ALCOHOL AND PHENOL
Alcohols:
➢Hydroxy derivatives of aliphatic hydrocarbons , in which one or
more hydrogen atoms are replaced by hydroxyl(-OH) group.
➢ general formula R-OH
➢Depending upon the number of hydroxyl group present in
molecules , alcohols are classified into mono- ,di- and trihydric
alcohols.
➢Alcohols with more than 3 –OH groups are called polyhydric
alcohols.
1. Monohydric alcohols: only one hydroxyl group
Example: CH3OH (methyl alcohol) CH3CH2OH (C2H5OH)
methanol Ethanol(ethyl alcohol)
2. Dihydric alcohols: two hydroxyl group
Example: CH2OH
CH2OH
1,2- Ethanediol ( ethylene glycol)
3. Trihydric alcohols: three hydroxyl group
CH2OH
1,2,3-propanetriol (glycerol)
CHOH
CH2OH
Nomenclature :
➢ Common name : alkyl alcohol
If alcohol contain 3 or more than 3 carbon atom, abbreviations n-,
sec-, tert- , iso- are used .
➢ IUPAC name : alkanol
Formula Common name IUPAC name
CH3CH2OH Ethyl alcohol Ethanol
CH3CH2CH2OH n-propyl alcohol 1-propanol
Iso-propyl alcohol 2-propanol
CH3 Sec-butyl alcohol 2-butanol
CH3CH2CHOH
CH3 Iso-butyl alcohol 2-methyl-1-propanol
CH3CHCH2OH
Tert-butyl alcohol 2-methyl-2-propanol
Classification of Monohydric alcohols:
➢ Depending upon the attachment of hydroxyl group monohydric
alcohol is classified as primary , secondary and tertiary alcohols.
1. Primary alcohols(1°): -OH group attached to primary carbon
atom. (-CH2OH) Example: CH3CH2OH ethanol
2. Secondary alcohols(2°): -OH group attached to secondary
carbon atom. (>CHOH)
Example:
2- propanol 2- butanol
(isopropyl alcohol)
3. Tertiary alcohols(3°): -OH group attached to
tertiary carbon atom.
2-methyl-2-propanol(Tertiary butyl alcohol)
Structural isomerism in alcohol:
➢ Three types of structural isomerism
1. Chain isomerism : due to difference in nature of carbon chain
attached to hydroxyl group.
CH3CH2CH2CH2OH CH3
n-butyl alcohol CH3CHCH2OH
Iso-butyl alcohol
2. Position isomerism : due to difference in position of –OH group
in the same carbon chain.
OH
CH3CH2CH2OH CH3CHCH3
n-propyl alcohol Iso-propyl alcohol
3. Functional isomerism : monohydric alcohol containing 2 or more
than 2 carbon atoms show functional isomerism . Functional
isomers differ in the nature of their functional group.
CH3CH2OH
CH3-O-CH3
Ethyl alcohol
Methoxy methane
(dimethyl ether)
Preparation of alcohols:
1. From alkyl halides: alcohols can be prepared from alkyl
halide by heating with aqueous KOH or NaOH or moist silver
oxide.
R-X + KOH R-OH + KX
Example :
C2H5Br + aq.KOH C2H5 -OH + KBr
+ aq.KOH + KBr
2- propanol
2. From aldehyde and ketone
i. By reduction: alcohols can be prepared from aldehyde and
ketone by reduction with may be both catalytic or chemical.
H2/Ni
CH3CHO or CH3CH2OH or
Acetaldehyde Ethanol
OH
LiAlH4 or CH3-CH-CH3
Acetone isopropyl alcohol
(2-propanol)
Aldehyde always gives primary alcohol and ketones gives secondary alcohol.
# how would you obtained 2-butanol by reduction method?
ii. By reacting with grignard reagent: alcohols can be prepared
from aldehyde and ketone by reacting with grignard reagent.
For example :
a) Formaldehyde with grignard reagent gives primary alcohol.
O
H2O/H+
=
H-C-H +CH3-Mg-Br + Mg(OH)Br
Formaldehyde ethanol
b) When aldehyde other than formaldehyde reacts with grignard reagent it
gives secondary alcohol.
+CH3-Mg-Br H2O/H+
+ Mg(OH)Br
c) When ketone reacts with grignard reagent it gives tertiary alcohol.
