HYDROXY COMPOUNDS

ALCOHOLS
 Alcohols
Introduction—Structure and Bonding

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

hybridized carbon.

2
 Classification

• Primary: carbon with –OH is bonded to one other

carbon.
• Secondary: carbon with –OH is bonded to two other
carbons.
• Tertiary: carbon with –OH is bonded to three other
carbons.
• Aromatic (phenol): -OH is bonded to a benzene
ring.
• OH group takes priority over -ene
- it must be in the parent chain
- the direction of numbering gives it the

lowest possible number

• -ol suffix with number designation

• name other substituents and multiple bonds as usual

• more than one alcohol named as a -diol, -triol, etc.

 Classify these:

CH3 CH3
CH3 CH CH2OH CH3 C OH
CH3

OH OH
CH3 CH CH2CH3
Example
 NOMENCLATURE OF ALCOHOLS
The IUPAC nomenclature is based on the longest continuous carbon
chain containing the –OH group as the parent alcohol. The
following rules are followed.
(a) Select the longest carbon chain that contains the –OH group.
The parent alcohol is obtained by replacing the "e" of the
corresponding alkane with the suffix "ol".

Some examples are:

(b) Number the parent chain beginning at the end nearer to the –
OH group, to give the hydroxyl group the lowest possible number.
Complete the name by naming all other substituents with their
numerical positions, listing the substituents in alphabetical order.
(c) When the –OH group is attached to a ring, the ring is numbered
beginning with the carbon atom that bears the –OH group. The
number 1 is not used in the name to indicate the position of the
hydroxyl group. Numbering continues in the direction that gives the
lowest numbers to carbon atoms with substituents.
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.
• Unsaturated alcohols
– Show the double bond by changing the infix from -an- to -en-.
– Show the the OH group by the suffix -ol.
– Number the chain to give OH the lower number.

2-hexen-1-ol
(d) Alcohols that contain two or more –OH groups are known as
diols, triols and so on.
• Examples

OH
OH OH
1-Propanol 2-Propan ol 1-Bu tanol
(Propyl alcohol) (Isoprop yl alcoh ol) (Bu tyl alcoh ol)

OH
OH OH

2-Butanol 2-Meth yl-1-p ropan ol 2-Meth yl-2-p ropan ol

(s ec-Butyl alcohol) (Isobutyl alcohol) (tert -Butyl alcohol)
 Naming Phenols

• -OH group is assumed to be on carbon 1.

• For common names of disubstituted phenols, use
ortho- for 1,2; meta- for 1,3; and para- for 1,4.
• Methyl phenols are cresols.

OH
OH

H3C

Cl
4-methylphenol
3-chlorophenol para-cresol
meta-chlorophenol
 Name these:

CH3
OH
CH3 CH CH2OH
CH3 CH CH2CH3

CH3 OH
CH3 C OH
CH3
Br CH3
 PHYSICAL PROPERTIES OF ALCOHOLS

Solubility
• Alcohols exhibit properties of both alkane and water.
• The alkyl group acts like an alkane and is said to be
hydrophobic ("water-hating").
• The -OH group can form hydrogen bonds to neighbouring
water molecules and is hydrophilic ("water-loving").
• Each alcohol molecule can form two hydrogen bonds to
water molecules: two hydrogen bonds are formed between
the two sets of lone pair electrons of the alcohol oxygen
atom.
• When the hydrocarbon chain is short, the alcohols are miscible
(soluble in any proportions) with water. Methanol, ethanol and 1-
propanol are infinitely soluble in water.
• As the hydrocarbon chain becomes longer, the hydrophobic
character of the molecule increases, that is, the alcohol becomes
more like an alkane, less like water, and nonpolar overall.
• As a result, the solubility of the alcohol in water gradually
decreases until it becomes essentially insoluble in water. After the 7-
carbon heptanol, alcohols are considered immiscible. 1-decanol is
insoluble in water.
• Branching increases the solubility of alcohols in water. Although
1-butanol is only slightly soluble in water, t-butanol is miscible with
water because the t-butyl group is more compact and less
hydrophobic than the n-butyl group in 1-butanol.
• An increase in the number of –OH groups also increases
hydrophilicity and water solubility.
• Thus sucrose or table sugar, which has 8 –OH groups is readily
soluble in water.
• Alcohols are polar compounds due to the polar C-O and O-H
bonds
• They interact with themselves and with other polar compounds
by dipole-dipole interactions
• Dipole-dipole interaction:
the attraction between the positive end of one dipole and the
negative end of another.
• Hydrogen Bonding
 Physical Properties

