The Wonderful World of

Alcohols: A Comprehensive
Guide for BSc Students
Welcome to an in-depth exploration of alcohols, fundamental organic compounds with
diverse applications and fascinating chemical properties. This presentation will cover
everything from their basic structure to their wide-ranging uses in medicine and industry,
providing a solid foundation for your understanding.
Introduction to Alcohols

Structure, Classification and Nomenclature

Alcohols are organic compounds characterised by the presence of at least one hydroxyl (-OH) functional group attached to a saturated carbon atom. Their
general formula is R-OH, where R represents an alkyl or substituted alkyl group. They are classified based on the number of alkyl groups attached to the
carbon bearing the hydroxyl group: primary (1°), secondary (2°), and tertiary (3°) alcohols.

1 2 3

Primary Alcohols (1°) Secondary Alcohols (2°) Tertiary Alcohols (3°)

The -OH group is attached to a carbon atom The -OH group is attached to a carbon atom The -OH group is attached to a carbon atom
that is bonded to only one other carbon that is bonded to two other carbon atoms that is bonded to three other carbon atoms
atom (e.g., ethanol). (e.g., propan-2-ol). (e.g., 2-methylpropan-2-ol).

Nomenclature typically follows IUPAC rules, with the '-ol' suffix indicating the presence of the hydroxyl group and its position in the longest carbon chain.
For example, CH£CH¢OH is ethanol, and (CH£)¢CHOH is propan-2-ol.
Chapter 1: Properties of Alcohols

Physical Properties: Polarity, Hydrogen Bonding and

Solubility
Alcohols exhibit unique physical properties primarily due to the highly polar nature of the hydroxyl group. The electronegativity difference between oxygen
and hydrogen creates a partial negative charge on oxygen and a partial positive charge on hydrogen, making the molecule polar.

Hydrogen Bonding
The presence of the -OH group allows alcohols to form strong
intermolecular hydrogen bonds with each other. This strong attraction
leads to higher boiling points compared to alkanes of similar molecular
weight, as more energy is required to overcome these forces.

For example, ethanol (boiling point 78°C) has a significantly higher boiling
point than ethane (boiling point -88°C), despite their comparable
molecular masses.

The ability to form hydrogen bonds with water molecules also makes lower molecular weight alcohols highly soluble in water. As the non-polar alkyl chain
increases in size, the solubility in water decreases due to the diminishing influence of the polar hydroxyl group. For instance, methanol and ethanol are
miscible with water, while hexan-1-ol is only sparingly soluble.
Chapter 2: Preparation of Alcohols

Industrial and Laboratory Preparation Methods

Alcohols are synthesised through various methods, both for large-scale industrial production and for smaller-scale laboratory synthesis.

Industrial Methods Laboratory Methods

Fermentation: Primarily for ethanol production from sugars Grignard Reagents: Reaction of alkyl halides with magnesium to
(e.g., glucose) using yeast. form Grignard reagents (RMgX), which then react with carbonyl
Hydration of Alkenes: Addition of water to alkenes, typically compounds (aldehydes, ketones, esters) to form alcohols upon
catalysed by strong acids (e.g., H¢SO¤), to produce alcohols. hydrolysis.
This is used for producing propan-2-ol from propene. Reduction of Carbonyl Compounds: Aldehydes and ketones can
Hydroformylation and Hydrogenation: Reaction of alkenes with be reduced to alcohols using reducing agents like lithium
carbon monoxide and hydrogen (syngas) followed by aluminium hydride (LiAlH¤) or sodium borohydride (NaBH¤).
hydrogenation, yielding primary alcohols.

Each method has specific advantages and is chosen based on the desired alcohol, scale of production, and available starting materials.
Preparation of Alcohols via Nucleophilic Substitution
Reactions
Alcohols can be effectively synthesised from haloalkanes (alkyl halides) through nucleophilic substitution reactions. This involves the replacement of a
halogen atom by a hydroxyl group.

The reaction typically proceeds via SN1 or SN2 mechanisms, depending on the structure of the haloalkane (primary, secondary, or tertiary) and the
reaction conditions.

SN2 Mechanism SN1 Mechanism

Primary haloalkanes readily undergo SN2 reactions, where a strong Tertiary haloalkanes prefer SN1 reactions, which involve a two-step
nucleophile (like hydroxide ion, OH{) attacks the carbon bearing the process. First, the leaving group (halogen) departs to form a carbocation
halogen from the backside, leading to inversion of configuration. This is a intermediate. Second, the nucleophile attacks the carbocation. This often
concerted, one-step process. results in a racemic mixture if the carbocation is chiral.

R 2 CH2 2 X + OH 2 ³ R 2 CH2 2 OH + X 2 (CH3 )3 C 2 X ³ (CH3 )3 C + + X 2

For example, bromoethane reacting with aqueous potassium hydroxide (CH3 )3 C + + H2 O ³ (CH3 )3 C 2 OH2+
yields ethanol.
(CH3 )3 C 2 OH2+ ³ (CH3 )3 C 2 OH + H +

Secondary haloalkanes can react via both SN1 and SN2 mechanisms, with
the preferred pathway dependent on factors such as solvent polarity and
nucleophile strength.
Preparation of Alcohols via Reduction of Carbonyl
Compounds
The reduction of carbonyl compounds (aldehydes, ketones, carboxylic acids, and esters) is a highly versatile and important method for synthesising
various types of alcohols.

