 2-diol) 3
CH2 OH
Glycerol
{Propane-1, 2, 3-trio
~ ~ p le st hydrox l)
y derivative of benz
ene is phenol. The
substituted phenol
1H s are na m ed as derivatives of

@-c.
OH
(9) OH
02~02
Phenol
3-Chloropbcnol

N 02
Picric acid
Methyl phenols ar (2,4,6-Trinitrophenol) \
e known as cresol
s.

OH
·~83 I
© -c H 3
o-Cresol \
(2-Methylpbenol) m-Cresol
(3-Methylphenol)
H3 2,6-Dimethylpheno
p-Cresol l
(4-Methylpbenol)

Xamidea
 - - - A l c o h o l s , Phenols and Ethers 1415
-----------------------------

some dihydric and trihydric phenols are given below:

@ru
Catechol
&u
Resorcinol
(Ben7.ene-1,2-diol) (Benune-1.3-diol)
Quinol or hydroquinone
(Benzene-1,4-diol)

1 8
.,0H

CSX.on
Pyrogallol
(Benfflle-1,2,3-triol)
Hydroxyquinol Phloroglucinol
(Benune-1,2,4-triol) (Benzene-1,3,5-triol)

AlcOhols
3. Structure of R-OH : In alcohols, both the carbon atoms
of R (e.g., -CH3) and oxygen atom of -OH
below.
groups are sp hybridised. The structure of CH3-0H is shown
3

~on epai rs

H f/{J
0
1.JJ<..o...,,_a
H..:--C '-..:/ ,......_ff
0
la \ 10s.so
H 142pm
Structure of Methanol
8~) due to repulsions between lone
The C-OH bond angle is slightly less than tetrahedral angle (109°2
polar because of high electronegativity
pairs of electrons of oxygen atom. The C-0 and 0-H bonds are
of oxygen atom.
4. Methods of Preparation
Alcohols are prepared by following methods:
(a) From alkenes
(i) By acid catalysed hydration:
Addition occurs according to Markovnikov's rule.
H+
R-C H=C H2 +H20 R-CH -CH3
I
OH
(ii) By hydroboration oxidation:
Addition occurs in accordance with anti-Markovnikov's way.
1
R-C H= CH2 + (BH3) 2 --)(R -CH2 -CH2 ) 3B
Diborane
8202
>R-C H2 -CH2 -OH +H3B03
OH-,H 20 1° Alcohol

(ii,) By oxymercuration-demercuration:

-z:-
I
Addition occurs according to Markovnikov 's rule.
CH3- CH=C H2 CH3 CH2 - HgOOCCH3
Propeoe
NoBH, ! OH-

Cff3 -CH -Cff J

6H
Propan-2-ol

Xamidea
• 4161 Xam idea Chemistry-X
II

(b) From carbonyl compound

. s
ction of aldehydes and
(1) By redu red ·ng age ketones: . .
nts used are lithium alurm h dride (LiAIH ), sodium
Common uc1 n1um duyction give 4 borohydride
(NaBH4), H2in the presence f N' or Pt Aldehydes on re 1o alcohols whereas ketone
o • • s
on reduction give 20 alcoho
ls.
0
11
R- C- H+ 2( H) LiAIH, + R- CH 2 -O H
or 1° Alcohol
Aldehyde NaBH4
R
Ni or Pt
"- c= O +H 2
R '/
Ketone 2° Alcohol
( ii) From Grignard' s reagen
ts
(\ 6- 6+ HO
)c ~ R -M g -X "-.. - + 2
> ,,. .-y -O M gX > ~- O H +M g( O H )X
•

Aldehyde or Grignard
ketone reagent R R
Adduct Alcohol
The reaction of Grignard'
s reagents with formaldehyd
aldehydes it produc~s second e produc~s a primary alc
ary alcohols and tertiary alc ohol, with other
ohols with ketones.

