ALCOHOLS

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 ALCOHOLS
 Alcohols are the organic compounds
containing the hydroxyl (-OH) group
attached to the saturated carbon.

 The -OH group acts as a functional

group of alcohols that determines the
characteristic properties of alcohols.
 Alcohol and phenols are derived from
water by replacing H atom of water
with alkyl or aryl group 3
Classification of Alcohols

 Monohydric alcohols are classified as

primary alcohols
 Secondary alcohols
 Tertiary alcohols
Depending upon whether the -OH is
present on primary, secondary, and tertiary
carbon

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Types of alcohols

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Structure of alcohol
 In alcohol both carbon and oxygen
atoms are sp3 hybridized with C-O-H
bond and of 108.5° which is slightly
greater than water due large alkyl
group

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Physical properties
 Upto butane they are colourless
liquids with sweet smell , higher
members are waxy solids
 They have higher boiling points due to
H-bonding , boiling point increase as
number of carbon atoms increase in
chain
 They are soluble in water but solubility
decrease as number of carbon atoms
in chain increase
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Water derivatives

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Acidity of alcohols

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Acidity of alcohol
 Reaction of anhydrous alcohol with with
metals like Na or K to form alkoxides
CH3 − CH2 − OH + Na → CH3 − CH2 O𝑁𝑎 + H2

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Preparation of acohol
 Hydratio n of alkene :
In presence of conc: sulphuric acid at100℃
.

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Preparation of acohol
 Hydrolysis of alkyl halide in presence of
NaOH , KOH

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Preparation of acohol
 Reaction of Grignard reagent with aldehyde
and ketones produce unstable addition
product , they on further hydrolysis will
produce primary , sec: , and tertiary
alcohols

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Preparation of alcohol
 Reaction of Grignard reagent with
aldehyde and ketones

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Preparation of alcohol
 Reduction of aldehydes and ketones:
In presence of NI , Pt , Pd catalysts

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Preparation of alcohol
 Reduction of aldehydes and ketones:
In presence of LiALH4 or
NaBH4 (sodium borohydride). Aldehydes
give primary alcohols and ketones give
sec: alcohols

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Preparation of alcohol
 Reaction of R-Mg-X with esters to
form ketone , this ketone further
reacts with Grignard reagent to form
tertiary alcohol on hydrolysis in acidic
medium.
R-Mg-X + R-COO-R → R-CO-R
R-CO-R + R-Mg-X →
intermediate addition product
intermediate addition product + H—
OH → Ter : alcohol 18
Preparation of alcohol from ester
R-Mg-X + R-COO-R → R-CO-R
R-CO-R + R-Mg-X →
intermediate addition product
intermediate addition product + H—
OH → Ter : alcohol

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Preparation of alcohol
 From reduction of carboxylic acids and esters: in presence
of strong reducing agent like LiALH4 to form primary
alcohols

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Preparation of alcohol
 From reduction of carboxylic acids and esters: in presence
of strong reducing agent like LiALH4 to form primary
alcohols
 esters give mixture of alcohols

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Reactivity of alcohols
 Alcohol are reactive due to polarity of
C-O and O—H bond
 Reactions of alcohol are substitution
reaction either electrophilic or
nucleophilic
 Splitting of C—O bond are nucleophilic
 Splitting of O—H are electrophilic in
nature

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Reactivity of alcohols
 Towards nucleophilic attack (C—O bond
splitting)
 Tertiary > Secondary > Primary
Because alkyl groups are electron releasing
group

 Towards electophilic attack (O-H bond

splitting)
 Primary > Secondary >Tertiary
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Reaction with halogen acid(HX)
 With lucas reagent (mixture of conc:
HCL and ZnCL2 ) to produce alkyl
halide .

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Chemical properties
 Reaction of alcohol with thionyl chloride 𝑆𝑂2 𝐶𝐿2 in pyridine
solvent

 Reaction of alcohol with P𝐶𝐿3 𝑎𝑛𝑑 𝑃𝐶𝐿5

3CH3 − CH2 − OH+ P𝐶𝐿3 → CH3 − CH2 −CL +
H3 PO3

𝐶𝐻3 − 𝐶𝐻2 − 𝑂𝐻+ P𝐶𝐿5 → 𝐶𝐻3 − 𝐶𝐻2 −CL +

𝑃𝑂𝐶𝐿3 +HCL
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Acid catalyzed dehydration
 While the dehydration of primary
alcohols requires high temperatures
and acid concentrations, secondary
and tertiary alcohols can lose a water
molecule under relatively mild
conditions.

