Alcohols: - Structure and Bonding

Alcohols
Introduction—Structure and Bonding
CH3
CH3 CH CH2OH
• Alcohols contain a hydroxy group (OH) bonded to an sp3

hybridized carbon.
1
Alcohols
• Compounds having a hydroxy group on a sp2 hybridized
carbon—enols and phenols—undergo different reactions
than alcohols.
Alcohols
• The oxygen atom in alcohols, ethers and epoxides is sp3
hybridized. Alcohols and ethers have a bent shape like
that in H2O.
• The bond angle around the O atom in an alcohol or ether
is similar to the tetrahedral bond angle of 109.5°.
• Because the O atom is much more electronegative than
carbon or hydrogen, the C—O and O—H bonds are all
polar.
3
Alcohols
Nomenclature of Alcohols
4
Alcohols
• When an OH group is bonded to a ring, the ring is numbered
beginning with the OH group.
• Because the functional group is at C1, the 1 is usually omitted
from the name.
• The ring is then numbered in a clockwise or counterclockwise
fashion to give the next substituent the lowest number.
Figure 9.2
Examples: Naming
cyclic alcohols
5
Alcohols
• Common names are often used for simple alcohols. To
assign a common name:
Name all the carbon atoms of the molecule as a single
alkyl group.
Add the word alcohol, separating the words with a
space.
6
Alcohols
• Compounds with two hydroxy groups are called diols or
glycols. Compounds with three hydroxy groups are
called triols and so forth.
7
Alcohols
Physical Properties
• Alcohols have dipole-dipole interactions because they have a
bent structure with two polar bonds.
• Alcohols are capable of intermolecular hydrogen bonding. Thus,
alcohols are polar
• Steric factors affect hydrogen bonding.
8
Alcohols
9
Alcohols
Interesting Alcohols
Figure 9.3
Ethanol—The alcohol in
alcoholic beverages
10
Alcohols
Interesting Alcohols
Figure 9.4
Some simple alcohols
11
Alcohols
METHODS OF PREPARING ALCOHOLS
Alcohols can be prepared in two major ways. These are
industrial preparation which we shall refer to as Manufacture and
also Laboratory preparation. Manufacturing will be considered
first.
A. Manufacture of Alcohols
(i) From petroleum raw material - Methanol
Nowadays, petroleum sources provide the raw materials for the
manufacture
of well over 80% of these alcohols, the rest being manufactured
by the ancient methods of fermentation of starchy product and
the distillation of wood and coal.
12
Alcohols
A. Manufacture of Alcohols (contd.)
The major process for the production of methanol involves

passing a mixture of two volumes of hydrogen and one volume
of carbon - monoxide (synthesis gas) over a zinc (II) oxide,
chromium oxide catalyst at about 300oc and about 300
atmospheres pressure.
13
14
15
16
(ii) Manufacture of Ethanol by Fermentation
• Known to man from earliest times.

• the principal active ingredient of beers, wines
• fruits or starchy materials such as wheat, barley, cassava,
grapes, yam, apples, corn, rice, potatoes bananas and
plantains to ferment.
The fermentation is carried out by the addition of yeast to

a slurry of the raw material in water. Yeast contains
biological catalysts called enzymes such as maltase and
zymase.
• Ethanol produced by this method must be properly distilled
to remove primary alcohols and fused oil that are the bye-
products. 17
(ii) Manufacture of Ethanol by Fermentation
18
Methods of Preparation
Alcohols can be formed from many, many different sources.
More than 7 different functional groups can be converted to
an alcohol.
Ethers Ketones O
Alkenes Aldehydes
R HC CH2 C
R OR' R
R'
O
Alkyl Halides
R X Epoxides
Alcohols
R
R OH
Carboxylic Acids
OH
R C
Acid chlorides
O
Esters OR'
Cl
R C
R C
O
O
Methods of Preparation
METHODS OF PREPARATION
Hydrolysis of alkyl halides
 The term hydrolysis generally means the
introduction of a hydroxyl group
 into a molecule, usually in the place of some
other functional group. When
 an alkyl halide is treated with boiling aqueous
alkali or a suspension of silver
 oxide in boiling water, the halide functional
group is replaced by a hydroxyl group converting
it to an alcohol
Alcohols
Preparation of Alcohols
Reduction of Aldehydes, Ketones, Esters and Acids

