Oxygen Containing Organic Compounds

Organic compounds (alcohols, aldehydes, ketones, carboxylic acids, ethers,

esters, phenols etc.) containing oxygen atom(s) in their molecules in addition to
carbon and hydrogen as essential atoms are termed oxygen organic
compounds. In the focus of this part of organic chemistry are alcohols, the
widespread organic class of compounds.

ALCOHOLS
Introduction
Alcohols are hydroxyl derivatives of hydrocarbons having hydroxyl group as
a functional that is directly attached to an aliphatic, saturated, sp3 hybridized
carbon atom. Alcohols have the general formula R OH.
R H

R OHI

-OHI

Hydrocarbon

Alcohol
(hydroxyl derivatives of hydrocarbons)

Alcohols can be also considered as alkyl derivatives of water, in which one Hatom in a water molecule is displaced by an alkyl group, R.
R

H OH
water

R OH
alcohol

Saturated alcohols have the

general formula: CnH2n+1OH.

FEW classes of oxygen based organic compounds contain hydroxyl group in their
molecules but they are not alcohols since do not exhibit properties of alcohols. Enols,
phenols, and carboxylic acids are some examples.
Compounds having a hydroxyl group and a double bond directly attached to an
unsaturated sp2-hybridized carbon atom are called enols. Similar, phenols differ from
alcohols by the carbon atom bearing the OH group. The OH group in phenols is directly
attached to the aromatic sp2-hybridized C-atom in the benzene ring. These compounds
have the general formula Ar-OH. Carboxylic acids also contain hydroxyl group in their
structure but the C-atom which the hydroxyl group is attached to is unsaturated, sp2hybridized, like in enols and phenols, hence this organic class display different properties
than alcohols. Here from, enols, organic acids and phenols have nothing in common with
the alcohols. Compounds in which the saturated C-atom holds two hydroxyl groups, does
not belong to the class of alcohols either.
R OH

CH3 CH = C CH3

OH

Alcohol

OH
Enol

RC=O
OHI

Phenol

Carboxylic acid

Classification of alcohols
Alcohols are classified according to the
number of the OH groups;
type of the C-atom which the hydroxyl group is attached to;
type of the radical which the hydroxyl group is attached to.
According to the number of hydroxyl group/s in an alcohol molecule they are
classified as monohydric, dihydric and polyhydric alcohols;
Ex.

CH3 CH2 OH

CH2 CH CH2 polyhydric alcohol

monohydric alcohol

OH

OH

OH I

According to the type of the carbon atom baring the hydroxyl group, alcohols
can be primary (1), secondary (2) and tertiary (3);
1

CH3
1

CH3 CH2 OH

CH3 CH CH3

CH3 C CH3

OH

OH

According to the type of the alkyl radical which the hydroxyl group is attached
to, alcohols are classified as aliphatic (can be saturated or unsaturated, acyclic or
alicyclic) and aromatic alcohols containing aromatic ring in their molecules.
CH3 CH CH = CH CH2 OH
I

CH3

CH3 CH CH2 CH CH3

OH

aliphatic acyclic, unsaturated alcohol

C 6 H5

aromatic alcohol (phenyl radical)

Nomenclature of alcohols
Alcohols are named following the IUPAC rules the same as the other hydrocarbons.
1 Select the longest continuous carbon chain including the C-atom baring the OHgroup. Change the name of the alkane corresponding to this chain by deleting the
final e and adding the suffix -ol. E.g. CH3OH, methanol (methane -ol),
CH3CH2OH is named ethanol, propanol etc.
2 Number the carbon atom in the longest continuous carbon chain starting from
the end nearest to the hydroxyl group. The carbon atom bearing the OH-group
takes the lower number. The position of OH-group in the final name must be
indicated using the proper number (E.g. propan-2-ol). If more than ones substituent
appears, indicate the other substituents (as prefix) by using the numbers
corresponding to their positions along the carbon chain.
3

Ex:

