Monofunctional Organic Chemistry

Fifth meeting
 Alcohols and Ethers
1. General Features
Alcohols and ethers are two functional groups that contain carbonoxygen bonds.

Alcohols contain a hydroxy group (OH group) bonded to an sp hybridized carbon

atom. Alcohols are classified as primary (1), secondary (2), or tertiary (3) based on
the number of carbon atoms bonded to the carbon with the OH group.
Ethers have two alkyl groups bonded to an oxygen atom. An ether is symmetrical if the
two alkyl groups are the same, and unsymmetrical if they are different.

Both alcohols and ethers are organic derivatives of HO, formed by replacing one or
both of the hydrogens on the oxygen atom by R groups, respectively.

O O O
H H R H R R
2. Structure and Bonding

3. Nomenclature

3.1 Naming Alcohols

hexan-3-ol

Answer: 5-methylhexan-3-ol
3-methylcyclohexanol

2,5,5-trimethylcyclohexanol
ethylene glycol
(ethane-1,2-diol)

glycerol
(propane-1,2,3-triol)

trans-cyclopentane-1,2-diol
3.2 Naming Ethers
Name the longer chain as an alkane and the shorter chain as an alkoxy group.

Apply the other nomenclature rules to complete the name.

Answer: 4-ethoxyoctane
4. Physical Properties
 Property Observation
Boiling point (bp) For compounds of comparable molecular weight, the stronger
and the intermolecular forces, the higher the bp or mp.
melting point (mp)

Bps increase as the extent of hydrogen bonding increases.

Solubility Alcohols and ethers having 5 Cs are HO soluble because they

each have an oxygen atom capable of hydrogen bonding to HO.
Alcohols and ethers having > 5 Cs are HO insoluble because the
nonpolar alkyl portion is too large to dissolve in HO.
Alcohols and ethers of any size are soluble in organic solvents.
5. Preparation of Alcohols and Ethers
Alcohols and ethers are both common products of nucleophilic substitution. They
are synthesized from alkyl halides by SN2 reactions using strong nucleophiles. As
in all SN2 reactions, highest yields of products are obtained with unhindered
methyl and 1 alkyl halides.

The Williamson ether synthesis

The mechanism is SN2, the preferred path uses the less sterically hindered halide.
6. General FeaturesReactions of Alcohols and Ethers
6.1 Alcohols

Alkenes are formed by

elimination.

X Alkyl halides are formed by

nucleophilic substitution.
When an alcohol has two or three different carbons, dehydration is regioselective
and follows the Zaitsev rule. The more substituted alkene is the major product
when a mixture of constitutional isomers is possible.

More substituted alcohols dehydrate more readily, giving rise to the following
order of reactivity:
6.2 Ethers

Like alcohols, ethers do not contain a good leaving group, which means that
nucleophilic substitution and elimination do not occur directly. Ethers undergo
fewer useful reactions than alcohols.

Reaction of Ethers with Strong Acid

Cleavage of the 3 C O bond by an SN1 mechanism
Cleavage of the CH O bond by an SN2 mechanism