The most common reducing agents used are lithium aluminium hydride (LiAlH¤) and sodium borohydride (NaBH¤).

Reduction of Aldehydes Reduction of Ketones

Aldehydes are reduced to primary alcohols. For example, ethanal Ketones are reduced to secondary alcohols. For example, propanone
(acetaldehyde) yields ethanol. (acetone) yields propan-2-ol.

R 2 CHO + [H] ³ R 2 CH2 2 OH R 2 CO 2 R2 + [H] ³ R 2 CH(OH) 2 R2

Reduction of Carboxylic Acids Reduction of Esters

Carboxylic acids are reduced to primary alcohols. This reaction typically Esters are also reduced to primary alcohols using LiAlH¤. This reaction
requires a strong reducing agent like LiAlH¤, as NaBH¤ is generally not yields two alcohol molecules: one from the acyl portion and one from the
strong enough. alkoxyl portion of the ester.

R 2 COOH + [H] ³ R 2 CH2 2 OH R 2 COOR2 + [H] ³ R 2 CH2 2 OH + R2 2 OH

These reductions are highly chemoselective, allowing for the precise synthesis of desired alcohol structures.
Chapter 3: Reactions of Alcohols

Acidity and Basicity of Alcohols: Comparing Reactivity

Alcohols exhibit both acidic and basic properties, though they are generally weaker acids than water and weaker bases than ethers. Their reactivity in acid-
base reactions depends on the polarisation of the O-H bond and the availability of lone pairs on the oxygen atom.

Acidity
Alcohols can act as weak acids, donating a proton from the hydroxyl
group to a strong base to form an alkoxide ion (RO{).

R 2 OH + B 2 ³ R 2 O2 + BH

The acidity of alcohols follows the order: primary > secondary > tertiary.
This is due to the electron-donating inductive effect of alkyl groups, which
destabilise the negative charge on the alkoxide ion, making proton
removal more difficult.

For instance, methanol is slightly more acidic than ethanol, and tert-
butanol is significantly less acidic.

Conversely, alcohols can act as weak bases, accepting a proton from a strong acid to form an oxonium ion (ROH¢z), particularly at the oxygen atom's lone
pairs. This protonation often activates the hydroxyl group for subsequent nucleophilic reactions, such as dehydration.
Dehydration Reactions: Formation of Alkenes and Ethers
Dehydration is a crucial elimination reaction where alcohols lose a molecule of water to form unsaturated compounds (alkenes) or ethers. The products
formed depend on the reaction conditions, specifically temperature and the presence of acidic catalysts.

Formation of Alkenes Formation of Ethers

When alcohols are heated with strong acids (e.g., concentrated H¢SO¤ or At lower temperatures (around 140°C for primary alcohols) and in the
H£PO¤) at higher temperatures (typically 170°C for primary alcohols, lower presence of an acid catalyst, two molecules of alcohol can undergo
for secondary and tertiary), they undergo intramolecular dehydration to intermolecular dehydration to form an ether. This reaction is particularly
form alkenes. effective for symmetrical ethers derived from primary alcohols.

R 2 CH2 2 CH2 2 OH ³ R 2 CH = CH2 + H2 O 2R 2 OH ³ R 2 O 2 R + H2 O

The ease of dehydration follows the order: tertiary > secondary > primary This process, often called the Williamson ether synthesis, is generally a
alcohols, consistent with the stability of carbocation intermediates substitution reaction (SN2 type) where one alcohol molecule acts as a
formed during the reaction (E1 mechanism) or steric hindrance (E2 nucleophile and the other as a substrate.
mechanism).

These reactions are essential in organic synthesis for preparing various hydrocarbons and oxygen-containing compounds from alcohols.
Esterification and Other Important Reactions of Alcohols
Beyond oxidation and dehydration, alcohols undergo several other significant reactions, making them versatile intermediates in organic synthesis.

Esterification Reaction with Active Metals Halogenation

Alcohols react with carboxylic acids (or acid Alcohols react with active metals (e.g., Alcohols can react with hydrogen halides (HX)
derivatives like acid chlorides/anhydrides) in sodium, potassium) to produce hydrogen gas or phosphorus halides (PCl£, PBr£, SOCl¢) to
the presence of an acid catalyst to form esters and alkoxide salts. This demonstrates their form haloalkanes. The reactivity with HX
and water. This is a reversible condensation weakly acidic nature. follows the order HI > HBr > HCl.
reaction.
2R 2 OH + 2N a ³ 2R 2 R 2 OH + HX ³ R 2 X + H2 O
2
R 2 COOH + R 2 OH O 2 N a + + H2
This reaction is important for converting
Esters are widely used as flavourings, Alkoxides are strong bases and useful alcohols into other functional groups.
fragrances, and solvents. nucleophiles.

These reactions highlight the diverse synthetic utility of alcohols as starting materials for a vast array of organic compounds.