[IT] Alcohols, Phenols and Ethers J

I POINTS TO REMEMBER (a brief concept ) I

Introduction
Ethers
Alcohols Phenols
* Inert solvent for many
* Ethanol = Wood polish * Adhesive
reactions
* In pe rfume rv
* Menthol - Flavour to food * Antise ptic
* Was used as surgical
* Solvent for many organic co mpounds * Disinfectant
anaesthetic

Alcohols I
Alcohol s are h ydroxy d erivatives of a lkan es in which one or more H-atoms are replaced by - OH group . They
have general form ula C 11 H 2 11 , 1 OH .

Classification of Alcohols
Alcohols
I

Trihydric Poly hydric

Monohy dric Dihydric
alcohols alcohols
alcohols alcohols
(contains two -OH (contains (contains more than three
(co ntains only
groups on different three -OH groups on -OH groups on different
one -OH gr.)
carbon atoms) different carbon atoms) carbon atoms)
e.g. CH 3 CH 2 CH 2 - OH e.g. CH - CH - CH e .g. CH 2 - CH - CH 2 e.g. CH 2 -CH-CH-CH-CH-CH 2
I 2 2 I 2
I I I I I I I I I
(Propyl alcohol) OH OH OH OH OH OH OH OH OH OH OH

I (Propan-1 , 3-diol) (Glycerol) (Sorbitol)

J
Alcohols containing Alcohols containing
Cs 3 - OH bond Cs 2 -OH bond
(-OH gr attached to sp3 (-OH gr attached to sp 2 hybridised
(hybridized ca rbon atom) carbon atom)

J
l J
e.g. CH 2 = CH - OH (Vinyl alcohol)

Alkyl Allylic B enzylic

alcohols alcohols alcohols
(-OH gr. attached to sp 3 (-OH gr. attached to sp 3 (-OH gr. attached to sp3
hybridized C-atom hybridized carbon atom next hybridized C-atom next
of alkyl gr.) to the C = C bond) to an aromatic ring)
20 e.g. CH 2 = CH - CH 2 - OH CH 3
e.g. CH 3 - CH - CH 3 (Prop -2-en - 1-o l) I
I ~ CH-OH
OH
(sec . Propyl alcohol) e .g . ~

( 1- Phenylethanol)

(510)
 ~ Phenols and Ethers
AfcoIio I.. 511

j:IC:Nomenclature of ~
Accordi n g to IUPAC s vstem I
' a coho! a . II '
Sr. re ca ed a lka nol s', by replacin g ' e' of alkane by ' ol'
No. Alcohol Common name IUPAC name
1. CH3 - CH2 - CH - CH (Alkyl alcohol) (Alkanol)
2 2 - OH
2. CH3 - CH - CH n -Butyl alcohol Butan - 1-ol
I 2 - OH
CH 3 iso-Butyl alco hol 2-Methyl butan - 1-ol
3. CH 3 - CH - CH
I 2 - CH 3
OH sec-Butyl alcohol Butan -2-ol
4. CH 3
I t-Butyl alcohol
CH 3 - C - OH 2- Methyl propan-2-ol
I
CH 3
5. CH 3
I neo-Pentyl alcohol
CH3 - C - CH2 - OH 2, 2-Dimethyl propan-1-ol
I
CH 3
6. OH
-

7.
QCH
CH 3 CH
3
CH CH 3
3-Methyl cyclohexanol

I I - Butane-2 , 3-diol
OH OH

Preparation of Alcohols \
• Alcohols are generally prepared by -
(1) Hydrolysis of alkyl halides:
!:,
RX + aq . KOH ~ ROH + KX
(2) Hydration of alkenes:
CH 3
Hp I
RCH = CH 2 + H2SO4 ~ R - TH - HSO4 R-CH-OH
boil
(Alkene) (Alcohol)
CH 3
(3) Hydroboration-oxidation of alkenes:
BH 3 3HP2
3CH 3 CH = CH 2 THF (CH 3 CH 2CH 2hB Olf' l 3CH 3 CH 2 CH 20H + H 3B0 3

