ALCOHOLS

Alcohols are the family of compounds that contain one or more hydroxyl (-OH) groups attached to a single bonded
alkane. Alcohols are represented by the general formula R-OH.

functional group of alcohol

C O H

Alcohols can be viewed in two ways structurally: (1) as hydroxyl derivatives of

alkanes and (2) as alkyl derivatives of water.

CH3CH2 O H

ethane water
ethanol
(ethyl alcohol)

3.1 Nomenclature of Alcohols and Phenols

Step 1. Name the longest chain to which the hydroxyl (-OH) group is attached. The name for this chain is obtained
by dropping the final -e from the name of the hydrocarbon parent name and adding the ending -ol.

Step 2. Number the longest chain to give the lowest possible number to the carbon bearing the hydroxyl group.

Step 3. Locate the position of the hydroxyl group by the number of the C to which it is attached.

Step 4. Locate and name any other substituents.

Step 5. Combine the name and location for other groups, the hydroxyl group location, and the longest chain into the
final name.

Give the IUPAC names of the following alcohols

OH
CH3-CH2-CH2-CH2-CH2-OH CH3-CH2-CH2-C-CH2-CH3
CH2-OH

OH
OH
CH2CHCH3

OH

6. If there is more than one OH group, a counting prefix (di-, tri-, tetra-, etc.) is placed immediately in

front of the suffix –ol (diol, triol, tetraol, etc.).

– Usually, the final “e” of the parent hydrocarbon is not dropped (e.g., 1,2-propanediol).
– The position of each alcohol group is indicated by carbon number, separated by commas (e.g., 1,3-butanediol).

For cyclic alcohols, the carbon bearing the OH is numbered as “1.”

Provide acceptable IUPAC names for the following compounds

OH
OH
HO-CH2-CH2-CH2-OH CH2-CH-CH3
OH OH OH OH
OH

3.2 Classification of alcohols

Alcohols may be classified as primary, secondary or tertiary alcohols.

Primary alcohols are those in which the carbon attached to the OH is attached to 0 or 1 other carbon atom. In other
words, they are molecules in which the functional group is at the end of the chain.
H H H H H

R C OH H C C C C OH
H H H H
H
1o alcohol
1o alcohol 1-butanol

Secondary alcohols are those in which the carbon attached to the OH is attached to 2 other carbon atoms. In other
words, they are molecules in which the functional group is not at the end of the chain.
H H H H
H
H C C C C H
R C OH
H OH H H
R
2o alcohol
2o alcohol 2-butanol

Tertiary alcohols are those in which the carbon atom attached to the OH is attached to 3 other carbon atoms. In other
words, they are molecules in which the functional group is attached to a carbon which also has a branch attached to
it.
H CH3H H
R
H C C C C H
R C OH
H OH H H
R
3o alcohol
3o alcohol 2-methyl-2-butanol

3.3 Synthesis of alcohols

1. Hydration of alkenes
Alcohols are produced when alkenes react with cold concentrated sulphuric acid and then treated with water. On
adding the acid to the alkene the reaction mixture warms and a vigorous addition reaction takes place following
the Markonikov’s addition.
 C C + H2SO4 C C
H OSO3H

H2O + H2SO4
C C C C

H OSO3H H OH

Examples

H H H H H H
H2SO4 H2O
C C H C C H H C C H + H2SO4
H H H OSO3H H OH
ethene ethyl hydrogen sulphate ethanol

H2SO4 H2 O
CH3CH2CH CH2 CH3CH2CH CH2 CH3CH2CH CH2 + H2SO4

HO3SO H HO H
1-butene sec-butyl hydrogen sulphate 2-butanol

2. Reduction of carbonyl compounds with Lithium aluminium hydride and sodium borohydride

Alcohols may be synthesized by the reduction of carbonyl compounds ( aldehydes and ketones) by reducing
agents such as Lithium aluminum hydride and sodium borohydride. Primary alcohols are produced from the
reduction of aldehydes whereas secondary alcohols are obtained from ketones.

The limitation of this method is that it cannot be used to synthesize tertiary alcohols.