When aldehydes, ketones, esters and acid are treated with
appropriate reducing agents the corresponding alcohols are
formed.
• The traditional reducing agents include Na in ethanol or Na/Hg
in ether or alcohol and molecular H2 in the presence of a catalyst
such as Pt or Pd or Ni.
• However the complex hydrides of Group 1 and 3 metals e.g.,
lithum tetrahydro aluminate (LiAlH4) and sodium hydroborate
(NaBH4) are now commonly used. (in a dry solvent e.g.
Ether) excess of the hydride is destroyed by the drop wise
addition of cold water with vigorous stirring.
22
Alcohols
Reduction of Aldehydes, Ketones, Esters and Acids

When aldehydes, ketones, esters and acid are treated with
appropriate reducing agents the corresponding alcohols are
formed.
• The traditional reducing agents include Na in ethanol or Na/Hg
in ether or alcohol and molecular H2 in the presence of a catalyst
such as Pt or Pd or Ni.
• However the complex hydrides of Group 1 and 3 metals e.g.,
lithum tetrahydro aluminate (LiAlH4) and sodium hydroborate
(NaBH4) are now commonly used. (in a dry solvent e.g.
Ether) excess of the hydride is destroyed by the drop wise
addition of cold water with vigorous stirring.
23
• Lithium aluminum hydride LiAlH4 and and sodium borohydride
NaBH4reduce carbonyl groups without affecting carbon -
carbon double bonds,
• NaBH4 is a milder reducing agent and will not reduce acids and
esters.
• Aldehydes and acids give primary alcohol, e.g.
24
Esters give two alcohols, one of which coming from the acid,
this portion is a primary alcohol while the other is from the
alcohol from which it was made,
25
(iii) Using a Grignard Reagent
This method is used for the preparation of the three classes of
alcohols. In this method, reagents RMgX - Grignard reagents
are reacted with carbonyl compound such as aldehydes,
ketones, esters and epoxides to form organometallic
intermediates which are hydrolysed to alcohol.
SYNTHESIS OF 1° ALCOHOLS: Methanal gives primary
alcohol.
Grignard + formaldehyde yields a primary alcohol with one
additional carbon.
CH3 H H CH3 H
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H
H H H
CH3 H
HOH
CH3 CH CH2 CH2 C O H
H
26
SYNTHESIS OF 2º ALCOHOLS : Alkanal gives secondary
alcohol
Grignard
.
+ aldehyde yields a secondary alcohol.
CH3 H H3C CH3 CH3

H
H H H
CH3 CH3
HOH
H
27
SYNTHESIS OF 3º ALCOHOLS : Alkanone gives tertiaryalcohol.
Grignard + ketone yields a tertiary alcohol.
CH3 H H3C CH3 CH3