bp Solubility
Structural Formula Name MW (°C) in Water
CH3 OH Methanol 32 65 Infinite
CH3 CH3 Ethane 30 -89 Insoluble
CH3 CH2 OH Ethanol 46 78 Infinite
CH3 CH2 CH3 Propane 44 -42 Insoluble
CH3 CH2 CH2 OH 1-Propanol 60 97 Infinite
CH3 CH2 CH2 CH3 Butane 58 0 Insoluble
CH3 ( CH 2 ) 2 CH 2 OH 1-Butanol 74 117 8 g/100 g
CH3 ( CH 2 ) 3 CH3 Pentane 72 36 Insoluble
HOCH2 ( CH2 ) 2 CH2 OH 1,4-Butanediol 90 230 Infinite
CH3 ( CH 2 ) 3 CH2 OH 1-Pentanol 88 138 2.3 g/100 g
CH3 ( CH 2 ) 4 CH3 Hexane 86 69 Insoluble
 Example
Which compound would be more soluble in water, 1-pentanol or
cyclopentanol?
Cyclopentanol is less soluble than 1-pentanol in water.
 SYNTHESIS OF ALCOHOLS
1. Fermentation Process
• The fermentation of sugars has been used since ancient times to make
alcohol. In fermentation, the sugars are broken down by microbes,
usually yeasts, in an anaerobic environment.
• Ethanol is produced when yeast enzymes convert sugars into alcohol
and carbon dioxide.
• The fermentation reaction, which is represented by a simple equation.

C6H12O6 (aq) enzyme zimase/25-30°C 2 CH3CH2OH (aq) + 2 CO2 (g)

condition : sugar and yeast , warm , mild acidity , aqueous , dilute

Yeast contains enzymes that promote series of reaction to convert a simple sugar
(C6H12O6) into ethanol and CO2
2. Hydration of Alkenes
Alkene reacts with water in the presence of an acid catalyst, such as
sulphuric acid or phosphoric acid, to form an alcohol. The general
equation is:

Examples:

Acid-catalyzed hydration of alkenes follows Markovnikov's rule:

H adds to the carbon of the double bond with the greater number of hydrogens
and OH adds to the carbon of the double bond with the lesser number of
hydrogens.
3. Hydrolysis of Haloalkanes
Primary alcohols may be prepared by reacting haloalkanes with
aqueous hydroxide solution.

NaOHaq
boiling

4. Reduction of Aldehydes and Ketones

Aldehydes and ketones are readily reduced to alcohols.
Reduction of an aldehyde gives a primary alcohol while
reduction of a ketone gives a secondary alcohol.
 CHEMICAL PROPERTIES
1. Dehydration of Alcohols
Alkenes can add water to yield alcohols.
In a reverse reaction, alcohols can lose water molecule when they
are heated with an acid catalyst such as H2SO4.

During the dehydration of an alcohol, a H– and –OH are removed

from adjacent carbon atoms of the same alcohol to produce a
water molecule. A double bond forms between the same two
carbon atoms to produce an alkene.
H OH
H+, heat
H-C-C-H H-C=C-H + H2O

H H H H
alcohol (ethanol) alkene (ethene)
Dehydration of Alcohols

• 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.
Mechansim: Elimination
Acid-catalyzed dehydrations normally follow Zaitzev's rule,
giving the more highly substituted alkene as the major
product.
2. Conversion into Haloalkanes
Alcohols react with hydrogen halides, HX, (HCl, HBr, HI) to give the
corresponding haloalkane.

