CHM 123: BASIC ORGANIC CHEMISTRY II

Sunday .A. Adeniyi

Department of Chemistry
Igbinedion University, Okada

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OUTLINES:
Chemistry of Polar Functional Groups
1. Alcohols and Phenols
(a) Alcohols
Introduction
Industrial Uses of Methanol
Classification of Alcohols
Naming of Alcohols
Physical Properties of Alcohols
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(b) Phenols
Introduction
Naming of Phenols
Reactions of Phenols
2. Aldehydes and Ketones
Introduction
Naming of Aldehydes and Ketones
Physical Properties of Aldehydes and Ketones
Reactions of Aldehydes and Ketones

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3. Carboxylic acids and Derivatives (e.g. Acid halides,
Anhydrides, Amides)
Introduction
Naming of Carboxylic acids and Derivatives
Physical Properties of Carboxylic acids and Derivatives
Reactions of Carboxylic acids
Reactions of Esters
Acid halides, Acid anhydrides and Amides
Naming of Acid halides, Acid anhydrides and Amides
Reactions of Acid halides
 Reactions of Acid anhydrides
Reactions of Amides
4. Amino acids and Proteins
Introduction
Classification of Amino acids
Reactions of Amino acids
5. Fats and Oils
6. Carbohydrate

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 Alcohols and Phenols
(1a) Alcohols
Alcohols can be described as compounds that contain a
hydroxyl group (i.e. -OH) bonded directly to an sp 3 hybrid
carbon atom i.e.
sp3 hybrid carbon atom

HO C

In other words, alcohols could be described as aliphatic

hydroxyl compounds, simply because they contain straight or
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branched chain hydrocarbons.
The most common example of alcohol is the ethanol.
Ethanol can be sourced from the natural fermentation of
sugars and starch. The word “fermentation” is a complex
series of chemical reactions by which the enzymes of yeast
decompose the aqueous solutions of sugars and starches to
produce ethanol and carbondioxide.
Another widely used alcohol is Methanol which was
originally obtained by heating wood in the absence of air.
But the modern method of producing methanol is by
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catalytic reduction of carbon monoxide by hydrogen gas i.e.
Catalyst
2H2 + CO CH3OH
Heat
The industrial uses of methanol are as follows:
(i) Methanol is a raw material in the production of methanol
(H2C=O).
(ii) Methanol is also used as an antifreeze in washer
solutions.
(iii) Methanol serves as an additive to jet fuels.

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Classification of Alcohols:
The classification of alcohols depends on the number of
alkyl groups (i.e. R) directly bonded to the sp 3 hybrid carbon
atom. For example, if only one alkyl group (i.e. R) is
attached to the sp3 hybrid carbon atom such alcohol is called
Primary alcohol (1o alcohol) i.e.
H

R C OH

H
o
1 Alcohol

Example of 1o alcohols are ethanol, CH3CH2OH; 9

1-propanol, CH3CH2CH2OH; 1-butanol,

CH3CH2CH2CH2OH; 2,2-Dimethyl-1-propanol,

(CH3)3CCH2OH etc.
If two alkyl groups (i.e RR’) are directly attached to the
sp3 hybrid carbon atom, this alcohol is called Secondary
alcohol (2o alcohol) i.e. R'

R C OH

H
2o Alcohol

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Examples of 2o alcohols are
OH OH
OH
CH3CHCH3 CH3CHCH2CH3
2-propanol 2-butanol Cyclopentylalcohol