(Propene) (Propanol)
(4) Reduction of carbonyl compounds:
Ni or Pt or Pd catalyst
RCHPH
RCHO + 2H NaBH 4 or LiAIH 4 or Na/C 2 HsOH

(5) Addition of Grignard's reagent:

RMgX
dry ether "- c / Hp
"'
/
C = 0 + RMgX / "- R H'

* Mechanism of Hydration of alkenes:

Step-I: Attack of H30+ and formation of carbocation:
H 0 + H+ --) H30+
2
H
\ C ,f~
c/ +-.....,H
~ I
- o+-
/ "' .. H ___::,.
~
512 Ullom '.1· MHT-CET (Chem .
1.ltry)

Step-ll: Nucleophilic attack of water on carb~~ation:

H II JI
,...~
I -1 /✓ .. I I I
- C - C ➔ H20 _ , - C- C- 0 I- H
"- .. '°" I I
Step-ill: Deprotonation to form alcohol:
H H H
I I I.. .. I I .•
- C- C- C- H+H O ~ - C - C - OH+ Hp '
I I •· ? ,. I I .. .
Structure of Alcohols
• R - OH bond angle has tetrahedral value
E 3
Cl. • Both carbon and oxygen of C - OH are sp hybridised. 3 3
N

H"'
H/ i
~
108 .90 H
pm
•
•
So - OH group attached to carbon by a -bond (overlap of sp C and sp 0) .
Bond angle C - 0 - H is slightly less than tetrahedral as oxygen atom cames two
lon e pairs of e·, so repulsion between these lone pair e· occurred. .
H • H _ o bond in alcohols is polar covalent bond and hydrogen carnes a partial
(Structure of methanol) I'>+ &--
positive charge (H - 0 )

f M Physical Properties of Alcohol

(1) State : Lower members are colourless liquid and distinctive smell while higher members are colourless solid.
(2) Boiling point : Presence of polar - OH group and hydrogen bonding in alcohol results higher boiling point than
alkanes, alkyl halides , aldehydes, ketones and ethers.
Number of C-atom increases---) BP increases (due to increase in van der Waals forces).
Branching in C-atom increases---) BP decreases (due to decrease in van der waals forces).
Number of -OH group in creases---) BP increase s
(3) Solubility :- Lower alcohols are highly soluble in H2 0
- Solubility of alcohol is due to for mation of intermolecular hydrogen bonding between R - OH
and Hp.
R R
&-
/ o,_
I I&-
✓ 0- ,
/ ', , . O+ O+ (~ , 0t. +
H ~• H ,H 'H ,

~ o6 - - - - ~ ' ' o6- -/

1 I
R Hydrogen bond s R

Fig. Intermolecular hydrogen bonding in alcohols

Th e solubnity decreases with increase in size of an alkyl groups .
For isomeri c al cohols , solubility in creases with increase in branching: 1o < 20 < 30.
(4) Density : Alcohols are ligh ter than water.
(5) Toxicity : All al cohols are toxic except ethanol.
 /.
l·/)/10'·
J ,, , " .. 5l3
.l1,

- _ : _ - - - - - - - 1 Alcohols (R - OH)
t
, (1'1 aeactions involving (B) Reactions involving
breaking of O - H bond breaking of C - 0 bond:
Na or K

i{
~
MgorCa
Al
RO- Na+ H 2

(ROJiCa + H 2
HX / Anhyd. Zn C12
11
R-X+Hp

(ROb Al + H2
1
R-OH 7 RCOOH / H. PX5
RO- COR + H 2 o 1 - - - - - - - ~R - X + POX3 + HX
-~ { RCOCI / Pyridine
i.;:: RO - COR + HCl
·c::11)
t, (RC0) 2 0 / ff SOCl2
~ RO - COR + RCOOH ~, t - - -- - -- ~ RCl + SO 2 i + HCI
~ Pyridine

