THINGS TO LEARN :

 Classification of Alcohols
 Nomenclature and Structure
 Physical Properties of the Alcohols
 Uses of Some Common Alcohols
 Synthesis of Alcohols
 Chemical Reactions
 ALCOHOLS
are compounds of the general
formula R-OH, where R is any alkyl or
substituted alkyl group.
All alcohols contain the hydroxyl
(-OH) group, which, as functional
group, determines the properties and
characteristics of this family.
CLASSIFICATION
OF
ALCOHOLS
 1. According to the number of –OH group per
molecule
a. Monohydric alcohols

Ex:
CH3 OH methanol or methyl alcohol

b. Dihydric alcohols or glycols or diols

Ex:
CH2- CH2
| | 1,2 – ethanediol
OH OH
c. Trihydric alcohols or triols
Ex:
CH2-CH-CH2 1,2,3- propanetriol
| | |
OH OH OH
 2. According to the kind of carbon that holds the –
OH group
a. Primary alcohol
Ex: CH3 CH2OH

b. Secondary alcohol
Ex: CH3CH-OH
|
CH3
c. Tertiary alcohol
CH3
Ex:
| CH3CH2-C-
OH
|
CH3
 NOMENCLATURE AND STRUCTURE

The systematic name of an

alcohol consists of the
characteristic stem plus n –ol
ending. A numeric prefix
indicates the position of the –
OH group on a chain of 3 or
more carbon atoms.
 EXAMPLES IUPAC NAME

CH3CH2OH Ethanol

CH3CH2CH2OH 1- propanol

CH3CHCH2CH3 2- butanol
|
OH
2- chloroethanol
CH2-CH2
| |
Cl OH
 An alcohol containing a double
bond is named as an alkenol, with
numbers to indicate the positions of
the double bond and the hydroxyl
group. The –ol takes priority over –
ene; -ol appears last in the name,
and, where possible, is given the
lower number.
 3 2 1

CH2 = CH – CH2OH 2- propen-1-ol

4 3 2 1
CH2 = CH – CH – CH3
3-buten-2-ol
|
OH
 When two or more OH groups are
present, name endings such as diol
( for two –OH groups ), and triol ( for
three –OH groups ) are used.
Immediately in front of the name of
the parent portion of the alcohol,
numbers that show the location of the
–OH groups are written.
 3 2 1
CH3CH – CH2
1,2 – propanediol

| |
OH OH
4 3 2 1
CH3CH – CHCH2OH 1,2,3 – butanetriol
| |
OH OH

CH3
3 |2 1 2 – methyl – 1,2 –propanediol
CH3 – C – CH2OH

|
OH
Physical Properties of
Alcohols
 exist in the form of liquids or solids

 In monohydric series, the lower members are volatile

liquids;
The higher members (from C14 and above) are
odorless and colorless waxy solids.
 methanol, ethanol and the propanol are completely
soluble in water, but alcohols of five or more carbons
show slight solubility

 have densities less than one

  
Uses of Some Common
Alcohols
Methyl alcohol
a very poisonous alcohol, is not used in medical
procedure because of the formation in the tissues
of toxic formic acid, which may first cause
blindness and then death

used as a solvent for shellacs and resins

used in the preparation of formaldehyde in

preparing denatured alcohol
Ethyl alcohol
used in alcohol sponge baths and rubs

it evaporates rapidly and consequently reduces body temperature

used as a solvent in tinctures (alcoholic solutions), essences and

extracts

an excellent rubbing liquid

used to preserve biological specimens

used in the manufacture of ether, chloroform, ethylene, iodoform

and many other preparations
 Glycerol
used in the preparation of toothpaste to keep them
moist and in the manufacture of hand lotions ; in the
manufacture of dynamite and other explosives

Ethylene Glycol
-used as a permanent antifreeze in
the radiators of automobiles
NAME THESE:

1. CH3
|
CH3CH2CH2CH2CH2CH2CHCH2OH
2 - methyl - 1 - octanol
CH3
2. |
CH3CCH3
|
OH 2 – methyl – 2 - propanol

CH3CH3
3. | |
CH3CH2CHCCH3
2,3 - dimethyl – 2- pentanol
|
OH
 4. CH3
|
CH3CHCHCHCHCH2CH3
| | | 3,5 – dichloro – 4 – methyl - 2 - heptanol
OH Cl Cl

5. CH3CH2CHCHCH2CH2OH
| | 1,3,4 - hexanetriol
OH OH

6. CH3CH2CH = CHCH2CH2CHCH3
|
5 – octen – 2 - ol
OH
7. CH3CHCH2CH2OH
| 1,3 - butanediol
OH
SYNTHESIS OF ALCOHOLS
 1. Hydrolysis of Alkyl Halides
This reaction occurs in the presence of base
catalysts in accord with the following equation