If three alkyl groups (i.e RR’R”) are directly attached to

the sp3 hybrid carbon atom,
R'
it is called Tertiary alcohol (3 o

alcohol) i.e. R C OH

R"
3o Alcohol
Examples of 3o alcohols are
OH

CH3CCH2CH3
CH3 COH
CH3
3
2-Methyl-2-propanol 2-Methyl-2-butanol 11
Naming of Alcohols:
Alcohols and some other organic compounds are best
named by using the IUPAC rules. The following IUPAC
rules are needed to name alcohols.
(1) Select the longest continuous chain of carbon atoms that
contains the –OH group.
(2) Obtain the parent alkane name of the longest continuous
chain of carbon atom.
(3) Replace the terminal –e of the parent alkane name with –
ol.
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(4) If the compound contains more than one –OH, the endings
are -diol for two, -triol for three etc.; but the parent alkane
name is retained for ease of pronunciation.
(5) If the compound contains more than one substituents (e.g.
Br, Cl, Cl, CH3, I, F etc.), the substituents are named
alphabetically before the alcohol name.
(6) If the compound contains another functional group (e.g.
alkene, alkyne group etc.), the functional groups are named
alphabetically, and hence, the parent alkane name changes to
either alkene or alkyne name. 13
 For example, the following compounds are named
according to the IUPAC rules:
OH

CH3CH2 CH2OH CH3CHCH3 (CH3)3CCH2OH

1-Propanol 2-Propanol 2,2-Dimethyl-1-propanol

OH OH

HOCH2CH2OH CH3CHCH2CH2CH2OH ClCH2CH(CH3)CH2CHCH3

1,2-Ethanediol 1,4-Pentanediol 5-Chloro-4-methyl-2-pentanol

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 Cl

CH3C CCHCH2CHCH2OH

Br
4-Bromo-2-Chloro-5-heptyn-1-ol

Physical Properties of Alcohols:

An alcohol can be visualized as being formed by
replacing one hydrogen atom of a water molecule by an
alkyl group i.e. the hydrogen atom of a water molecule was
replaced by an sp3 hybrid carbon atom e.g.
H

H O

O
C
H
Water Alcohol
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Therefore alcohols can be regarded as organic derivative of
water. In this view, an alcohol consists of two parts, namely,
(i) the non-polar alkane-like alkyl group which is insoluble in
water and called the hydrophobic (i.e. water- hating) or
lipophilic (i.e. fat- loving) part.
(ii) the polar water-like hydroxyl group which is soluble in
water and called the hydrophilic (i.e. water- loving) or
lipophobic (i.e. fat- hating) part.
Solubility:
The solubility of straight chain alcohols containing a single
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hydroxyl group in water decreases as the number of carbon
atoms increases. For example, the decreasing order of
solubility of alcohols in water is as follows,
CH3OH > CH3CH2OH > CH3(CH2)2OH > CH3(CH2)3OH
etc.
But we should bear in mind that alcohols containing nine
and above carbon atoms resembles alkanes in their water
solubilities (i.e. insoluble in water).
Boiling Point:
Generally, the boiling point of alcohols containing a 17
single hydroxyl group increases as the number of carbon
atoms increases. For example, the high molecular weight
alcohols have higher boiling point than the low molecular
weight alcohols due to the differences in their intermolecular
forces.
Polarity:
Moreover, the polarity of any alcohol depends on the
number of polar and non-polar parts in the compound. As the
number of carbon atoms increases, the polarity decreases.

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Reactions of Alcohols:
1. Reaction With Strong Base:
Reaction of alcohol with a strong base forms an alkoxide
ion. Alkoxide ions, RO-, are commonly used in organic
chemistry as nucleophiles (nucleus-loving) in nucleophilic
substitution reactions. An example of strong base commonly
used for this reaction is Sodium amide, NaNH2 e.g.
- +
CH3CH2OH + NaNH2 CH3CH2O Na + NH3
Ethanol Sodium ethoxide Ammonia