Cone. H 2 S0 4
-4_3_ K _ _~
i - - -4 ) c = c( + Hp

[OJ fO]
'---~ RCHO --~)RCOOH

K.Mn0 4 / H' or OH-

RCOOH
or ~Cr0 7 /H'
PCC
1or-CrO
- -C-H-N-HCI
- - -~ RCHO
3 5 5

L--_ _ C_u~/_S_73_K
_ ___,, RCHOorRCOR

* Mechanism of Dehydration of alcohols:

(1) Formation of protonated alcohols:
H H H
H H
I I ••~ fast , I I I+
H- C- C- 0 - H + H➔
H-C-C-0 - H
I I •• I I ••
H H H H
(2) Formation of carbocation:
H H H
r,il+ slow , I I+
CH 3 - CH 2 ..1. ~ - H H- C - C
I I
H H
(3 ) Elimination of proton:
H H
h.. I+ fast , H "-. / H
H-c l c ====-- C=C
I I H/ "- H
H H
(Ethene)
• . ase of dehydration of alcohols follow the order of stability of carbocations (as they are formed as an
E
intermediate).
30
alcohols > 2° alcohols > 1° alcohols
 Uttam 's MHT-CET (Chemist
514 'Y)

f I i e the more substituted alkene i

• Deh yd ration of alcohol a lways occurs in accorda nce with the Saytzef ru e · ., s
the major p rodu ct. t · ns
. . d carboca to .
• Dehydra tion of alcohols often give a lkenes denved from rearrange formed by elimination has greater
• Saytzeff's Rule: In dehydroge nation or in the dehydration, a n a lkene
number of alky l groups attached to the doubly bonded ca rbon atom.

CM Uses of Alcohols , . dyes drugs, cosmetics "

Solvent 1or o115, ' '"
Industrial solvent for fa ts, oil , gum s, etc.
Motor fuel
/ Dry cleaning
1 Thermometer

--. Perfumes and varnishes Beverages

Uses of
CH 3OH
Antiseptic
Antifreeze agent
Mouth washes
To denature ethanol Fuel

:::1 Starting material for Starting material for

CH 3 CJ, HCHO etc. CHCI3 , CH 3 COOH etc.

•u@
*
Phenols / . .
Phenols are the aromatic hydroxyl compounds m which one or more
(- OH) groups are directly attached to the I

aromatic nucleus. (i.e. benzene like ring)

Classification of Phenols /

Dihydric phenol Trihydric phenol

Monohydric phenol

e.g. (QJ
OH

00
OH

e.g.
J:oH
LSJ
J
~ OH
e.g.
HO@OH
OH

(Phenol) (a-Napthol) (Resorcinol) (Pyrogallol)

(Catechol) (Phloroglucinol)

•fM Nomenclature of Phenols

• The simplest hydroxyl derivatives of benzene is phenol also called carbolic acid . lt is its common name and also
an accepted JUPAC name .
As structure of phenol involves a benzene ring, in its substituted compounds the terms ortho (1, 2-
di substitu ted). meta (1 , 3-disubstituted ) and para (1 , 4-disubstitutedl are used in the common names .
Compound Common name IUPAC name

(fCH,
OH

I
o-Cresol 2-Methylphenol
~

(fNH,
I
OH

o-Aminophenol 2-Aminophenol
~

IE!! Structure of Functional group I

.
109° H

*
Q-o/.
- OH gr is attached to sp 2 hy bridised C-atom
* C - O bond Jen th in henol is less than in menthol alcohol
 . Phl'llo/s and Ethers
,4/tll/,OI., .
515
,·~ parti a. l ~. bond ch aracter
-- -on- - - - -- _
electrons of aromatic nng a nd sp2 h b . . account of the conJugation of un sh ,d -_-
- ---:------....:.._ Y nd1sed state f
~aratlon of Phenols
b
J are e pair of oxyg
o ca r on to which oxygen IS bonded.
.
,,n With n-