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Acid catalyzed dehydration
 Reactivity order

 3°alcohol > 2°alcohol > 1°alcohol >

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Chemical properties alcohol

 Oxidtaion : primary(form aldehyde) and sec:

alcohols(form ketones) produce carboxylic
acids through aldehyde and ketone
intermediate respectively.
 Tertiary alcohol cannot be oxidized due
absence of H on C atom to which –OH is
attached.

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Oxidation of alcohol

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Cleavage of 1,2-diols
 1,2-diols or vicinal diols react with per-
iodic acid , this reaction involve
oxidative cleavage of two carbon
atoms of –OH groups to produce
carbonyl compounds aldehyde or
ketones or both it depends upon
number of alkyl groups attached to
carbon atom bearing –OH group.
 In this reaction per-iodic acid(HIO4 ) is
reduced to iodic acid (HIO3 ).
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Cleavage of 1,2-diols

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Cleavage of 1,2-diols

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Cleavage of 1,2-diols

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Iodoform test (oxidation)
 Methyl alcohol doesnot give iodoform
test
 Alcohol in which –OH is attached on 2nd
carbon(sec: acohols) of the chain give
iodoform test
 In primary alcohols Only ethyl acohol give
iodoform test

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Ethyl alcohol
 Rectified spirit contain 92—95% ethyl
alcohol

 Absolute alcohol is 99.9% pure ,it is

obtained by absorbing water of rectified
spirit with CaO..
 Denatured alcohol : it is 85% ethyl alcohol
, 11% water and 4% methyl alcohol

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Uses of alcohol
 Ethanol used as solvent bevrages
 Ethanol used in low temperature
thermometers
 Ethanol used in perfumes (deodorized
alcohol)
 Ethanol used as fuel
 Ethanol used as solvent for resins ,
gums etc
 lacquers and varnishes
 Methyl alcohol used ethyl alcoho to
render it unfit for human use 36
Acidic strenghth

 Carboxylic
acid>phenol>water> 𝒂𝒍𝒄𝒐𝒉𝒐𝒍

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 PHENOL
(carbolic acid which means
Carbo = coal, oleum = oil)
also called as benzenol

……….

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Phenol
 Organic aromatic compounds in which
OH group is attached to benzene

 Phenol was isolated by Rung from

coaltatr in 1834
 Phenols may be monohydric , dihydric
or trihydric on the basis of –OH group
attached to aromatic ring

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Phenol

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Structure of phenol
 Oxygen atom of phenol is sp3 hybridized
with C-O-H bond angle of 109.5°

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Physical properties of phenol
 It is white crystalline soild
 Phenol has higher boiling point due to
hydrogen bonding
 It is toxic and corrosive in nature it
cause skin burns and tissue damage

 It is partially soluble in water due

hydrogen bonding

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Acidic strength of phenol
 Phenoxide ion is more stable than
ethoxide ion due negative charge
delocalized charge distribution through
resonance

 Carboxylic
acid>phenol>water> 𝒂𝒍𝒄𝒐𝒉𝒐𝒍

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Preparation of Phenol
 By Dow’s process (from
chlorobenzene)
 Chlorobenzene, obtained by the
chlorination of benzene, is treated with
sodium hydroxide to form sodium
phenoxide.
 Sodium phenoxide, in reaction with
dilute hydrochloric acid yields phenol.

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Preparation of Phenol
 By Dow’s process (from
chlorobenzene) at 350C and
150Atm

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Preparation of Phenol
 From benzene sulphonate : at 300C-
350C , on acidification produce phenol

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Hydrolysis of diazonium salt

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Reactivity of phenol
 Phenol is more reactive than benzene
because –OH group is ortho , para
director and ring activator .

 Phenol has higher boiling point than

alcohol

 Reaction of phenol either involve –OH

group or it involve benzene ring
through electrophilic substitution 48
Chemical properties of phenol
 Nitration: Phenol reacts with
concentrarted nitric acid in the
presence of sulphuric acid to form
2,4,6-trinitrophenol (picric acid).