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2. Reaction With Alkali Metals:
Alcohols are capable of reacting with alkali metals (Li, Na
or K) to form alkoxide ions e.g.
CH3CH2OH + Na CH3CH2O- Na+ + ½ H2
Ethanol Sodium ethoxide Hydrogen gas
Sodium metal reacts less vigorously with alcohol when
compare its reaction with water. As the number of alkyl
portion of the alcohol increases, the vigor of the reaction with
sodium metal continually decreases. The more reactive
potassium metal is used to prepare alkoxides from alcohols
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containing four or more carbon atoms. Note that order of
reactivity of alkali metal with alcohols is as follows:
Potassium > Sodium > Lithium
3. Reaction With Carboxylic Acids:
Alcohols reacts with carboxylic acids in the presence of
a strong acid (like H2SO4) as a catalyst to form esters of
carboxylic acids and water. This reaction is called
Esterification. For example, the acid-catalyzed reaction of
ethanoic acid with ethanol forms ethyl ethanoate and water.
i.e. O O
H2SO4
H3C C + CH3CH2OH H3C C + H2O

O H O CH2CH3
Ethanoic acid Ethanol Ethylethanoate

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4 (a) Reaction With Hydrogen Halides (HCl, HBr or HI):
Alcohols react with hydrogen halides (HCl, HBr or HI) to
form Haloalkanes. The general reaction is represented as
R OH + HX RX + H2O
Alcohol Hydrogen Haloalkane
halide

The typical example of such reaction is

CH3 CH3

HCl(g)
H3C C OH H3C C Cl + H2 O
(C2H5)2O
CH3 CH3
2-Methyl-2-propanol 2-Chloro-2-methylpropane

The hydroxyl group of the alcohol is replaced by a halogen

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atom in the reaction, which can be used to prepare 1o, 2o and
3o haloalkane depending on the type of alcohol used in the
reaction.
(b) Reaction With Phosphorus tribromide (PBr3):
This reaction is similar to reaction 4(a) in which the
hydroxyl group of the alcohol is replaced by a halogen atom.
Here, the hydroxyl group is replaced by bromine atom to
form bromoalkene
OH
e.g. Br

3CH3CHCH2CH3 + PBr3 3CH3CHCH2CH3 + H3PO3

2-Butanol Phosphorus 2-Bromobutane Phosphorus
tribromide acid 24
(c) Reaction With Thionyl Chloride (SOCl2):
This reaction is also similar to reaction 4(a) in which the
hydroxyl group of the alcohol is replaced by a halogen
atom. Likewise, chloroalkane is formed e.g.
OH Cl

3CH3CHCH3 + SOCl2 3CH3CHCH3 + SO3 + HCl

2-Propanol Thionyl 2-Chloropropane
chloride

5. Oxidation of Alcohols:
The oxidation of primary and secondary alcohols to
aldehydes and ketones can be carried out by reacting these 25
alcohols with oxidizing agents. The oxidizing agents that are
commonly used to oxidize primary and secondary alcohols
are
(i) Aqueous acidic chromium trioxide i.e. CrO3 / H2SO4 /

H2O

(ii) Aqueous acidic sodium dichromate i.e. Na2Cr2O7 /

H2SO4 / H2O

(iii) Aqueous acidic potassium permanganate i.e. KMnO 4 /

H2SO4 / H2O
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(v) Collin’s reagent
Primary alcohols are oxidized first to aldehydes that are
easily oxidized further to carboxylic acids e.g.
O O
[O] [O]
RCH2OH R C R C
1o Alcohol H OH
Aldehyde Carboxylic acid

Oxidation of primary alcohols can be stopped at the

aldehyde stage only by using special oxidizing agents like
Pyridinium chlorochromate (PCC) or Collin’s reagent in
anhydrous methylene chloride e.g. 27
 O
PCC
CH3(CH2)5CH2OH CH3(CH2)5C
CH2Cl2
1-Heptanol Heptanal H

The other oxidizing agents 1-3 listed above oxidize

primary alcohols to carboxylic acids and aldehydes are
present in these reactions as intermediates e.g.
O
CrO3
CH3(CH2)3CH2OH CH3(CH2)3C
H2SO4 /H2O
1-Heptanol H
Pentanoic acid

All the listed oxidizing agents (1-5) can oxidize secondary

alcohols to ketones e.g. 28
 OH O
Na2Cr2O7
CH3(CH2)3CHCH3 CH3(CH2)3CCH3
H2SO4 /H2O
2-Hexanol 2-Hexanone

The oxidation of tertiary alcohol is not possible because

its sp3 hybrid carbon atom does not attach to any hydrogen
atom.
(1b) Phenols
Introduction
Phenols are compounds that contain a hydroxyl group
bonded directly to a benzene ring. Phenol is otherwise 29
called hydroxybenzene i.e.