R- CH -O H + Mg(O
2 H)X.
1° Alcohol .
R- M gX --- -+ --+ _R _'-
::_ CH _O --- t~ CH -O H
Grignard' s reagent + Mg(OH)X
H2 0 20 Alcohol '

R"
+ R",:) C= O
L---_R_ _ _--? R '-C -R
I
+ Mg(OH)X
H2 0 I
OH
3° Alcohol
(iii ) By reduction of carbox
yli c acids and esters:
R- CO OH (i)L iAI H 4 >R- CH
2- 0H
Carboxylic acid (ii) H2 0 1° Alcohol
R- CO OR ' Hz /Pd > R- CH -0
2 H+ R' -O H
Ester
1° Alcohol
(c) By the hydrolysis of ba
loa lkanes
RX + KOH(aq.) >R- OH + KX
On hydrolysis with aqueou
s KOH, primary alkyl halide
alkyl halides give a mixture s give good yield of prima
of alcohol and alkene while ry alcohols·; secondary
S. Physical Properties of tertiary alkyl halides mainl
Alcohols: y give alkenes.
(a) The lower members of
alcohols are colourless, vol
burning taste whereas hig atile liquids with a charac
her alcohols are odourless teristic alcoholic smell and
carbon atoms are colourles and tasteless. Higher alcoh
s waxy solids. ols having 12 or more
(b) Solubility of alcohols:
The first three members
rapidly decreases with inc are completely miscible
rease in molecular mass. Th with water. Th e solubility
but are soluble in organic e higher members are alm
solvents like ether, benzen ost insoluble in water
due to their ability to form e, etc. The solubility of low
hydrogen bonds with water er alcohols in water is
molecules.
--- --- --- --- --- --- --
...
I
Alcohols, Phenols and Ethers 1417

H
o-
The solubility of alcohols in water decreases with increase in molecular mass because with increase in
molecular mass the non-polar ralkyl group becomes predominant and masks the effect of polar -OH
group. In addition, among the isomeric alcohols the solubility increases with branching of chain. It is
because the surface area of non-polar part in the molecule decreases, thus enhancing the solubility.
(c) Boiling points: Boiling points of alcohols are much higher than those of alkanes, haloalkanes or ethers
of comparable molecular masses. This is because in alcohols intennolecular hydrogen bonding exists
due to which a large amount of energy is required to break these bonds.
R R
•
I I
0°- 0°-
'H0+ H0; ••••• ' H0+ Ho+
••••··.. o 0-/ •••••·.. o 0_/

I I
R R
Among isomeric alcohols, the boiling point decreases with increase in branching in the alkyl group. For
isomeric alcohols, the boiling points generally foil ow the order:
Primary alcohol > secondary alcohol > tertiary alcohol.
6. Chemical Properties of Alcohols:
The reactions of alcohols can be classified into three types:
(a) Reactions involving the cleavage of oxygen-hydrogen bond.
(b) Reactions involving the cleavage of carbon-oxygen bond.
(c) Reactions involving both the alkyl as well as the hydroxyl group.
(a) Reactions involving cleavage of oxygen-hydrogen (0-H) bond
Acidity of alcohols: The acidic character of alcohols is due to the polar nature of 0-H bond. An
electron releasing group (alkyl group) increases electron density on oxygen tending to decrease the
polarity of 0-H bond. This decreases the acid strength. For this reason, the acid strength of alcohols
decreases in the following order:
R R~
R-CH2-0H > R,)CH-OH >> R'/C-OH
1° Alcohol R"
2° Alcohol
3° Alcohol
( i) Reaction with metals:
- +
2R-O-H + 2Na --> 2R-0Na + H2
Sodium alkoxide
- + 1
CH3 -CH2-OH+ Na --> CH3 -CH2-ONa + - H2
Sodium ethoxide 2
Ethyl alcohol
6(CH3)3-C -OH+2Al - - 2((CH3)3- C-0) 3 A1+3H2
3° Butyl alcohol Aluminium tert-butoxide
(i,) Esteriftcation:

R-COOH + R'-OH
Carboxylie acid Alcohol
= R-COOR' + H20
Ester
•
4181 Xam idea C h e m i
s try-XII-------
---------------
-
H+
(R -C 0)2 0 + R'- OH " » R- ~~ R' + R- CO OH
Acid anhydride
R-C OC I + R'- OH Pyridine > R- CO OR ' + HC
I
Acyl chloride Ester
(b) Reactlom involving cleavage of
carbot1-0xygen (C -0 ) ~n d
In such type of reactions, the order
of reactivity of alcohols 1s
• 3° Alcohol > 2° Alcohol > 1° Alcoho
l
(i) Reaction with hydrogen hal
ides:
R- OH + H- X > R- X
Alcohol + ~2 0
Alkyl halide
CH -C H -0 H+ H- Cl anhyd.ZnCl 2 > CH 3-C H2
3 2 -C l+H 20
(a) Reaction with phosphorus
hal ides:
R- OH + PC1 > R- Cl + POCl3 + HCI
5
3R -O H + PCl3 > 3R -C l + H3P03
•
3R -O H+ PB r3 _from(P&Br2)
> 3R -B r+H 3P 03
3R -O H+ Pl3 from (P& I 2) > 3R -I + H3P03