(ll rrolll cblorobenzene (Dow's proces■ ):

Cl ONa+

@+ 2Na0H
6 13 K
300atm . ➔
6
LgJ dil. HCI

(Chloroben zen e) (Phenol)

Frolll chlorobenzene (Raschig's me th od):
121
Cl OH

@ +H 20
Ca3(P04)2
698K
6
l9J +
HCI

(Chlorobenzene) (Phenol)
(31 From Benzene sulphonic acid:

ONa•
~ ,H ~ ;Na•

(Benzene
sulphonic acid)
+ NaOH
Neutralization
2 NaOH
fused/573K ©
ONa• OH

2@ + H 2 S0 4 ~
(di!. )
2@ + N32S0 4

(Phenol)
(41 From aniline (Diazotization) :
+
N = NCI- OH

~2 +
HN0 2 + HCI
273 -278K © ©
(Phenol)
+ N2i + HCl

(Aniline)
; {51 From cumene fCommercial method):
CH 3
OH

©
I
3

HC~ H + O, Co-naphthenate + CH 3COCH3

423K
(Phenol)
(Cumene)
Physical Properties of Phenol
~ It is colourless crystalline solid .
~ It has characteristic smell known as phenolic or carbolic odour.
➔ MP= 315K and BP= 458K
➔ High BP is due to intermolecular hydrogen bonding.
➔ Sparingly soluble in water but soluble in alcohol, ether etc.
~ It is weak acid , weaker than carbonic acid.
516 U11am 's MHT-CET (Chen-,,·.
HryJ

\.,.p Reacti~~Phenoi]

OH
S03'-I

© Zn SO (o-Ph enol sulphonic acid)

Co ne.~ ~
ZnO + - - 1\ ~ Room ternµ .
OH

Br * OH Br
3 Br21oq1
Cone. H SO4 ~ (p~Phcnol sulphonic acid)
< - - - - ----1 Room temp .

S0 3H
Br
(2 ,4 ,6-Tribromo phenol)

OH OH Na or ~ a (Sodium phenoxide)
NaOH
Br 2 in CS 2
0
~

Br
(major)
' l~ Br 273 K

1---_
N<Li---"'Cr
H2SO 4
--_,_P~1--;> rb
y1
(Benwquinone)

Phenol 0
OH NO (oxidation)

~.
2
dil . HN03
OH
298 K ONa
(major) NaOH ~ (i) CO 2 , 400K, 4-7 atm
& COOH
N0 2
l8J (ii)H '
(minor)
(Kolbe's reaction) (Salicylic acid)
OH
0 2N* Q N02 / one. HN0 3
cone. H2 N0 4 '~ -..-i'--,_..-~©f
ONa CHO-~- ~ CHO
HCl3 (i) H' -
N02 aq. NaOH (ii) H,0
340 K
(Picric acid) (Salicylaldehyde)
(Reimer-Tiemann
rea ction)

Distinguishing Tests Between Alcohol and Phenol

No. Test Alcohol Phenol

(1) Reaction with neutraJ FeC1 3 Do no give violet colour Give s violet colour
(Ferric chloride)
(2) Litmu s paper Test No action on litmus paper It turns blue litmus paper red
:. It is aJmost neutraJ :. It is weakly acidic in natu re

■ 1:@ Uses of Phenol

Explosive Plastic Bakeli te

Phenolphtha lein and

Selective weed killer certain dye

Drugs-Salicylic acid,
salol, aspirin Antiseptic - Dettol
 ~ phenols and Ethers
,4/cOI10I· ·
51 7