CH3 CH OH
1

CH3

propan-2-ol

OH

cyclohexanol

3 If the hydroxyl group is attached to an unsaturated radical, the two functional

groups are named by the following order:
4

CH3 C C CH2 OH

CH3 CH = CH CH2 OH
but-2-en-1-ol

but-2-yn-1-ol

4 If the OH group is in the middle of the chain, the numbering of the carbon atoms
starts at the end nearest the branching.
5

Ex:

CH3 CH2 CH CH CH3

OH

Br

CH2 CH CH3

OH

1-phenylpropan-2-ol

2-bromopentan-3-ol

5 If there are more than one OH group, the prefix di, tri, tetra are used before the
suffix ol and the numbers of carbons bearing the OH groups are written after the
name of the alcohol.
1

E.g.:

CH2 CH CH2

OH

OH

CH3 CH CH2 CH CH3

OH

OH

OH

propan-1,2,3-triol

pentan-2,4-diol

Preparation of alcohols
Synthesis of alcohols from alkenes
Hydration (addition of water) of alkenes is well-known method for preparing
alcohols. In presence of concentrated sulphuric acid as a dehydration agent, the
addition process takes place by Markovnikov rule, if the alkene is asymmetrical.
H2SO4

R CH = CH2 + H OH
alkene

R CH CH3

water

OH

secondary alcohol

Synthesis of alcohols from alkyl halides

A reaction of alkyl halide in aqueous hydroxide yields alcohol. In this nucleophillic
substitution, the halogen atom is being replaced by the OH group from hydroxide to
form a molecule of alcohol.
R X + NaOH
alkyl halide hydroxide
CH3 Cl +
chloromethane

NaOH

CH3 CH CH2 CH3

Br
2-bromobutane

R OH
alcohol

+ NaX
sodium halide

CH3 OH + NaCl
methanol (methyl alcohol)

+ NaOH CH3 CH CH2 CH3 +

OH
butan-2-ol

NaBr

 Synthesis of alcohols by reduction (hydrogenation) of aldehydes/ketones;

aldehyde + H2 primary alcohol

Pt

R C = O + H2 R CH2 OH

H
ketone + H2 secondary alcohol

Pt

R C = O + H2 R CH OH

R
Pt

CH3 C CH2 CH3 + H H CH3 CH CH2 CH3

ketone

primary alcohol

R
butan-2-ol
secondary alcohol

OH

Physical properties of alcohols

Alcohol molecules contain non-polar alkyl group (R-) and polar hydroxyl group.
These parts play an important role in determining physical properties of alcohols.
For example; the hydroxyl group in methanol has a strong influence. Methanol is
soluble in water in all proportions. It is polar and similar to water. Most alcohols are
colourless liquids at room temperature. Methyl, ethyl and isopropyl alcohol are
liquids with sharp, characteristic fruity odours. Alcohols containing 4 to 11 carbon
atoms are viscous (oily) with fruity odours. The normal alcohols (C1 C11) up to
dodecanol are liquids but those containing more than 12 carbons are solids. Lower
members are soluble in water. The polarity of alcohols decreases as the length of
the hydrocarbon chain in the molecule increases. Consequently, their solubility in
water decreases, so that the higher members are insoluble in water (in fact the long
alkyl radical mask the OH-group, disabling the formation of hydrogen bonds
between water and alcohol molecules). Branching alcohols increases solubility. The
solubility of butanol is 8,3 g per 100 ml of water while 2,2-dimethylethanol
(branched alcohol containing same number of C-atoms in the parent chain as
butanol) is completely soluble in water.
Polarity of alcohols increases as
the number of OH groups increases.
Ethane-1,2-diol (known as glycol) and
propane-1,2,3-trio (known as glycerol)
are soluble in water in all proportion.
The boiling points of alcohols are
much higher compare to the alkane
with correspond number of carbon
atoms, since alcohol molecules are
polar and undergo hydrogen bonding.
Methane for instance, has a boiling
point of 162C while methanol boils
at 64C. The melting point of alcohols
They are compared with the corresponding
increase as the number of carbon
alkane (methane to butane) with the same
atoms increase. Branching generally
number of carbon atoms.
decreases the boiling and melting
points.