KOH,aq. EtOH
R – X + H2 O R – OH + HX

Tertiary alkyl halides may often be

hydrolyzed by merely heating with water.
Since alkyl halides are water insoluble,
however, the reaction is usually conducted
in aqueous ethanol, in which the reactants
form a homogeneous solution.
chloroethane
KOH, aq. EtOH
CH3CH2Cl + H2O CH3CH2OH + HCl
ethanol hydrochloric acid

CH3 CH3
| l
CH3 – C – Br + H2O CH3 – C – OH + HBr
| |
hydrobromic
acid
CH3 CH3
2 – methyl – 2 - propanol
2 – bromo – 2 – methyl propane
 2. Reduction of Carbonyl Compounds
Lithium aluminum hydride ( LiAIH4),
dissolve in ethyl ether, provides the
most convenient laboratory reagent for
the reduction of aldehydes, ketones,
carboxylic acids, and esters to alcohols.
Reduction may also be achieved
catalytically with H2.
a. Reduction of an aldehyde ( R–CH = O) will form a primary alcohol.

LiAIH4
CH3CH=O + (H) CH3CH2OH
ethanal ethanol

CH3CH2CH2CH=O + H2
Ni
CH3CH2CH2CH2OH
1 - butanal 1 - butanol

b. Reduction of a ketone ( R-CO-R) will form a secondary alcohol

CH3-C-CH3 + (H) LiAIH

CH3CHCH3
4
|| 2-propanone |
O OH
2 - propanol
Pt
CH3CH2CCH3 + H2
CH3CH2CHCH3
2 - butanone |
OH
|| 2 - butanol
 c. Reduction of a carboxylic acid (R-COOH) will form a primary alcohol.

LiAIH
CH3COOH + (H) 4
CH3CH2OH
ethanoic acid ethanol

d. Reduction of an ester (R-CO-OR) will form two primary alcohols. The

ester is cleaved at the C-O bond to yield the alcohol from which it was
derived, and an alcohol corresponding to the acid portion of the ester.
LiAIH
CH3 CO – OCH3 4
CH3CH2OH + CH3OH
Methyl ethanoate Ethanol and methanol

LiAIH
CH3 CO – OC2H5 4
2 CH3CH2OH
Ethyl ethanoate Ethanol
 3. Grignard Synthesis
The kind of alcohol that is obtained
from a Grignard synthesis depends
upon the type of carbonyl compounds
used: formaldehyde, CH2=O, yields
primary alcohols; other aldehydes,
RCHO, yield secondary alcohols; and
ketones, RCOR, yield tertiary alcohols.
 a. RMgX + formaldehyde, CH2 = O primary alcohols

CH3CH2CH2MgBr + CH2 = O CH3CH2CH2CH2OMgBr

methanal butoxymagnesium bromide
Propyl magnesium
bromide H2O
CH3CH2CH2CH2OH
1- butanol

CH3CHCH2MgCl + CH2 = O CH3CHCH2CH2OMgCl

| methanal 3- methyl-
| butoxymagnesium
CH3 CH3 chloride
2 – methyl-propyl
H2O
magnesium chloride CH3CHCH2CH2OH
| 3 – methyl – 1 - butanol
CH3
b. RMgX + higher aldehydes, RCHO secondary alcohols

CH3CHMgBr + CH3 CHO CH3CH – CH – OMgBr

ethanal | |
|
CH3 CH3 CH3
3 – methyl –
Propyl magnesium bromide butoxymagnesium bromide
H2O
CH3CH - CH – OH
| |
CH3 CH3

3 – methyl – 2 - butanol
c. RMgX + ketones, R- CO - R tertiary alcohols

CH3
|
CH3CH2Mgl + CH3 CO CH3 CH3CH2 C – OMgl
2- propanoate
Ethyl magnesium iodide | 2 – methyl –
CH3 CH3 butoxymagnesium
iodide

|
CH3CH2 C – OH H 2O

|
CH3
2 – methyl – 2 - butanol
 4. Hydration of Alkenes

When alkenes react with water in the

presence of an acid medium ( a 50% H2SO4 is
often used), alkenes are readily converted
into secondary or tertiary alcohols by direct
addition of H2O across the C = C double
bond. By this process there can be obtained
only those alcohols whose formation is
consistent with the application of
Markonikov’s rule. The only primary alcohol
 ethene 50% H SO
2 4
CH2= CH2 + H2 O CH3CH2OH
ethanol