~thers . . --
Ethers a re denvat1ves of h ydroca rb . .
• ons in which a h ct .
(- OAr) group . Y rogen Atom 1s re placed by a n ::i lkoxy (- OR) or a n ary loxy
They have generaJ formu la C H. 0 h .
•
. 211, 2 w e re 11 is ulways grcutc r th a n I .
11

De nva tive of hydroca

- r b on = Hat om repla ced by OR (a lkox J
. .
De rivative of R- OH/ ArOH _ Y
- H atom repl a d 6
~ --+-----➔ Deriva tive of H O _ b ce Y R (Alkyl) / Ar (A ry l)
~ 2 - oth H ato
' Alkyl oxide R ms rep 1aced by R (Alky l) / Ar (Aryl)
i · 2 0/ Ar20 (Ary! oxid e)

1
Genera l formula = c n H2n +2 0
I j•@ Classification of Ethers
I
J
Simple/ Symmetrical ether
l
Mixed/Unsymmetrical ether
(Both - R or -Ar group attached to oxygen
(-R or -Ar group attached to oxygen are
are same)
different)
e.g. CH 3 - 0 - CH 3
e.g. CH 3 - 0 - C 2 H 5
(Dimethyl ether)
Eth I meth I ether

:- Nomenclature of Phenol

Ether Common name

alkane
l r1 Dieth 1 ether
l 2 3
l (2) CH 3 - C - CH 2 CH 2CH 3 Methyl n-propyl ether 1- Methoxy propane
1
CH
2 I 3
(3) CH 3 - 0 - C - CH t -Butyl methyl ether 2-Methoxy-2-methyl propan e
I 3
3
CH 3
Metho benzene

ffM Structure of Functional group

0
(1) Same tetrahedral geomet ry as H 2 0
~
CH.i 111 .7 CH .1
(2) Oxygen atom is sp 3 hybridi s ed (repulsive interaction between two R)
(3) C - 0 - C bond angle is slightly greate r than tetrahedral angle

If#
• M
Metamerism I
I c mula but diffe re nt a lkyl groups a ttac hed on either side of the oxygen
. .
etamers: They have same mo Iecu ar or
atom.
e.g. Metamers of C 4 H JOO are given below :
(1) Diethyl ether C 2H 5 - 0 - C 2H s
(2) Methyl n -propyl ether CH 3 - 0 - CH 2CH 2CH 3
(3) lsopropyl methyl ether CH 3 - CH - 0 - CH 3
I
CH 3
~I X t J11om ·.1 Ml /7'-( 'FT (Ow1111 111:v)

l1omerJ1m In Ether

J l
Funotlonal laomeriam
Chain laomerlam
I iJI diffi·rc nl
Su m c 11 H<v l 141Ol1p 011 c·11 lw1 s 1dC' ol oxyg(' n Snuw 111 ok1 ·1tl111 for ,nu I11 1 .

but ciilk1 111 nri 11 11 gt·1n t· 111 nl e n , l>on chri , 11 , ,111•1 '1 · ll w1 nnd monuliydrir: ulcoho l)
I 11
I 111 11'111 ,, . \ J
e.g. Cll 0 Cll }.' 11 1 C' ll 1 11 11d ( 'II () e ll (dirn cllly l e the r) 1Jnc
1 «,,g, I I

CII - 0 CII CII ( ' lf ( ' 1I/J II (1 •1h11 110I)

1
I I I

c11 1
B1111 Methods of Preparation of Ethers
~
J, t (3) From Alcohol and
( 1) From Alcohol (2) From Alkyl halide
Diazomethane
(Willi amson's sy nth es is )
(De hydrnt1o n)

2 R - OH
(Alcohol)
co n e . H)S0,1
4 13 K l ,:d~~:a:\t:;;' ~l
a lkoxide) ha li de)
R - OH + CH 2 N2
(Alcohol) (Di azomet han e)
R - 0 - CH 3 + N2 i
R - 0 - R + H2 0 R - 0 - It + NaX (Eth er)