R- OH + SOC12 - - R- Cl
+ S02 t + HC lt
(c) Reactions involving both the alk
yl as well as the hydroxyl group
(1) Dehydration: The ease of deh
ydration follows the following order:
3° Alcohol > 2° Alcohol > 1° Alc
ohol
CH3 -C H2 -0 H H2S04 > CH2 = CH2 + H2 0
Ethyl alcohol 443 K
Ethene
OH
.I
CH3-C H- CH SS% H 3P04 > CH3 -C H= CH2 + H 0
3
Isopropyl alcohol 440 K 2
Prop ylene
CH3
I CH3
CH3-C -C H
3
I
CH3 -C == CH +H 0
I 358K 2
Isobutylene
2
OH
tert- Butyl alcohol
(ii) Oxidation: Oxidation of alco
hol
s involves the formation of a carbon
cleavage of an 0-- H and C- H bon -oxygen double bond with the
d.
I
H -C -0 -H -- > C =
O
t t I
Bond breaking
1° alcohols on oxidation give aldehyd
es which on further oxidation give carb
same number of carbon atoms. oxylic acids with the

R- CH 2 -O H + [0] K2Cr20 7IH2S04 > R- CH O [O]

1° Alcohol or alk. KMn04
> R- CO OH
-H 20 Aldehyde Carboxylic acid
CH3 -C H= CH -C H2 -· OH
PCC > CH 3- CH = CH -C
But-2-enol HO
But-2-enal
__ __ __ __ __ __ __ __ __ __ __
__ _Alcohols, Phenols and Ethers 1419

2° Alcohols are oxidised to ketones by Cr0

3
R' R'
'-cH -OH Cr03 'c= o
R / '1!' Alcohol R/ Ketone
3° alcohols do not undergo oxidation reaction as they do not have a-hydr
ogens. However, when
oxidation is carried under strong reaction conditions and elevated temper
ature, they undergo
oxidation with the cleavage of C-C bond.
CH3
CH3
I
1
I
CH3 -C-C H3 Hot cone. HN03 > CH3 -C=. CH2
I -H20
+[OJ -H,o,-co,
OH
3° Butyl alcohol

CH3
CH3 -COO H
Acetic acid
[OJ '-c = 0
- H 20, - CO2 CH /
3
Acetone
(iii) Dehydrogenation
Primary alcohols are dehydrogenated to aldehydes.
• Cu
R-CH 2-OH R-CH O + H2
1° Alcohol 573 K Aldehyde
S~ondary alcohols are dehydrogenated to ketones.
R'. R
R' /
CH-O H Cu
573 K R'
\c/ = 0 + H2
2° Alcohol Ketone
Tertiary alcohols undergo dehydration to give alkenes.
CH3
CH3
I Cu I
CH3 -C-C H3 573 K CH3-C= CH2 +H2O
I Isobutylenc
OH
ten-Butyl alcohol
7. Prepantion of Phenols:
(,) From aryl halides

Cl -Na
@ +NaO H
623K
300atm 0 HO•~
Oilorobemenc
Phenol
(ii) From benzene sulphonic acid

_r>
3
Okum •
(8)
H_(-1)_N.;.;.,;;aO;.;;.;H~•
(i1)H•
1
(8)
0
HH

Phenol
(iii) From diazonium salts
+ -
NH2 N2Cl OH

@
•

Aniline
NaNOiJHCl
273-278 K l8J H20, warm
-HCl,- N2
@·
Pbeaol
 I
420 xam idea Chemistry-XII

8. Reactions of Phenol: -+
ONa

-H2
+Na
-@ -

Sodi um phenoxide

OH

@
Phenol
+NaOH
--

CH3-COCI yocH3
Pyridine
(Acetylation)
-- (gJ + HCI
Phenyl acetate

@
' OCOCH3
+(CH3-C0)20/H+ _
(Acetylation) -
·+ CH3COOH

OCOCJis
NaOH + C6"5COCI_
(Benzoylation) - @ +HCI
Phenyl benzoate

+NH3
ZnCl2, 675 K
Aniline 'J

+Zn, /l
-- + ZnO
(Reduction)