a Hydrogen bonding in alcohols

b - Hydrogen bonding in water

Chemical properties
The oxygen atom involved in the polar hydroxyl group holds two atoms (two single
sigma bonds), a carbon atom from the alkyl radical and hydrogen atom. The
electronegativities of oxygen, carbon and hydrogen are 3.44, 2.4 and 2.2
respectively. The electronegativity difference for O H is 1,4 and for C O is 1.
When the polarity of C O and O H is compared, it seems that the O H bond is
more polar then the C O bond. However both electron pairs between oxygen and
hydrogen or carbon are pooled towards more electronegative oxygen atom. For this
reason the oxygen atom became partial negative (O) whereas H and C-atoms
bearing positive charges (H+, C+). Thus in some reactions H-atom can easily be
substituted. In such reactions alcohols behave slightly acidic (act as Brnsted
acids) because donates a proton (H+). From primary to tertiary alcohols the polarity
of the O H bond and proton donating ability increases.
1 Since there are two polar places in an alcohol molecule (two reactive centres),
basically two kinds of reactions occur; reactions of OH and CO bond cleavage.

H
+

R C O H
2.4

3.44

2.2

H
REACTIONS OF ALCOHOLS INVOLVING O H BOND BREAKAGE
Reactions of Alcohols with Alkali Metals
Active metals (such as alkali metals) react with alcohols evolving gas of hydrogen.
In addition to hydrogen, metal-organic compounds known alcoholates as primary
product, are obtained. Alcohol molecule displays acidic property, because it gives
off a proton. The reaction between sodium and water proceeds vigorously whiles
the same reaction with methanol or ethanol occurs with insignificant rate.
Increasing the number of carbon atoms in the alcohol molecule slows down the
reaction.
2R O H + 2Na 2 R O Na+ + H2(g)
alcohol

2CH3 O H
methanol

alkali metal

2K

potassium

sodium alcoholate

2 CH3 O K+

potassium methanolate

H2(g)

 Esterification Reactions
An organic reaction between alcohols and carboxylic acids refers as esterification.
The reaction is reversible; forward reaction yields ester and water and the reversed
reaction gives back the initial substances. During this substitution reaction the O-H
bond in the alcohol molecule breaks and hydrogen atom has been replaced by the
acyl group (R-O) from carboxylic acid, in presence of H2SO4 as dehydration agent.
Initially, it was thought that hydrogen atom derives from the OH group found in the
carboxylic acids composition, but replacing the hydrogen atom by deuterium (one
of the hydrogen isotopes) determines the exact nature of this reaction.
O
ROH

H2SO4

+ R C

R C
OR

OH
alcohol

+ H2O

carboxylic acid

ester

H2SO4

Example: CH3 COOH + HO CH2CH3

acetic acid
ethanol

CH3COOCH2CH3 + H2O
ethyl ester of acetic acid

Inorganic oxyacids also react with alcohols forming esters. Acids such as
HNO3, H2SO4 and H3PO4 participate in the esterification processes.
RO H + HO NO2 R ONO2 + H2O
alcohol
nitric acid
alkyl nitrate

(R NO3)

CH3CH2O H + HO NO2 CH3CH2NO3 + H2O

ethanol
nitric acid
ethyl nitrate
REACTIONS OF ALCOHOLS INVOLVING C O BOND BREAKAGE
Reactions of Alcohols with Hydrogen Halides (HX)
In acidic solutions alcohols act as Brnsted bases because the OH group from
alcohols gains proton, so that a water molecule is removed from the alcohol
molecule as a result of C O breakage.
Alcohols react with concentrated hydroacids like HCl, HBr and HI producing
alkyl halides. Primary and secondary alcohols react with an acid in presence of
ZnCl2 as catalyst, but tertiary alcohols react directly without catalyst because of
their higher reactivity. This process is a reaction of nucleophilic substitution, in
which the negative OH group replaces the halide negative ion, X.
ZnCl2