Tertiary alcohols are readily converted to haloalkanes, while primary and

secondary alcohols react more slowly. The reactivity order of alcohols
towards HX is: 3º alcohol > 2º alcohol > 1º alcohol.
The reactivity of the hydrogen halides is HI > HBr > HCl.
Conversion of primary and secondary alcohols into haloalkanes are best
carried out with other halogenating reagents. Phosphorus tribromide, PBr3,
is often the best reagent for converting a primary or secondary alcohol to
bromoalkanes.
Reflux
CH3CH2CH2OH + HBr CH3CH2CH2Cl + H2O
H2O
 3. Esterification

• Acid + Alcohol yields Ester + Water

• Sulfuric acid is a catalyst.
• Need to reflux.

O CH3 + O CH3
H
CH3 C OH + H O CH2CH2CHCH3 CH3C OCH2CH2CHCH3
reflux
+ HOH
4. Oxidation
Primary alcohols can be oxidized to either aldehydes or
carboxylic acids. It depends on the reagents used.

Normal oxidizing agents such as chromium trioxide, CrO3 and

sodium dichromate, Na2Cr2O7 in aqueous acid oxidize primary
alcohols to carboxylic acids.

Strong oxidizing agents such as hot alkaline potassium

permanganate, KMnO4 will also oxidize primary alcohols.
Secondary alcohols are oxidized to ketones, which cannot be
oxidized further under normal conditions.

Secondary alcohols can be oxidized to ketones by using

sodium dichromate in aqueous acid. Acidified chromium
trioxide can also be used.
 5. Reaction with PX3 / PX5

• An alternative method for the synthesis of chloroalkanes

bromoalkanes is reaction of an alcohol with PCl3, PCl5, PBr3,
PBr5.

Reaction with phosphorus(III) chloride, PCl3

• Alcohols react with liquid phosphorus(III) chloride
(also called phosphorus trichloride) to make
chloroalkanes.
Reaction with phosphorus(V) chloride, PCl5
• Solid phosphorus(V) chloride (phosphorus
pentachloride) reacts violently with alcohols at room
temperature, producing white fumes of hydrogen
chloride gas. It isn't a good choice as a way of making
chloroalkanes, although it is used as a test for -OH
groups in organic chemistry.
6. Reaction with sodium metal
• Alcohols react with sodium metal to produce hydrogen
gas. (hydrogen of the OH group is displaced by Na)
 CHARACTERIZATION TEST
1. Reaction with PCl5

2. Oxidation
• Recall that 1º alcohols are oxidized to aldehydes and then to
carboxylic acids, on prolonged oxidation.
• 2º Alcohols are oxidized to ketones, while 3º alcohols do not
undergo oxidation under the stated reaction conditions.
• The common method is to heat the alcohol with a solution of
potassium dichromate, K2Cr2O7, acidified with dilute
sulphuric acid.
• As it oxidizes the alcohol, the orange chromic acid (VI oxidation
state) is reduced to the green chromium (III) ion which is easily
observed.

• Oxidation can also be carried out by heating with an alkaline

solution of potassium permanganate, KMnO4. The purple
permanganate colour is decolourized and a brown precipitate
of manganese(IV) oxide, MnO2, is formed.
 CHARACTERIZATION TEST
• PCl5
Reagent: PCl5
Condition: Room temperature
Equation:

CH3CH2CH2OH + PCl5 CH3CH2CH2Cl + POCl3 + HCl(g)

propan-1-ol 1-chloropropane white f umes

Observation: White fumes are observed for

propan-1-ol
No changes for X
 CHARACTERIZATION TEST
• Oxidation
Reagent: K2Cr2O7
Condition: H2SO4, heat
Equation:

+
CH3CH2CH2OH + K2Cr2O7 H
CH3CH2CHO
heat
Observation: The solution changes from orange
to green for propan-1-ol
No changes for X
 CHARACTERIZATION TEST

• Esterification
Observation: Sweet smell of ester will be formed

H2SO4

reflux
 Example

Q: Show how would you distinguish between 2-butanol and

2-methyl-2-propanol.