OH
dil. HN03 ~N02
Nitration
-
lSJ +

cone. HN03
cone. H2S04 --

Picric acid

1H~Br
+Br2 in CS2 -
273 K (Brominationf + CST
Br
(Ma

+ 3Br2 (aq)
- Br + 3HBr

Br
2,4,6-Tribromophenol
9. Some Commercially Important Compounds:
1. Methyl alcohol: It is produced by catalytic hydrogenation of carbon monoxide at high pressure and
temperature in presence of ZnO- Cr2 0 3 catalyst.
- Alcohols, Phenols and Ethers 1421

CO+ 2H 2 ZnO-Cr203 ) CH -OH

200-300 atm 3
575-673 K Methyl alcohol

2. Ethyl alcohol: It is obtained commercially by fermentation.

(,) C12H22O1 I + H2O Invertase C6H12O6 + C6H12O6
Sucrose yeast Glucose Fructose
(ii) C6H12O6 Zyma,;e ) 2C 2 H5 OH + 2CO2
Glucose or Yeast
fructose

3. Phenol: It is manufactured from cumene. Cumene is oxidised in air to cumene hydroperoxide. It is

converted to phenol and acetone by treating it with dilute acids.
CH3
I
CH3 iO-OH :,:

Cumcne Cumene Phenol Acetone

hydroperoxide

10. Ethers: Ethers are the compounds with general formula of C,,H21,+2O (same as monohydric alcohols).
These are represented by general structure, R-0-R'.
The groups R and R' in ether may either be same or different. I,-i case these groups are same, the
compounds are known as simple ethers or symmetrical ethers. On the other hand, if R and R' groups are
different, the compounds are called mixed ether or unsymmetrical ethers.
Nomenclature: According to IUPAC system, ethers are named as alkoxyalkanes. The larger alkyl group
forms the part of parent chain while smaller alkyl group constitutes the alkoxy group.
Table 11.2: Common and IUPAC Names of Some Ethers
Common Name Strnctural Formula IUPACName
Dimethyl ether CH1-0-CH1 Methoxymethane
Diethyl ether CR1-CH2-0-CH2-CH 1 Ethoxyethane

f"3
Methyl isopropyl ether CH3-0-CH-CH3 2-Methoxypropane
CH 3
I
Methyl tert.-butyl ether CH3-0-C-CH3 2-Methoxy-2-methyl propane
I
CH 3

Anisole rH3
Methoxybenzene
I
O--CH2-CH3
I
Phenetole @ I
Ethoxybenzene

r"3
J:::<H2--CH2-CH-CH3

Phenyl is_o_penty_lether_ _ _ _ _....,___CS)__ __ 3-Methyl-butoxybenzene

H 3C CH3
(J-o-cH2-CH3
CH3 -~CH 2 -CH2 -~CH3
I. 2-Dimcthoxyethanc 2-Ethoxy-l, 1-dimethylcyclohexane

liamidea
 f
422 Xam idea Chemistry-XII _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __

I
• I

CH3
I
. @ CH3 -CH-CH-C H2-0-CH2 -CH
3 .,
[>-0-cH- CH2 -CH3
2-Cyclopropoxybutane
1-Ethoxy-2-iodo-3-phenylbutane

11. Preparation of Ethers:

(a) By dehydration of alcohols
2CH3 -CH2 -OH co~.t~io, > CH3 -CH2 -O-CH2-CH3 + H2 O
(excess) Diethyl ether
This method is suitable for the preparation of ethers having primary alkyl groups only.
(6) WiUiamson synthesis
+ -
R-X + Na-0--R' - - R-0--R' + NaX
Alkyl halide Sodium alkoxide , Ether
-+
ONa