R OH + H X R X + H2O
alcohol

acid

alkyl halide
ZnCl2

CH3CH2 OH + H Cl CH3 CH2 Cl + H2O

ethanol

chloroethane (ethyl chloride)

2 COMBUSTION REACTIONS
Like other hydrocarbons, alcohols combustion also produces carbon dioxide and
water. Ethanol is often used as a fuel in a so-called Spirit lamp. It burns with a pale
blue flame releasing CO2 and water vapor. In general, the combustion of saturated
alcohols is described by the following equation:
CnH2n+1OH + 3n/2 O2 nCO2 + (n+1)H2O
C3H7OH + 9/2 O2 3CO2 + 4H2O
3 DEHYDRATION OF ALCOHOLS
Alcohols can be dehydrated. Depends on the temperature at which the dehydration
occurs different products are obtained. When one mole of monohydric alcohol is
heated in presence of a concentrated H2SO4, at 180C, one mole of water and
alkene is produced. Deprived water comes from the functional OH group bonded to
one of C-atoms in the parent chain and a hydrogen atom located on the adjacent
carbon atom. The reaction follows the Markovnikov rule.
180C

CH3 CH CH CH3 H2O + CH3 CH = CH CH3

H
OH.
butan-2-ol

but-2-ene

At lower temperatures, 140C, in

(dehydration agent), dehydration of two
ethers.
H2SO4
R OH + HO R
140C
alcohol
alcohol

presence of concentrated sulphuric acid

moles of monohydric alcohols produces
R O R + H2O
ether
water

H2SO4

CH3 OH + HO CH3
CH3 O CH3 + H2O
140C
methanol
methanol
dimethyl ether
R O R
H2SO4

R OH + HO R
140C

ROR

+ H2 O

1 mol

R O R

1 mol mixture of ethers

1 mol

Ethers are organic compounds containing two identical or different radicals linked
through oxygen atom. Two types of ethers are distinguished - symmetrical and
asymmetrical. The first type contains identical radicals; therefore its general formula
is R O R while the other consists of different alkyl radicals with general formula
R O R. According to the radical nomenclature, radicals are named first
following the word ether. The alphabet order is observed regardless of radicals
order. Here are some examples:
C2H5 O C2H5
diethyl ether
(symmetrical)

C6H5 O CH3

C6H5 O C6H5

CH3 O CH2CH3

methyl phenyl ether

(asymmetrical)

diphenyl ether
(symmetrical)

ethyl methyl ether

(asymmetrical)

4 OXIDATION REACTIONS
To oxidized alcohols, acidic solutions of strong oxidizing agents, such as KMnO4 or
K2Cr2O7 are used. The degree of oxidation of alcohols depends on the number of H
atoms bonded to the carbon atom bearing the OH group.

Primary alcohols
can be oxidized by two degrees

Secondary alcohols
can be oxidized by one degree

Tertiary alcohols
cannot be oxidized

Oxidation of Primary Alcohols. Except methanol, which has three H-atoms,

primary alcohols have two H-atoms bonded to the carbon atom holding the OH
group. Consequently, primary alcohols can be oxidized in two degree. In the first
oxidation, an aldehyde is produced, whereas in the second oxidation, a carboxylic
acid is produced.
O

[O]

[O]

R CH2 OH R C

H2O

R C

alcohol

OH

aldehyde

carboxylic acid
[O]

[O]
H2O

CH3 CH2 OH CH3 CHO CH3 COOH.

ethanol

ethanol
(methyl aldehyde)

ethanoic acid
acetic acid

Oxidation of Secondary Alcohols. In secondary alcohols, there is only one

hydrogen atom bonded to the carbon atom that hold the hydroxyl group, therefore
the oxidation process goes in one step. The end products are ketones.
R

OH

[O]

C
R
H
secondary alcohol

CH3 CH CH3

H2O

R
ketone

[O]

H2O

CH3 C CH3

OH
propan-2-ol

O
propan-2-on

Tertiary alcohols can not be oxidized because do not have a hydrogen atom that
can be replaced.

