5.

Alcohols and Phenols

Prepared by
Joyce Tiong
For UEMK1013
October 2012
 Introduction to Alcohol
General formula of R-OH.
Has hydrogen bonding as intermolecular forces.
Soluble in water (or other polar solvents) due to
hydrogen bonds.
Ethyl alcohol (grain alcohol): found in alcoholic
beverages, cosmetics and drug preparations.
Methyl alcohol (wood alcohol): fuel and solvent.
Isopropyl alcohol (rubbing alcohol): skin cleanser
for injections and minor cuts.

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 Types of Alcohols
Primary (1o) alcohol:
-OH group attached to CH2.
eg.: CH3OH, CH3CH2OH.
Secondary (2o) alcohol:
-OH group attached to CH.
eg.: CH3CH(OH)CH3, CH3CH(OH)CH2CH3.
Tertiary (3o) alcohol:
-OH group attached to C without H atom.
eg.:
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 Structure of Alcohols
Structure resembles water, with alkyl group
replacing H atom of water.
C-O-H bond angle of 108.9o and C-O bond
length of 1.4 . C has larger covalent radius
than H.

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 IUPAC Nomenclature of Alcohols
Suffix ol.
General rule of naming remains the same
Example:

1-bromo-3,3-dimethylbutan-2-ol
trans-2-bromocyclohexanol
1-ethylcclopropanol
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 IUPAC Naming Priorities
Compounds with multi-functional groups should follow
the below naming orders:
Acids
Esters
Aldehydes
Ketones
Alcohols
Amines
Alkenes
Alkynes
Alkanes
Ethers
Halides

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 More Examples:

Alcohol and alkene is present in this compound.

Based on naming priority, alcohol has to be
named first.
Therefore the carbon that is attached to OH
should have the lowest C number.
This should be named: 2-penten-1-ol.

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More Examples:

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 Diols
When there are 2 OH.
Example:

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 Glycols
1,2 diols are also called glycols
Common names of glycols:

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 Phenols
-OH group attached to a benzene ring.
Naming starts with C attached to OH.
Example:

Common names: 1,2 = ortho-; 1,3 = meta-; 1,4 =

para-
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 Physical Properties of Alcohols
Higher boiling points than alkanes of similar
chain lengths due to the presence of hydrogen
bond.
Solubility in water decreases with the increase
of chain length.

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 Methanol
Naturally produced by destructive distillation
of wood chips in the absence of air.
Industrially synthesised:

Used as industrial solvent.

Cheap and less toxic.
Fuel for internal combustion of engines.

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 Advantages and Disadvantages of
Methanol
Advantages Disadvantages
Methanol produced fire can be Low energy content
extinguished with water
High octane rating Invisible flame
Low emission

*High octane rating: high compression fuel to give high performance

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 Ethanol
Produced by fermentation of sugar / starch.

Industrially synthesised:

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 Properties of Ethanol
Alcoholic solutions produced from
fermentation contains 12-15% of alcohol as
yeast dies at higher concentrations.
Hard liquors are produced via distillation,
producing 40% alcohol.
Azeotropic mixture of 95% ethanol + 5% water
boils at 78.15oC. Pure ethanol boils at 78.3oC.
Used as fuel: 10% ethanol in gasoline.

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 Acidity of Alcohols
Acidity of alcohol decreases as alkyl group
increases.
Hydroxyl proton of alcohol can be extracted by
a base to form alkoxide ion.

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 Formation of Alkoxide Ions
Alcohols react with sodium and potassium
metal to form alkoxides.

More hindered alcohols (eg. 2-propanol / tert-

butanol) react faster with potassium.

For alcohols that react slower, sodium hydride is

used (in tetrahydrofuran, THF).

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 Formation of Phenoxide Ion
Phenol is 100 million times more acidic than
cyclohexanol.
It forms phenoxide ions readily in the
presence of hydroxide ion (OH-).

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 Reactions of Alcohols (I)
Combustion
Complete combustion gives CO2 and H2O.
eg.:
CH3CH2OH + O2
CH3CH2CH2OH + O2

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 Reactions of Alcohols (II)
Subtitution
OH group can be substituted to give
halogenalkanes
Two methods:
(i) Reflux with conc. aqueous HX (HCl, HBr, HI) with strong
acid catalyst.
eg.: CH3CH2OH + HCl
(ii) Reflux with phosphorus halides (PX3 or PX5)
eg.: CH3CH2OH + PCl3
CH3CH2OH + PCl5 CH3CH2Cl + POCl3 + HCl

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 Reactions of Alcohols (III)
Oxidation
by heating with oxidising agents such as acidified
dichromate (IV) ions (Cr2O72-) or acidified
manganate (VII) ions (MnO42-).
Oxidation is indicated by:
Cr2O72- solution: orange to green
MnO42- solution: purple to colourless

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 Reactions of Alcohols (III):
Oxidation of Alcohols (I)
Primary (1o) alcohol:
Oxidised to aldehydes, further oxidised to
carboxylic acids.
eg.:
[O] [O]
CH3CH2OHCH3CHO H2O CH3COOH
ethanol ethanal ethanoic acid

[O] [O]
CH3CH2CH2OHCH3CH2CHO H2O CH3CH2COOH
propanol propanal propanoic acid
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 Reactions of Alcohols (III):
Oxidation of Alcohols (II)
Secondary (2o) alcohol:
Oxidised to ketones.
eg.: [O]
CH3CH(OH)CH3 CH3COCH3 H2O
2-propanol propanone

[O]

2-methylpentan-3-ol 2-methylpentan-3-one24
 Reactions of Alcohols (III):
Oxidation of Alcohols (III)
Tertiary (3o) alcohol:
Does NOT oxidise.
There is NO hydrogen atom to be removed from
the carbon atom of which the OH group is
attached.
eg.: CH3
(CH3)3COH OH
H3C CH3

2-methylpropan-2-ol 2-methylbutan-2-ol
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 Reactions of Alcohols (IV)
Dehydration to alkenes:
Heat with Al2O3 with H3PO4 in excess conc. H2SO4.
eg.:
CH3CH2OH CH2=CH2 + H2O
CH3CH2CH(OH)CH3 CH3CH=CHCH3 +H2O
or
CH3CH2CH=CH2
(CH3)3COH CH2=C(CH3)2 +H2O

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Reactions of Alcohols (IV).. contd
contd..
Dehydration to alkene
Dehydration of cyclohexanol with H2SO4:
(i) protonation of hydroxide
(ii) loss of water
(iii) deprotonation

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 Reactions of Alcohols (V)
Ester formation:
Method (I):
Esterification
Heat alcohol + carboxylic acid with conc. H2SO4 as catalyst

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 Examples of Esterification
Esterification::
(i) CH3CH2O-H + CH3COOH

(ii) CH3OH + CH3COOH

(iii) CH3CH2OH + HCOOH

(iv) CH3CH(OH)CH3 + CH3COOH

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 Ester formation (Method 2)
Acylation
Alcohol + acyl chloride Ester
No heating
Complete reaction

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Summary

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