FUNCTIONAL GROUPS
Carbon can form more compounds than any other element because carbon
atoms are able not only to form single, double, and triple carbon-carbon bonds but
also to link up with each other in chains and ring structures. The branch of chemistry
that deals with carbon compounds is organic chemistry.
Classes of organic compounds can be distinguished according to the functional
groups they contain. A functional group is a group of atoms that is largely responsible
for the chemical behavior of the parent molecule. Different molecules containing the
same kind of functional group or groups undergo similar reactions. Thus, by learning
the characteristic properties of a few functional groups, we can study and understand
the properties of many organic compounds.
Some Functional Groups and Their Reactions
Functional Group Name Reactions
Carbon-carbon Addition reactions with halogens,
hydrogen halides, and water;
double bond
hydrogenation to yield alkanes
Carbon-carbon Addition reactions with halogens,
hydrogen halides; hydrogenation to yield
triple bond
alkenes and alkanes
Halogen Exchange reactions:
(X = F, Cl, Br, I) CH3CH2Br + KI → CH3CH2I + KBr
Esterification (formation of an ester) with
Hydroxyl carboxylic acids; oxidation to aldehydes,
ketones, and carboxylic acids
Carbonyl Reduction to yield alcohols; oxidation of
aldehydes to yield carboxylic acids
Esterification with alcohols; reaction with
Carboxyl phosphorus pentachloride to yield acid
chlorides
Ester Hydrolysis to yield acids and alcohols
(R = Hydrocarbon)
Amine Formation of ammonium salts with acids
(R = H or Hydrocarbon)
We now examine in greater depth some organic functional groups, groups that
are responsible for most of the reactions of the parent compounds. In this lesson, we
will focus on oxygen-containing and nitrogen-containing organic compounds.
Alcohols
All alcohols contain the hydroxyl functional group, –OH. Some common
alcohols are shown below:
Ethyl alcohol, or ethanol, is by far the best known. It is produced biologically by
the fermentation of sugar or starch. In the absence of oxygen, the enzymes present
in bacterial cultures or yeast catalyze the reaction,
This process gives off energy, which microorganisms, in turn, use for growth
and other functions. Commercially, ethanol is prepared by an addition reaction in
which water is combined with ethylene at about 280°C and 300 atm:
Ethanol has countless applications as a solvent for organic chemicals and as a
starting compound for the manufacture of dyes, synthetic drugs, cosmetics, and
explosives. It is also a constituent of alcoholic beverages.
The simplest alcohol is methanol, CH 3OH. Also called wood alcohol, it was
prepared at one time by the dry distillation of wood. It is now synthesized industrially
by the reaction of carbon monoxide and molecular hydrogen at high temperatures and
pressures:
Methanol is highly toxic. Ingestion of only a few milliliters can cause nausea and
blindness. Ethanol intended for industrial use is often mixed with methanol to prevent
people from drinking it. Ethanol containing methanol or other toxic substances is called
denatured alcohol.
Two other familiar aliphatic alcohols are 2-propanol (or isopropanol), commonly
known as rubbing alcohol, and ethylene glycol, which is used as an antifreeze. Most
alcohols–especially those with low molar masses–are highly flammable.
Ethers
Ethers contain the R–O–R’ linkage, where R and R’ are a hydrocarbon
(aliphatic or aromatic) group. They are formed by the reaction between an alkoxide
(containing the RO- ion) and an alkyl halide:
Diethyl ether is prepared on an industrial scale by heating ethanol with sulfuric
acid at 140°C,
C2H5OH + C2H5OH → C2H5OC2H5 + H2O
This reaction is an example of a condensation reaction, which is
characterized by the joining of two molecules and the elimination of a small molecule,
usually water.
Like alcohols, ethers are extremely flammable. When left standing in air, they
tend to slowly form explosive peroxides:
Diethyl ether, commonly known as “ether,” was used as an anesthetic for many
years. It produces unconsciousness by depressing the activity of the central nervous
system. The major disadvantages of diethyl ether are its irritating effects on the
respiratory system and the occurrence of postanesthetic nausea and vomiting.
“Neothyl,” or methyl propyl ether, CH 3OCH2CH2CH3, is currently favored as an
anesthetic because it is relatively free of side effects.
Aldehydes and Ketones
The functional group in these compounds is the carbonyl group, . In
an aldehyde at least one hydrogen atom is bonded to the carbon in the carbonyl group.
In a ketone, the carbon atom in the carbonyl group is bonded to two hydrocarbon
groups.
The simplest aldehyde, formaldehyde (H2C=O). Higher molar mass aldehydes,
such as cinnamic aldehyde have a pleasant odor and are used in the manufacture of
perfumes.
cinnamic aldehyde
Under mild oxidation conditions, it is possible to convert alcohols to aldehydes
and ketones:
Carboxylic Acids
Under appropriate conditions both alcohols and aldehydes can be oxidized to
carboxylic acids, acids that contain the carboxyl group, –COOH:
Some common carboxylic acids:
Carboxylic acids are widely distributed in nature; they are found in both the plant
and animal kingdoms. All protein molecules are made of amino acids, a special kind
of carboxylic acid containing an amino group (–NH2) and a carboxyl group (–COOH).
Glycine is one of the amino acids found in proteins.