H3C
H H CH3
CH3 CH3
HOH
CH3
28
SYNTHESIS OF 3º ALCOHOLS : Ester gives tertiary alcohol.
Esters will give tertiary alcohol with two molecules of the Grignard reagent.
The first molecule will convert the ester to a ketone and the second
molecule of Grignard reagent will react to give a tertiary alcohol.
29
SYNTHESIS OF 1º ALCOHOLS : Epoxides gives tertiary
alcohol
Epoxides:
. Epoxides could also be made to react with Grignard reagent to
produce a primary alcohol with two carbon atoms added..
30
(iv) Hydroboration / Oxidation of compounds containing
carbon - carbon double bond
This reaction occurs in two steps. Step one is the hydroboration of the carbon -
carbon and the second step involves the oxidation using hydrogen peroxide in
alkaline medium.
This reaction gives predominant products corresponding to anti-Markownikoff's
orientation - that is the hydroxyl group is directed to the carbon with more hydrogen
atoms attached to it.
31
(iv) Hydroboration / Oxidation of compounds containing
carbon - carbon double bond
This reaction occurs in two steps. Step one is the hydroboration of the carbon -
carbon and the second step involves the oxidation using hydrogen peroxide in
alkaline medium.
This reaction gives predominant products corresponding to anti-Markownikoff's
orientation - that is the hydroxyl group is directed to the carbon with more hydrogen
atoms attached to it.
32
PROPERTIES OF ALCOHOLS
B. Chemical Properties of Alcohols
The chemical properties of an alcohol are determined by its

functional group-OH.
Reactions of alcohol can involve breakage of either

(i) C - OH bond with removal of OH group
(ii) O - H bond with removal of H.
Both involve substitution of OH or elimination of H in which a

double bond is formed.
Alcohols show amphoteric behaviour i.e. act as acid and bases.
33
The alcohols with general formula
(i) R - OH can be considered as derivatives of water H - OH:
Like water they show both acidic and basic characters.
An alcohol as an acid
• releases a proton plus RO- alkoxide ion (conjugate base)
Acidity depends on how well the conjugate base can
accommodate the negative charge i.e. any factor that
stabilizes the RO- more than it stabilizes R - OH should
increase acidity and vice - versa.
• Electron withdrawing substituents on R should disperse the

negative charge, stabilize RO and this increases acidity.
• Electron releasing substituent on R, should disperse the

negative charge, to - destabilize the anion and thus 34
decrease acidity.
The acidity of alcohol is shown by their reaction with active
metal to give hydrogen and metal alkoxide.
An alcohol as a base accepts protons using a lone pair of

electrons on oxygen.
It reacts most rapidly with HI and HCl requires presence of
ZnCl2 as catalyst for the reaction with primary and secondary
alcohol. This reaction can actually be used to identify
different classes of alcohol using conc. HCl
/ ZnCl2 - known as Lucas reagent.
35
REACTION WITH HCL

Chloride is a weaker nucleophile than
bromide.
Add ZnCl2, which bonds strongly with
–OH, to promote the reaction.
The chloride product is insoluble.
Lucas test: ZnCl2 in concentrated HCl:
1° alcohols react slowly or not at all.
2 alcohols react in 1-5 minutes.
3 alcohols react in less than 1 minute.
36
LUCAS REAGENT
37
Reaction with inorganic halides:

The hydroxyl group of the alcohol may be replaced by a
halogen atom using an inorganic halide such
as phosphorus pentachloride or sulphur dichloride oxide
also called thionyl chloride. In the case of thionyl chloride
reaction, the two bye-products are gases leaving the product
alone in the flask.
38
Reaction with inorganic halides:

The hydroxyl group of the alcohol may be replaced by a
halogen atom using an inorganic halide such
as phosphorus pentachloride or sulphur dichloride oxide
also called thionyl chloride. In the case of thionyl chloride
reaction, the two bye-products are gases leaving the product
alone in the flask.
39
Esterification: when an alcohol is refluxed with a carboxylic acid,

an, ester is slowly formed.
This reaction is carried out in the presence of a catalyst
concentrated sulphuric acid or dry hydrogen chloride to remove
the water and pushes the equilibrium to the right.
Isotopic experiments have established that the overall reaction

involves loss of a hydrogen atom from the alcohol and not
the hydroxyl group.
40
iv) Oxidation : This can be used to distinguish the three