SOME IMPORTANT ALCOHOLS

Methanol (by IUPAC) or methyl alcohol (radical nomenclature) is colourless,
flammable liquid with a characteristic odour. Its taste is similar to ethanol but it is
highly toxic. Ingestion of even small quantities of methanol can cause blindness,
large quantities (5 g) cause death. Since methyl alcohol can be deadly, pyridine,
which has a bad odour or dyes is added to prevent its use as a drink. Because of

the low freezing point (- 97C) it has been used as

antifreeze in radiators. Methyl alcohol is
completely soluble in water. It can be easily
oxidized, so in the first oxidation converts to
formaldehyde, into formic acid in the second
degree and CO2 and H2O in the third.
Ethanol (by IUPAC) or better known as ethyl
alcohol is colourless liquid and has a characteristic smell. It is miscible in water in any
To distinguish ethanol from
proportions and toxic, affecting the central nervous
methanol
the borax test is used.
system. It freezes at 114C and boils at 78.3C.
When boric acid reacts with
The ethyl alcohol commercially used as a solvent
methanol, a pale green flame is
in labs usually is 96% (96 g of ethanol and 4 g of
observed.
water in 100 g sample). This mixture is the com mon ethyl alcohol. 100% pure ethyl alcohol is known as absolute alcohol. Pure
ethyl alcohol can be prepared by adding lime (CaO) to common ethanol. The rest
water is eliminated as white precipitate of Ca(OH)2. Ethyl alcohol is an important
organic solvent. It is used as a solvent in iodine tincture, paints, perfumes and
cosmetics. It is also found in drinks, spirit and cologne. In schools usually takes in
the spirit lamps. It is a starting substance for many synthesis processes. Its widely
use as a disinfectant because kills the organisms by denaturing their proteins and it
is effective against bacterial spores. Ethyl alcohol which is taken into the body via
alcoholic beverages slowly causes permanent harmful effects.
Blood Alcohol Level Affect on the Body and Behaviour
The effects of drinking
alcoholic beverages depend
upon the amount of actual
ethyl alcohol consumed and
body weight. The level of
alcohol in the blood is
calculated in milligrams of
pure ethyl alcohol per
deciliter of blood and is
commonly expressed as a
percentage.

Blood alcohol
level

Effect

0.01 0.02%
0.05%
0.08 0.1%
0.15 0.2%
0.3 0.4%

Changes in behavior and ability to think clearly

Sedation and tranquilized feeling
Legal intoxication in some countries
Person is intoxicated and may show signs of delirium
Loss of consciousness
Heart and respiration become so depressed that they cease
to function and death follows

0.5%

Glycol (ethylene glycol) or ethane-1,2-diol (IUPAC name) is dihydric alcohol

with molecular formula C2H4(OH)2. It is a colourless, odorless, syrupy liquid, highly
soluble in water. Since it has a low freezing point it is used as antifreeze in
automobiles. A high boiling point (197C) and heat of vaporization also makes it
useful for this purpose. It is also used as a paint, oil, ink and resin solvent. Ethylene
glycol produces oxalic acid (dicarboxylic acid) and various side-products when it is
oxidized.
Glycerine (glycerol) or propane-1,2,3-triol (IUPAC name) is nonpoisonous,
syrupy liquid that absorbs moisture well. It freezes at 18C and boils at 290C.
Glycerol mixes with water, methanol and ethanol in all proportions. It is used as a
moisturizing substance in tobacco, shaving and toilet soaps, cosmetics and lotions
and in the manufacture of plastics, cellophane, water colours, printing press-ink,
dynamite and hydraulic brakes fluid in cars.