Sie sind auf Seite 1von 53

Carboxylic Acids and

Carboxylic Acid Derivatives


Chapter 14
1. Carboxylic acids
The carboxyl group consists of carbonyl and hydroxyl
groups attached to the same carbon.

carbonyl + hydroxyl = carboxyl







An aliphatic or aromatic group can be attached to the carboxyl
group.


1. Carboxylic acids
The acyl group is a carboxyl group with either a hydroxyl or
alkoxy group.







If R is a hydroxyl group, the compound is a carboxylic acid.
If R is an alkoxy group, the compound is an ester.
1. Carboxylic acids: boiling points
Intermolecular forces are
strong in carboxylic acids
due to

the high polarity of the
carboxyl group;



the presence of hydrogen-
bonding between
carboxylic acid molecules.

1. Carboxylic acids: boiling points

When two hydrogen
bonds form between
two carboxylic acid
molecules, the result is
a dimer.

Dimer formation can
cause carboxylic acids
to seem to have double
their actual molecular
mass.
1. Carboxylic acids: boiling points
Compare molecules with similar molar masses and different
functional groups:
1. Carboxylic acids: boiling points
Boiling point (
o
C) vs. number
of carbons for acids,
alcohols, aldehydes, and
alkanes.
Lower molecular weight carboxylic acids are very soluble in
water.
Vinegar is a solution of ethanoic acid.



Solubility falls off as molecular weight increases.
Why?
Hexadecanoic acid is insoluble in water.
1. Carboxylic acids: solubility
1. Carboxylic acids: solubility


Solubility (g acid/g H
2
O)
vs. number of carbons for
saturated, unbranched-
chain carboxylic acids.
1. Carboxylic acids: nomenclature

Determine the parent compound from the
longest chain that includes the carboxyl
carbon.
Number the chain so that the carboxyl
carbon is carbon 1.
Replace the e ending with oic acid.
Assign numbers to any remaining substituents.

1. Carboxylic acids: nomenclature
Additional notes:
If two carboxyl groups are present use dioic acid.
For cycloalkanes, add carboxylic acid to the name of
the cycloalkane.
For aromatic acids, the simplest acid is benzoic
acid.
If the acid group is attached to the aromatic ring, name after
benzoic acid.
If the acid group is not attached to the aromatic ring, name
after the longest chain, with a phenyl substituent.
1. Carboxylic acids: nomenclature





pencast
1. Carboxylic acids: nomenclature
Name the following compounds:
pencast
1. Carboxylic acids: nomenclature
Draw structures for the following compounds:
2,5-dimethylhexanoic acid
3-bromo-5-chlorooctanoic acid
2,2-dimethylbutanedioic acid
3-methylcyclohexanecarboxylic acid
2,4-dichlorobenzoic acid
3-phenylpentanoic acid
pencast
1. Carboxylic acids
Is alpha-hydroxy an actual substance?

glycolic acid


lactic acid


tartaric acid
1. Carboxylic acids
The last paragraph in the inset box on pages 460-461 of
your textbook states:
"For the time being, biodegradable plastics cannot outcompete their
nonbiodegradable counterparts. Future research and development
will be required to reduce the cost of commercial production and
fulfill the promise of an 'environmentally friendly' garbage bag.
This statement gives the impression that there are no biodegradable
plastics available to consumers at a reasonable cost.
Compostable plastic bags
1. Carboxylic acids: reactions
Preparation is by complete oxidation of primary alcohols or
oxidation of aldehydes.
1
o
alcohol aldehyde carboxylic acid
1. Carboxylic acids: reactions
Carboxylic acids are proton donors and therefore react as
acids.
Carboxylic acids are weak acids, dissociating only slightly
in solution.

>95% <5%
1. Carboxylic acids: reactions
When a strong base is added to a carboxylic (weak) acid,
water and salt are formed.
Although the carboxylic acid isnt initially completely
dissociated, as H
+
is removed by reaction with OH
-
, more
acid dissociates.
Remember le Chateliers principle?




When product (H
+
) is removed, the equilibrium shifts to make more
product (and less undissociated acid).
1. Carboxylic acids: reactions
Acid-base reaction






carboxylic acid + strong base carboxylic acid salt + water
1. Carboxylic acids: reactions
Naming salts of carboxylic acids
Name the carboxylic acid.
Replace the ic acid ending with ate.
Precede this name with the name of the cation.

Name the salts formed in the following reactions:
ethanoic acid + KOH
benzoic acid + LiOH
hexanoic acid + NaOH
pencast
1. Carboxylic acids: reactions
Esterification is the formation of water and an ester from a
carboxylic acid and an alcohol.







More about this in the next section
2. Esters
Esters are carboxylic acid derivatives, in which the acidic
-H of the acid has been replaced by an alkyl or aryl group
R.
carboxylic acid ester derivative
2. Esters: properties
Esters

are slightly polar;

boil at about the same temperature as corresponding aldehydes and
ketones;

are somewhat soluble in water when they are small.

have pleasant aromas.

2. Esters: nomenclature
Recall nomenclature of salts of carboxylic acids.
Name the carboxylic acid.
Replace the ic acid ending with ate.
Precede this name with the name of the cation.