H2O/H+
+ CH3-Mg-Br
+ Mg(OH)Br
2-methyl 2-propanol
# how would you prepare following alcohol from grignard reagent?
i. ii. CH3-CH-CH2-CH3
OH
H2O/H+
+CH3CH2-Mg-Br
+ Mg(OH)Br
# starting from methylmagnesium bromide (CH3MgBr) how would you obtained
1. Ethanol
2. Propan-2-ol
O
=
3. From ester (R-C-OR’)
i. By reduction: alcohols can be prepared from ester by reduction.
For example:
O
=
LiAlH4
CH3-C-OC2H5 CH3CH2OH + C2H5OH
Ethyl acetate ethanol ethanol
(Ethyl ethanoate)
ii. By hydrolysis: alcohols can be prepared from ester by hydrolysis
in presence of acid or alkali.
For example:
O
=
H+ or OH-
CH3-C-OC2H5 or CH3COOC2H5 CH3COOH + C2H5OH
ethanoic acid ethanol
4. From amine: alcohols can be prepared from primary amine by
reacting with nitrous acid(i.e NaNO2 +HCl HNO2 +NaCl).
For example:
C2H5NH2 + HNO2 C2H5OH + N2 + H2O
Ethyl amine ethanol
5. From carboxylic acid: alcohols can be prepared from carboxylic
acid by reduction
For example
LiAlH4
CH3COOH CH3CH2OH
ethanol
6. From Alkene: alcohols can be prepared from alkene by reacting
with conc. H2SO4 followed by hydrolysis.
For example:
H2O
CH2=CH2 + H2SO4 CH3-CH2-HSO4 CH3CH2OH +H2SO4
Ethene or ethanol
OSO3H
CH3-CH2
Note: ethyl alcohol is the only primary alcohol which is obtained by
hydrolysis of alkene because addition of sulphuric acid to unsymmetrical
alkenes follow s Markovnikov’s rule.
H2O
CH3CH=CH2 + H2SO4 CH3-CH-CH3 CH3CH2CH3 +H2SO4
OSO3H OH
ii. By oxo-process: when alkene is heated with the mixture of carbon monoxide
and hydrogen in presence of cobalt carbonyl and aldehyde is formed which
on reduction gives alcohols.
For example: [Co(CO)4]2 H2/Ni
CH2=CH2 + CO +H2 CH3-CH2-CHO CH3CH2CH2OH
iii. By hydroboration: when alkene is reacting with borane,
trialkylborane is formed which on oxidation with an alkaline hydrogen
peroxide and alcohol is formed. This process is called hydroboration.
For example:
H2O2/OH-
CH2=CH2 + BH3 (CH3-CH2) 3B CH3CH2OH +H3BO3
Ethene ethanol
iv. fermentation: fermentation is biodegradation (slow
decomposition) of acomplex molecules by enzyme into simpler
molecules .in nepal alcoholic fermentation is made by molasses i.e
dark coloured syrupy liquid left after crstallization of sugar from
sugar cane.
a. Sugar :
For example:
C12H22O11 + H2O Invertase
From yeast C6H12O6 + C6H12O6
Sucrose glucose fructose
C6H12O6 zymase 2CH3CH2OH + 2CO2
ethanol
b. starch:
For example: diastase
2(C6H11O5)n + nH2O nC12H22O11
maltose
Physical properties :
1. State , colour and odour: lower members are colourless volatile liquid with
characteristic odour and higher members are colourless tasteless and waxy solid.
2. Boiling points :alcohols have higher boiling points than alkane and alkyl halides
due to that alcohol contains hydrogen atom attached to the strongly
electronegativity oxygen atom which formed strong hydrogen bonding among
alcohol molecules.
For example:
Compounds CH4 CH3Cl CH3OH
b.P 111 250 338
Boiling points of alcohols increases with increasing molecular mass because the
heavier molecular have stronger intermolecular force and higher energy is
required to separate the molecules .
For example: ethyl alcohol has higher boiling point than methyl alcohol.
………… O-H ………… O-H ………… O-H
Intermolecular H- bond
R R R
Among the isomeric alcohols, more branch alcohol has lower boiling point because of
lower surface area and then lower intermolecular force.
Primary > secondary > teritary..
3. Solubility:lower alcohols are highly soluble in water due to formation of hydrogen
bond between alcohol and water. But solubility of alcohol rapidly decreases as the
length of hydrocarbon chain increases because hydrocarbon part is non-polar and
water repelling character.