Phenols occur widely in nature. They are particularly

prominent in plants, where they perform a variety of
functions. Some are found as pigments of flowers and fruits,
while some contribute to the aroma of flowers. Since
inception, many phenols have been isolated from plants for
use as colouring materials, disinfectants, germicides and
deodorants etc.
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 One of the major differences between phenols and
alcohols is their acidity. While both phenols and alcohols are
acids, their acidities differ greatly. The acidity (pK a) phenol
is 10, while that of most alcohols falls in the range 15-18.
Therefore, phenol is about 106 times more acidic than a
typical alcohols e.g.

The presence of substituents on the benzene ring of 31

phenols affect their acidity. However, the substituent effects
are generally very small, with the exception of the
nitrophenols. For example, o-nitrophenol and p-nitrophenol
are much stronger acids than phenol. Increasing the number
of nitro groups on the ring greatly increases the acidity of
nitrophenol e.g.

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 Although phenols are acidic, they tend to be less acidic
than carboxylic acids e.g.
C2H5OH < C6H5OH < CH3COOH
Ethanol,pKa = 15.5 Phenol, pKa = 10.0 Ethanoic acid, pKa = 4.74

Naming of Phenols:
The naming of phenols follows the same pattern with
alcohols, but when naming phenols that contain carboxyl or
carbonyl functional groups, these groups take precedence
over the hydroxyl group. For example, the following
phenols are named according to the IUPAC rules
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34
Reactions of Phenols:
1. Reaction with Bromine or Bromination of Phenols::
Phenols are capable of reacting with a dilute solution of
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bromine both in polar and non-polar solvents. If phenol reacts
with a dilute solution of bromine in an acidic solvent such as
acetic acid or in non-polar solvent such as CCl4, it does not
ionize and bromination occurs at the para-position of phenol
i.e.

But if phenol is brominated in polar solvents like water,

phenol ionizes to give phenoxide ion which undergoes 36
electrophilic aromatic substitution with bromine atoms to
form 2,4,6-Tribromophenol i.e.

2. Nitration of Phenols:
Phenol is nitrated in dilute nitric acid (HNO 3) to form both
the ortho- and para- isomers i.e.

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The temperature of this reaction should not exceed 20oC, in
order, to avoid the formation of quinone. The ortho- and
para- isomers can be separated by steam distillation. The
ortho- isomer is very volatile while the para- isomer is less
volatile.
3. Acylation of Phenols:
Phenols react with acyl chloride to form ester 38
derivatives. The acylation reaction takes place in the
presence of pyridine, in order, to neutralize the HCl that also
forms. For example, the reaction of phenol with propanoyl
chloride in the presence of pyridine gives phenyl propanoate
i.e.

4. Reaction with Haloalkanes:

The reaction of phenols with haloalkanes resulted in the
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formation of aryl ethers. The reaction is usually carried out
by heating a mixture of the phenol, haloalkane and potassium
carbonate (K2CO3) in a suitable solvent e.g.

The best results are obtained when primary and secondary

haloalkanes are used. This reaction is called Williamson
Ether Synthesis. 40
5. Oxidation of Phenols:
Phenols, like alcohols, can be oxidized to carbonyl-
containing compounds. The oxidation of phenol by chromic
acid forms a quinone e.g.

Mono- and polycyclic aromatic hydrocarbons that contain

two hydroxyl groups can also be oxidized to quinones.
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Examples include 1,2-Benzenediol and 1,4-Benzenediol being
oxidized by aqueous acidic sodium dichromate to form 1,2-
Benzoquinone and 1,4-Benzoquinone respectively i.e.

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