50% H SO

CH3 CH2CH = CH2 + H2 O

2 4
CH3CH2CHCH3 l

1 - butene
OH

2 - butanol
CHEMICAL REACTIONS
1. Ester Formation
Esters are oxygen-containing products
formed by the reactions of alcohols with
inorganic and organic acids. Inorganic
esters result by intermolecular
dehydration on merely warming an alcohol
with a mineral acid, excess H2SO4
sometimes being added to combine with
the H2O formed.
Organic esters are formed by the reaction between an
alcohol and an organic acid. The process in forming
organic esters is referred to as O-acylation, since the acyl
group, RC=O, of the acid replaces the H of the – OH
function of the alcohol. H SO
2 4
CH3COOH + CH3OH CH3COOCH3 + H2O
ethanoic methanol Methyl
acid ethanoate
H SO
HCOOH + CH3CH2CH2OH 2 4 HCOOCH2CH2CH3 + H2O
Methanoic 1 - propanol Propyl
acid methanoate
 2. Reaction with Hydrogen Halides
Alcohols react readily with hydrogen halides to yield alkyl halides
and water. The reaction is carried out either by passing the dry HX
gas into the alcohol, or by heating the alcohol with concentrated
aqueous acid. Even though the aqueous hydrogen halides are
themselves strong acids, the presence of additional H2SO4 speeds up
the formation of alkyl halides.

The reactivity of the hydrogen halides is in the order HI > HBr

> HCl, while reactivity of the alcohols is 30> 20> 10

The least reactive HCl generally requires the presence of ZnCl2

for reaction with primary and secondary alcohols; tertiary
alcohols are converted to the chloride by simply being shaken
with concentrated HCl at room temperature.
 CH3CHOH + HBr CH3CHBr + H2O
| |
CH3 2 - propanol CH3
2- bromopropane

ZnCl,
CH3CH2CH2OH + HCl CH3CH2CH2Cl + H2O
1 - propanol
1 – chloropropane
 3. Dehydrogenation of Alcohols
Primary and secondary alcohols may be dehydrogenated to
aldehydes (R-CHO)and ketones (R-CO), respectively, if their
vapors are passed over certain metal catalysts at high
temperatures. These reactions constitutes a reversal of the
previously discussed catalytic hydrogenation and ketones.
1 - propanol
Cu-Ni, 3200
CH3CH2CH2OH CH3CH2CHO + H2
1 - propanal
Pt , heat
CH3CHCH3 CH3COCH3 + H2
| 2 - propanone
OH 2 - propanol
NOTE :
Tertiary alcohols, having no hydrogen atom on the carbon
bearing the –OH group, do not undergo dehydrogenation.
4. Oxidation of Alcohols
With the use of strong oxidizing agents such as KMnO 4,
K2Cr2O7 or Na2Cr2O7 in aqueous media, a primary alcohol is
oxidized to an aldehyde (R-CHO). An aldehyde, however, is
susceptible to further oxidation under these conditions and
a carboxylic acid (R-COOH)ultimately results.
aq. KMnO4 (O)
CH3CH2OH + (O) CH3CHO CH3COOH
ethanol ethanal ethanoic acid
For the purpose of converting a primary alcohol to only an
aldehyde, the particular oxidizing agent used is pyridinium
chlorochromate (C5H5NHCRO3Cl) in
C5H5NHCRO3Cl
CH3CH2OH + (O) CH3CHO
ethanol ethanal
 The oxidation of secondary alcohols by aqueous KMnO 4, K2Cr2O7 or Na2Cr2O7
yields ketones.

CH3CHOH + (O) CH3COCH3

| 2- propanone
2 - propanol
CH3
 Tertiary alcohols are resistant to chemical oxidizing
agents in alkaline or neutral media. In strongly acidic
medium, however, they tend to dehydrate to form an
alkene, which becomes oxidized into CO2 (for terminal
carbons), a ketone, and\or a carboxylic acid.

CH3 CH3
| KMnO , H SO
|
4 2 4
CH3- CH2CCH3 CH3CH = CCH3 + H20
|
2 – methyl – 2 - butanol 3 – methyl – 2 -
OH (O)
butene

CH3COOH + CH3COCH3
ethanoic acid 2- propanone
 CH3 CH3
| K2Cr2O7 , H2SO4 |
CH3C – CH3 CH3C = CH2 + H2O
| 2 – methyl – 1 -
(O) propene
OH
2 – methyl – 2 - propanol
CH3COCH3 + CO2
2 - propanone
 5. Dehydration of Alcohols
Alkenes that alcohols can be dehydrated by the action of heat and
an acid (H2SO4 or H3PO4) catalyst to give alkenes. The precise acid
concentration and temperature that work best have to be discovered
experimentally for each alcohol, because if the proper conditions are
not set correctly, a different pathway for dehydration can occur.
Water can be removed from within one alcohol molecule, yielding an
alkene, or between two alcohol molecules, yielding an ether. The
dehydration that produces an alkene usually requires a higher
temperature than that which gives an ether.
95% H SO , 170 C
0

CH3CH2OH
2 4
CH2 = CH2 + H2O
ethene
ethanol
H2SO4, 1400 C
2 CH3CH2OH CH3CH2 – O – CH2CH3 + H2O
ethanol Ethoxy ethane