ALCOHOLS, PHENOLS and ETHERS

Methods of preparation of ALCOHOLS

From alkenes
Acid catalysed hydration
Reagents
H2O/H+
Remarks
Rearrangement
Markonikof rule followed
possible
Oxymercuration-Demercuration
Reagents
i)Hg(OCOCH3)/H2Oii)NaBH4
Remarks
No
Rearrangement Markonikof rule followed
possible
Hydroboration-Oxidation
Reagents
i)BH3ii)H2O2/OHRemarks
No
Rearrangement AntiMarkonikof rule
possible
followed
From reduction reactions
By reduction of aldehydes and ketones
Reagents
Pd, NaBH4,LiAlH4, Ni.
Remarks
Aldehydes give primary alcohols and ketones give secondary
alcohols
By reduction of carboxylic acids
Reagents
LiAlH4
Remarks
LiAlH4 is expensive,alternatively acid is converted into esters
and reduced with cheap Pd/C
From Grignard reagents
Reagents
RMgX followed by H3O+
Remarks
Formaldehyde gives 10alcohol
Acetaldehyde gives 20alcohol
ketone gives 30alcohol
Methods of preparation of PHENOLS
From
Haloarenes
Reagents
Chlorobenzene and NaOH heated to high temp
Remarks
Dows process
From benzene sulfonic acid
Reagents
Benzene sulfonic acid is fused with molten NaOH
Remarks
Benzene sulfonic acid is prepared from benzene and oleum
From benzene diazonium salt
Reagents
benzene diazonium salt is warmed with water
Remarks
benzene diazonium salt is prepared from aniline and NaNO 2
and HCl at 0 0 C to 50C
From Cumene(Cumene Hydroperoxide synthesis)

Reagents
Remarks

Cumene+O2+Free radical initiator+HCl

Cumene is also called isopropyl benzene which is made from
benzene and isopropyl chloride and AlCl 3.Acetone is the
byproduct

Methods of preparation of PHENOLS

From dehydration of ethers
Reagents
When alcohols are heated with conc H 2SO4 at 413K
dehydration between two molecules of alcohols takes place
and ethers are formed.
Remarks
At above 413K intramolecular dehydration takes place and
ethers are formed.
Williamson ether synthesis
Reagents
Sodium alkoxides are reacted with alkyl halides to give
ethers
Remarks
It is better to keep alkyl halide primary.If tertiary halide is
used elimination to alkene take place.Vinyl halides and aryl
halides are unreactive.
Reactions of ALCOHOLS
Acidic property.
Reagents
Sodium metal
Remarks
Alcohols react with Na to form sodium alkoxides.Phenols can
be made sodium salt with NaOH.The higher acidity of
phenols is because of stability of phenoxide ion by
resonance.
Dehydration
Reagents
Conc H2SO4, H3PO4, anh ZnCl2,Alumina etc.
Remarks
Reactivity of different alcohols is 30>20>10
Oxidation
Reagents
PCC, CrO3,KMnO4,K2Cr2O7 and Copper
Remarks
PCC converts 10 and20 alcohols to aldehydes and
ketones.CrO3,KMnO4,K2Cr2O7 will oxidize aldehydes further to
carboxylic acids. Copper oxidizes 10 and 20 alcohols to
aldehydes and ketones. 30 alcohols are dehydrated to
alkenes.
Esterification
Reagents
Alcohols can be converted to esters by reacting with
carboxylic acids in the presence of little acid
Remarks
Esters can also be made from anhydrides and acid chlorides.
Reaction with phosphorous halides. Refer alkyl halides.
Reactions of PHENOLS
OH group of alcohols is highly activating ortho para directing group.

Nitration
Reagents
Remarks

Bromination
Reagents
Remarks

HNO3
Dilute HNO3 at low temperature gives mixture of ortho and
para nitro phenols which can be separated using steam
distillation ortho isomer is steam volatile. Conc HNO 3 give
picric acid.
Br2
Bromination of phenol with bromine water gives 2,4,6tribromophenol which is
white solid.Bromine in organic
solvent like CCl4 gives ortho and para bromo phenols.

Kolbes reaction
Reagents
NaOH and CO2
Remarks
The product is the ortho substituted compound called
salicylic acid (2-hydroxy benzoic acid)
Reimer Tiemann reaction
Reagents
CHCl3 and NaOH.
Remarks
R-T reaction converts phenol into salicylaldehyde.If CCl 4 is
used salicylic acid is the product.
Reduction
Reagents
Zn
Remarks
Phenol is converted into benzene
Reactions of ETHERS
Hydrolysis
Reagents
H2O/H+
Remarks
Hyrolysis of ethers with aq acid give 2 molecules of alcohols
Cleavage
Reagents
Conc HI
Remarks
Symmetrical ethers give one molecule of alcohol and one
molecule of iodocompound. In the case of unsymmetrical
reagents bulky substituent bicomes alcohol and the other
becomes halide.

SO3Na

(i) H2SO4/heat

(ii) NaOH

2NaOH
fuse/350oC

Cl
+

NaOH

NCl

350oC
high pressure

H3O +
heat

benzenediazonium
chloride
AlCl3/ether

heat

Cl

AlCl3

Cl

AlCl3

O2(air)

heat
H3O /heat
cumene

OH
2

2Na

NaOH

OH

RMg X + HCHO
RMg X + R1CHO

i) conc. H2SO4

+ H2O

ii) aq./70o C

Hg(CH3.COO)2 /H2O
R

NaBH4

BH3
..
H2O2, OH

NaBH4

O
O
R

4[H]

OH

O
RMg X + R1

C R2

ketone

LiAlH4

RO H + 2Na
O
R1O

H + R2

H+

OH

+ HBr
OH

H2SO4
Heat
O

CH3 CH2 O

H + HO

Cr

OH

O
(CH3)2CHOH

acidified K2Cr2O7

isopropyl alcohol
OH

H3PO4

Na
CH3COOH/Conc.H2SO4
CH3COCl / Pyridine
(CH3CO)2O
RMgX
Conc. HCl / Anhy.ZnCl2
PCl5
KBr/Conc.H2SO4
KI/Conc.H3PO4
PX3
SOCl2/Pyridine

C2H5OH
Ethyl alcohol

Cu /573
[O];K2Cr2O7/H2SO4
383 K

Conc.H2SO4

410 K
433 K

HI
HI; Red P
NH3; Al2O3,633K
513 - 523 K ; Al2O3
CaOCl2

Bromination
Br2/CCl4
0oC

Bromine water
Br2/aq

OH

Nitration
dil HNO3

ONa

phenol
+

CHCl3 +

0oC

2NaOH
Nitrosation
HNO2/6-7oC

ONa
+

CO2

120-140oC
6-7 atm

conc HNO3 +
conc H2SO4/heat

ONa
NaOH

CH3I

H2 O

NaI

CH2N2
ether

(CH3)2SO4/NaOH

OH

CH3COCl

(CH3CO)2O

phenol
C6H5COCl
benzoylation

O
Cl

S
O
TsCl

zinc dust
distillation

NH3
ZnCl2/300oC