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Chemical properties of phenol
 Nitration:
 But in the presence of dilute nitric
acid, it gives a mixture of ortho and
para nitrophenol.

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Chemical properties of phenol
 Sulphonation :
 At 15 to 20C Ortho phenol sulphonic
acid is major product
 At 100C para phenol sulphonic acid is
major product

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Oxidation of phenol
 With K2Cr2O4 as oxidizing agent and
sulphuric acid as catalyst phenol oxidized to
yellow colored benzoquinone (conjugated
diketone) . Benzoquinone is used to
prepare nylone , polyester polymer it is also
used photographic developer

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Reaction of phenol with Na metal
 This reaction show acidity of phenol with
sodium metal

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Uses of phenol
 Used as antiseptic and disenfectant
 Used as ink preservative
 Used to prepare lozenges , ointments, and
gargles
 Used to prepare aspirin(acetyl salicylic
acid ) 2-Acetoxybenzoic acid

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Identification alcohol and phenol
 Sodium metal test: brisk effervescence(the fast or
vigorous evolution of a gas in a chemical reaction.) in solution
is produced indicate presence of alcoholic group

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Identification alcohol and phenol
 Ester test: reaction of alcohol with
acetic acid with alcohol in presence of
sulphuric acid produce friuty smell
ester indicate presence of alcoholic
group

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Identification alcohol and phenol
 Ferric chloride test:
Phenol react with FeCL3 solution will
form ferric phenoxide complex which
has violet , purple or blue colour
indicate presence of phenol

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Identification alcohol and phenol
 Bromine water test:
 This is the electrophilic substitution reaction
of phenol , in this reaction brown color of
bromine disappaer and appearance of
white precipitates of 2,4,6-tribromophenol

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ETHER

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 Ether
 Ethers are organic compounds with
general formula R-O-R .
 In ether two alkyl groups are attached
with oxygen atoms ,
 Ethers are less reactive compounds
except combustion reaction ethers are
inflammble .

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 Ethers
 Ethers are generally classified into two
categories on the basis of substituent
groups attached:
 symmetrical ether (when two
identical groups are attached to the
oxygen atom)
 unsymmetrical ether (when two
different groups are attached to the
oxygen atom)
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Ethers

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 Structure of Ethers
 Ether and water have same Sp3
hybridization but have different bond
angle due to presence of different
groups or alkyl group around central
oxygen atom ethers have larger bond
angle than water and alcohol due to
presence of larger bulky alkyl groups.

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Preparation of ether
Dehydration of alcohol:
With excess of alcohol with concentrated
H2SO4 at 140℃ give ether

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Preparation of ether
Williamson synthesis :
Reaction of sodium ethoxide with alkyl halide
(primary) are 𝑆𝑁 2 reaction , sodium ethoxide
produce strong nucleophile ethoxide ion .
CH3 − CH2 − OH + Na → CH3 − CH2 O𝑁𝑎 + H2

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Preparation of ether
Williamson synthesis :
Reaction of sodium ethoxide with alkyl halide
(primary) are 𝑆𝑁 2 reaction , sodium ethoxide
produce strong nucleophile ethoxide ion .
CH3 − CH2 − OH + Na → CH3 − CH2 O𝑁𝑎 + H2

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PHYSICAL PROPERTIES OF ETHER
Dimethyl ether and ethyl methyl ether
are gase , but higher members are
volatile liquids
Due to absence of hydrogen bonding
ethers have low boiling points than
alcohol

They are moderately soluble in water

due to polar oxygen atom solubility
decrease as carbon atoms increase 67
Chemical reactivity of ethers
 Due to stability of C—O bond ethers
are less reactive towards electrophile
and nucleophile , due to low reactivity
ethers are used as solvent and
anaesthetic
 Ethers act as weak bases due to
presence of lone pairs on oxygen
atom , they react with acids to form
oxonium salts

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Chemical reactivity of ethers

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Uses of ether
 Used as solvent for gums , waxes
 Used as solvent in wurtz reaction

 Used as solvent in preparation of Grignard reagent 70

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