classes of alcohols. Oxidants commonly used include acidic
potassuim permanganate, Jones reagent (Na2Cr2O7/H+),
Ca/300oC, Cr(VI)O3 in pyridine.
Primary alcohols are oxidised to aldehyde and prolonged
oxidation results in the formation of the carboxylic acid having
the same number of carbon atoms as the primary alcohol.
1° alcohol to aldehyde to carboxylic acid
Difficult to stop at aldehyde
Use pyridinium chlorochromate (PCC) to limit the oxidation.
OH N H CrO3Cl O
CH3CH2CH2CH2 CH3CH2CH2CH
41
Secondary alcohol is oxidised to ketone. Further oxidation leads

to oxidative degradation. As a result of this, it is converted to a
mixture of carboxylic acid containing fewer carbon atoms than
the original ketone
42
Tertiary alcohols are generally resistant to oxidation especially

under neutral or alkaline conditions. In acidic solution, however
they also undergo oxidation degradation to give a mixture of acids
and ketones.
43
Dehydration
• Dehydration, like dehydrohalogenation, is a  elimination
reaction in which the elements of OH and H are removed from
the  and  carbon atoms respectively.
• Dehydration is typically carried out using H2SO4 and other

strong acids, or phosphorus oxychloride (POCl3) in the
presence of an amine base.
44
• Typical acids used for alcohol dehydration are H2SO4 or p-

toluenesulfonic acid (TsOH).
• More substituted alcohols dehydrate more easily, giving rise

to the following order of reactivity.
45
• Secondary and 3° alcohols react by an E1 mechanism,

whereas 1° alcohols react by an E2 mechanism.
46
(vii) The lodoform / Haloform Reaction Alcohols which contain

the alkyl group
Such as ethanol and propan-2-ol give a pale yellow precipitate

of tri-iodomethane - iodoform (CHI3 when warmed with a
mixture of potassium iodide) and excess sodium chlorate
(sodium hypochlorite) solution or with iodine and sodium
hydroxide solution. This is because under the mild oxidising
condition this type of alcohol group is converted to
CH3C=O which can then undergo iodination and cleavage,
giving tri-iodomethane as a product.
47
(vii) The lodoform / Haloform Reaction Alcohols which contain

the alkyl group
48
49

Alcohols: - Structure and Bonding

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Alcohols: - Structure and Bonding

Uploaded by

Copyright:

Available Formats

Alcohols

Introduction—Structure and Bonding

• Alcohols contain a hydroxy group (OH) bonded to an sp3

• Steric factors affect hydrogen bonding.

A. Manufacture of Alcohols (contd.)

The major process for the production of methanol involves

A. Manufacture of Alcohols (contd.)

• Known to man from earliest times.

The fermentation is carried out by the addition of yeast to

Reduction of Aldehydes, Ketones, Esters and Acids

Reduction of Aldehydes, Ketones, Esters and Acids

CH3 H H3C CH3 CH3

CH3 H H3C CH3 CH3

The chemical properties of an alcohol are determined by its

Reactions of alcohol can involve breakage of either

Both involve substitution of OH or elimination of H in which a

Alcohols show amphoteric behaviour i.e. act as acid and bases.

• Electron withdrawing substituents on R should disperse the

• Electron releasing substituent on R, should disperse the

An alcohol as a base accepts protons using a lone pair of

REACTION WITH HCL

Reaction with inorganic halides:

Reaction with inorganic halides:

Esterification: when an alcohol is refluxed with a carboxylic acid,

Isotopic experiments have established that the overall reaction

iv) Oxidation : This can be used to distinguish the three

Secondary alcohol is oxidised to ketone. Further oxidation leads

Tertiary alcohols are generally resistant to oxidation especially

• Dehydration is typically carried out using H2SO4 and other

• Typical acids used for alcohol dehydration are H2SO4 or p-

• More substituted alcohols dehydrate more easily, giving rise

• Secondary and 3° alcohols react by an E1 mechanism,

(vii) The lodoform / Haloform Reaction Alcohols which contain

Such as ethanol and propan-2-ol give a pale yellow precipitate

(vii) The lodoform / Haloform Reaction Alcohols which contain

You might also like