Chemistry of the functional groups

Alcohol
Ethers
Aldehyde
Ketones
Carboxylic Acids & derivates

Ethers: the constitutional isomer of

alcohol
R-O-R
containing C-O-C less reactive
valuable as solvent
diethyl ether the most well known, used
as an anesthetic (medicinal) and solvent
(industry)
other examples: THF (tetrahydrofuran, a
cyclic ether for solvent), anisole (aromatic
ether used in perfumery)

Nomenclature

substitutive IUPAC: as alkoxy derivatives of

alkanes.
Functional class IUPAC: derived by listing the
two alkyl groups in the general structure ROR in
alphabetical order as separate words, and then
adding the word ether at the end.
When

both alkyl groups are the same, the prefix diprecedes the name of the alkyl group

the name of the alkyl group.

diethyl ether
ethoxyethane

ethyl methyl ether 3-chloroprophyl ethyl ether

methoxyethane 1-chloro-3-ethoxypropane

Nomenclature

if R=R symmetrical ether, otherwise

unsymmetrical or mixed ether
For cyclic ethers: the ring is numbered starting at
the oxygen
The IUPAC rules also permit:
oxirane

(without substituents) to be called ethylene oxide.

tetrahydrofuran oxolane and tetrahydropyran oxane

are acceptable synonyms for oxolane and oxane

ethylene oxide
ethoxyethane oxetane

tetrahydrofuran
oxolane

tetrahydropyran
oxane

Nomenclature

ethers having more than 1 ether linkage diether

and triether

diethylene glycol dimethyl ether

1,2-dimethoxyethane 1,4-dioxane

diglyme

Structure and bonding

Van der Waals strain involving alkyl groups
the bond angle at oxygen to be larger in ethers
than alcohols, and larger in alcohols than in
water.
ditert-butyl ether -- steric hindrance between
the tert-butyl groups

Typical C-O bond distances in ethers are

similar to those of alcohols (142 pm)
and are shorter than C-C bond distances in
alkanes (153 pm).

Structure and bonding

Incorporating an oxygen atom into a three-membered ring requires its

bond angle distorted from the normal tetrahedral value.
Thus epoxides, like cyclopropanes, are strained tend to undergo
reactions that open the three-membered ring by cleaving one of the C-O
bonds.

Structure and bonding

Ethers, like water and alcohols, are polar.
Diethyl ether 1.2 D.
Cyclic ethers have larger dipole moments
ethylene oxide and tetrahydrofuran have dipole
moments in the 1.7- to 1.8-D rangeabout the same
as that of water.
PROBLEM. The heats of combustion of 1,2-epoxybutane (2-ethyloxirane)
and tetrahydrofuran have been measured: one is 2499 kJ/mol (597.8
kcal/mol); the other is 2546 kJ/mol (609.1 kcal/mol).
Match the heats of combustion with the respective compounds.

Physical properties
Boiling points: ethers resemble alkanes more than alcohols.
Solubility in water: ethers resemble alcohols more than alkanes.

Why?
Boiling point: 35 oC
36 oC
Solubility in water: 7.5g/100 mL insoluble

117 oC
9 g/100 mL

hydrogen bonding in alcohol Bp higher

Attractive forces in the liquid phases of ethers and alkanes -- lack -OH groups,
cannot form intermolecular hydrogen bonds Bp lower.
in ethers -- the presence of an oxygen atom permits to participate in hydrogen
bonds to water molecules ethers dissolve in water ~ to constituted alcohols.
Alkanes cannot engage in hydrogen bonding to water.

H bonding in water

Ether preparation

A long-standing method for the preparation of ethers is the Williamson ether

synthesis.
Nucleophilic substitution of an alkyl halide by an alkoxide gives the carbon oxygen
bond of an ether

caution !
Most ethers are hazardous materials precautions must be
taken when using them.
Diethyl ether is extremely flammable, high volatility can
form explosive mixtures in air relatively quickly.
Open flames must never be present in laboratories
Easily to undergo oxidation in air to form explosive
peroxides.

1-ethoxyethyl hydroperoxide

Chemistry of the functional groups

Alcohol
Ethers
Aldehyde
Ketones
Carboxylic Acids & derivates

Aldehydes and ketones contain an acyl group bonded

either to hydrogen or to another carbon.

Nomenclature
1. The longest continuous chain that contains the group provides the base
name for aldehydes.
2. The -e ending of the corresponding alkane name is replaced by al
3. substituents are specified in the usual way. It is not necessary to specify the
location of the group in the name, since the chain must be numbered by
starting with this group as C-1.
4. The suffix -dial is added to the appropriate alkane name when the
compound contains two aldehyde functions.

5-hexenal
4,4-dimethylpentanal
2-phenylpropanedial

Nomenclature
5. When a formyl group (-CH=O) is attached to a ring, the ring name is followed
by the suffix -carbaldehyde.

6. Certain common names of familiar aldehydes are acceptable as IUPAC

names. A few examples include

exercise: provide IUPAC name

With ketones, the -e ending of an alkane is replaced by -one in the longest continuous
chain containing the carbonyl group.
The chain is numbered in the direction that provides the lower number for this group.

Although substitutive names of the type just described are preferred, the IUPAC
rules also permit ketones to be named by functional class nomenclature.
The groups attached to the carbonyl group are named as separate words followed
by the word ketone. The groups are listed alphabetically.

exercise
Convert each of the following functional class IUPAC
names to a substitutive name.
(a) Dibenzyl ketone
(b) Ethyl isopropyl ketone
(c) Methyl 2,2-dimethylpropyl ketone
(d) Allyl methyl ketone

structure and bonding: geometry and

polarity

10

The carbonyl group makes aldehydes and ketones rather polar, with
molecular dipole moments that are substantially larger than those of
comparable compounds that contain carboncarbon double bonds.

resonance structure
The chemistry of the carbonyl group is
considerably simplified if you
remember that carbon is partially
positive (has carbocation character)
and oxygen is partially negative
(weakly basic).

11

Alkyl substituents stabilize a carbonyl group in much the same

way that they stabilize carboncarbon double bonds and
carbocationsby releasing electrons to sp2-hybridized carbon.
Thus, as their heats of combustion reveal, the ketone 2butanone is more stable than its aldehyde isomer butanal.

Physical properties

Aldehydes and ketones can form hydrogen bonds with the protons of OH
groups. This makes them more soluble in water than alkenes, but less
soluble than alcohols.

12