I
1
•
(Eth er)
Limitation• of preparation methods:
(a} From alcohol:
(El her)
.
( J) As temperature in creases, formation of alkenes predominates.
O
(2) Ethers can be obtained using J alcohols, 2° and 3° alcohols from alkenes .
(3) On ly simple ether can be obtained .
(b} From alkyl halide: ( J) Best yie ld of un symm etri cal eth er wh en 1° R - X and 3° R - ON a are used .
(2) But if 3° R - X and 1° R - ON a u sed th en 3° (Tertiary) alkyl halides
und ergoes elimination and form aJkenes .
(c} From R - OH and CH 2 N 2 : On ly methyl eth ers are obta in ed.

ffW Physical Properties of Ethers /

/1) - C - 0 - C - bond angle in et her is 111.7°.
/2/ It 's p olar molec ule with dipole moment 1. 18D.
(3) Ethers are soluble in water to some extent as it ca n form hydrogen bonding with H2 0.
(4) BP of eth ers are slightly high er than aJkanes but lowe r th a n alcohols as hydrogen bonding present in alcohols .

f {•A Chemical Properties of Ethers /

( 1) Action of HX: (a) Simple ether:
cold
R - 0 - R + HX R - OH+ R - X
R - 0 - R + 2HX ~ 2RX + H2 0
(b) Mixed ether:
cold
R - 0 - R' ➔ HX R - X + R' - OH
(lower) (hi gh er)
R - 0 - R' + 2 HX ~ R - X + R' - X + H 0
2
(a) Simple ether:
di /. l-1 2 S0 4
R - 0 - R + Hp 2 R - OH
ti , press ure
(b) Mixed ether:
dil. l-1 2 S0 4
R - 0 - R' + H20 R - OH+ R' - OH
ti, press ure
 \
phenols and Ether~ 519
ilcOho/s .

uapbillc Substitution Reactiona:

.,,131 &lee
OC H3 OCH 3

Br,/ Ethano1c acid

7
A I
~ Br
or Br,J CS ,
~ ~
o- Brom oan1sole
Br (:'Amor}
p -Bromoanisole
(Major)

OCH 3 OCH 3
,,....__ / CH ,
CH Cl ~ -1/"
3
-:--:---:--"---~
Anhyd . AlC1 / CS3
> '
2
y I, ~
'V -

2- Methoxy toluene
CH 3 (M inor)

&-
4-Methoxy toluene
(Major)

OCH 3
(Anisole)
--.-:-C.:-H-;3C~O-:--;C~l; ----~
Anhyd . AlC1 3
) !iH
y, ~ COCH 3

~
2-Methox:,· acetophe none
COCH 3
(Minor)
4- Methoxy acetophenone
(Major)

OCH ,

+ (f
2- Nitroanisole
I
~ O--

N0 2 (Minor)
4-Nitroanisole
(Major)

fM Uses of Diether
J
"
Industrial solvent Solvent in reaction Refrigerant Natalite
of Grignard Reagent lfuel-substitute of petrol)
mix. of dietl1y\ ethe r and
C:H 50H

IJ:i Crown Ether \

Ill Macrocylic polyethers containing large rings of carbon and oxygen .
; (2) Discovered by Charles J. Pederson .
3
1 ) Name= n-Crown-m where n is the total no . of C and ~l~
i - I
(4) (o
oxygen and mis the number of oxygen .
Crown ethers form strongly bonded complexes with metal O
) t 8-crown-6-ether

(5) Th
ions or NH 4
ion by co-ordination through oxygen .
ey are used to increase the solubility of ionic salts or
organic solvent.
lo) They are used to separate readioactive elements from
1v V O
O
l
0 -1 O>..')'gen atoms
• - CH~- groups

I
I

radioactive waste.
18
crown-6-ethers are used to extract Cesium and Strontium .
000
I