Unlike the inorganic acids HCl, HNO3, and H2SO4, carboxylic acids are usually
weak. They react with alcohols to form pleasant-smelling esters:
Other common reactions of carboxylic acids are neutralization,
and formation of acid halides, such as acetyl chloride
Esters
The functional group in esters is the –COOR group. Esters have the general
formula R’COOR, where R’ can be H or a hydrocarbon group and R is a hydrocarbon
group. Esters are used in the manufacture of perfumes and as flavoring agents in the
confectionery and soft-drink industries. Many fruits owe their characteristic smell and
flavor to the presence of small quantities of esters. For example, bananas contain 3-
methylbutyl acetate [CH3COOCH2CH2CH(CH3)2], oranges contain octyl acetate
(CH3COOCHCH3C6H13), and apples contain methyl butyrate (CH3CH2CH2COOCH3).
In the presence of an acid catalyst, such as HCl, esters undergo hydrolysis
to yield a carboxylic acid and an alcohol. For example, in acid solution, ethyl acetate
hydrolyzes as follows:
Ester hydrolysis is usually carried out in basic solutions. The term
saponification (meaning soapmaking) was originally used to describe the alkaline
hydrolysis of fatty acid esters to yield soap molecules (sodium stearate):
Saponification has now become a general term for alkaline hydrolysis of any
type of ester.
Amines
Amines are organic bases having the general formula R3N, where R may be H
or a hydrocarbon group. As with ammonia, the reaction of amines with water is,
Like all bases, the amines form salts when allowed to react with acids:
These salts are usually colorless, odorless solids. Aromatic amines are used
mainly in the manufacture of dyes. Aniline, the simplest aromatic amine, itself is a toxic
compound; several other aromatic amines such as 2-naphthylamine and benzidine
are potent carcinogens:
CLASSES OF ORGANIC COMPOUNDS
R indicates an Alkyl group and Ar indicates Aryl group.
General Example
FAMILY Class
Formula Structural Formula Chemical Name
Alkanes RH Ethane
Ethylene
Alkenes RC=CR
(ethene)
HYDRO- Acetylene
CARBONS Alkynes RC≡CR
(ethyne)
Arenes ArH Benzene
Alkyl Ethyl chloride
RX
HALOGEN- Halides (chloroethane)
CONTAINING
COMPOUNDS
(X indicates a
Halogen) Aryl
ArX Chlorobenzene
Halides
Ethyl Alcohol
Alcohols ROH
(ethanol)
Phenols ArOH Phenol
Ethers ROR Diethyl ether
OXYGEN-
CONTAINING
COMPOUNDS
Acetaldehyde
Aldehydes RCHO
(ethanal)
Acetone
Ketones RRC=O
(2-propanone)
Carboxylic Acetic Acid
RCO2H
Acids (ethanoic acid)
Esters
Methyl Acetate
(carboxylic
RCO2R (methyl
acid
ethanoate)
CARBOXYLIC derivatives)
ACIDS
DERIVATIVES Amides
(carboxylic N-methyl-
RCONHR
acid acetamide
derivatives)
RNH2,
Amines RNHR, Ethylamine
RNRR
NITROGEN-
CONTAINING Nitrile RC≡N Acetonitrile
COMPOUNDS
Nitro
ArNO2 Nitrobenzene
compounds
Part 1. Make a similar diagram and fill it up using the keywords inside the box.
Classes of Organic
Compounds
Oxygen-Containing
Hydrocarbons
Compounds
Aryl halides Amides
Nitriles
Carbons Amines Halogen-Containing Compounds Alkyl halides
Alkenes Nitriles Phenols Amides Carboxylic Acid Derivatives
Fluorine-Containing Compounds Alkynes Aryl halides Aldehydes
Alcohols Arenes Ketones Nitrogen-Containing Compounds Alkanes
Ethers Hydrocarbons Nitro compounds Carboxylic acid Esters
Part 2. Draw the Lewis structure for each of the following functional groups.
1. Ether
2. Aldehyde
3. Ketone
4. Carboxylic acid
5. Ester
Part 3. Name the functional group for each of the following classes of organic
compounds.
1. Alcohol
2. Aldehyde
3. Carboxylic acid
4. Ester
5. Amine
Part 4. Classify each of the following molecules as alcohol, aldehyde, ketone,
carboxylic acid, amine, or ether.
1.
2.
3.
4.
5.
6.
7.
Part 5. Draw structures for molecules with the following formulas and encircle the
functional group present.
1. CH4O
2. C2H6O
3. C3H6O2
4. C3H8O
5. C2H4
Part 6. Name the classes to which the following compounds belong.
1. C4H9OH
2. CH3OC2H5
3. C2H5CHO
4. C6H5COOH
5. CH3NH2
Part 7. Identify the functional groups in each of the following molecules.
1. CH3CH2COCH2CH2CH3
2. CH3COOC2H5
3. CH3CH2OCH2CH2CH2CH
4. CH3COOCH2CH2CH(CH3)2
5. CH3CH2CH2CH2OH
Part 8. Predict the product or products of each of the following reactions.
1. CH3CH2OH + HCOOH →
2. H–C≡C–CH3 + H2 →
3.
4. CH3OH + CH3CH2COOH →
5. C2H5OH + C2H5OH →
Part 9. Provide a compound containing the functional group in the first column. Place
it in the second column and draw the structure of the compound in the third column.
Compounds found in the notes are not counted.
Functional Group Compound Name Structure