O H O H
LiAlH4 LiAlH4
R C H R C OH CH3 C H CH3 C OH
H H
aldehyde primary alcohol ethanal ethanol

O OH O OH
NaBH4 NaBH4
R C R R C R CH3 C CH3 CH3 C CH3
H H
ketone secondary alcohol propanone 2-propanol
Examples

3. Reduction of carbonyls with Grignard reagents

Carbonyl compounds react with Grignard reagents to form alcohols.
Methanol will react to form primary alcohols
Other aldehydes react to form secondary alcohols whiles ketones will produce tertiary alcohols.
 O H
(1) RMgCl
H C H R C OH
(2) H3O+
H
methanal Primary alcohol

O H
(1) RMgCl
CH3 C H CH3 C OH
(2) H3O+
R
ethanal secondary alcohol

O OH
(1) RMgCl
CH3 C CH3 CH3 C CH3
(2) H3O+
R
propanone tertiary alcohol

3.4 Reactions of alcohols

Alcohols are important in organic chemistry because they can be converted to and from many other types of
compounds. Reactions with alcohols fall into two different categories. Reactions can cleave the R-O bond or they can
cleave the O-H bond.

1. Dedydration of alcohols

Heating most alcohols with a strong acid causes them to lose a molecule of water and form an alkene:

HA + H2O
C C heat C C
H OH

The reaction is an elimination and is favored at higher temperatures. The most commonly used acids are the Brønsted
acids such as sulfuric acid and phosphoric acid.

1. Esterification

Esters are compounds that are commonly formed by the reaction of oxygen-containing acids with alcohols. The ester

functional group is

Alcohols can be converted to esters by means of the Fischer Esterification Process. In this method, an alcohol is
reacted with a carboxylic acid in the presence of an inorganic acid catalyst.

Because the reaction is an equilibrium reaction, in order to receive a good yield, one of the products must be removed
as it forms. Doing this drives the equilibrium to the product side.
The mechanism for this type of reaction takes place in seven steps:

i. The mechanism begins with the protonation of the acetic acid.

ii. The π electrons of the carboxyl group, , migrate to pick up the positive charge.

iii The oxygen of the alcohol molecule attacks the carbocation.

The oxonium ion that forms loses a proton.

One of the hydroxyl groups is protonated to form an oxonium ion.

An unshared pair of electrons on another hydroxy group reestablishes the carbonyl group, with the loss of a water
molecule.

The oxonium ion loses a proton, which leads to the production of the ester.

2. Oxidation of alcohols

Alcohol are oxidized by dilute potassium permanganate to form aldehydes and ketones. Primary alcohols are oxidized
to aldehydes whereas secondary alcohols are oxidized to ketones.
Tertiary alcohols cannot undergo oxidation with potassium permanganate.

H O
KMO4
R C OH R C H
H
primary alcohol aldehyde

OH O
KMO4
R C R R C R

H
ketone
secondary alcohol

OH KMO4
R C R no reaction
R
tertiary alcohol

Another commonly used oxidizing agent is acidic K2Cr2O7.

3. Reaction of alcohols with hydrogen halides

Alcohols react with hydrogen halides to form organic halides

ROH + HX RX + H2 O

Lucas Test for Secondary and Tertiary Alcohols

Lucas reaction is used to identify the three classes of alcohols. Lucas reaction employs hydrochloric acid and Zinc
chloride to produce alkyl halides which precipitates from the aqueous medium as a cloudy mass.

Tertiary alcohol react to form a cloudy solution instantly. Secondary alcohols form cloudy solution within 3-5 minutes
but primary alcohols do not form cloudy solution even after 30 minutes. The alkyl halides formed from primary
alcohols are soluble.

H
HCl, ZnCl2 no precipitate after 30 minutes
R C OH
H
primary alcohol

OH Cl
HCl, ZnCl2
R C R R C R cloudy within 3-5 minutes
H H
secondary alcohol

OH HCl, ZnCl2 Cl
R C R R C R instant cloudiness
R R
tertiary alcohol