DEPARTMENT OF CHEMISTRY

MODULE: INTRODUCTION TO ORGANIC CHEMISTRY

MODULE CODE: CHM 102

LECTURE TOPIC: ALCOHOLS AND THEIR REACTIONS

OBJECTIVES

At the end of this unit, students should be able to

i. Structurally explain alcohols.

ii. State the Methods of Preparation of Alcohols.

iii. State the comparative physical properties of alcohols, ethers and epoxides.

iv. Give the chemical reactions of alcohols

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 ALCOHOLS

Introduction—Structure and Bonding

Alcohols contain a hydroxyl group (OH) bonded to an sp3 hybridized carbon.

Monohydric alcohols has one hydroxyl group. Dihydric alcohols called diols or
glycols have two hydroxyl groups while trihydric alcohols or triols have three.
Others are called polyols.

Monohydric alcohols are classified into primary (10), secondary (20) and tertiary
(30) depending on the number of alkyl carbons connected directly to the hydroxyl
carbon.

Compounds having a hydroxyl group on a sp2 hybridized carbon—enols and

phenols—undergo different reactions than alcohols.

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Physical Properties

Alcohols, ethers and epoxides exhibit dipole-dipole interactions because they have
a bent structure with two polar bonds. However alcohols are capable of
intermolecular hydrogen bonding. Thus, they are more polar than ethers and
epoxides.

Steric factors affect hydrogen bonding. The more substituted (overcrowded) the
alcohol the less the H-bonding.

Summary of Methods of Preparation of Alcohols

1. By hydrolysis of haloalkanes : R-X + aq. KOH →ROH +KX

2. By reduction of Carbonyl compounds

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 3. By the action of Grignard’s Reagent on aldehydes, ketones and esters

4. By Aliphatic Primary Amines: RCH2NH2 + HNO2 → RCH2OH + N2 + H2O

5. By Hydration of alkenes:

6. By Oxymercuration-demercuration:

7 By Hydroboration-oxidation:

8. Hydroxylation of alkenes

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REACTIONS OF ALCOHOLS

1. Combustion

Alcohols burn in air to give carbon (IV) oxide and water. For example, ethanol
burns in air with a pale blue flame to give carbon (IV) oxide and water.

C2H5OH + 3O2 2CO2 + 3H2O

(REACTIONS INVOLVING R-OH
CLEAVAGE)

(Rate of reaction follows the order 3°alcohol >2°alcohol>1°)

2. Halogenation to Alkyl Halides

Halogenation of alcohols is a nucleophilic substitution reaction. Chlorination is

used in the Lucas test for distinguishing the three classes of monohydric alcohols.
Concentrated hydrochloric acid is put into absolute alcohol and then refluxed in the
presence of an anhydrous zinc chloride as catalyst. An insoluble haloalkane will be
formed and a cloudy mixture appears.

The time it takes for the cloudiness to appear indicates the types of alcohol.

For 3° alcohols form cloudiness immediately, 2° alcohols forms cloudiness in

about 10minutes while for 1o alcohols, a cloudy appearance is noticed after
refluxing for a few hours.

The reaction is believed to proceed via SN1 mechanism (involving carbocation

intermediate), hence the order of reactivity based on carbocation stability is:
3°alcohol >2°alcohol>1°. ( )

For bromination and iodination the corresponding hydrogen halide is produced in

situ by sodium halide and a concentrated acid.

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Other reagents that may also be used to convert alcohols to alkyl halides are
Phosphorus halides (PCl5, PCl3, PBr3 or PI3) and sulphur dichloride oxide (thionyl
chloride, SOCl2)

3. Dehydration of Alcohols to Alkenes

Dehydration of alcohols to corresponding alkenes can be carried out when alcohol

vapour is passed over an aluminium oxide catalyst heated to 350°C or by
heating to 170°C with excess concentrated sulphuric (VI) acid, the
corresponding alkene is formed by intramolecular dehydrogenation. p-
toluenesulfonic acid , ( TsOH ) or phosphorus oxychloride (POCl3) in the
presence of an amine base may also be used.

When the reaction involves secondary or tertiary alcohols having more than three
carbon atoms, more than one alkene can result. Such dehydration is regioselective
and follows the Zaitsev rule [‘the more substituted (and thus more stable) alkene is
the major product.

4. Dehydration of Alcohols to Ethers

When an excess alcohol is heated with concentrated sulphuric (VI) acid at a

lower temperature of about 140°C ether (instead of alkene) is formed by
intermolecular dehydration. For example,

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(REACTIONS INVOLVING RO-H CLEAVAGE)

(Rate of reaction follows the order below: 1o alcohol > 2o alcohol > 3o alcohol

5. Reaction with reactive metals

Alcohols react with reactive metals like sodium and potassium to form metal
alkoxides and hydrogen gas. This reaction is slower but similar to the reaction of
water with reactive metals.