@
Sodium pheooxide Anisole
NaCl

12. Physical Properties:

1. Physical state: The lower homologues of ethers are colourless, pleasant smelling, volatile liquids with a
typical 'ether' smelt . • .. .
2. Boiling points: Ethers have much lower boiling points as compared to isomeric alcohols. Unlike
alcohols, ether molecules are not associated by hydrogen bonds. The interparticle forces existing in their
liquid states are weak dipole-dipole forces.
3. Solubility: The solubility of ethers is comparable to those of correspon~g alcohols. The solubility of
ethers is due to the ability of their molecules to form hydrogen bond with water molecules.
R, ....•··H""'- _ __,,,. H
"o·· tr
R / ······•... H____..... °'-... H
Howeve~, solubility of ethers in water decreases from lower members to higher members. This i s ~
of the relative increase in the hydrocarbon portion of the molecule which decreases the tendency of H-bond
formation. Ethers are appreciably soluble in organic solvents like alcohol, benzene, acetone, etc.
13. Chemical Reactions: Ethers are relatively inert compounds in spite of the presence of oxygen atom
canying two Ione pairs of electrons in their molecules. It is because of this reason that these are used
solvents. They undergo chemical reactions under specific conditions. Some of the reactions of ethers are
being described as follows:
(a) Cleavage of C--0 bond: Carbon oxygen bond in ethers can be cleaved by the use of reagents lite- j
halogen acids, sulphuric acid and phosphorus pentachloride, etc. . id
Cleavage with halogen add: Ethers can be cleaved by the use of hydroiodic acid or hydrobroDllC ac
to give alkyl halide and alcohol.
R-0-R + HX 373K ROH+ RX (X=Br,I)
Ether Alcohol Alkyl halide

. C i.1-QC ffs
+ID 373K C2H50H+C2ffsl
, I 'odi'd The overall
2 u-, 2
. used the alcohol formed reacts further with }fl to fonn alley t e.
In case excess of HI 1s ,
reaction can be written as
C2ffsOC2~ + 2m 373 K 2C2Hsl + H20
(Excess)
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Alcohols, Phenols and Ethers 1423

If ~ne group is ~thyl ~nd other group is tertiary alkyl group, the main product is methyl alcohol and
te~ary alkyl h~ide. It 1s because the departure of leaving group (CH 3 -OH) creates a more stable
ternary carbocatton.
CH3 CH3
I 373 K
I
CH3 -C-OCH3 + HI CH3 -C-I + CH3 OH
I I Methyl alcohol

CH3 CH3
tert-Butyl methyl ether tcrt-Butyl iodide

In case of anisole, the products formed are phenol and methyl iodide.
O-CH3 OH
~Q
lS) +HI
373K
---. l8J + CH3I
Anisole Phenol Methyl iodide
The bond between ~CH3 is weaker than the bond between O-C 6 H5 because the carbon of phenyl
2
group is sp hybridised and there is a partial double bond character. Therefore, the attack of 1- ion
breaks 0-CH3 bond to fonn CH3I.
(b) Ring substitution in aromatic ethers: The alkoxy group (-OR) attached to aromatic ring activates the
ring towards electrophilic substitution and directs the incoming electrophile to ortho and para positions.
!OR

V
The presence of negative charge at ortho and para positions indicates that electron density is more at
these positions. Therefore, electrophile is likely to attack on these positions resulting in the formation of
ortho and para substituted products.
OCH3
$"3
Br2 in acetic acid
+ @Jar
(Bromination)
(Minor)
Br
., p-Bromoanisolc
(Major)
. OCH3
$"3
CH3CVanhyd. AICl3
(Friedel craft alkylation)
+ (§rcu3
(Minor)
CH3
p-Mcthoxytoluene
(Major)

0 _OCH3
II $"3
Anisolc CH3-C-CVanhyd. AICl3
+ (§rcOCH3
(Friedel craft acylation)
(Minor)
COCH3
p-Methoxy acetophenone
(Major)
OCH3
HN03 (conc.)IH2S04 (cont.) $3· + @-No2
Nitration
(Minor)
NO2
p-NitroanisoJc
(Major)

Xamidea
 f
424 Xam idea Chemistry-XII

14. Uses of Ethers

Ethers are used in several ways:
1. Dimethyl ether is used as refrigerant and as a solvent at low temperature.
2. Diethyl ether is used as a solvent for organic reactions and aJso as an industrial solvent for oils
resins, etc. It is also used as an extracting solvent. 'gullls,
IS. Some Important Name Reactions
(1) Kolbe's reaction: When sodium phenoxide is heated with CO2 at 400 K under a pressure of 4-?
the resulting product on acidification yields salicylic acid. • atrn,

NaOH " Na 4~1!. H OONa ff+ • ~COOH

l2J Sodium
+CO2
Sodium
l2J
Salicylic acid
phenoxide salicylate (2-Hydroxybenzoic acid)
Major product

Salicylic acid i~ the starting materia1 for the manufacture of 2-ace!oxybenzoic acid (aspirin).
1

OH OCOCH3
~COOH cone. H2S04 @JCOOH
l2) + (CH3CO)iO _ _ __.,. 0 . + CH3COOH •
Acetic acid
Salicylic Acetic anhydride 2-Aceto~y
acid benzoic acid
(Aspirin) '" •

(ii) Reimer-Tiemann reaction: Treatment of phenol with chloroform in the pr~nce of aqueous alkali at
3~ K followed bJ hydrolysis of resulting prbduct gives o-hydroxybenzaldehyde (salicylaldehyde) as a
maJor product.