Esters are named in the same way, except the alkyl or aryl
portion of the alcohol is used in place of the cation name.
Name the carboxylic acid.
Replace the ic acid ending with ate.
Precede this name with the name of the alkyl or aryl portion of the
alcohol.
2. Esters: nomenclature
Name the following esters.
pencast
2. Esters: nomenclature
Draw the structures of the following esters.
propyl ethanoate
octyl decanoate
methyl methanoate
2-methylpropyl propanoate
3-methylbutyl ethanoate
phenyl pentanoate
pencast
2. Esters: reactions
Preparation of esters is by reaction of a carboxylic acid and
an alcohol to produce an ester and water.
This is a dehydration reaction. [water is lost]
Heat and a trace of acid catalyst (H
+
) are required.
The reaction produces an equilibrium mixture.
heat
2. Esters: reactions
Show the esterification reaction that would produce butyl
propanoate.
pencast
2. Esters: reactions
Esters can be synthesized starting from alcohols only.
An alcohol can be oxidized to an aldehyde, and further oxidized to a
carboxylic acid.
This carboxylic acid can undergo an esterification reaction with
another alcohol.

Name the required alcohols and show the necessary
reactions to produce
pentyl butanoate (apricots).
octyl ethanoate (oranges).
pencast
2. Esters: reactions
Hydrolysis (hydration) of esters, when it is acid-catalyzed,
is the reverse of the esterification reaction.
ester carboxylic acid alcohol
H
2
O
2. Esters: reactions
Hydrolysis of esters, when it is base-catalyzed, is called
saponification.



ester carboxylic acid salt alcohol
2. Esters: reactions
The carboxylic acid that forms when the ester breaks up
reacts immediately with the base, forming the carboxylate
anion, associated with the cation of the base.
2. Esters: reactions
What are the products of the following reactions?
+ H
2
O
+ H
2
O
+ H
2
O
+ H
2
O
pencast
2. Esters: saponification
+ +
(salts of carboxylic acids)
2. Esters: saponification
A soap (carboxylic acid salt)

has a nonpolar end that dissolves in nonpolar fats and oils, and a
polar end that dissolves in water.

forms groups of soap molecules called micelles that dissolve in
water and are washed away.

2. Esters: saponification
EXTRA CREDIT QUESTION
Radioactive isotopes of an element behave chemically in exactly
the same manner as the nonradioactive isotopes. As a result,
they can be used as tracers to investigate the details of chemical
reactions. A scientist is curious about the origin of the bridging
oxygen atom in an ester molecule. She has chosen to use the
radioactive isotope
18
O to study the following reaction:




Design experiments using
18
O that will demonstrate whether the
oxygen in the water molecule came from the OH of the alcohol
or the OH of the carboxylic acid.
Post your answer in the Journal for this module with tag = XC.
3. Acid chlorides and acid anhydrides
Acid chlorides are carboxylic acid derivatives in which the
hydroxyl group, -OH, has been replaced by Cl.





Naming
Name the corresponding carboxylic acid.
Replace the -oic acid ending with oyl chloride.
3. Acid chlorides and acid anhydrides
Examples
ethanoic acid ethanoyl chloride
benzoic acid benzoyl chloride
3. Acid chlorides and acid anhydrides
Name the following acid chlorides.






Draw structures for the following acid chlorides.
heptanoyl chloride
2-hydroxypropanoyl chloride
pencast
3. Acid chlorides and acid anhydrides
Preparation of acid chlorides







The reagents PCl
3
, PCl
5
, and SOCl
2
are inorganic acid chlorides
PCl
3
or
+ PCl
5
or
SOCl
2

+ inorganic products
3. Acid chlorides and acid anhydrides
PCl
3
, PCl
5
, and SOCl
2
replace the hydroxyl group on the
acid with a chloride, by the following mechanism!
3. Acid chlorides and acid anhydrides
Write an equation for the reaction of benzoic acid with
SOCl
2
and name the organic product.
SOCl
2

benzoyl chloride
pencast
3. Acid chlorides and acid anhydrides
Acid anhydrides are two carboxylic acid molecules with a
water molecule removed.
+ H
2
O
3. Acid chlorides and acid anhydrides
Acid anhydrides with identical acyl groups are symmetrical.






Symmetrical acid anhydrides are named after the acid from
which they are made, with the acid ending replaced with
anhydride.
The molecule above, made from two molecules of ethanoic acid, is
called ethanoic anhydride.
3. Acid chlorides and acid anhydrides
Unsymmetrical anhydrides have two different acyl groups.






Unsymmetrical anhydrides are named using both parent
carboxylic acid names, in alphabetical order, followed by the
word anhydride.
The molecule above is called butanoic ethanoic anhydride.
3. Acid chlorides and acid anhydrides
Name the following acid anhydrides.
pencast
3. Acid chlorides and acid anhydrides
Acid anhydrides can be prepared from an acid chloride and
a carboxylate anion.

Direct reaction of the two parent carboxylic acids is usually not
possible.
acid chloride carboxylate anion acid anhydride
3. Acid chlorides and acid anhydrides
Write equations for the synthesis of butanoic anhydride,
beginning with butanoic acid.
pencast
3. Acid chlorides and acid anhydrides
Acid anhydrides react with water, if it is present, to produce
two carboxylic acids.
+ H
2
O
3. Acid chlorides and acid anhydrides
What are the products of the hydrolysis of


ethanoic anhydride?




ethanoic methanoic anhydride?
pencast
3. Acid chlorides and acid anhydrides
An acid anhydride can also react with an alcohol, in a
reaction analogous to hydrolysis.
Hydrolysis: products are two carboxylic acids.




Reaction with alcohol: products are an ester and an acid.

Das könnte Ihnen auch gefallen