6. Esterification

This is a reaction in which an alcohol reacts with carboxylic acid in the presence of
concentrated sulphuric acid to form esters (alkanoates).

The backward reaction is called acid – hydrolysis of ester. Esterification is slow

and of poor yield. Acyl chloride or acid anhydride may be used in place of the acid
to speed up the reaction.

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7. Oxidation of alcohols

Alcohols can be oxidized by making use of common oxidizing agents such as

acidified potassium permanganate (VII) or acidified potassium dichromate
(VI) to give the corresponding carbonyl compound or carboxylic acid.

Primary alcohols are readily oxidized on heating to aldehydes but in the presence
of excess of the oxidizing agent the reaction proceeds further to yield the
carboxylic acid.

The oxidation with K2Cr2O7 results in colour change from orange to green. In the
drunken driver test, K2Cr2O7 coated paper is exposed to the breath of a suspected
drunken driver. Ethanol vapour from the breath will change the orange colour of
the paper strap to green.

Secondary alcohols are oxidized to the corresponding ketone. Ketones are quite
resistant to oxidation else cleavage occurs.

Tertiary alcohols are also resistant to oxidation.

8 Triiodoform Formation (Iodoform Reaction)

Some alcohols with the structure: ― ―

react with an iodoform reagent
(iodine in the presence of sodium hydroxide), a mild oxidizing agents to give
sodium carboxylate and triiodomethane (also called iodoform).

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The product, triiodomethane appears as a yellow precipitate in the reaction
mixture. The reaction is a useful reaction for confirming the presence of the group

― ―
in an alcohol and for making acids with one carbon less.

SOME QUESTIONS
1. a.(i) Briefly discuss the solubility of alcohols.(2)
(ii) Butane, methoxy-ethane and 1-propanol have about the same molecular weight. Justify
their boiling points as shown below.(3)

b. (i) Draw the structures of the following alcohols and identify each of the alcohols as
primary secondary and tertiary.(4)

(I) 3-Chloro-1-propanol (II) 2-methyl-4-heptanol (III) 3- methyl-3-pentanol (IV)

Cyclohexanol

(ii) Give the IUPAC names for the following compounds (3)

c.(i) In the dehydration of the following two alkanols, draw the product(s) formed and indicate
the major product when more than one product is possible.(5)

(b) Show the alcohols that would yield the following alkenes on dehydration? (3)

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 ,

2.a (i) State the conditions each for the dehydration of an alcohol to a alkene and to an ether (4)
(ii) State the difference between the two reactions in 2a (i) (1)
(iii) Compare the reactions of reactive metals (eg Na, K) with water and their reaction with
alcohols.(2)

b. Provide the following information about alcohols.

(i) What to do to obtain an aldehyde as the only product from an alcohol.(3)
(ii) How to do to obtain a ketone from an alcohol.(1)
(iii) Why a tertiary alcohol cannot be used for 2 b (i) and (ii) above.(1)

c. Lucas reagent is a popular reagent for distinguishing different classes of monohydric alcohols.
(i) What are monohydric alcohols.(1)
(ii) State the composition of Lucas reagent.(1)
(iii) State the observation with Lucas Reagent that confirms a primary, secondary and tertiary
alcohols.(3)
(iv) How would you distinguish ethanol from 2-propanol and 1-propanol from 2-methyl-2-
propanol?(2)
(v) Provide a chemical explanation for the observations in 2c (iii) (2)

3a. (i) State how to recognize an alcohol that can undergo the iodoform test.(2)

(ii) State the observation for a positive iodoform test and the chemistry behind it (3)

(ii) Show which of the following alcohols will be positive to iodoform test? (4)

I) CH3CH2CH(OH)CH2CH3 I) CH3CH(CH3)CH2CH(OH)CH3 III) CH3CH(OH)(CH2)2CH3

b. (i) Describe the ‘alcohol breath test’ (field sobriety test) test usually deployed by the Federal
Road Safety Corps to detect drunken drivers.(2)

(ii) Explain the chemistry behind the test. (3)

c. Provide the following information on esterification of alcohols.

(i) The reactants and conditions.(2)

(ii) The name for the reverse reaction.(1)

(iv) How to manipulate the reverse reaction to undertake soap preparation (saponification).(2)

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(ii) How to make the reaction faster or irreversible.(1)

REFERENCES

1. K.S.TEWARI and N.K. VISHNOI (2006) - A Textbook of Organic Chemistry.

Third Edition

2. Robert Thornton Morrison and Robert Neilson Boyd(2008) – Organic

Chemistry- Sixth Edition

3. W.C.Wong; C.T.Wong; S.O.Onyiruka and L.E.Akpanisi(2001)-University

Organic Chemistry-The Fundamentals

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