OH ONa OH

@ CHCI3 + (aq) NaOH

340K
@CHO • @{CHO

Salicylaldehyde
/ . . (2-Hydroxybenzaldehyde)

(iii) Oxymercuration and demercuration of alkenes: Alkenes react with mercuric acetate in a mixture of
tetrahydrofuran and water to give hydroxy mercurial compound, involving addition of -OH and
-HgOAc to the double bond.· This is called oxymercuration. Then NaBH4 reduces -HgOAc and
replaces with hydrogen. This is called demercuration.
Hg (OAc)i
CH3 -CH2-CH=CH2 CH3 -CH2.-CH-CH2
THF,H 20
Butene · I I
OH HgOAc
NaBH 4 CH3-CH2 -fH-CH3

OH
sec-Butyl alcohol
. th f CS2 as solvent
(iv) Fries rearrangement: Phenyl esters on heating with anhydrous AICl3 m e presence_ 0 F ·es
. ortho and para hydroxyketones. Th·1s rearrangement 1s known
undergo rearrangement to give • as n
rearrangement.
OH OH
:r;,OCH3 Heal

Phenyl
acetate
AICl 3 .$ COCH3
+
(§:(COCH3

o-Hydroxy
acetophenone
j,-Hydroxy
acetophenone .. f the
• . th Orth 0 or para position o
The reaction involves migration of acyl group from phenohc oxygen to e
aromatic ring.
 Alcohols, Phenols and Ethers 1425

(v) Williamson synthesis: It consists of reacting an alkyl halide with sodium alkoxide or sodium phenoxide
to form ether.
+ -
lt-X + Na-0-R' - - R-0-R' + NaX
Alkyl halide Sodium alkoxide Ether
It is a convenient method for the preparation of symmetrical as well as unsymmetrical ethers.
+ -
CH3 -CH2 - I + Na-O-CH2 -CH3 CH 3 -CH 2 -O-CH 2 -CH3 + Nal
Ethyl iodide Sodium ethoxide Diethyl ether
(Symmetrical ether)

CH 3 CH3··
+ - I I
CH3 -Br + NaO-C-CH3 CH 3 -0-C-CH3 + NaBr
Methyl
bromide
I I
CH3 CH3
Sodium tert-butoxide Methyl tert-butyl ether (Unsymmetrical ether)
-+
ONa

CH3 - I + @ NaI
Sodium phenoxide Anisole
16. Distinction between Primary, Secondary and Tertiary Alcohols
(a) Lucas test: In this test, the alcohol is tre~ted with Lucas reagent which is an equimolar mixture of HCI
and ZnCl 2 . Alcohols are soluble in Lucas reagent and form a clear solution. On reaction, alkyl chlorides
are formed which being insoluble result in turbidity in the solution.
Alcohol HCI Alkyl chloride•.; H2 0
ZnCl 2

If turbidity appears immediately, tertiary alcohol is indicated.

If turbidity appears within ijve minutes, secondary alcohol is indicated.
If turbidity appears only upon heating, primary alcohol is indicated.

OH l
(b) Iodofonn test: When ethyl alcohol or any alcohol containing the group CH _.tH4 is heated with
3
iodine and aqueous NaOH or Na2C03 solution at 333-343 K, a yellow precipitate of iodoform is obtained.
CH3CH20H + 412 + 6Na0H A > CHI3 + HCOONa + 5Nal + 5H 0
2
Iodoform
A·
CH30H + 12 + NaOH --> No reaction

CH3CH2CH2CHCH3 + 412 + 6Na0H _A_ CHI 3 + CH3CH2CH2COONa + 5Nal + 5H 0

2
I Iodofonn
OH

CH3CH2CHCH2CH3 + 12 + NaOH A No reaction

I
OH
(c) Fenic chloride test for phenols: Phenol gives a violet-coloured water soluble complex with ferric chloride.
6C6Hs0H+ FeCl3 - ~ [Fe(OC H ) ] 3- +3H+ +3HCI 6 5 6
Violet complex

I
In general, all compounds containing enolic group(= C-01-1) respond to this test.
However, the colours of complexes are different such as green, blue, violet, etc., and depend upon the
structure of phenols.

1
Xamidea_•_<_ _